[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP0377409A2 - Process for dyeing leather - Google Patents

Process for dyeing leather Download PDF

Info

Publication number
EP0377409A2
EP0377409A2 EP89810976A EP89810976A EP0377409A2 EP 0377409 A2 EP0377409 A2 EP 0377409A2 EP 89810976 A EP89810976 A EP 89810976A EP 89810976 A EP89810976 A EP 89810976A EP 0377409 A2 EP0377409 A2 EP 0377409A2
Authority
EP
European Patent Office
Prior art keywords
dye
formula
sulfo
substituted
amino
Prior art date
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.)
Granted
Application number
EP89810976A
Other languages
German (de)
French (fr)
Other versions
EP0377409B1 (en
EP0377409A3 (en
Inventor
Bruno Martinelli
Markus Ghezzi
Günter Streicher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=4177193&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0377409(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0377409A2 publication Critical patent/EP0377409A2/en
Publication of EP0377409A3 publication Critical patent/EP0377409A3/en
Application granted granted Critical
Publication of EP0377409B1 publication Critical patent/EP0377409B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • D06P1/44—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 insoluble pigments or auxiliary substances, e.g. binders
    • 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
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid 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
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • D06P3/3226—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo
    • 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
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • D06P3/3226—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo
    • D06P3/3233—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo using dis-polyazo premetallised dyes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing

Definitions

  • the present invention relates to a method for dyeing leather and dye mixtures suitable therefor.
  • compositions which contain an anionic dye, an inorganic pigment and a suitable binder, for example an acrylic resin; the colored composition forms e.g. after the application by spraying a film on the leather surface.
  • the invention therefore relates to a process for dyeing leather by the exhaust process, characterized in that an aqueous liquor which has a dye mixture comprising an anionic dye and a pigment is allowed to act on the leather.
  • Anionic dyes that can be used are all dyes usually used in leather dyeing; Acid dyes and direct dyes such as, in particular, sulfo-containing monoazo, disazo and polyazo dyes and metal complex dyes are preferred.
  • the anionic dyes can have any color; black dyes are preferred, this term also including, for example, dyes with a dark blue, blue-gray, gray or yellowish, reddish or greenish black shade.
  • a group of particularly suitable anionic dyes corresponds to the formula where one X is hydroxy and the other X is amino or hydrogen, A is an optionally substituted phenyl or naphthyl radical, B represents a phenyl or naphthyl radical containing at least one amino and / or hydroxyl group and optionally further substituents, Z a rest R and R 'independently of one another are hydrogen, sulfo, C1-C4-alkyl or C1-C4-alkoxy and n is 1 or 2.
  • the phenyl or naphthyl radical A can carry one or more identical or different substituents, for example: C1-C4-alkyl, which here and in general methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or includes tert-butyl; C1-C4 alkoxy, which generally means methoxy, ethoxy, n- or iso-propoxy or n-, iso, sec.- or tert.-butoxy; Halogen, which means for example fluorine, bromine and especially chlorine; Trifluoromethyl; C1-C4 alkylsulfonyl, especially methyl or ethylsulfonyl; Sulfamoyl, for example -SO2NH2 or N-mono- or N, N-di-C1-C4-alkylaminosulfonyl; Carbamoyl, for example -CONH2 or N-mono
  • A is preferably an unsubstituted or substituted by halogen, nitro, sulfo, C1-C4-alkyl and / or C1-C4-alkoxy phenyl radical.
  • the phenyl or naphthyl radical B can carry other radicals besides amino and hydroxy, e.g. an N-mono- or N, N-di-C1-C4-alkylamino, phenylamino, o-, m- or p-methylphenylamino, an unsubstituted or e.g. benzoylamino, C1-C4alkanoylamino or carboxymethylamino or methyl, chlorine or nitro substituted or one of the substituents mentioned above for A.
  • an N-mono- or N, N-di-C1-C4-alkylamino, phenylamino, o-, m- or p-methylphenylamino an unsubstituted or e.g. benzoylamino, C1-C4alkanoylamino or carboxymethylamino or methyl, chlorine or nitro substituted or one of the substituents mentioned above for A
  • B is preferably a phenyl radical which has a hydroxyl or amino group and a further substituent selected from the group consisting of hydroxyl, amino, phenylamino, o-, m- or p-methylphenylamino, C1-C4alkoxy and phenoxy.
  • B particularly preferably represents the remainder of 1,3-dihydroxybenzene, 1,3-diaminobenzene or 3-aminophenol.
  • R and R 'independently of one another are preferably hydrogen, methyl, methoxy or sulfo.
  • Preferred Z radicals are: where R ⁇ means, for example, hydrogen, methyl, methoxy or sulfo.
  • n is preferably the number 2.
  • the anionic dyes of the formula (1) have as the naphthol coupling component e.g. 2-amino-5-naphthol-7-sulfonic acid (I-acid), 1-amino-8-naphthol-4,6-disulfonic acid (K-acid) or preferably 1-amino-8-naphthol-3,6-disulfonic acid (H acid).
  • the naphthol coupling component e.g. 2-amino-5-naphthol-7-sulfonic acid (I-acid), 1-amino-8-naphthol-4,6-disulfonic acid (K-acid) or preferably 1-amino-8-naphthol-3,6-disulfonic acid (H acid).
  • a group of anionic dyes which is particularly preferred for the process according to the invention corresponds to the formula wherein A 'is a phenyl radical which is unsubstituted or substituted by halogen, nitro, sulfo, C1-C4-alkyl and / or C1-C4-alkoxy, B' is a phenyl radical which has a hydroxyl or amino group and a further substituent selected from the group hydroxyl , Amino, phenylamino, o-, m- or p-methylphenylamino, C1-C4 alkoxy and phenoxy, means Z 'is a radical of the formula wherein R ⁇ has the meaning given above, and one X ′ is hydroxy and the other X ′ is amino.
  • the dyes of the formula (1) or (1a) are known per se or can be obtained in a manner known per se.
  • anionic dyes are heavy metal-containing monoazo, disazo or polyazo dyes and azomethine dyes.
  • the anionic character of these dyes can be achieved by metal complex formation alone and / or by acidic salt-forming substituents, such as carboxylic acid groups, phosphonic acid groups and especially sulfonic acid groups.
  • the 1: 1 or 1: 2 metal complex dyes are preferred.
  • the 1: 1 metal complexes preferably have one or two sulfonic acid groups and contain, for example, a copper, nickel, iron or in particular a chromium atom as the heavy metal.
  • the 1: 2 metal complex dyes contain a heavy metal atom as the central atom, e.g. an iron, cobalt or in particular a chromium atom.
  • Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules.
  • the two dye molecules involved in the complex formation can be the same or different from one another.
  • the 1: 2 metal complex dyes can e.g. contain two azomethine molecules, an azo and an azomethine dye or preferably two azo dyes, which dyes can be substituted with further arylazo and / or arylazoaryleno groups.
  • Aryl means above all benzene or naphthalene residues, which can be optionally substituted, e.g. by nitro, sulfo, halogen, C1-C4-alkyl or C1-C4-alkoxy.
  • the azo or azomethine dye molecules can have water solubilizing groups such as e.g. Carbamoyl, C1-C4 alkylsulfonyl or the acid groups mentioned above. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo or disazo dyes which have sulfonic acid groups.
  • the complex dyes particularly suitable for the process according to the invention correspond, for example, to the formula in the form of the free acid where D and D ′ independently of one another each represent an optionally further substituted benzene or naphthalene radical which contains a hydroxyl group in the ortho position to the azo group, K and K 'each independently represent the remainder of a coupling component of the benzene or naphthalene series, which contains a hydroxy group in the ortho position to the azo group and is optionally further substituted, and Me stands for chrome or cobalt.
  • Both symmetrical and asymmetrical 1: 2 metal complexes are suitable as dyes of the formula (2).
  • Me in formula (2) is preferably chromium.
  • D and D 'independently of one another preferably represent a phenyl or naphthyl radical which may be substituted by sulfo, nitro, C1-C4-alkylsulfonyl, C1-C4-alkyl, halogen and / or in the phenyl part optionally by C1-C4-alkyl, C1- C4-Alkoxy, sulfo, nitro or halogen substituted phenylazo is substituted.
  • residues D and D ' can e.g. derived from the following compounds: anthranilic acid, 4- or 5-sulfo-2-aminophenol, 4- or 5-nitro-2-aminophenol, 4-nitro-6-sulfo-2-aminophenol, 6-nitro-4-sulfo-2 -aminophenol, 4-chloro-5-nitro-2-aminophenol, 4-methyl-2-aminophenol, 6-chloro-4-sulfo2-aminophenol, 4-chloro-6-sulfo-2-aminophenol, 4-chloro or 4-methyl-6-nitro-2-aminophenol, 4-chloro-2-aminophenol, 4-methylsulfonyl-2-amino phenol, 4- (2-methoxyphenylazo) -2-aminophenol, 4- (2-, 3- or 4-sulfophenylazo) -2-aminophenol, 4-phenylazo-2-aminophenol, 1-amino-2-hydroxynaphthalene-4-sul
  • D and D 'independently of one another particularly preferably represent the remainder of a 2-aminophenol, which optionally one or more times by identical or different substituents from the series nitro, sulfo, chlorine, methyl, methoxy, methylsulfonyl and optionally by sulfo, methyl, methoxy , Nitro or chlorine substituted phenylazo is substituted, or for the remainder of a 1-amino-2-hydroxynaphthalene, which is optionally substituted by sulfo and / or nitro.
  • K and K ′ mean e.g. a phenol or 1- or 2-naphthol residue, which may be e.g. by amino, hydroxy, C1-C4 alkoxy, C1-C4 alkyl, C1-C4 alkanoylamino, e.g. Acetylamino, benzolyamino, sulfo, halogen or optionally substituted in the phenyl part by C1-C4-alkyl, C1-C4-alkoxy, sulfo, nitro or halogen-substituted phenylazo.
  • a phenol or 1- or 2-naphthol residue which may be e.g. by amino, hydroxy, C1-C4 alkoxy, C1-C4 alkyl, C1-C4 alkanoylamino, e.g. Acetylamino, benzolyamino, sulfo, halogen or optionally substituted in the
  • suitable coupling components that can be the basis of the residues K and K ′ are: 1-naphthol, 2-naphthol, 1,3- or 1,5-dihydroxynaphthalene, 2-hydroxy-8-acetylaminonaphthalene, 2-naphthol-3-, -4-, -5-, -6-, -7- or -8-sulfonic acid, resorcinol, 3-dimethylamino- or 3-diethylaminophenol, phenylazoresorcinol, o-, m- or p-chlorophenylazoresorcinol, bis- (o-, m- or p-chlorophenylazo) -resorcinol.
  • K and K 'independently of one another represent an unsubstituted or substituted by hydroxy, amino, sulfo or acetylamino 1- or 2-naphthol residue or an unsubstituted or optionally substituted by methyl, methoxy, chlorine, sulfo or nitro substituted resorcinol.
  • the complex dyes of formula (2) have e.g. 0 to 4, preferably 1 to 4 and particularly preferably 1 or 2 sulfo groups.
  • Black complex dyes which are in the form of the free acid of the formula are particularly preferred for the process according to the invention correspond in which D1 and D2 independently of one another the residue of an unsubstituted or substituted by sulfo and / or nitro 1-amino-2-hydroxynaphthalene or the residue of an unsubstituted or 2-aminophenol substituted by nitro, sulfo, chlorine, methyl, methoxy, methylsulfonyl or phenylzo substituted by sulfo, methyl, methoxy, nitro or chlorine and K1 and K2 independently of one another represent an unsubstituted or substituted by hydroxy, amino, sulfo or acetylamino 1- or 2-naphthol residue or an unsubstituted or optionally substituted by methyl, methoxy, chlorine, sulfo or nitro-substituted resorcinol residue, and in which the Has complex dye 1 or 2
  • Examples of preferred black complex dyes are:
  • the metal complex compounds of the formula (2) which are advantageously used in the form of their salts, in particular alkali metal salts, such as lithium, potassium and especially sodium salts or also ammonium salts, are known per se or can be obtained in a manner known per se.
  • the pigment used for the process according to the invention is e.g. all common inorganic white, black and colored pigments, e.g. from Kirk Othmer, Encyclopedia of Chemical Technology Vol. 17, pages 788-838, John Wiley 1982.
  • Examples are: titanium dioxide, zinc oxide, barium sulfate, silicon dioxide [white]; Chromium oxide green (Cr2O3) [green]; Cobalt blue (CoOAl2O3), ultramarine blue (Na (6-8) Al6Si6O24S (2-4) ), iron blue (FeNH4Fe (CN) 6) [blue]; natural and artificial iron oxides, for example Siena brown, iron black (Fe3O4); Russ [black].
  • black pigments in particular carbon black, is preferred, all types of carbon black being suitable.
  • the pigments have an average particle size of e.g. 0.01 to 100 ⁇ m, preferably 0.01 to 1 ⁇ m and particularly preferably 0.015 to 0.5 ⁇ m.
  • the pigment is a carbon black, it preferably has an average particle size of 10 to 100 nm and particularly preferably 20 to 50 nm.
  • the dye mixtures used according to the invention contain the anionic dye and the pigment e.g. in a weight ratio of 95: 5 to 50:50, preferably 90:10 to 60:40 and particularly preferably 80:20 to 70:30; Mixtures of various anionic dyes and / or pigments are also possible.
  • the dye mixtures may also optionally contain a dusting agent, e.g. a dust oil.
  • Mixtures of a black anionic dye and a black inorganic pigment are preferably used for the process according to the invention.
  • Dye mixtures containing a black dye of the formula (1) or (2) given above and a carbon black pigment are particularly preferred.
  • a dye mixture comprising a black anionic dye of the formula (1a) or (2a) given above and a carbon black pigment in a weight ratio of 90:10 to 60:40, and in particular 80:20 to 70: 30th
  • the above-mentioned dye mixtures which essentially consist of an anionic dye and an inorganic pigment, are new and a further subject of the present invention. They can be made e.g. by mechanically mixing the components in a suitable mixing device, e.g. in a ball or pin mill or in a kneader or mixer.
  • the process according to the invention is advantageously carried out by first pretreating the leather to be dyed, e.g. subject to retanning, neutralization and / or Walke.
  • the leather pretreated in this way is then dyed by means of a pull-out method known per se, using one of the aforementioned dye mixtures; for example, the leather is dyed in an aqueous solution with a liquor ratio of 1: 1.5 to 1:20, preferably 1: 2 to 1:10 and a temperature of e.g. 20 to 100 ° C, preferably 40 to 60 ° C.
  • a liquor ratio of 1: 1.5 to 1:20, preferably 1: 2 to 1:10
  • a temperature e.g. 20 to 100 ° C, preferably 40 to 60 ° C.
  • the dyeing time also depends on the type of leather to be dyed, but is generally e.g. 20 to 180 minutes.
  • the dye bath can optionally be added before, during or after the dyeing, other generally customary additives, for example wetting agents, leveling agents, color deepening agents and / or fatty agents.
  • the dyeing process is advantageously acidified, for example with formic acid, to improve bath exhaustion and is allowed to continue for some time.
  • the dyed leather is finished in a manner known per se.
  • the dyeing process according to the invention is suitable for all types of leather, e.g. Grain and suede leather - chrome leather, retanned leather or suede from goat, sheep, beef and pork - suitable.
  • Level, deep, well covering dyeings with good general fastness properties are obtained, e.g. Water, washing, welding, dry cleaning, acid, alkali, solvent and diffusion fastness to soft PVC;
  • the outstanding lightfastness of the dyeings obtainable according to the invention and the coloration of the leather achieved deserve special mention.
  • 100 parts of intermediate-dried sheep nappa leather are pretreated in a liquor prepared from 1000 parts of water, 2 parts of a nonionic wetting agent (polyethylene glycol ether derivative) and 1 part of ammonia 24% strength at 50 ° C. for 60 minutes and then rinsed well.
  • a nonionic wetting agent polyethylene glycol ether derivative
  • the leather prepared in this way is now dyed in a fresh liquor consisting of 500 parts of water and 5 parts of one of the color mixtures mentioned in the table at 50 ° C. for 30 minutes.
  • a fatliquor mixture consisting of 2 parts of sulfited marine oil, 2 parts of a mixture of sulfitated fatty acid esters and animal fat and 4 parts of a mixture of sulfited natural oils and animal fat.
  • a cationic color deepening agent polyquaternary amine / ethylene oxide adduct
  • the dye mixtures used according to Examples 1 to 16 are obtained by simply mixing the components in a mixer.
  • chrome cowhide 100 parts are pretreated in a liquor consisting of 200 parts of water, 1 part of sodium formate and 2 parts of an anionic wetting agent (Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids) for 15 minutes at 30 ° C, then 2 parts of an anionic fatliquor (sulfited marine oil) , 2 parts of an anionic retanning agent (condensation product of aromatic sulfonic acids) and 1.5 parts of sodium hydrogen carbonate are added and the mixture is left to run for 60 minutes.
  • an anionic wetting agent Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids
  • the leather is rinsed well with warm water and then retanned in a fresh liquor consisting of 100 parts of water and 8 parts of an anionic retanning agent (condensation product of aromatic sulfone derivatives with dialkylolcarbamide) at 40 ° C. for 30 minutes. Then 5 parts of the aforementioned anionic fatliquor are added, the mixture is left to run for 60 minutes, 0.5 parts of 85% formic acid are subsequently added and the treatment is continued for a further 15 minutes.
  • an anionic retanning agent condensation product of aromatic sulfone derivatives with dialkylolcarbamide
  • the leather retanned in this way is now dyed in a fresh liquor consisting of 100 parts of water, 0.5 part of ammonia, 1 part of a leveling agent (polyglycol ether derivative) and 2.65 parts of the dye mixture according to Example 2 at 30 ° C. for 30 minutes. Then 8 parts of the above-mentioned fatliquor and 4 parts of a hydrophobizing agent are added. After a further 60 minutes, it is acidified with 2.5 parts of 85% formic acid and the treatment is then continued for 30 minutes.
  • a leveling agent polyglycol ether derivative
  • the liquor additionally contains 0.5 parts of a cationic color deepening agent (polyquaternary amine-ethylene oxide adduct). Then 1 part of 85% strength formic acid is added to the dyebath and after a further 15 minutes 1.5 parts of a cationic fatliquor (preparation based on chlorinated hydrocarbons and n-alkyl derivatives) are added. After a final treatment period of

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Abstract

A process for dyeing leather by the exhaustion method, which is characterised in that an aqueous liquor which contains a dye mixture containing an anionic dye and a pigment is allowed to act on the leather, is described. The leather dyeings obtainable by the process are distinguished by good fastness properties.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Färben von Leder sowie dafür geeignete Farbstoffmischungen.The present invention relates to a method for dyeing leather and dye mixtures suitable therefor.

Es ist bereits bekannt, Leder mit Zusammensetzungen, die einen anionischen Farbstoff, ein anorganisches Pigment und einen geeigneten Binder, etwa ein Acrylharz, enthalten, zu beschichten; die farbige Zusammensetzung bildet dabei nach dem Auftrag z.B. durch Besprühen einen Film auf der Lederoberfläche.It is already known to coat leather with compositions which contain an anionic dye, an inorganic pigment and a suitable binder, for example an acrylic resin; the colored composition forms e.g. after the application by spraying a film on the leather surface.

Es wurde nun überraschend gefunden, dass sich Mischungen, die im wesentlichen aus einem anionischen Farbstoff und einem Pigment bestehen, hervorragend für das Färben von Leder nach dem Ausziehverfahren eignen.It has now surprisingly been found that mixtures which consist essentially of an anionic dye and a pigment are outstandingly suitable for dyeing leather by the exhaust process.

Gegenstand der Erfindung ist daher ein Verfahren zum Färben von Leder nach dem Ausziehverfahren, dadurch gekennzeichnet, dass man auf das Leder eine wässrige Flotte, die eine Farbstoffmischung enthaltend einen anionischen Farbstoff und ein Pigment aufweist, einwirken lässt.The invention therefore relates to a process for dyeing leather by the exhaust process, characterized in that an aqueous liquor which has a dye mixture comprising an anionic dye and a pigment is allowed to act on the leather.

Als anionische Farbstoffe kommen alle üblicherweise in der Lederfärberei verwendeten Farbstoffe in Frage; bevorzugt sind hierbei Säurefarbstoffe und Direktfarbstoffe wie insbesondere sulfogruppenhaltige Monoazo-, Disazo- und Polyazofarbstoffe sowie Metallkomplexfarbstoffe.Anionic dyes that can be used are all dyes usually used in leather dyeing; Acid dyes and direct dyes such as, in particular, sulfo-containing monoazo, disazo and polyazo dyes and metal complex dyes are preferred.

Die anionischen Farbstoffe können eine beliebige Farbe aufweisen; bevorzugt sind schwarze Farbstoffe, wobei dieser Begriff z.B. auch Farbstoffe mit einer dunkelblauen, blaugrauen, grauen oder gelbstichig, rotstichig oder grünstichig schwarzen Nuance mitumfasst.The anionic dyes can have any color; black dyes are preferred, this term also including, for example, dyes with a dark blue, blue-gray, gray or yellowish, reddish or greenish black shade.

Eine Gruppe von besonders geeigneten anionischen Farbstoffen entspricht der Formel

Figure imgb0001
worin ein X Hydroxy und das andere X Amino oder Wasserstoff bedeutet,
A ein gegebenenfalls substituierter Phenyl- oder Naphthylrest ist,
B einen Phenyl- oder Naphthylrest enthaltend mindestens eine Amino- und/oder Hydroxygruppe sowie gegebenenfalls weitere Substituenten bedeutet,
Z einen Rest
Figure imgb0002
 R und R′ unabhängig voneinander Wasserstoff, Sulfo, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy bedeuten und n 1 oder 2 ist.A group of particularly suitable anionic dyes corresponds to the formula
Figure imgb0001
 where one X is hydroxy and the other X is amino or hydrogen,
A is an optionally substituted phenyl or naphthyl radical,
B represents a phenyl or naphthyl radical containing at least one amino and / or hydroxyl group and optionally further substituents,
Z a rest
Figure imgb0002
 R and R 'independently of one another are hydrogen, sulfo, C₁-C₄-alkyl or C₁-C₄-alkoxy and n is 1 or 2.

Der Phenyl- oder Naphthylrest A kann einen oder mehrere gleiche oder verschiedene Substituenten tragen, z.B.: C₁-C₄-Alkyl, welches hier und im weiteren generell Methyl, Ethyl, n- oder iso-Propyl oder n-, iso-, sec.- oder tert.-Butyl umfasst; C₁-C₄-Alkoxy, worunter generell Methoxy, Ethoxy, n- oder iso-Propoxy oder n-, iso, sec.- oder tert.-Butoxy zu verstehen ist; Halogen, womit z.B. Fluor, Brom und insbesondere Chlor gemeint ist; Trifluormethyl; C₁-C₄-Alkylsulfonyl, besonders Methyl-, oder Ethylsulfonyl; Sulfamoyl, z.B. -SO₂NH₂ oder N-Mono- oder N,N-Di-C₁-C₄-­alkylaminosulfonyl; Carbamoyl, z.B. -CONH₂ oder N-Mono- oder N,N-Di-­C₁-C₄-alkylaminocarbonyl, Sulfo; Nitro; Cyano; Carboxy; Phenoxy.The phenyl or naphthyl radical A can carry one or more identical or different substituents, for example: C₁-C₄-alkyl, which here and in general methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or includes tert-butyl; C₁-C₄ alkoxy, which generally means methoxy, ethoxy, n- or iso-propoxy or n-, iso, sec.- or tert.-butoxy; Halogen, which means for example fluorine, bromine and especially chlorine; Trifluoromethyl; C₁-C₄ alkylsulfonyl, especially methyl or ethylsulfonyl; Sulfamoyl, for example -SO₂NH₂ or N-mono- or N, N-di-C₁-C₄-alkylaminosulfonyl; Carbamoyl, for example -CONH₂ or N-mono- or N, N-di-C₁-C₄-alkylaminocarbonyl, sulfo; Nitro; Cyano; Carboxy; Phenoxy.

Vorzugsweise steht A für einen unsubstituierten oder durch Halogen, Nitro, Sulfo, C₁-C₄-Alkyl und/oder C₁-C₄-Alkoxy substituierten Phenylrest.A is preferably an unsubstituted or substituted by halogen, nitro, sulfo, C₁-C₄-alkyl and / or C₁-C₄-alkoxy phenyl radical.

Der Phenyl- oder Naphthylrest B kann ausser Amino und Hydroxy noch weitere Reste tragen, z.B. einen N-Mono- oder N,N-Di-C₁-C₄-Alkylamino-, Phenylamino-, o-, m- oder p-Methylphenylamino-, einen unsubstituierten oder z.B. durch Methyl, Chlor oder Nitro substituierten Benzoylamino-, C₁-C₄-Alkanoylamino- oder Carboxymethylaminorest oder einen der zuvor für A genannten Substituenten.The phenyl or naphthyl radical B can carry other radicals besides amino and hydroxy, e.g. an N-mono- or N, N-di-C₁-C₄-alkylamino, phenylamino, o-, m- or p-methylphenylamino, an unsubstituted or e.g. benzoylamino, C₁-C₄alkanoylamino or carboxymethylamino or methyl, chlorine or nitro substituted or one of the substituents mentioned above for A.

Vorzugsweise handelt es sich bei B um einen Phenylrest, der eine Hydroxy- oder Aminogruppe und einen weiteren Substituenten ausgewählt aus der Gruppe Hydroxy, Amino, Phenylamino, o-, m- oder p-Methylphenylamino, C₁-C₄-Alkoxy und Phenoxy trägt.B is preferably a phenyl radical which has a hydroxyl or amino group and a further substituent selected from the group consisting of hydroxyl, amino, phenylamino, o-, m- or p-methylphenylamino, C₁-C₄alkoxy and phenoxy.

B steht besonders bevorzugt für den Rest von 1,3-Dihydroxybenzol, 1,3-Diaminobenzol oder 3-Aminophenol.B particularly preferably represents the remainder of 1,3-dihydroxybenzene, 1,3-diaminobenzene or 3-aminophenol.

R und R′ bedeuten unabhängig voneinander vorzugsweise Wasserstoff, Methyl, Methoxy oder Sulfo.R and R 'independently of one another are preferably hydrogen, methyl, methoxy or sulfo.

Bevorzugte Reste Z sind:

Figure imgb0003
worin R˝ z.B. Wasserstoff, Methyl, Methoxy oder Sulfo bedeutet.Preferred Z radicals are:
Figure imgb0003
 where R˝ means, for example, hydrogen, methyl, methoxy or sulfo.

n steht vorzugsweise für die Zahl 2.n is preferably the number 2.

Die anionischen Farbstoffe der Formel (1) weisen als Naphthol-Kupplungskomponente z.B. 2-Amino-5-naphthol-7-sulfonsäure (I-Säure), 1-Amino-8-naphthol-4,6-disulfonsäure (K-Säure) oder vorzugsweise 1-Amino-8-naphthol-3,6-disulfonsäure (H-Säure) auf.The anionic dyes of the formula (1) have as the naphthol coupling component e.g. 2-amino-5-naphthol-7-sulfonic acid (I-acid), 1-amino-8-naphthol-4,6-disulfonic acid (K-acid) or preferably 1-amino-8-naphthol-3,6-disulfonic acid (H acid).

Eine für das erfindungsgemässe Verfahren besonders bevorzugte Gruppe von anionischen Farbstoffen entspricht der Formel

Figure imgb0004
worin A′ ein unsubstituierter oder durch Halogen, Nitro, Sulfo, C₁-C₄-Alkyl und/oder C₁-C₄-Alkoxy substituierter Phenylrest ist, B′ einen Phenylrest, der eine Hydroxy- oder Aminogruppe und einen weiteren Substituenten ausgewählt aus der Gruppe Hydroxy, Amino, Phenylamino, o-, m- oder p-Methylphenylamino, C₁-C₄-Alkoxy und Phenoxy aufweist, bedeutet, Z′ einen Rest der Formel
Figure imgb0005
 worin R˝ die zuvor angegebene Bedeutung hat, darstellt und ein X′ Hydroxy und das andere X′ Amino ist.A group of anionic dyes which is particularly preferred for the process according to the invention corresponds to the formula
Figure imgb0004
 wherein A 'is a phenyl radical which is unsubstituted or substituted by halogen, nitro, sulfo, C₁-C₄-alkyl and / or C₁-C₄-alkoxy, B' is a phenyl radical which has a hydroxyl or amino group and a further substituent selected from the group hydroxyl , Amino, phenylamino, o-, m- or p-methylphenylamino, C₁-C₄ alkoxy and phenoxy, means Z 'is a radical of the formula
Figure imgb0005
 wherein R˝ has the meaning given above, and one X ′ is hydroxy and the other X ′ is amino.

Beispiele für besonders bevorzugte schwarze Farbstoffe der Formel (1) sind

Figure imgb0006
Figure imgb0007
 Examples of particularly preferred black dyes of the formula (1) are
Figure imgb0006
Figure imgb0007

Die Farbstoffe der Formel (1) bzw. (1a) sind an sich bekannt oder können in an sich bekannter Weise erhalten werden.The dyes of the formula (1) or (1a) are known per se or can be obtained in a manner known per se.

Eine weitere Gruppe von geeigneten anionischen Farbstoffen stellen schwermetallhaltige Monoazo-, Disazo- oder Polyazofarbstoffe sowie Azomethinfarbstoffe dar. Der anionische Charakter dieser Farbstoffe kann durch Metallkomplexbildung allein und/oder durch saure salzbildende Substituenten, wie z.B. Carbonsäuregruppen, Phosphonsäuregruppen und insbesondere Sulfonsäuregruppen, bedingt sein. Bevorzugt sind die 1:1- oder 1:2-Metallkomplexfarbstoffe. Die 1:1-Metallkomplexe weisen bevorzugt eine oder zwei Sulfonsäuregruppen auf und enthalten als Schwermetall z.B. ein Kupfer-, Nickel-, Eisen- oder insbesondere ein Chromatom.Another group of suitable anionic dyes are heavy metal-containing monoazo, disazo or polyazo dyes and azomethine dyes. The anionic character of these dyes can be achieved by metal complex formation alone and / or by acidic salt-forming substituents, such as carboxylic acid groups, phosphonic acid groups and especially sulfonic acid groups. The 1: 1 or 1: 2 metal complex dyes are preferred. The 1: 1 metal complexes preferably have one or two sulfonic acid groups and contain, for example, a copper, nickel, iron or in particular a chromium atom as the heavy metal.

Die 1:2-Metallkomplexfarbstoffe enthalten als Zentralatom ein Schwermetallatom wie z.B. ein Eisen-, Kobalt- oder insbesondere ein Chromatom. Mit dem Zentralatom sind zwei komplexbildende Komponenten verbunden, von denen mindestens eine ein Farbstoffmolekül ist, vorzugsweise jedoch beide Farbstoffmoleküle sind. Dabei können die beiden an der Komplexbildung beteiligten Farbstoffmoleküle gleich oder voneinander verschieden sein. Die 1:2-Metallkomplexfarbstoffe können z.B. zwei Azomethinmoleküle, einen Azo- und einen Azomethinfarbstoff oder bevorzugt zwei Azofarbstoffe enthalten, wobei diese Farbstoffe mit weiteren Arylazo- und/oder Arylazoarylenazogruppen substituiert sein können. Mit Aryl sind hier vor allem Benzol- oder Naphthalinreste gemeint, welche gegebenenfalls substituiert sein können, z.B. durch Nitro, Sulfo, Halogen, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy. Die Azo- oder Azomethinfarbstoffmoleküle können wasserlöslichmachende Gruppen aufweisen wie z.B. Carbamoyl-, C₁-C₄-Alkylsulfonyl- oder die obengenannten sauren Gruppen. Bevorzugt sind 1:2-Kobalt- oder 1:2-Chromkomplexe von Monoazo- oder Disazofarbstoffen, die Sulfonsäuregruppen aufweisen.The 1: 2 metal complex dyes contain a heavy metal atom as the central atom, e.g. an iron, cobalt or in particular a chromium atom. Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules. The two dye molecules involved in the complex formation can be the same or different from one another. The 1: 2 metal complex dyes can e.g. contain two azomethine molecules, an azo and an azomethine dye or preferably two azo dyes, which dyes can be substituted with further arylazo and / or arylazoaryleno groups. Aryl means above all benzene or naphthalene residues, which can be optionally substituted, e.g. by nitro, sulfo, halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy. The azo or azomethine dye molecules can have water solubilizing groups such as e.g. Carbamoyl, C₁-C₄ alkylsulfonyl or the acid groups mentioned above. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo or disazo dyes which have sulfonic acid groups.

Die für das erfindungsgemässe Verfahren besonders geeigneten Komplexfarbstoffe entsprechen in Form der freien Säure z.B. der Formel

Figure imgb0008
worin D und D′ unabhängig voneinander je einen gegebenenfalls weitersubstituierten Benzol- oder Naphthalinrest, der in ortho-Stellung zur Azogruppe eine Hydroxygruppe enthält, bedeuten,
K und K′ unabhängig voneinander je den Rest einer Kupplungskomponente der Benzol- oder Naphthalinreihe, der in ortho-Stellung zur Azogruppe eine Hydroxygruppe enthält und gegebenenfalls weitersubstituiert ist, darstellen und
Me für Chrom oder Kobalt steht.The complex dyes particularly suitable for the process according to the invention correspond, for example, to the formula in the form of the free acid
Figure imgb0008
 where D and D ′ independently of one another each represent an optionally further substituted benzene or naphthalene radical which contains a hydroxyl group in the ortho position to the azo group,
K and K 'each independently represent the remainder of a coupling component of the benzene or naphthalene series, which contains a hydroxy group in the ortho position to the azo group and is optionally further substituted, and
Me stands for chrome or cobalt.

Als Farbstoffe der Formel (2) kommen sowohl symmetrische als auch asymmetrische 1:2 Metallkomplexe in Frage.Both symmetrical and asymmetrical 1: 2 metal complexes are suitable as dyes of the formula (2).

Me in Formel (2) steht vorzugsweise für Chrom.Me in formula (2) is preferably chromium.

D und D′ stehen unabhängig voneinander bevorzugt für einen Phenyl- oder Naphthylrest, der gegebenenfalls durch Sulfo, Nitro, C₁-C₄-Alkylsulfonyl, C₁-C₄-Alkyl, Halogen und/oder im Phenylteil gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Sulfo, Nitro oder Halogen substituiertes Phenylazo substituiert ist.D and D 'independently of one another preferably represent a phenyl or naphthyl radical which may be substituted by sulfo, nitro, C₁-C₄-alkylsulfonyl, C₁-C₄-alkyl, halogen and / or in the phenyl part optionally by C₁-C₄-alkyl, C₁- C₄-Alkoxy, sulfo, nitro or halogen substituted phenylazo is substituted.

Die Reste D und D′ können sich z.B. von folgenden Verbindungen ableiten: Anthranilsäure, 4- oder 5-Sulfo-2-aminophenol, 4- oder 5-Nitro-2-amino­phenol, 4-Nitro-6-sulfo-2-aminophenol, 6-Nitro-4-sulfo-2-aminophenol, 4-Chlor-5-nitro-2-aminophenol, 4-Methyl-2-aminophenol, 6-Chlor-4-sulfo­2-aminophenol, 4-Chlor-6-sulfo-2-aminophenol, 4-Chlor- oder 4-Methyl-­6-nitro-2-aminophenol, 4-Chlor-2-aminophenol, 4-Methylsulfonyl-2-amino phenol, 4-(2-Methoxyphenylazo)-2-aminophenol, 4-(2-, 3- oder 4-Sulfo­phenylazo)-2-aminophenol, 4-Phenylazo-2-aminophenol, 1-Amino-2-hydroxy­naphthalin-4-sulfonsäure, 1-Amino-2-hydroxy-6-nitronaphthalin-4-­sulfonsäure.The residues D and D 'can e.g. derived from the following compounds: anthranilic acid, 4- or 5-sulfo-2-aminophenol, 4- or 5-nitro-2-aminophenol, 4-nitro-6-sulfo-2-aminophenol, 6-nitro-4-sulfo-2 -aminophenol, 4-chloro-5-nitro-2-aminophenol, 4-methyl-2-aminophenol, 6-chloro-4-sulfo2-aminophenol, 4-chloro-6-sulfo-2-aminophenol, 4-chloro or 4-methyl-6-nitro-2-aminophenol, 4-chloro-2-aminophenol, 4-methylsulfonyl-2-amino phenol, 4- (2-methoxyphenylazo) -2-aminophenol, 4- (2-, 3- or 4-sulfophenylazo) -2-aminophenol, 4-phenylazo-2-aminophenol, 1-amino-2-hydroxynaphthalene-4-sulfonic acid, 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid.

D und D′ stehen unabhängig voneinander besonders bevorzugt für den Rest eines 2-Aminophenols, welches gegebenenfalls ein- oder mehrfach durch gleiche oder verschiedene Substituenten aus der Reihe Nitro, Sulfo, Chlor, Methyl, Methoxy, Methylsulfonyl und gegebenenfalls durch Sulfo, Methyl, Methoxy, Nitro oder Chlor substituiertes Phenylazo substituiert ist, oder für den Rest eines 1-Amino-2-hydroxynaphthalins, welches gegebenfalls durch Sulfo und/oder Nitro substituiert ist.D and D 'independently of one another particularly preferably represent the remainder of a 2-aminophenol, which optionally one or more times by identical or different substituents from the series nitro, sulfo, chlorine, methyl, methoxy, methylsulfonyl and optionally by sulfo, methyl, methoxy , Nitro or chlorine substituted phenylazo is substituted, or for the remainder of a 1-amino-2-hydroxynaphthalene, which is optionally substituted by sulfo and / or nitro.

K und K′ bedeuten z.B. einen Phenol- oder 1- oder 2-Naphtholrest, welcher gegebenenfalls z.B. durch Amino, Hydroxy, C₁-C₄-Alkoxy, C₁-C₄-Alkyl, C₁-C₄-Alkanoylamino, z.B. Acetylamino, Benzolyamino, Sulfo, Halogen oder gegebenenfalls im Phenylteil durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Sulfo, Nitro oder Halogen substituiertes Phenylazo substituiert ist.K and K ′ mean e.g. a phenol or 1- or 2-naphthol residue, which may be e.g. by amino, hydroxy, C₁-C₄ alkoxy, C₁-C₄ alkyl, C₁-C₄ alkanoylamino, e.g. Acetylamino, benzolyamino, sulfo, halogen or optionally substituted in the phenyl part by C₁-C₄-alkyl, C₁-C₄-alkoxy, sulfo, nitro or halogen-substituted phenylazo.

Beispiele für geeignete Kupplungskomponenten, die den Resten K bzw. K′ zugrunde liegen können, sind:
1-Naphthol, 2-Naphthol, 1,3- oder 1,5-Dihydroxynaphthalin, 2-Hydroxy-8-­acetylaminonaphthalin, 2-Naphthol-3-, -4-, -5-, -6-, -7- oder -8-sulfon­säure, Resorcin, 3-Dimethylamino- oder 3-Diethylaminophenol, Phenyl­azoresorcin, o-, m- oder p-Chlorphenylazoresorcin, Bis-(o-, m- oder p-Chlorphenylazo)-resorcin.Examples of suitable coupling components that can be the basis of the residues K and K ′ are:
1-naphthol, 2-naphthol, 1,3- or 1,5-dihydroxynaphthalene, 2-hydroxy-8-acetylaminonaphthalene, 2-naphthol-3-, -4-, -5-, -6-, -7- or -8-sulfonic acid, resorcinol, 3-dimethylamino- or 3-diethylaminophenol, phenylazoresorcinol, o-, m- or p-chlorophenylazoresorcinol, bis- (o-, m- or p-chlorophenylazo) -resorcinol.

Vorzugsweise stehen K und K′ unabhängig voneinander für einen unsubstituierten oder durch Hydroxy, Amino, Sulfo oder Acetylamino substituierten 1- oder 2-Naphtholrest oder für einen unsubstituierten oder durch gegebenenfalls durch Methyl, Methoxy, Chlor, Sulfo oder Nitro substituiertes Phenylazo substituierten Resorcinrest.Preferably, K and K 'independently of one another represent an unsubstituted or substituted by hydroxy, amino, sulfo or acetylamino 1- or 2-naphthol residue or an unsubstituted or optionally substituted by methyl, methoxy, chlorine, sulfo or nitro substituted resorcinol.

Die Komplexfarbstoffe der Formel (2) weisen z.B. 0 bis 4, vorzugsweise 1 bis 4 und besonders bevorzugt 1 oder 2 Sulfogruppen auf.The complex dyes of formula (2) have e.g. 0 to 4, preferably 1 to 4 and particularly preferably 1 or 2 sulfo groups.

Besonders bevorzugt für das erfindungsgemässe Verfahren sind schwarze Komplexfarbstoffe, die in Form der freien Säure der Formel

Figure imgb0009
entsprechen, worin D₁ und D₂ unabhängig voneinander den Rest einer unsubstituierten oder durch Sulfo und/oder Nitro substituierten 1-Amino-2-hydroxynaphthalins oder den Rest eines unsubstituierten oder durch Nitro, Sulfo, Chlor, Methyl, Methoxy, Methylsulfonyl oder gege­benenfalls durch Sulfo, Methyl, Methoxy, Nitro oder Chlor substituiertes Phenylazo substituierten 2-Aminophenols bedeuten und
K₁ und K₂ unabhängig voneinander für einen unsubstituierten oder durch Hydroxy, Amino, Sulfo oder Acetylamino substituierten 1- oder 2-Naphtholrest oder für einen unsubstituierten oder durch gegebenenfalls durch Methyl, Methoxy, Chlor, Sulfo oder Nitro substituiertes Phenylazo substituierten Resorcinrest stehen, und worin der Komplexfarbstoff 1 oder 2 Sulfogruppen aufweist.Black complex dyes which are in the form of the free acid of the formula are particularly preferred for the process according to the invention
Figure imgb0009
 correspond in which D₁ and D₂ independently of one another the residue of an unsubstituted or substituted by sulfo and / or nitro 1-amino-2-hydroxynaphthalene or the residue of an unsubstituted or 2-aminophenol substituted by nitro, sulfo, chlorine, methyl, methoxy, methylsulfonyl or phenylzo substituted by sulfo, methyl, methoxy, nitro or chlorine and
K₁ and K₂ independently of one another represent an unsubstituted or substituted by hydroxy, amino, sulfo or acetylamino 1- or 2-naphthol residue or an unsubstituted or optionally substituted by methyl, methoxy, chlorine, sulfo or nitro-substituted resorcinol residue, and in which the Has complex dye 1 or 2 sulfo groups.

Beispiele für bevorzugte schwarze Komplexfarbstoffe sind:

Figure imgb0010
Figure imgb0011
 Examples of preferred black complex dyes are:
Figure imgb0010
Figure imgb0011

Die Metallkomplexverbindungen der Formel (2), die vorteilhaft in Form ihrer Salze, insbesondere Alkali-, wie Lithium-, Kalium- und vor allem Natriumsalze oder auch Ammoniumsalze, eingesetzt werden, sind an sich bekannt oder können in an sich bekannter Weise erhalten werden.The metal complex compounds of the formula (2) which are advantageously used in the form of their salts, in particular alkali metal salts, such as lithium, potassium and especially sodium salts or also ammonium salts, are known per se or can be obtained in a manner known per se.

Als Pigment kommen für das erfindungsgemässe Verfahren z.B. alle üblichen anorganischen Weiss-, Schwarz- und Buntpigmente, wie sie z.B. aus Kirk Othmer, Encyclopedia of Chemical Technology Vol. 17, Seiten 788-838, John Wiley 1982, bekannt sind, in Frage.The pigment used for the process according to the invention is e.g. all common inorganic white, black and colored pigments, e.g. from Kirk Othmer, Encyclopedia of Chemical Technology Vol. 17, pages 788-838, John Wiley 1982.

Beispiele sind: Titandioxid, Zinkoxid, Bariumsulfat, Siliciumdioxid [weiss]; Chromoxidgrün (Cr₂O₃) [grün]; Kobaltblau (CoOAl₂O₃), Ultramarin­blau (Na(6-8) Al₆Si₆O₂₄S(2-4)), Eisenblau (FeNH₄Fe(CN)₆) [blau]; natür­liche und künstliche Eisenoxide, z.B. Siena-Braun, Eisenschwarz (Fe₃O₄); Russ [schwarz].Examples are: titanium dioxide, zinc oxide, barium sulfate, silicon dioxide [white]; Chromium oxide green (Cr₂O₃) [green]; Cobalt blue (CoOAl₂O₃), ultramarine blue (Na (6-8) Al₆Si₆O₂₄S (2-4) ), iron blue (FeNH₄Fe (CN) ₆) [blue]; natural and artificial iron oxides, for example Siena brown, iron black (Fe₃O₄); Russ [black].

Bevorzugt ist die Verwendung von schwarzen Pigmenten, insbesondere von Russ, wobei alle Arten von Russ geeignet sind.The use of black pigments, in particular carbon black, is preferred, all types of carbon black being suitable.

Die Pigmente weisen eine mittlere Teilchengrösse von z.B. 0,01 bis 100 µm, vorzugsweise 0,01 bis 1 µm und besonders bevorzugt 0,015 bis 0,5 µm auf.The pigments have an average particle size of e.g. 0.01 to 100 µm, preferably 0.01 to 1 µm and particularly preferably 0.015 to 0.5 µm.

Handelt es sich bei dem Pigment um einen Russ, so weist dieser vorzugsweise eine mittlere Teilchengrösse von 10 bis 100 nm und besonders bevorzugt von 20 bis 50 nm auf.If the pigment is a carbon black, it preferably has an average particle size of 10 to 100 nm and particularly preferably 20 to 50 nm.

Die erfindungsgemäss verwendeten Farbstoffmischungen enthalten den anionischen Farbstoff und das Pigment z.B. in einem Gewichtsverhältnis von 95:5 bis 50:50, vorzugsweise 90:10 bis 60:40 und besonders bevorzugt 80:20 bis 70:30; möglich sind auch Gemische verschiedener anionischer Farbstoffe und/oder Pigmente. Die Farbstoffmischungen können ausserdem gegebenenfalls ein Entstäubungsmittel, z.B. ein Stauböl, enthalten.The dye mixtures used according to the invention contain the anionic dye and the pigment e.g. in a weight ratio of 95: 5 to 50:50, preferably 90:10 to 60:40 and particularly preferably 80:20 to 70:30; Mixtures of various anionic dyes and / or pigments are also possible. The dye mixtures may also optionally contain a dusting agent, e.g. a dust oil.

Vorzugsweise verwendet man für das erfindungsgemässe Verfahren Mischungen von einem schwarzen anionischen Farbstoff und einem schwarzen anorganischen Pigment.Mixtures of a black anionic dye and a black inorganic pigment are preferably used for the process according to the invention.

Besonders bevorzugt sind Farbstoffmischungen enthaltend einen schwarzen Farbstoff der zuvor angegebenen Formel (1) oder (2) und ein Russpigment.Dye mixtures containing a black dye of the formula (1) or (2) given above and a carbon black pigment are particularly preferred.

In einer besonders bevorzugten Ausführungsform des erfindungsgemässen Verfahrens verwendet man eine Farbstoffmischung enthaltend einen schwarzen anionischen Farbstoff der zuvor angegebenen Formel (1a) bzw. (2a) und ein Russpigment im Gewichtsverhältnis 90:10 bis 60:40, und insbesondere 80:20 bis 70:30.In a particularly preferred embodiment of the process according to the invention, a dye mixture comprising a black anionic dye of the formula (1a) or (2a) given above and a carbon black pigment in a weight ratio of 90:10 to 60:40, and in particular 80:20 to 70: 30th

Die oben genannten Farbstoffmischungen, die im wesentlichen aus einem anionischen Farbstoff und einem anorganischen Pigment bestehen, sind neu und ein weiterer Gegenstand der vorliegenden Erfindung. Sie können hergestellt werden z.B durch mechanisches Mischen der Komponenten in einer geeigneten Mischvorrichtung, z.B. in einer Kugel- oder Stiftmühle oder in einem Kneter oder Mixer.The above-mentioned dye mixtures, which essentially consist of an anionic dye and an inorganic pigment, are new and a further subject of the present invention. They can be made e.g. by mechanically mixing the components in a suitable mixing device, e.g. in a ball or pin mill or in a kneader or mixer.

Das erfindungsgemässe Verfahren wird vorteilhaft so ausgeführt, dass man das zu färbende Leder zunächst einer Vorbehandlung, z.B. einer Nachgerbung, Neutralisation und/oder Walke unterwirft.The process according to the invention is advantageously carried out by first pretreating the leather to be dyed, e.g. subject to retanning, neutralization and / or Walke.

Das solchermassen vorbehandelte Leder wird dann mittels eines an sich bekannten Ausziehverfahrens unter Verwendung einer der zuvor genannten Farbstoffmischungen ausgefärbt; beispielsweise färbt man das Leder in einer wässrigen Lösung mit einem Flottenverhältnis von 1:1,5 bis 1:20, vorzugsweise 1:2 bis 1:10 und einer Temperatur von z.B. 20 bis 100°C, vorzugsweise 40 bis 60°C. Man verwendet je nach Art des zu färbenden Leders z.B. 0,25 bis 15,0 Gew.-%, vorzugsweise 1,0 bis 10,0 Gew.-%, bezogen auf das Gewicht des Leders, der jeweiligen Farbstoffmischung. Auch die Färbedauer hängt von der Art des zu färbenden Leders ab, beträgt aber im allgemeinen z.B. 20 bis 180 Minuten.The leather pretreated in this way is then dyed by means of a pull-out method known per se, using one of the aforementioned dye mixtures; for example, the leather is dyed in an aqueous solution with a liquor ratio of 1: 1.5 to 1:20, preferably 1: 2 to 1:10 and a temperature of e.g. 20 to 100 ° C, preferably 40 to 60 ° C. Depending on the type of leather to be dyed, e.g. 0.25 to 15.0% by weight, preferably 1.0 to 10.0% by weight, based on the weight of the leather, of the respective dye mixture. The dyeing time also depends on the type of leather to be dyed, but is generally e.g. 20 to 180 minutes.

Dem Färbebad können gegebenenfalls vor, während oder nach der Färbung weitere allgemein übliche Zusätze, z.B. Netzmittel, Egalisiermittel, Farbvertiefungsmittel und/oder Fettungsmittel zugegeben werden. Am Ende des Färbevorgangs wird vorteilhaft z.B. mit Ameisensäure zur besseren Baderschöpfung angesäuert und noch einige Zeit weiterlaufen gelassen. Die Fertigstellung des gefärbten Leders erfolgt in an sich bekannter Weise.The dye bath can optionally be added before, during or after the dyeing, other generally customary additives, for example wetting agents, leveling agents, color deepening agents and / or fatty agents. At the end the dyeing process is advantageously acidified, for example with formic acid, to improve bath exhaustion and is allowed to continue for some time. The dyed leather is finished in a manner known per se.

Das erfindungsgemässe Färbeverfahren ist für alle Ledersorten, z.B. Narben- und Rauhleder - Chromleder, nachgegerbte Leder oder Velourleder von Ziege, Schaf, Rind und Schwein - geeignet. Man erhält egale, tiefe gut deckende Färbungen mit guten Allgemein-Echtheiten, z.B. Wasser-, Wasch-, Schweiss-, Trockenreinigungs-, Säure-, Alkali-, Lösungsmittel­und Diffusionsechtheit gegenüber Weich-PVC; besondere Erwähnung verdient die hervorragende Lichtechtheit der erfindungsgemäss erhältlichen Färbungen sowie die erzielte Durchfärbung des Leders.The dyeing process according to the invention is suitable for all types of leather, e.g. Grain and suede leather - chrome leather, retanned leather or suede from goat, sheep, beef and pork - suitable. Level, deep, well covering dyeings with good general fastness properties are obtained, e.g. Water, washing, welding, dry cleaning, acid, alkali, solvent and diffusion fastness to soft PVC; The outstanding lightfastness of the dyeings obtainable according to the invention and the coloration of the leather achieved deserve special mention.

Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung, ohne sie darauf zu beschränken. Teile bedeuten Gewichtsteile und Prozente Gewichtsprozente.The following examples serve to illustrate the invention without restricting it. Parts mean parts by weight and percentages percent by weight.

Beispiele 1-16:Examples 1-16:

100 Teile zwischengetrocknetes Schafnappaleder werden in einer aus 1000 Teilen Wasser, 2 Teilen eines nichtionogenen Netzmittels (Polyethylenglykolether-Derivat) und 1 Teil Ammoniak 24 %ig zubereiteten Flotte während 60 Minuten bei 50°C vorbehandelt und anschliessend gut gespült.100 parts of intermediate-dried sheep nappa leather are pretreated in a liquor prepared from 1000 parts of water, 2 parts of a nonionic wetting agent (polyethylene glycol ether derivative) and 1 part of ammonia 24% strength at 50 ° C. for 60 minutes and then rinsed well.

Das derart vorbereitete Leder wird nun in einer frischen Flotte, bestehend aus 500 Teilen Wasser und 5 Teilen einer der in der Tabelle genannten Farbmischungen, 30 Minuten bei 50°C gefärbt. Danach erfolgt ein Zusatz von 8 Teilen eines Fettungsmittelgemisches, das aus 2 Teilen sulfitiertem Seetieröl, 2 Teilen eines Gemisches aus sulfitierten Fettsäureestern und animalischen Fettstoffen sowie 4 Teilen eines Gemisches aus sulfitierten natürlichen Ölen und animalischen Fettstoffen besteht. Nach weiteren 60 Minuten wird mit 4 Teilen Ameisensäure 85 %ig angesäuert (pH ca. 3,2) und hierauf die Behandlung 20 Minuten fortgesetzt. Man gibt 2 Teile eines kationischen Farbvertiefungsmittels (Polyquaternäres Amin-Ethylenoxid-Addukt) hinzu und lässt noch 20 Minuten weiterlaufen.The leather prepared in this way is now dyed in a fresh liquor consisting of 500 parts of water and 5 parts of one of the color mixtures mentioned in the table at 50 ° C. for 30 minutes. This is followed by the addition of 8 parts of a fatliquor mixture consisting of 2 parts of sulfited marine oil, 2 parts of a mixture of sulfitated fatty acid esters and animal fat and 4 parts of a mixture of sulfited natural oils and animal fat. After a further 60 minutes, it is acidified with 4 parts of 85% formic acid (pH approx. 3.2) and the treatment is then continued for 20 minutes. 2 parts of a cationic color deepening agent (polyquaternary amine / ethylene oxide adduct) are added and the mixture is left to run for a further 20 minutes.

Anschliessend wird in einem frischen Bad noch mit 5 Teilen der oben eingesetzten Farbstoffmischung in 500 Teilen Wasser während 30 Minuten bei 50°C nachgefärbt. Dann werden dem Färbebad 3 Teile eines nichtionischen synthetischen Nachfettungsmittels (Fettsäure-Polyamid-Kondensationsprodukt) und nach weiteren 20 Minuten noch 1 Teil Ameisensäure 85 %ig zugesetzt. Nach einer abschliessenden Behandlungsdauer von 20 Minuten wird gespült und wie üblich fertiggestellt. Es ergeben sich jeweils egale tiefe Schwarzfärbungen mit guten Allgemeinechtheiten.

Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
 Subsequently, in a fresh bath, 5 parts of the dye mixture used above are dyed in 500 parts of water for 30 minutes at 50 ° C. Then 3 parts of a nonionic synthetic refatting agent (fatty acid-polyamide condensation product) are added to the dyebath and, after a further 20 minutes, 1 part of 85% formic acid is added. After a final treatment time of 20 minutes, rinsing and finishing as usual. This results in level black coloring with good general fastness.
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018

Die gemäss den Beispielen 1 bis 16 verwendeten Farbstoffmischungen werden durch einfaches Mischen der Komponenten in einem Mixer erhalten.The dye mixtures used according to Examples 1 to 16 are obtained by simply mixing the components in a mixer.

Beispiel 17:Example 17:

100 Teile Chromrindleder werden in einer aus 200 Teilen Wasser, 1 Teil Natriumformiat und 2 Teilen eines anionischen Netzmittels (Na-Salze aromatischer Sulfonsäuren und aliphatischer Dicarbonsäuren) bestehenden Flotte 15 Minuten bei 30°C vorbehandelt, anschliessend 2 Teile eines anionischen Fettungsmittels (sulfitiertes Seetieröl), 2 Teile eines anionischen Nachgerbmittels (Kondensationsprodukt aus aromatischen Sulfonsäuren) und 1,5 Teile Natriumhydrogencarbonat zugegeben und 60 Minuten weiterlaufen gelassen.100 parts of chrome cowhide are pretreated in a liquor consisting of 200 parts of water, 1 part of sodium formate and 2 parts of an anionic wetting agent (Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids) for 15 minutes at 30 ° C, then 2 parts of an anionic fatliquor (sulfited marine oil) , 2 parts of an anionic retanning agent (condensation product of aromatic sulfonic acids) and 1.5 parts of sodium hydrogen carbonate are added and the mixture is left to run for 60 minutes.

Das Leder wird gut mit warmem Wasser gespült und anschliessend in einer frischen Flotte bestehend aus 100 Teilen Wasser und 8 Teilen eines anionischen Nachgerbmittels (Kondensationsprodukt aromatischer Sulfon­derivate mit Dialkylolcarbamid) 30 Minuten bei 40°C nachgegerbt. Dann werden 5 Teile des zuvor genannten anionischen Fettungsmittels zugegeben, 60 Minuten weiterlaufen gelassen, in der Folge 0,5 Teile Ameisensäure 85%ig addiert und noch 15 Minuten weiterbehandelt.The leather is rinsed well with warm water and then retanned in a fresh liquor consisting of 100 parts of water and 8 parts of an anionic retanning agent (condensation product of aromatic sulfone derivatives with dialkylolcarbamide) at 40 ° C. for 30 minutes. Then 5 parts of the aforementioned anionic fatliquor are added, the mixture is left to run for 60 minutes, 0.5 parts of 85% formic acid are subsequently added and the treatment is continued for a further 15 minutes.

Das derart nachgegerbte Leder wird nun in einer frischen Flotte, be­stehend aus 100 Teilen Wasser, 0,5 Teilen Ammoniak, 1 Teil eines Egali­siermittels (Polyglycolether-Derivat) und 2,65 Teilen der Farbstoff­mischung gemäss Beispiel 2 30 Minuten bei 30°C gefärbt. Danach erfolgt ein Zusatz von 8 Teilen des zuvor genannten Fettungsmittels und 4 Teilen eines Hydrophobiermittels. Nach weiteren 60 Minuten wird mit 2,5 Teilen Ameisensäure 85%ig angesäuert und hierauf die Behandlung 30 Minuten fortgesetzt.
Anschliessend wird in einem frischen Bad mit 1,35 Teilen der oben eingesetzten Farbstoffmischung in 200 Teilen Wasser während 30 Minuten nachgefärbt, wobei die Flotte zusätzlich noch 0,5 Teile eines kationischen Farbvertiefungsmittels (polyquaternäres Amin-Ethylenoxid-­Addukt) enthält. Dann werden dem Färbebad 1 Teil Ameisensäure 85%ig und nach weiteren 15 Minuten 1,5 Teile eines kationischen Fettungsmittels (Zubereitung auf Basis chlorierter Kohlenwasserstoffe und n-Alkyl-­Derivaten) zugesetzt. Nach einer abschliessenden Behandlungsdauer vonThe leather retanned in this way is now dyed in a fresh liquor consisting of 100 parts of water, 0.5 part of ammonia, 1 part of a leveling agent (polyglycol ether derivative) and 2.65 parts of the dye mixture according to Example 2 at 30 ° C. for 30 minutes. Then 8 parts of the above-mentioned fatliquor and 4 parts of a hydrophobizing agent are added. After a further 60 minutes, it is acidified with 2.5 parts of 85% formic acid and the treatment is then continued for 30 minutes.
Subsequently, in a fresh bath with 1.35 parts of the dye mixture used above in 200 parts of water for 30 minutes, the liquor additionally contains 0.5 parts of a cationic color deepening agent (polyquaternary amine-ethylene oxide adduct). Then 1 part of 85% strength formic acid is added to the dyebath and after a further 15 minutes 1.5 parts of a cationic fatliquor (preparation based on chlorinated hydrocarbons and n-alkyl derivatives) are added. After a final treatment period of

20 Minuten wird gespült und wie üblich fertiggestellt. Es ergibt sich eine egale tiefe Schwarzfärbung mit guten Allgemeinechtheiten.It is rinsed for 20 minutes and finished as usual. The result is a level, deep black color with good general fastness properties.

Claims (17)

1. Verfahren zum Färben von Leder nach dem Ausziehverfahren, dadurch gekennzeichnet, dass man auf das Leder eine wässrige Flotte, die eine Farbstoffmischung enthaltend einen anionischen Farbstoff und ein Pigment aufweist, einwirken lässt.1. A process for dyeing leather by the exhaust process, characterized in that an aqueous liquor which has a dye mixture comprising an anionic dye and a pigment is allowed to act on the leather. 2. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass die Farbstoffmischung einen schwarzen anionischen Farbstoff und ein schwarzes anorganisches Pigment enthält.2. The method according to claim 1, characterized in that the dye mixture contains a black anionic dye and a black inorganic pigment. 3. Verfahren gemäss Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei dem anionischen Farbstoff um einen Säurefarbstoff, Direkt­farbstoff oder Metallkomplexfarbstoff handelt.3. The method according to claim 1 or 2, characterized in that it is the anionic dye is an acid dye, direct dye or metal complex dye. 4. Verfahren gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der anionische Farbstoff der Formel
Figure imgb0019
 worin ein X Hydroxy und das andere X Amino oder Wasserstoff bedeutet,
A ein gegebenenfalls substituierter Phenyl- oder Naphthylrest ist,
B einen Phenyl- oder Naphthylrest enthaltend mindestens eine Amino- und/oder Hydroxygruppe sowie gegebenenfalls weitere Substituenten bedeutet,
Z einen Rest
Figure imgb0020
 4. The method according to any one of claims 1 to 3, characterized in that the anionic dye of the formula
Figure imgb0019
 where one X is hydroxy and the other X is amino or hydrogen,
A is an optionally substituted phenyl or naphthyl radical,
B represents a phenyl or naphthyl radical containing at least one amino and / or hydroxyl group and optionally further substituents,
Z a rest
Figure imgb0020
 R und R′ unabhängig voneinander Wasserstoff, Sulfo, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy bedeuten und n 1 oder 2 ist, entspricht.R and R 'independently of one another are hydrogen, sulfo, C₁-C₄-alkyl or C₁-C₄-alkoxy and n is 1 or 2, corresponds. 5. Verfahren gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der anionische Farbstoff der Formel
Figure imgb0021
 worin A′ ein unsubstituierter oder durch Halogen, Nitro, Sulfo, C₁-C₄-Alkyl und/oder C₁-C₄-Alkoxy substituierter Phenylrest ist, B′ einen Phenylrest, der eine Hydroxy- oder Aminogruppe und einen weiteren Substituenten ausgewählt aus der Gruppe Hydroxy, Amino, Phenylamino, o-, m- oder p-Methylphenylamino, C₁-C₄-Alkoxy und Phenoxy aufweist, bedeutet, Z′ einen Rest der Formel
Figure imgb0022
 worin R˝ Wasserstoff, Methyl, Methoxy oder Sulfo ist, darstellt und ein X′ Hydroxy und das andere X′ Amino ist, entspricht.5. The method according to any one of claims 1 to 4, characterized in that the anionic dye of the formula
Figure imgb0021
 wherein A 'is a phenyl radical which is unsubstituted or substituted by halogen, nitro, sulfo, C₁-C₄-alkyl and / or C₁-C₄-alkoxy, B' is a phenyl radical which has a hydroxyl or amino group and a further substituent selected from the group hydroxyl , Amino, phenylamino, o-, m- or p-methylphenylamino, C₁-C₄ alkoxy and phenoxy, means Z 'is a radical of the formula
Figure imgb0022
 where R˝ is hydrogen, methyl, methoxy or sulfo, and one X 'is hydroxy and the other X' is amino. 6. Verfahren gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass der anionische Farbstoff in Form der freien Säure der Formel
Figure imgb0023
 worin D und D′ unabhängig voneinander je einen gegebenenfalls weitersubstituierten Benzol- oder Naphthalinrest, der in ortho-Stellung zur Azogruppe eine Hydroxygruppe enthält, bedeuten, K und K′ unabhängig voneinander je den Rest einer Kupplungskomponente der Benzol- oder Naphthalinreihe, der in ortho-Stellung zur Azogruppe eine Hydroxygruppe enthält und gegebenenfalls weitersubstituiert ist, darstellen und Me für Chrom oder Kobalt steht, entspricht.6. The method according to any one of claims 1 to 3, characterized in that the anionic dye in the form of the free acid of the formula
Figure imgb0023
 wherein D and D 'independently of one another each represent an optionally further substituted benzene or naphthalene radical which contains a hydroxy group in the ortho position to the azo group, K and K' independently of one another each represent the residue of a coupling component of the benzene or naphthalene series which is in ortho Position to the azo group contains a hydroxy group and is optionally further substituted, represent and Me stands for chromium or cobalt, corresponds. 7. Verfahren gemäss einem der Ansprüche 1 bis 3 oder 6, dadurch gekenn­zeichnet, dass der anionische Farbstoff der Formel
Figure imgb0024
 worin D₁ und D₂ unabhängig voneinander den Rest eines unsubstituierten oder durch Sulfo und/oder Nitro substituierten 1-Amino-2-hydroxy-­naphthalins oder den Rest eines unsubstituierten oder durch Nitro, Sulfo, Chlor, Methyl, Methoxy, Methylsulfonyl oder gegebenenfalls durch Sulfo, Methyl, Methoxy, Nitro oder Chlor substituiertes Phenylazo substituierten 2-Aminophenols bedeuten und
K₁ und K₂ unabhängig voneinander für einen unsubstituierten oder durch Hydroxy, Amino, Sulfo oder Acetylamino substituierten 1- oder 2-Naphtholrest oder für einen unsubsituierten oder durch gegebenenfalls durch Methyl, Methoxy, Chlor, Sulfo oder Nitro substituiertes Phenylazo substituierten Resorcinrest stehen, und worin der Komplexfarbstoff 1 oder 2 Sulfogruppen aufweist, entspricht.7. The method according to any one of claims 1 to 3 or 6, characterized in that the anionic dye of the formula
Figure imgb0024
 in which D₁ and D₂ independently of one another the residue of an unsubstituted or substituted by sulfo and / or nitro 1-amino-2-hydroxy-naphthalene or the residue of an unsubstituted or by nitro, sulfo, chlorine, methyl, methoxy, methylsulfonyl or optionally by sulfo, Methyl, methoxy, nitro or chlorine substituted phenylazo substituted 2-aminophenol mean and
K₁ and K₂ independently of one another for an unsubstituted or substituted by hydroxy, amino, sulfo or acetylamino 1- or 2-naphthol residue or for an unsubstituted or by optionally phenylzo-substituted resorcinol radical substituted by methyl, methoxy, chlorine, sulfo or nitro, and in which the complex dye has 1 or 2 sulfo groups. 8. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass das Pigment ein Russpigment ist.8. The method according to any one of claims 1 to 7, characterized in that the pigment is a carbon black pigment. 9. Verfahren gemäss Anspruch 8, dadurch gekennzeichnet, dass das Russpigment eine mittlere Teilchengrösse von 10 bis 100 nm, vorzugsweise 20 bis 50 nm, aufweist.9. The method according to claim 8, characterized in that the carbon black pigment has an average particle size of 10 to 100 nm, preferably 20 to 50 nm. 10. Verfahren gemäss einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die verwendete Farbstoffmischung den anionischen Farbstoff und das Pigment im Gewichtsverhältnis 95:5 bis 50:50, vorzugsweise 90:10 bis 60:40 und besonders bevorzugt 80:20 bis 70:30, enthält.10. The method according to any one of claims 1 to 9, characterized in that the dye mixture used the anionic dye and the pigment in a weight ratio of 95: 5 to 50:50, preferably 90:10 to 60:40 and particularly preferably 80:20 to 70 : 30, contains. 11. Verfahren gemäss einem der Ansprüche 1 bis 10, dadurch gekenn­zeichnet, dass die Farbstoffmischung einen schwarzen anionischen Farbstoff der im Anspruch 4 angegebenen Formel (1) oder der im Anspruch 6 angegebenen Formel (2) und ein Russpigment enthält.11. The method according to any one of claims 1 to 10, characterized in that the dye mixture contains a black anionic dye of the formula (1) or the formula (2) given in claim 6 and a carbon black pigment. 12. Verfahren gemäss einem der Ansprüche 1 bis 11, dadurch gekenn­zeichnet, dass die Farbstoffmischung einen schwarzen anionischen Farb­stoff der im Anspruch 5 angegebenen Formel (1a) oder der im Anspruch 7 angegebenen Formel (2a) und ein Russpigment im Gewichtsverhältnis 90:10 bis 60:40, vorzugsweise 80:20 bis 70:30 enthält.12. The method according to any one of claims 1 to 11, characterized in that the dye mixture comprises a black anionic dye of the formula (1a) given in claim 5 or the formula (2a) given in claim 7 and a carbon black pigment in a weight ratio of 90:10 to 60 : 40, preferably 80:20 to 70:30. 13. Farbstoffmischung enthaltend einen anionischen Farbstoff und ein anorganisches Pigment.13. dye mixture containing an anionic dye and an inorganic pigment. 14. Farbstoffmischung gemäss Anspruch 13 enthaltend einen schwarzen anionischen Farbstoff der im Anspruch 4 angegebenen Formel (1) oder der im Anspruch 6 angegebenen Formel (2) und ein Russpigment.14. A dye mixture according to claim 13 containing a black anionic dye of the formula (1) given in claim 4 or the formula (2) given in claim 6 and a carbon black pigment. 15. Farbstoffmischung gemäss Anspruch 13 enthaltend einen schwarzen anionischen Farbstoff der im Anspruch 5 angegebenen Formel (1a) oder der im Anspruch 7 angegebenen Formel (2a) und ein Russpigment im Gewichts­verhältnis 90:10 bis 60:40, vorzugsweise 80:20 bis 70:30.15. Dye mixture according to claim 13 containing a black anionic dye of the formula (1a) given in claim 5 or of the formula (2a) given in claim 7 and a carbon black pigment in a weight ratio of 90:10 to 60:40, preferably 80:20 to 70: 30th 16. Verwendung von Farbstoffmischungen gemäss den Ansprüchen 13 bis 15 zum Färben von Leder.16. Use of dye mixtures according to claims 13 to 15 for dyeing leather.
EP89810976A 1989-01-02 1989-12-21 Process for dyeing leather Revoked EP0377409B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2/89 1989-01-02
CH289 1989-01-02

Publications (3)

Publication Number Publication Date
EP0377409A2 true EP0377409A2 (en) 1990-07-11
EP0377409A3 EP0377409A3 (en) 1991-04-24
EP0377409B1 EP0377409B1 (en) 1995-03-08

Family

ID=4177193

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89810976A Revoked EP0377409B1 (en) 1989-01-02 1989-12-21 Process for dyeing leather

Country Status (10)

Country Link
US (1) US5007941A (en)
EP (1) EP0377409B1 (en)
JP (1) JPH02229282A (en)
KR (1) KR0143078B1 (en)
AR (1) AR245514A1 (en)
BR (1) BR9000005A (en)
DE (1) DE58909090D1 (en)
ES (1) ES2068915T3 (en)
HU (1) HU209331B (en)
YU (1) YU249289A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497238A1 (en) * 1991-01-30 1992-08-05 Hoechst Aktiengesellschaft Process for dyeing of leather
WO1997035927A1 (en) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Stable dye compositions
WO2005038124A1 (en) * 2003-10-21 2005-04-28 Clariant International Ltd Process and compositions for pigment-dyeing of leather

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0433229B1 (en) * 1989-12-11 1994-01-26 Ciba-Geigy Ag Process for dyeing leather
ES2079627T3 (en) * 1990-07-24 1996-01-16 Ciba Geigy Ag USE OF POLYAZOIC DYES FOR LEATHER STAINING.
DE4105772A1 (en) * 1991-02-23 1992-08-27 Cassella Ag METHOD FOR DYING LEATHER WITH WATER-INSOLUBLE SULFUR DYES
DE4244006A1 (en) * 1992-12-24 1994-06-30 Bayer Ag Cationic pigment binders
DE19626318A1 (en) * 1996-07-01 1998-01-08 Basf Ag Dye mixtures containing polyazo dyes
US20070289072A1 (en) * 2000-12-18 2007-12-20 Vilmax S.A.C.I.F.I.A. New anionic coloring agents to dye leather, paper, cardboard and textile substrates: mixtures of coloring agents including these new products, and substrates dyed using the above coloring agents
AR027004A1 (en) * 2000-12-18 2003-03-12 Vilmax S A C I F I A NEW ANIONIC COLORS FOR LEATHER, PAPER, CATON AND TEXTILE SUBSTRATES; COLOR MIXTURES THAT INCLUDE THESE NEW PRODUCTS AND SUBSTRATES HAD USED BY USING THE MENTIONED COLORS.
JP5374642B2 (en) * 2009-06-03 2013-12-25 ジーエルティー テクノヴェーションズ、エルエルシー Materials used with capacitive touch screens
KR101137761B1 (en) * 2009-09-10 2012-04-24 한국신발피혁연구소 Method for improved the surface of vegetable lamb crust by re-dyeing process

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2162122A1 (en) * 1971-11-30 1973-07-13 Bayer Ag
FR2360634A1 (en) * 1976-08-03 1978-03-03 Ugine Kuhlmann NEW WATER-SOLUBLE TRISAZOIC DYES
JPS5625557A (en) * 1979-08-06 1981-03-11 Chubu Koki Method of temporarily fitting drain
DE3825755A1 (en) * 1987-08-08 1989-02-16 Sandoz Ag Dyeing and printing of leather

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1164266A1 (en) * 1984-04-13 1985-06-30 Ленинградское Проектно-Конструкторское И Технологическое Бюро Легкой Промышленности Leather finishing composition
CH672969B5 (en) * 1984-12-17 1990-07-31 Ciba Geigy Ag
CH671023A5 (en) * 1987-02-10 1989-07-31 Ciba Geigy Ag
DE3823826A1 (en) * 1988-07-14 1990-01-18 Hoechst Ag METHOD FOR BAD PIGMENTATION OF LEATHER

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2162122A1 (en) * 1971-11-30 1973-07-13 Bayer Ag
FR2360634A1 (en) * 1976-08-03 1978-03-03 Ugine Kuhlmann NEW WATER-SOLUBLE TRISAZOIC DYES
JPS5625557A (en) * 1979-08-06 1981-03-11 Chubu Koki Method of temporarily fitting drain
DE3825755A1 (en) * 1987-08-08 1989-02-16 Sandoz Ag Dyeing and printing of leather

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI,no 74-76430v Derwent Publications Ltd, London, GB, & JP-A-56025557 (YAMAMOTO KAGAKU GOSEI CO) *
Ullmanns Encyklopädie der techn Chemie, Bd.. 14, 1977, S.635, 636, 643 *
Ullmanns Encyklopädie der techn. Chemie, Bd. 16, 1978, S. 148-161 *
Ullmanns Encyklopädie der techn. Chemie, Bd. 18, 1979, S.593-594 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0497238A1 (en) * 1991-01-30 1992-08-05 Hoechst Aktiengesellschaft Process for dyeing of leather
WO1997035927A1 (en) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Stable dye compositions
US6080209A (en) * 1996-03-26 2000-06-27 Basf Aktiengesellschaft Stable colorant compositions
WO2005038124A1 (en) * 2003-10-21 2005-04-28 Clariant International Ltd Process and compositions for pigment-dyeing of leather

Also Published As

Publication number Publication date
AR245514A1 (en) 1994-01-31
EP0377409B1 (en) 1995-03-08
KR0143078B1 (en) 1998-07-01
HUT52833A (en) 1990-08-28
ES2068915T3 (en) 1995-05-01
JPH02229282A (en) 1990-09-12
DE58909090D1 (en) 1995-04-13
KR900011938A (en) 1990-08-02
YU249289A (en) 1991-02-28
EP0377409A3 (en) 1991-04-24
HU209331B (en) 1994-04-28
US5007941A (en) 1991-04-16
BR9000005A (en) 1990-10-09
HU896806D0 (en) 1990-03-28

Similar Documents

Publication Publication Date Title
EP0433229B1 (en) Process for dyeing leather
EP0377409B1 (en) Process for dyeing leather
EP0061670B1 (en) Process for dyeing leather and pelts with dye mixtures
DE3034686A1 (en) CHROME COMPLEXES OF DISAZO CONNECTIONS, THEIR PRODUCTION AND USE
DE2704364C2 (en)
EP0558450B1 (en) Process for dyeing leather with mixtures of dyes
EP0577556B1 (en) Process for the trichromatic dyeing of leather with dye mixtures
DE1155548B (en) Process for the production of metallized azo dyes
DE69719345T2 (en) TETRAKISAZO DYES, THEIR PRODUCTION AND USE
DE4133166A1 (en) IRON COMPLEXES, THEIR PRODUCTION AND USE
EP0110825B1 (en) Asymmetrical 1:2 chromium complex dyestuffs containing one azo and one azomethine compound
EP0260561B1 (en) Process for dyeing leather with dyestuff mixtures
EP0648816B1 (en) Dyeing of leather with dyestuff mixtures
DE1012007B (en) Process for the production of chromium-containing azo dyes
DE19511830C2 (en) Polyazometal complex dyes, their production and use
DE4319020B4 (en) Blue chromium complex dyes, their preparation and use
DE3008086A1 (en) MONOMETAL COMPLEXES, THEIR PRODUCTION AND USE
EP0181836A1 (en) Process for improving the light fastness of dyed leathers
DE4124437A1 (en) Water soluble anionic poly:azo dyestuff cpds. mfr. for dyeing leather - by tetrazotising di:amino:di:phenylamine sulphonic acid, coupling with amino:naphthol and then e.g. phenol etc.
EP0113643A1 (en) 1:2-cobalt complexes of disazo dyestuffs
DE961830C (en) Process for the preparation of water-soluble and licensing azophthalocyanine dyes
DE951526C (en) Process for the production of heavy metal containing azo dyes
DE2608535A1 (en) NEW CHROME COMPLEX DYES, THEIR PRODUCTION AND USE
DE2501827A1 (en) HYDRO-SOLUBLE TRISAZO DYES, METHOD FOR MANUFACTURING AND USING them
EP0583607B1 (en) Asymmetrie 1:2-chromium complex dyestuffs

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19891227

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): CH DE ES FR GB IT LI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): CH DE ES FR GB IT LI

17Q First examination report despatched

Effective date: 19920828

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19950308

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19950308

ET Fr: translation filed
REF Corresponds to:

Ref document number: 58909090

Country of ref document: DE

Date of ref document: 19950413

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2068915

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950421

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: HOECHST AKTIENGESELLSCHAFT WERK CASELLA

Effective date: 19951122

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: HOECHST AKTIENGESELLSCHAFT WERK CASSELLA

Effective date: 19951122

R26 Opposition filed (corrected)

Opponent name: HOECHST AG

Effective date: 19951122

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: CIBA-GEIGY AG TRANSFER- CIBA SC HOLDING AG

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Ref country code: CH

Ref legal event code: PFA

Free format text: CIBA SC HOLDING AG TRANSFER- CIBA SPECIALTY CHEMICALS HOLDING INC.

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: NOVARTIS AG

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: CIBA SPECIALTY CHEMICALS HOLDING INC.

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: CLARIANT GMBH PATENTE, MARKEN, LIZENZEN

Effective date: 19951122

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19981102

Year of fee payment: 10

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19991029

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19991112

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19991115

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19991202

Year of fee payment: 11

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19970217

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Free format text: 970217

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO