EP0350803A2 - Process for the pigmentation of leather in a bath - Google Patents

Process for the pigmentation of leather in a bath Download PDF

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Publication number
EP0350803A2
EP0350803A2 EP89112426A EP89112426A EP0350803A2 EP 0350803 A2 EP0350803 A2 EP 0350803A2 EP 89112426 A EP89112426 A EP 89112426A EP 89112426 A EP89112426 A EP 89112426A EP 0350803 A2 EP0350803 A2 EP 0350803A2
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EP
European Patent Office
Prior art keywords
leather
hydrogen
pigment
alkyl
dyed
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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.)
Granted
Application number
EP89112426A
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German (de)
French (fr)
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EP0350803A3 (en
EP0350803B1 (en
Inventor
Jan Hilbert Mast
Lothar Dr. Schlösser
Rainer Winter
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Hoechst AG
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Hoechst AG
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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
    • D06P1/44—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
    • 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
    • D06P1/60—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 using compositions containing polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6131—Addition products of hydroxyl groups-containing compounds with oxiranes
    • D06P1/6135—Addition products of hydroxyl groups-containing compounds with oxiranes from aromatic alcohols or from phenols, naphthols
    • 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

Definitions

  • the invention relates to a pigment dyeing process which can be applied to chrome-moist leather (wet blue) or intermediate-dried (crusted) leather and to leather of all animal species.
  • Pigment dyeings of leather have been known for a long time.
  • the first such dyeings were obtained by rubbing insoluble colored pigment particles (marble dust, soot, clay) into the leather.
  • Pigment stains are still of interest today, e.g. Titanium dioxide is used to enhance the tanning process after retanning or after the leather has dried. Soot is also occasionally used to deepen the shade.
  • the deficient binding of the pigment to the leather has a disadvantageous effect in the pigment dyeings common today.
  • the result is insufficient fixation and poor wet and dry abrasion values.
  • a leather treated with pigments is usually not completely colored.
  • the dyeing of leather with soluble dyes also has some disadvantages. Depending on the dye, lower light, sweat or migration fastness values are obtained. Problems with insufficient fastness to wet and / or dry rubbing are also known here.
  • pigments used in the leather industry today are characterized, as described, by inadequate binding, unegality and, in part, by unsightly appearance due to the encrustation of the pigments on the leather surface.
  • the leather can be colored through, the lightfastness values of the leather are better than those of the leather dyed with dyes.
  • the fastness to wet and dry rubbing is established, the fastness to migration is good (no migration), the fastness to sweat is excellent, minor grain defects of the leather can be covered, the leather is colored no matter and does not change its grip.
  • the working methods correspond to the usual dyeing methods, so that no major changes in the operational sequence are necessary for the implementation of this method.
  • R 1 is hydrogen
  • R 2 and R 3 are hydrogen or alkyl having 1 to 12 C atoms, advantageously 1 to 9 C atoms
  • R is hydrogen and / or alkyl having 1 to 4 C atoms
  • n is a number from 2 to 20
  • m is a number from 4 to 10, advantageously 4 to 8
  • M is hydrogen, an alkali metal, suitably sodium, an equivalent of alkaline earth metal and / or an ammonium group which is substituted by lower alkyl and / or lower hydroxyalkyl can be substituted, as well as an ammonium group obtained from ammonia or lower alkylamines by addition of up to 150, advantageously from 5 to 30, ethylene oxide and / or propylene oxide units.
  • These compounds are prepared by novolak oxalkylates of the formula I, in which A is hydrogen and Ar, X, R 1 , R 2 , R 3 , R, n and m have the meaning given above, with 1 to m mol of a Treated benzoyl and / or naphthoyl radical introducing O-acylating compound and with 1 to m mol of maleic anhydride and optionally 1 to m mol of sulfite or hydrogen sulfite or 0.5 to 0.5 m mol of disulfite and optionally free acid groups with one introducing the rest of M Base neutralized.
  • the pigment dispersions can also contain lecithin as a further dispersant.
  • aqueous pigment dispersions can be prepared in a known manner by the pigments, e.g. Azo pigments, lacquered azo pigments, triphenylmethane pigments, thioindigo pigments, perylene tetracarboxylic acid pigments, dioxazine pigments, quinacridone pigments, phthalocyanine pigments or inorganic pigments with these dispersants with the addition of ethylene glycol, water and, if appropriate, small quantities of other dispersants, a dispersing agent, a dispersing agent, for example, a dispersing agent, a small amount of other dispersing agent .
  • a dispersing agent e.g. Azo pigments, lacquered azo pigments, triphenylmethane pigments, thioindigo pigments, perylene tetracarboxylic acid pigments, dioxazine pigments, quinacridone pigments, phthalocyanine pigments or inorganic pigments
  • the ratio of distribution agents to pigment powder can vary within wide limits and is generally 0.1 to 0.2 parts by weight of dispersant to one part of dry pigment powder.
  • the compounds of the formula (I) mentioned can also be used as coupling aids.
  • the amount of lecithin is 0.05 to 0.25% by weight, based on the pigment powder.
  • the dispersions of pigment powder and compounds of the formula 1 were prepared in the presence of water and are obtained in the form of doughs which can be used in this form in the process according to the invention. However, these water-containing dispersions can also be dried. The powder thus obtained is also suitable for dyeing leather in the process according to the invention.
  • the term dispersion here and below includes both the water-based dispersions and the water-free powders.
  • the leather is first broached by customary methods, for example using the above. 2% conc. Ammonia solution and 0.1 to 2, preferably 0.2 to 0.5% of a wetting agent, based on the dry weight of the leather.
  • Suitable wetting agents for this stage are, for example, polyethylene glycols with a molecular weight of 100 to 2000, preferably from 200 to 1000, esters of the formula Ri-COO- (CH 2 ) n-S0 3 Na, where R 1 is C ⁇ -C 2 s-, preferably C 12 -C 1 -alkyl and n are numbers from 1 to 12, preferably 2 to 5, or ethoxylated fatty alcohols, fatty acids, fatty acid amides, sec. Alkanesulfonates, phenol, naphthol and alkylphenols with a content of 1 to 100, preferably 3 to 20, oxyethylene units,
  • the leather is rinsed and placed in a fresh ammoniacal liquor. This is followed by a treatment that serves to introduce substances into the leather that fix the subsequent pigmentation. This treatment is called "pre-fixation” below.
  • Water-soluble polyurethanes and condensation products of formaldehyde with melamine (molar ratio 3: 1 to 12: 1, preferably 4: 1 to 6: 1), dicyandiamide (molar ratio 1: 1 to 3: 1 urea (molar ratio 1: 1 to 3 : 1, preferably 1.5: 1 to 2.8: 1 phenol (molar ratio 0.5: 1 to 2: 1), naphthol (molar ratio 0.5: 1 to 2: 1) and aromatic sulfonic acids, preferably naphthalenesulfonic acid (molar ratio 3: 1 to 12: 1, preferably 5: 1 to 8: 1).
  • condensation products in their sulfonated form are suitable for pre-fixing.
  • the amount of such condensation products is approximately 0.2 to 4, preferably 1.5 to 2.5%, based on the shaved weight of the leather and approximately 0.3 to 5, preferably 1 to 3%, based on the dry weight of the leather .
  • the actual pigment coloring takes place in the same liquor. This step requires the use of substances that allow the pigments to be evenly applied to the leather (leveling agent).
  • leveling agents are the wetting agents previously described for the brochure and also lecithin and condensation products from protein hydrolyzates with a molecular weight of approximately 100 to 10,000, preferably 300 to 3000 and C 6 -C 30 -, preferably C 8 -C 18 - Fatty acids. These leveling agents are used in amounts of 0.1 to 3%, preferably 0.8 to 1.2%, based on the shaved weight of the leather and 0.5 to 2, preferably 0.8 to 1.5, based on the dry weight of the leather used.
  • the fleet also contains the pigment that is described in the introduction NEN dispersants has been treated and wherein the pigment is in an average grain size of 50 to 500, preferably 80 to 300 nm.
  • the amount of pigment dispersion is 0.5 to 3, preferably 1 to 2%, based on both the shaved weight and the dry weight of the leather.
  • the process is carried out in a short liquor (approx. 30 to 300%) and at temperatures of 20 to 40 ° C.
  • the leather thus dyed can then be greased using known methods. After the oiling or immediately after pigment coloring, the pigments are fixed and refixed. Both fixing and post-fixing are carried out by treating the leather by known methods with an organic acid, for example with formic acid or acetic acid or glycol diformate.
  • the amount of these acids is approximately 2 to 5%, preferably 2 to 4%, based on the shaved weight of the leather or 5 to 8%, preferably 4 to 6%, based on the dry weight of the leather.
  • the molecular weights of these polymers are in the range from 100 to 10,000, preferably from 150 to 3000.
  • the amount of these auxiliaries is 1 to 4, preferably 1.5 to 2.5%, based on the shaved weight of the leather or 1 to 6, preferably 2 to 3%, based on the dry weight of the leather.
  • the actual post-pigmentation is carried out in the same way as the first pigmentation described above with 0.5 to 4, preferably 1.5 to 3% pigment, based on the shaved weight of the leather, or with 1 to 4, preferably 1.5 to 3% on the dry weight of the leather. With this post-pigmentation, too, the same leveling agents are used in the same amount as before with the first pigmentation. After post-pigmentation is fixed and post-fixed, as described above.
  • the previously described workflow relates to intermediate-dried leather.
  • the brochure is not required for the bath pigmentation of folded leather. Instead, the leather is rinsed, neutralized and rinsed again before the bath pigmentation. After the bath pigmentation, but before any greasing, the leather is retanned. In all processes, it is also possible to additionally dye the leather with soluble dyes by known methods. This can be done before the bath pigmentation, after the bath pigmentation or after the fixation.
  • the leathers are finished in the normal way.
  • the leathers are finished in the normal way.
  • the leathers are finished in the normal way.
  • the pigments or pigment mixtures I, II, III, V, VI and VIII contain the pigments in extremely fine-particle form according to the present invention; they are the same as in Example 3.5.1. DE-OS 31 20 697 described connection treated.
  • the pigments and pigment mixtures IV and VII contain the pigments in the usual coarser form.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

Verfahren zur Badpigmentierung von Leder, wobei man das Leder mit Pigmentdispersionen färbt, die eine Verbindung <IMAGE> der Formel (I) enthalten, in welcher Ar Benzol der Naphthalin, X -CH2-CH2- und/oder -CH2-CH(CH3)-, 0 bis (m-1) der Reste A Wasserstoff, 1 bis m der Reste A Benzoyl und/oder Naphthoyl, 1 bis m der Reste A -CO-CH=CH-COOM und/oder -CO-CH2-CH(SO3M)-COOM sind, wobei M für ein Kation steht, R¹,R² und R³ Wasserstoff oder Alkyl mit 1 bis 14 C-Atomen, R Wasserstoff und/oder Alkyl mit 1 bis 9 C-Atomen, n eine Zahl von 1 bis 150 und m eine Zahl von 2 bis 12 bedeuten, und worin das Pigment eine durchschnittliche Korngröße von 50 bis 500, vorzugsweise 80 bis 300 nm aufweist. Durch die Verwendung dieser Dispersionen, die die Pigmente in sehr feinteiliger Form enthalten, erreicht man eine gute Durchfärbung des Leders mit verbesserter Lichtechtheit.Process for the bath pigmentation of leather, in which the leather is dyed with pigment dispersions which contain a compound <IMAGE> of the formula (I) in which Ar benzene is naphthalene, X -CH2-CH2- and / or -CH2-CH (CH3) -, 0 to (m-1) of the radicals A hydrogen, 1 to m of the radicals A benzoyl and / or naphthoyl, 1 to m of the radicals A -CO-CH = CH-COOM and / or -CO-CH2-CH ( SO3M) -COOM, where M is a cation, R¹, R² and R³ are hydrogen or alkyl having 1 to 14 carbon atoms, R is hydrogen and / or alkyl having 1 to 9 carbon atoms, n is a number from 1 to 150 and m is a number from 2 to 12, and wherein the pigment has an average grain size of 50 to 500, preferably 80 to 300 nm. Through the use of these dispersions, which contain the pigments in a very finely divided form, the leather is thoroughly colored with improved lightfastness.

Description

Die Erfindung betrifft ein Pigmentfärbeverfahren, das auf chromfeuchte Leder (wetblue) oder zwischengetrocknete (crusted) Leder und auf Leder sämtlicher Tierarten angewendet werden kann.The invention relates to a pigment dyeing process which can be applied to chrome-moist leather (wet blue) or intermediate-dried (crusted) leather and to leather of all animal species.

Pigmentfärbungen von Leder sind schon lange bekannt. Die ersten derartigen Färbungen erhielt man durch Einreiben von unlöslichen farbigen Pigmentteilchen (Marmorstaub, Ruß, Lehm) ins Leder. Auch heute sind Pigmentfärbungen noch von Interesse, so wird z.B. Titan-dioxid zum Schönen einer Weißgerbung in der Nachgerbung beziehungsweise nach dem Trocknen des Leders eingesetzt. Gelegentlich wird auch Ruß zur Farbtonvertiefung verwendet.Pigment dyeings of leather have been known for a long time. The first such dyeings were obtained by rubbing insoluble colored pigment particles (marble dust, soot, clay) into the leather. Pigment stains are still of interest today, e.g. Titanium dioxide is used to enhance the tanning process after retanning or after the leather has dried. Soot is also occasionally used to deepen the shade.

Nachteilig wirkt sich bei den heute gängigen Pigmentfärbungen die mangelhafte Bindung des Pigments an das Leder aus. Ungenügende Fixierung und schlechte Naß- und Trockenabriebswerte sind die Folge. Ein mit Pigmenten behandeltes Leder ist normalerweise nicht durchgefärbt.The deficient binding of the pigment to the leather has a disadvantageous effect in the pigment dyeings common today. The result is insufficient fixation and poor wet and dry abrasion values. A leather treated with pigments is usually not completely colored.

Auch die Färbung von Leder mit löslichen Farbstoffen weist teilweise Nachteile auf. Je nach Farbstoff erhält man geringere Werte der Licht-, Schweiß- oder Migrationsechtheit. Probleme mit ungenügender Naß-und/oder Trockenreibechtheit sind auch hier bekannt.The dyeing of leather with soluble dyes also has some disadvantages. Depending on the dye, lower light, sweat or migration fastness values are obtained. Problems with insufficient fastness to wet and / or dry rubbing are also known here.

Diese Nachteile können mit der im folgenden beschriebenen Pigmentfärbung vermieden werden.These disadvantages can be avoided with the pigment coloring described below.

Seit einigen Jahren zeigt sich der Trend, alle Lederarten, insbesondere solche, die nicht oder kaum zugerichtet werden (Bekleidungsleder, Möbelleder, vollnarbiges Schuhoberleder), mit Hilfe von Pigmenten lichtechter zu machen. Auch soll das Sortiment durch Abdecken kleiner Narbenfehler mit Pigmenten verbessert werden. Die heute in der Lederindustrie verwendeten Pigmente zeichnen sich aber wie beschrieben, durch ungenügende Bindung, Unegalität und teilweise durch Unansehlichkeit durch Verkrusten der Pigmente auf der Lederoberfläche aus.For some years now there has been a trend to use pigments to make all types of leather, especially those that are not or barely finished (clothing leather, furniture leather, full-grain upper leather), more lightfast. The range should also be improved by covering small scar defects with pigments. However, the pigments used in the leather industry today are characterized, as described, by inadequate binding, unegality and, in part, by unsightly appearance due to the encrustation of the pigments on the leather surface.

Es wurde nun gefunden, daß diese Nachteile sich durch den Einsatz von äußerst feinteiligen Pigmenten umgehen lassen. Eine Durchfäbrung des Leders ist möglich, die Lichtechtheitswerte des Leders sind besser als bei den mit Farbstoffen gefärbten Ledern. Die Naß- und Trockenreibechtheit ist einwandfrei, die Migrationsechtheit ist gut (keine Migration), die Schweißechtheit ist ausgezeichnet, kleinere Narbenfehler des Leders können abgedeckt werden, die Leder sind egal gefärbt und verändern nicht ihren Griff. Die Arbeitsmethoden entsprechen den üblichen Färbemethoden, so daß für die Durchführung dieses Verfahrens keine großen Umstellungen im betrieblichen Ablauf nötig sind.It has now been found that these disadvantages can be avoided by using extremely finely divided pigments. The leather can be colored through, the lightfastness values of the leather are better than those of the leather dyed with dyes. The fastness to wet and dry rubbing is impeccable, the fastness to migration is good (no migration), the fastness to sweat is excellent, minor grain defects of the leather can be covered, the leather is colored no matter and does not change its grip. The working methods correspond to the usual dyeing methods, so that no major changes in the operational sequence are necessary for the implementation of this method.

Gegenstand der Erfindung ist somit ein Verfahren zur Badpigmentierung von Leder, bei dem man das Leder mit Pigmentdispersionen färbt, die eine Verbindung der Formel (I)

Figure imgb0001
enthalten, in welcher

  • Ar Benzol der Naphthalin,
  • X -CH2-CH2- und/oder -CH2-CH(CH3)-,
  • 0 bis (m-1) der Reste A Wasserstoff,
  • 1 bis m der Reste A Benzoyl und/oder Naphthoyl,
  • 1 bis m der Reste A -CO-CH=CH-COOM und/oder -CO-CH2-CH(SOSM)-COOM sind, wobei M für ein Kation steht,
  • RI,R2 und R3 Wasserstoff oder Alkyl mit 1 bis 14 C-Atomen,
  • R Wasserstoff und/oder Alkyl mit 1 bis 9 C-Atomen,
  • n eine Zahl von 1 bis 150 und
  • m eine Zahl von 2 bis 12 bedeuten,
  • und worin das Pigment eine durchschnittliche Korngröße von bis 500, vorzugsweise 80 bis 300 nm aufweist.
The invention thus relates to a process for the bath pigmentation of leather, in which the leather is dyed with pigment dispersions which comprise a compound of the formula (I)
Figure imgb0001
 included in which
  • Ar benzene the naphthalene,
  • X -CH 2 -CH 2 - and / or -CH 2 -CH (CH 3 ) -,
  • 0 to (m-1) of the radicals A are hydrogen,
  • 1 to m of the residues A benzoyl and / or naphthoyl,
  • 1 to m of the radicals A are -CO-CH = CH-COOM and / or -CO-CH 2 -CH (SO S M) -COOM, where M is a cation,
  • R I , R 2 and R 3 are hydrogen or alkyl having 1 to 14 carbon atoms,
  • R is hydrogen and / or alkyl having 1 to 9 carbon atoms,
  • n is a number from 1 to 150 and
  • m is a number from 2 to 12,
  • and wherein the pigment has an average grain size of up to 500, preferably 80 to 300 nm.

Die zuvor genannten Verbindungen und die Herstellung von Pigmentdispersionen mit Hilfe dieser Verbindungen sind in der DE-A 31 20 697 beschrieben. Bevorzugt sind solche Verbindungen der obigen Formel, worin R1 Wasserstoff, R2 und R3 Wasserstoff oder Alkyl mit 1 bis 12 C-Atomen, zweckmäßigerweise 1 bis 9 C-Atomen, R Wasserstoff und/oder Alkyl mit 1 bis 4 C-Atomen, zweckmäßigerweise Wasserstoff, n eine Zahl von 2 bis 20, zweckmäßigerweise 8 bis 20, m eine Zahl von 4 bis 10, zweckmäßigerweise 4 bis 8, M Wasserstoff, ein Alkalimetall, zweckmäßigerweise Natrium, ein Äquivalent Erdalkalimetall und/oder eine Ammoniumgruppe, die durch niederes Alkyl und/oder niederes Hydroxyalkyl substituiert sein kann, sowie eine aus Ammoniak oder niederen Alkylaminen durch Anlagerung von bis zu 150, zweckmäßigerweise von 5 bis 30 Ethylenoxid- und/oder Propylenoxideinheiten erhaltene Ammoniumgruppe bedeuten.The compounds mentioned above and the preparation of pigment dispersions with the aid of these compounds are described in DE-A 31 20 697. Preferred compounds of the above formula are those in which R 1 is hydrogen, R 2 and R 3 are hydrogen or alkyl having 1 to 12 C atoms, advantageously 1 to 9 C atoms, R is hydrogen and / or alkyl having 1 to 4 C atoms , suitably hydrogen, n is a number from 2 to 20, advantageously 8 to 20, m is a number from 4 to 10, advantageously 4 to 8, M is hydrogen, an alkali metal, suitably sodium, an equivalent of alkaline earth metal and / or an ammonium group which is substituted by lower alkyl and / or lower hydroxyalkyl can be substituted, as well as an ammonium group obtained from ammonia or lower alkylamines by addition of up to 150, advantageously from 5 to 30, ethylene oxide and / or propylene oxide units.

Diese Verbindungen werden hergestellt indem man Novolak-Oxalkylate der Formel I, in welchen A Wasserstoff ist und Ar, X, R1, R2, R3, R, n sowie m die vorstehend genannte Bedeutung haben, mit 1 bis m Mol einer den Benzoyl- und/oder Naphthoylrest einführenden O-acylierenden Verbindung sowie mit 1 bis m Mol Maleinsäureanhydrid und gegebenenfalls 1 bis m Mol Sulfit bzw. Hydrogensulfit oder 0,5 bis 0,5 m Mol Disulfit behandelt und gegebenenfalls freie Säuregruppen mit einer den Rest M einführenden Base neutralisiert.These compounds are prepared by novolak oxalkylates of the formula I, in which A is hydrogen and Ar, X, R 1 , R 2 , R 3 , R, n and m have the meaning given above, with 1 to m mol of a Treated benzoyl and / or naphthoyl radical introducing O-acylating compound and with 1 to m mol of maleic anhydride and optionally 1 to m mol of sulfite or hydrogen sulfite or 0.5 to 0.5 m mol of disulfite and optionally free acid groups with one introducing the rest of M Base neutralized.

Neben den oben genannten Verbindungen der Formel I können die Pigmentdispersionen auch Lecithin als weiteres Dispergiermittel enthalten.In addition to the compounds of the formula I mentioned above, the pigment dispersions can also contain lecithin as a further dispersant.

Mit diesen Dispergiermitteln können in bekannter Weise wäßrige Pigmentdispersionen hergestellt, indem man die Pigmente, wie z.B. Azopigmente, verlackte Azopigmente, Triphenylmethanpigmente, Thioindigopigmente, Perylentetracarbonsäurepigmente, Dioxazinpigmente, Chinacridonpigmente, Phthalocyaninpigmente oder anorganische Pigmente mit diesen Dispergiermitteln unter Zusatz von Ethylenglykol, Wasser und gegebenenfalls geringen Mengen anderer Dispergiermittel in einer geeigneten Dispergiervorrichtung, wie zum Beispiel einer Rührwerksmühle, Perlmühle oder einem Doppelmuldenkneter dispergiert. Das Verhältnis von Verteilungsmitteln zu Pigmentpulver kann in weiten Grenzen variieren und beträgt im allgemeinen 0,1 bis 0,2 Gewichtsteile Dispergiermittel auf ein Teil trockenes Pigmentpulver. Außer als Dispergiermittel können die genannten Verbindungen der Formel (I) auch als Kupplungshilfsmittel eingesetzt werden. Die Menge an Lecithin beträgt 0,05 bis 0,25 Gew.-%, bezogen auf das Pigmentpulver. Die Dispersionen aus Pigmentpulver und Verbindungen der Formel 1 wurden in Gegenwart von Waser hergestellt und fallen in Form von Teigen an, die in dieser Form im Rahmen des erfindungsgemäßen Verfahrens eingesetzt werden können. Man kann diese wasserhaltigen Dispersionen jedoch auch trocknen. Das so erhaltene Pulver eignet sich ebenfalls zum Färben von Leder im Rahmen des erfindungsgemäßen Verfahrens. Der Begriff Dispersion umfaßt also hier und im folgenden sowohl die wasserhaltigen Dispersionen als auch die wasserfreien Pulver.With these dispersants, aqueous pigment dispersions can be prepared in a known manner by the pigments, e.g. Azo pigments, lacquered azo pigments, triphenylmethane pigments, thioindigo pigments, perylene tetracarboxylic acid pigments, dioxazine pigments, quinacridone pigments, phthalocyanine pigments or inorganic pigments with these dispersants with the addition of ethylene glycol, water and, if appropriate, small quantities of other dispersants, a dispersing agent, a dispersing agent, for example, a dispersing agent, a small amount of other dispersing agent . The ratio of distribution agents to pigment powder can vary within wide limits and is generally 0.1 to 0.2 parts by weight of dispersant to one part of dry pigment powder. In addition to being a dispersant, the compounds of the formula (I) mentioned can also be used as coupling aids. The amount of lecithin is 0.05 to 0.25% by weight, based on the pigment powder. The dispersions of pigment powder and compounds of the formula 1 were prepared in the presence of water and are obtained in the form of doughs which can be used in this form in the process according to the invention. However, these water-containing dispersions can also be dried. The powder thus obtained is also suitable for dyeing leather in the process according to the invention. The term dispersion here and below includes both the water-based dispersions and the water-free powders.

Zur Vorbereitung für das erfindungsgemäße Verfahren wird das Leder zuvor nach üblichen Methoden broschiert, beispielsweise mit oa. 2 % konz. Ammoniak-Lösung und 0,1 bis 2, vorzugsweise 0,2 bis 0,5 % eines Netzmittels, bezogen auf das Trockengewicht des Leders. Als Netzmittel für diese Stufe eignen sich beispielsweise Polyethylenglykole mit einem Molgewicht von 100 bis 2000, vorzugsweise von 200 bis 1000, Ester der Formel Ri-COO-(CH2)n-S03Na, wobei R1 Cε-C2s-, vorzugsweise C12-C1s-Alkyl und n Zahlen von 1 bis 12, vorzugsweise 2 bis 5 bedeuten, oder oxethylierte Fettalkohole, Fettsäuren, Fettsäureamide, sek. Alkansulfonate, Phenol, Naphthol und Alkylphenole mit einem Gehalt von 1 bis 100, vorzugsweise 3 bis 20 Oxethyleneinheiten,To prepare for the process according to the invention, the leather is first broached by customary methods, for example using the above. 2% conc. Ammonia solution and 0.1 to 2, preferably 0.2 to 0.5% of a wetting agent, based on the dry weight of the leather. Suitable wetting agents for this stage are, for example, polyethylene glycols with a molecular weight of 100 to 2000, preferably from 200 to 1000, esters of the formula Ri-COO- (CH 2 ) n-S0 3 Na, where R 1 is Cε-C 2 s-, preferably C 12 -C 1 -alkyl and n are numbers from 1 to 12, preferably 2 to 5, or ethoxylated fatty alcohols, fatty acids, fatty acid amides, sec. Alkanesulfonates, phenol, naphthol and alkylphenols with a content of 1 to 100, preferably 3 to 20, oxyethylene units,

Nach der Broschur wird das Leder gespült und in frische ammoniakalische Flotte gebracht. Anschließend erfolgt eine Behandlung, die dazu dient, Substanzen in das Leder einzubringen, die die nachfolgende Pigmentfärbung fixieren. Diese Behandlung wird nachfolgend "Vorfixierung" genannt.After the brochure, the leather is rinsed and placed in a fresh ammoniacal liquor. This is followed by a treatment that serves to introduce substances into the leather that fix the subsequent pigmentation. This treatment is called "pre-fixation" below.

Zur Vorfixierung eignen sich wasserlösliche Polyurethane sowie Kondensationsprodukte des Formaldehyds mit Melamin (Molverhältnis 3:1 bis 12:1, vorzugsweise 4:1 bis 6:1), Dicyandiamid (Molverhältnis 1:1 bis 3:1 Harnstoff (Molverhaltnis 1:1 bis 3:1, vorzugsweise 1,5:1 bis 2,8:1 Phenol (Molverhältnis 0,5:1 bis 2:1), Naphthol (Molverhältnis 0,5:1 bis 2:1) und aromatischen Sulfosäuren, vorzugsweise Naphthalinsulfonsäure (Molverhältnis 3:1 bis 12:1, vorzugsweise 5:1 bis 8:1).Water-soluble polyurethanes and condensation products of formaldehyde with melamine (molar ratio 3: 1 to 12: 1, preferably 4: 1 to 6: 1), dicyandiamide (molar ratio 1: 1 to 3: 1 urea (molar ratio 1: 1 to 3 : 1, preferably 1.5: 1 to 2.8: 1 phenol (molar ratio 0.5: 1 to 2: 1), naphthol (molar ratio 0.5: 1 to 2: 1) and aromatic sulfonic acids, preferably naphthalenesulfonic acid (molar ratio 3: 1 to 12: 1, preferably 5: 1 to 8: 1).

Dergleichen sind diese Kondensationsprodukte in ihrer sulfonierten Form zum Vorfixieren geeignet. Die Menge solcher Kondensationsprodukte beträgt ca. 0,2 bis 4, vorzugsweise 1,5 bis 2,5 %, bezogen auf das Falzgewicht des Leders und ca. 0,3 bis 5, vorzugsweise 1 bis 3 %, bezogen auf das Trockengewicht des Leders.Likewise, these condensation products in their sulfonated form are suitable for pre-fixing. The amount of such condensation products is approximately 0.2 to 4, preferably 1.5 to 2.5%, based on the shaved weight of the leather and approximately 0.3 to 5, preferably 1 to 3%, based on the dry weight of the leather .

Nach der Vorfixierung erfolgt in der gleichen Flotte die eigentliche Pigmentfärbung. Dieser Arbeitsschritt macht den Einsatz von Substanzen erforderlich, die ein gleichmäßiges Aufziehen der Pigmente auf das Leder ermöglichen (Egalisiermittel).After the pre-fixation, the actual pigment coloring takes place in the same liquor. This step requires the use of substances that allow the pigments to be evenly applied to the leather (leveling agent).

Als Egalisiermittel kommen in Frage die zuvor für die Broschur beschriebenen Netzmittel und darüberhinaus auch Lecithin und Kondensationsprodukte aus Eiweißhydrolysaten mit einem Molgewicht von ca. 100 bis 10 000, vorzugsweise 300 bis 3000 und C6-C30-, vorzugsweise C8-C18-Fettsäuren. Diese Egalisiermittel werden in Mengen von 0,1 bis 3 %, vorzugsweise 0,8 bis 1,2 % bezogen auf das Falzgewicht des Leders und 0,5 bis 2, vorzugsweise 0,8 bis 1,5, bezogen auf das Trockengewicht des Leders eingesetzt.Possible leveling agents are the wetting agents previously described for the brochure and also lecithin and condensation products from protein hydrolyzates with a molecular weight of approximately 100 to 10,000, preferably 300 to 3000 and C 6 -C 30 -, preferably C 8 -C 18 - Fatty acids. These leveling agents are used in amounts of 0.1 to 3%, preferably 0.8 to 1.2%, based on the shaved weight of the leather and 0.5 to 2, preferably 0.8 to 1.5, based on the dry weight of the leather used.

Neben diesen Egalisiermitteln enthält die Flotte noch das Pigment, das mit den eingangs beschriebenen Dispergiermitteln behandelt wurde und worin das Pigment in einer durchschnittlichen Korngröße von 50 bis 500, vorzugsweise 80 bis 300 nm vorliegt. Die Menge an Pigmentdispersion beträgt 0,5 bis 3, vorzugsweise 1 bis 2 %, bezogen sowohl auf das Falzgewicht als auch auf das Trockengewicht des Leders. Um eine unegale Pigmentfärbung durch zu schnelles Aufziehen der Pigmente zu vermeiden, wird in kurzer Flotte (ca. 30 bis 300%) und bei Temperaturen von 20 bis 40 C gearbeitet.In addition to these leveling agents, the fleet also contains the pigment that is described in the introduction NEN dispersants has been treated and wherein the pigment is in an average grain size of 50 to 500, preferably 80 to 300 nm. The amount of pigment dispersion is 0.5 to 3, preferably 1 to 2%, based on both the shaved weight and the dry weight of the leather. In order to avoid uneven pigment coloring due to the pigments being drawn up too quickly, the process is carried out in a short liquor (approx. 30 to 300%) and at temperatures of 20 to 40 ° C.

Bei der Auswahl der Pigmente ist es empfehlenswert, nur solche Pigmente zu verwenden, die eine gute Fettbeständigkeit aufweisen. Insbesondere in der Trichromie-Pigmentierung besteht die Gefahr eines ungleichmäßigen Aufziehens der Einzelbestandteile.When selecting the pigments, it is advisable to use only those pigments that have good fat resistance. Trichromatic pigmentation in particular poses a risk of the individual components being drawn up unevenly.

Bei einer vorgesehenen Glanzstoßzurichtung ist außerdem darauf zu achten, daß nur Pigmente genommen werden, welche eine ausreichende Temperaturbeständigkeit besitzen. Hierdurch werden Farbtonänderungen beim Glanzstoßen vermieden. Auch wenn badpigmentierte Leder unzugerichtet in Bügelmaschinen mit Temperaturen über 120°C bearbeitet werden, sollte die Temperaturbeständigkeit der Pigmente überprüft werden. Dies gilt auch bei einer etwaigen Vulkanisierung in der Schuhherstellung.In the case of a planned gloss surge finish, care must also be taken that only pigments are used which have sufficient temperature resistance. In this way, changes in color are avoided during gloss bumping. Even if bath pigmented leather is processed untreated in ironing machines with temperatures above 120 ° C, the temperature resistance of the pigments should be checked. This also applies to any vulcanization in shoe manufacture.

Das so gefärbte Leder kann anschließend nach bekannten Methoden gefettet werden. Im Anschluß an die Fettung oder auch direkt nach der Pigmentfärbung erfolgt die Fixierung und eine Nachfixierung der Pigmente. Sowohl Fixierung als auch Nachfixierung erfolgen durch Behandlung des Leders nach bekannten Methoden mit einer organischen Säure, beispielsweise mit Ameisensäure oder Essigsäure oder Glykoldiformiat. Die Menge dieser Säuren beträgt ca. 2 bis 5, vorzugsweise 2 bis 4%, beogen auf das Falzgewicht des Leders oder 5 bis 8 %, vorzugsweise 4 bis 6 %, bezogen auf das Trockengewicht des Leders.The leather thus dyed can then be greased using known methods. After the oiling or immediately after pigment coloring, the pigments are fixed and refixed. Both fixing and post-fixing are carried out by treating the leather by known methods with an organic acid, for example with formic acid or acetic acid or glycol diformate. The amount of these acids is approximately 2 to 5%, preferably 2 to 4%, based on the shaved weight of the leather or 5 to 8%, preferably 4 to 6%, based on the dry weight of the leather.

Es ist auch möglich, das Leder zusätzlich noch einer Nachpigmentierung zu unterwerfen. In dieser Nachpigmentierung sollen nur die Pigmente oberflächlich abgelagert werden, um eine Abdeckung der Fehler im Narben des Leders zu erreichen und so die Lederqualität zu verbessern. Diese Nachpigmentierung erfolgt entweder mit üblichen grobteiligen Pigmenten oder auch mit den feinteiligen Pigmenten, wie sie zuvor für die erste Pigmentfärbung genommen wurden.It is also possible to subject the leather to additional pigmentation. In this post-pigmentation, only the pigments should be superficially deposited in order to cover the defects in the grain of the leather and thus improve the leather quality. This post-pigmentation is carried out either with customary coarse-particle pigments or with the fine-particle pigments as were previously used for the first pigment coloring.

Werden zur Nachpigmentierung die feinteiligen Pigmente eingesetzt, ist vor ihrem Einsatz eine spezielle Vorbehandlung des Leders erforderlich (Grundierung). Für diese Vorbehandlung kommen Polyurethane in Frage oder Polymerisate, die aus folgenden Monomeren in verschiedenen Mengenverhältnissen polymerisiert werden können:

  • Acrylsäure und deren Methyl-, Ethyl-, Propyl-, Butyl-, Hexyl-, Methylhexyl-, Octadecylester; Methacrylsäure und deren Methyl-, Ethyl-, Propyl-, Butyl-, Hexyl-, Methylhexyl, Ocatdecylester; Acrylamid, Acrylnitril, Vinylacetat, Ethylen, Styrol, Maleinsäureanhydrid, Maleinsäure, Maleinsäuremono- und diester, N-Vinyl-N-methylacetamid, Acrylamidomethylenpropylsulfonat, Vinylformamid, Glycidylmethacrylat, Diallyldimethylammoniumchlorid.
If the finely divided pigments are used for post-pigmentation, special pretreatment of the leather is required before use (primer). Polyurethanes or polymers that can be polymerized in various proportions from the following monomers are suitable for this pretreatment:
  • Acrylic acid and its methyl, ethyl, propyl, butyl, hexyl, methylhexyl, octadecyl ester; Methacrylic acid and its methyl, ethyl, propyl, butyl, hexyl, methylhexyl, Ocatdecylester; Acrylamide, acrylonitrile, vinyl acetate, ethylene, styrene, maleic anhydride, maleic acid, maleic acid mono- and diesters, N-vinyl-N-methylacetamide, acrylamidomethylene propyl sulfonate, vinyl formamide, glycidyl methacrylate, diallyldimethylammonium chloride.

Die Molekulargewichte dieser Polymere liegen im Bereich 100 bis 10 000, vorzugsweise 150 bis 3000. Bevorzugt sind Polymere aus Vinylacetat (50-80 %) und Ethylen (20-50 %) oder Styrol (30-60 %) und Maleinsäureanhydrid (40-70 %) oder Hydroxistyrol. Die Menge dieser Hilfsmittel beträgt 1 bis 4, vorzugsweise 1,5 bis 2,5 %, bezogen auf das Falzgewicht des Leders oder 1 bis 6, vorzugsweise 2 bis 3 %, bezogen auf das Trockengewicht des Leders. Die eigentliche Nachpigmentierung erfolgt in der gleichen Weise wie die oben beschriebene erste Pigmentierung mit 0,5 bis 4 vorzugsweise 1,5 bis 3 % Pigment, bezogen auf das Falzgewicht des Leders oder mit 1 bis 4, vorzugsweise 1,5 bis 3 %, bezogen auf das Trockengewicht des Leders. Auch bei dieser Nachpigmentierung werden die gleichen Egalisiermittel in der gleichen Menge genommen wie zuvor bei der ersten Pigmentierung. Nach der Nachpigmentierung wird fixiert und nachfixiert, wie oben beschrieben.The molecular weights of these polymers are in the range from 100 to 10,000, preferably from 150 to 3000. Polymers of vinyl acetate (50-80%) and ethylene (20-50%) or styrene (30-60%) and maleic anhydride (40-70 %) or hydroxystyrene. The amount of these auxiliaries is 1 to 4, preferably 1.5 to 2.5%, based on the shaved weight of the leather or 1 to 6, preferably 2 to 3%, based on the dry weight of the leather. The actual post-pigmentation is carried out in the same way as the first pigmentation described above with 0.5 to 4, preferably 1.5 to 3% pigment, based on the shaved weight of the leather, or with 1 to 4, preferably 1.5 to 3% on the dry weight of the leather. With this post-pigmentation, too, the same leveling agents are used in the same amount as before with the first pigmentation. After post-pigmentation is fixed and post-fixed, as described above.

Der zuvor beschriebene Arbeitsablauf bezieht sich auf zwischengetrocknete Leder. Bei der Badpigmentierung von gefalzten Ledern entfällt die Broschur. Stattdessen wird das Leder vor der Badpigmentierung ·gespült, neutralisiert und wieder gespült. Nach der Badpigmentierung, aber vor einem eventuellen Fetten, wird das Leder dann nachgegerbt. Bei allen Verfahren ist es auch möglich, das Leder zusätzlich noch mit löslichen Farbstoffen nach bekannten Methoden zu färben. Dies kann vor der Badpigmentierung, im Anschluß an die Badpigmentierung oder nach der Fixierung erfolgen.The previously described workflow relates to intermediate-dried leather. The brochure is not required for the bath pigmentation of folded leather. Instead, the leather is rinsed, neutralized and rinsed again before the bath pigmentation. After the bath pigmentation, but before any greasing, the leather is retanned. In all processes, it is also possible to additionally dye the leather with soluble dyes by known methods. This can be done before the bath pigmentation, after the bath pigmentation or after the fixation.

Beispiel 1example 1

Figure imgb0002
Figure imgb0002

Beispiel 2Example 2

Badpigmentierung von Möbelleder.Bath pigmentation of furniture leather.

Material: Zwischengetrocknetes Rindleder (crusted).

Figure imgb0003
Figure imgb0004
Figure imgb0005
 Material: intermediate dried cowhide (crusted).
Figure imgb0003
Figure imgb0004
Figure imgb0005

Badpigmentieren 2:Bath pigmentation 2:

Figure imgb0006
Figure imgb0006
Figure imgb0007
Figure imgb0007

Die Leder werden betriebsüblich fertiggestellt.The leathers are finished in the normal way.

Beispiel 3Example 3

Badpigmentierung von SchuhoberlederBath pigmentation of upper leather

Material: Chromfeuchtes, gefalztes Rindleder (wetblue).

Figure imgb0008
Figure imgb0009
 Material: Chrome-damped, folded cowhide (wet blue).
Figure imgb0008
Figure imgb0009

Die Leder werden betriebsüblich fertiggestellt.The leathers are finished in the normal way.

Beispiel 4Example 4

Badpigmentierung von SchuhoberlederBath pigmentation of upper leather

Material: Chromfeuchtes, gefalztes Rindleder (wetblue).

Figure imgb0010
Figure imgb0011
Figure imgb0012
 Material: Chrome-damped, folded cowhide (wet blue).
Figure imgb0010
Figure imgb0011
Figure imgb0012

Die Leder werden betriebsüblich fertiggestellt.The leathers are finished in the normal way.

Beispiel 5Example 5

Figure imgb0013
Figure imgb0013

Beispiel 6Example 6

Figure imgb0014
In den Beispielen 1 bis 6 wurden folgende Pigmente bzw. Pigmentmischungen eingesetzt:
Figure imgb0015
Figure imgb0014
 The following pigments or pigment mixtures were used in Examples 1 to 6:
Figure imgb0015

Die Pigmente bzw. Pigmentmischungen I, II, III, V, VI und VIII enthalten die Pigmente in äußerst feinteiliger Form gemäß der vorliegenden Erfindung; sie sind mit der in Beispiel 3.5.1. der DE-OS 31 20 697 beschriebenen Verbindung behandelt. Die Pigmente und Pigmentmischungen IV bzw. VII enthalten die Pigmente in der üblichen gröberteiligen Form.The pigments or pigment mixtures I, II, III, V, VI and VIII contain the pigments in extremely fine-particle form according to the present invention; they are the same as in Example 3.5.1. DE-OS 31 20 697 described connection treated. The pigments and pigment mixtures IV and VII contain the pigments in the usual coarser form.

Claims (7)

1. Verfahren zur Badpigmentierung von Leder, dadurch gekennzeichnet, daß man das Leder mit Pigmentdispersionen färbt, die eine Verbindung der Formel (I)
Figure imgb0016
enthalten, in welcher Ar Benzol der Naphthalin, X -CH2-CH2- und/oder -CH2-CH(CH3)-, 0 bis (m-1) der Reste A Wasserstoff, 1 bis m der Reste A Benzoyl und/oder Naphthoyl, 1 bis m der Reste A -CO-CH = CH-COOM und/oder -CO-CH2-CH(SO3M)-COOM sind, wobei M für ein Kation steht, RI,R2 und R3 Wasserstoff oder Alkyl mit 1 bis 14 C-Atomen, R Wasserstoff und/oder Alkyl mit 1 bis 9 C-Atomen, n eine Zahl von 1 bis 150 und m eine Zahl von 2 bis 12 bedeuten, und worin das Pigment eine durchschnittliche Korngröße von 50 bis 500, vorzugsweise 80 bis 300 nm aufweist. 1. A process for the bath pigmentation of leather, characterized in that the leather is dyed with pigment dispersions which comprise a compound of the formula (I)
Figure imgb0016
 included in which Ar benzene the naphthalene, X -CH 2 -CH 2 - and / or -CH 2 -CH (CH 3 ) -, 0 to (m-1) of the radicals A are hydrogen, 1 to m of the residues A benzoyl and / or naphthoyl, 1 to m of the radicals A are -CO-CH = CH-COOM and / or -CO-CH 2 -CH (SO 3 M) -COOM, where M is a cation, R I , R 2 and R 3 are hydrogen or alkyl having 1 to 14 carbon atoms, R is hydrogen and / or alkyl having 1 to 9 carbon atoms, n is a number from 1 to 150 and m is a number from 2 to 12, and wherein the pigment has an average grain size of 50 to 500, preferably 80 to 300 nm. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Leder mit Pigmentdispersionen färbt, die eine Verbindung der Formel (I) enthalten, worin R1 Wasserstoff, R2 und R3 Wasserstof oder Alkyl mit 1 bis 12 C-Atomen, R Wasserstoff und/oder Alkyl mit 1 bis 4 C-Atomen, n eine Zahl von 2 bis 20, m eine Zahl von 4 bis 10, M Wasserstoff, ein Alkalimetall, ein Äquivalent Erdalkalimetall und/oder eine Ammoniumgruppe, die durch niederes Alkyl und/oder niederes Hydroxyalkyl substituiert sein kann, sowie eine aus Ammoniak oder niederen Alkylaminen durch Anlagerung von bis zu 150, Ethylenoxid- und/oder Propylenoxideinheiten erhaltene Ammoniumgruppe bedeuten. 2. The method according to claim 1, characterized in that the leather is dyed with pigment dispersions which contain a compound of the formula (I), in which R 1 is hydrogen, R 2 and R 3 are hydrogen or alkyl having 1 to 12 carbon atoms, R is hydrogen and / or alkyl having 1 to 4 carbon atoms, n is a number from 2 to 20, m is a number from 4 to 10, M is hydrogen, an alkali metal, an equivalent of alkaline earth metal and / or an ammonium group, which may be substituted by lower alkyl and / or lower hydroxyalkyl, and an ammonium group obtained from ammonia or lower alkylamines by addition of up to 150, ethylene oxide and / or propylene oxide units mean. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Leder mit Pigmentdispersionen färbt, die eine Verbindung der Formel (I) enthalten, worin R Wasserstoff M Wasserstoff, Natrium und/oder eine Ammoniumgruppe, die durch niederes Alkyl und/oder niederes Hydroxyalkyl substituiert sein kann, sowie eine aus Ammoniak oder niederen Alkylaminen durch Anlagerung von 5 bis 30 Ethylenoxid und/oder Propylenoxideinheiten erhaltene Ammoniumgruppe bedeuten. 3. The method according to claim 1, characterized in that the leather is dyed with pigment dispersions which contain a compound of the formula (I), in which R is hydrogen M is hydrogen, sodium and / or an ammonium group, which can be substituted by lower alkyl and / or lower hydroxyalkyl, and an ammonium group obtained from ammonia or lower alkylamines by addition of 5 to 30 ethylene oxide and / or propylene oxide units. 4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Leder mit Pigmentdispersionen färbt, die eine Verbindung der Formel (I) enthalten, worin Ar Benzol R2 und R3 Wasserstoff oder Alkyl mit 1 bis 9 C-Atomen n eine Zahl von 8 bis 20 und m eine Zahl von 4 bis 8 bedeuten. 4. The method according to claim 1, characterized in that the leather is dyed with pigment dispersions which contain a compound of the formula (I), in which Ar benzene R 2 and R 3 are hydrogen or alkyl having 1 to 9 carbon atoms n is a number from 8 to 20 and m is a number from 4 to 8. 5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Leder mit Pigmentdispersionen färbt, die eine Verbindung der Formel (I) enthalten, worin Ar Naphthalin R2 und R3 Wasserstoff oder Alkyl mit 1 bis 9 C-Atomen n eine Zahl von 8 bis 20 und m eine Zahl von 4 bis 8 bedeuten. 5. The method according to claim 1, characterized in that the leather is dyed with pigment dispersions which contain a compound of the formula (I), in which Ar naphthalene R 2 and R 3 are hydrogen or alkyl having 1 to 9 carbon atoms n is a number from 8 to 20 and m is a number from 4 to 8. 6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man das Leder mit Pigmentdispersionen färbt, die das Pigment mit einer durchschnittlichen Korngröße von 50 bis 500 nm enthalten.6. The method according to any one of claims 1 to 5, characterized in that the leather is dyed with pigment dispersions which contain the pigment with an average grain size of 50 to 500 nm. 7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man das Leder mit 0,5 bis 2 Gew.-% der Pigmentpräparation, bezogen auf das Gewicht des Leders, färbt.7. The method according to any one of claims 1 to 6, characterized in that the leather is dyed with 0.5 to 2 wt .-% of the pigment preparation, based on the weight of the leather.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0414117A2 (en) * 1989-08-19 1991-02-27 Hoechst Aktiengesellschaft Process for the pigmentation of leather with a bath
EP0525797A2 (en) * 1991-08-01 1993-02-03 Hoechst Aktiengesellschaft Cocondensates containing sulfonic groups, process for producing same and use thereof
EP0549968A1 (en) * 1991-12-20 1993-07-07 Hoechst Aktiengesellschaft Surface-active compounds based on modified oxalkylated novolaks, their preparation and their application

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5007941A (en) * 1989-01-02 1991-04-16 Ciba-Geigy Corporation Process for dyeing leather: aqueous bath containing mixture of carbon black and acid dye, direct dye or metal complex dye
PT94345A (en) * 1989-06-16 1991-02-08 Hoechst Ag METHOD FOR OBTAINING STANDARD EFFECTS IN TINTING OR PRINTING OF TEXTILE MATERIAL IN THE ABSENCE OF ALCALIS OR REDUCING AGENTS
US5306435A (en) * 1991-07-11 1994-04-26 Nihon Junyaku Co., Ltd. Treating agent composition for leather, for fibrous materials
DE4244006A1 (en) * 1992-12-24 1994-06-30 Bayer Ag Cationic pigment binders
FR2800095B1 (en) * 1999-10-22 2002-01-04 Jerome Maini PROCESS FOR TREATING SKIN, AND SKIN THUS OBTAINED
US7951452B2 (en) * 2002-09-30 2011-05-31 Kuraray Co., Ltd. Suede artificial leather and production method thereof
DE102005011494A1 (en) * 2005-03-12 2006-09-14 Patrik Lutz Dyeing leather through its thickness, using a disperse dye, particularly combined with a mordant, then drying and heat treatment for fixing the dye
JP5084485B2 (en) * 2007-12-19 2012-11-28 セーレン株式会社 Inkjet yellow ink, inkjet coloring method and colored product

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013576A1 (en) * 1979-01-16 1980-07-23 Hoechst Aktiengesellschaft Use of oxyalkylated novolac resins as compounding agents for dispersion dyes and the preparations thus obtained
EP0058384A1 (en) * 1981-02-12 1982-08-25 Hoechst Aktiengesellschaft Anionic surface-active compounds based on oxalkylated naphthol novolacquers, and their use
EP0065751A1 (en) * 1981-05-23 1982-12-01 Hoechst Aktiengesellschaft Anionic compounds based on modified novolak-oxyalkylates, their preparation and their use as foam-free surface-active agents

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0013576A1 (en) * 1979-01-16 1980-07-23 Hoechst Aktiengesellschaft Use of oxyalkylated novolac resins as compounding agents for dispersion dyes and the preparations thus obtained
EP0058384A1 (en) * 1981-02-12 1982-08-25 Hoechst Aktiengesellschaft Anionic surface-active compounds based on oxalkylated naphthol novolacquers, and their use
EP0065751A1 (en) * 1981-05-23 1982-12-01 Hoechst Aktiengesellschaft Anionic compounds based on modified novolak-oxyalkylates, their preparation and their use as foam-free surface-active agents

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0414117A2 (en) * 1989-08-19 1991-02-27 Hoechst Aktiengesellschaft Process for the pigmentation of leather with a bath
EP0414117A3 (en) * 1989-08-19 1991-10-16 Hoechst Aktiengesellschaft Process for the pigmentation of leather with a bath
EP0525797A2 (en) * 1991-08-01 1993-02-03 Hoechst Aktiengesellschaft Cocondensates containing sulfonic groups, process for producing same and use thereof
EP0525797A3 (en) * 1991-08-01 1993-02-24 Hoechst Aktiengesellschaft Cocondensates containing sulfonic groups, process for producing same and use thereof
EP0549968A1 (en) * 1991-12-20 1993-07-07 Hoechst Aktiengesellschaft Surface-active compounds based on modified oxalkylated novolaks, their preparation and their application

Also Published As

Publication number Publication date
IE892277L (en) 1990-01-14
KR900001926A (en) 1990-02-27
BR8903452A (en) 1990-03-06
EP0350803A3 (en) 1991-10-09
PT91142B (en) 1995-01-31
EP0350803B1 (en) 1994-05-18
KR0126470B1 (en) 1997-12-18
IE64114B1 (en) 1995-07-12
US4914764A (en) 1990-04-10
PT91142A (en) 1990-02-08
DE58907676D1 (en) 1994-06-23
ES2055760T3 (en) 1994-09-01
CA1334045C (en) 1995-01-24
JPH0274681A (en) 1990-03-14
AR246770A1 (en) 1994-09-30
DE3823826A1 (en) 1990-01-18

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