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EP0344555B1 - Process for dyeing leather using pigments - Google Patents

Process for dyeing leather using pigments Download PDF

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Publication number
EP0344555B1
EP0344555B1 EP89109121A EP89109121A EP0344555B1 EP 0344555 B1 EP0344555 B1 EP 0344555B1 EP 89109121 A EP89109121 A EP 89109121A EP 89109121 A EP89109121 A EP 89109121A EP 0344555 B1 EP0344555 B1 EP 0344555B1
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EP
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Prior art keywords
leather
pigment
pigments
oxyalkylated
amine
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EP89109121A
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German (de)
French (fr)
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EP0344555A3 (en
EP0344555A2 (en
Inventor
Rolf Streicher
Ortwin Dr. Schaffer
Horst Belde
Paul Dr. Guenthert
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BASF SE
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BASF SE
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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
    • 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
    • D06P1/607—Nitrogen-containing polyethers or their quaternary derivatives
    • D06P1/6076—Nitrogen-containing polyethers or their quaternary derivatives addition products of amines and alkylene oxides or oxiranes
    • 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
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose

Definitions

  • the present invention relates to a new process for dyeing leather using pigments, the dyeing being carried out in the presence of an oxyalkylated amine, the amine having at least 20 carbon atoms.
  • the object of the present invention was therefore to provide a process for dyeing leather with pigments as colorants, in which a uniformly colored surface and, in the case of thin leathers, also a full coloration of the leather is achieved.
  • Oxalkylated amines which can be used in the process according to the invention and which have at least 20 carbon atoms are to be understood as secondary or tertiary amines which have hydrocarbon radicals which are saturated or unsaturated, at least one of these radicals being interrupted by one or more oxygen atoms.
  • the hydrocarbon radicals are straight-chain, branched or cyclic and optionally interrupted by one or more imino groups and / or substituted by hydroxy.
  • amines can be obtained, for example, if C1-C30-alkylamines, C3-C30-alkenylamines or C2-C30-hydroxyalkylamines with alkylene oxides of the formula I. in which R1 and R2 are the same or different and, depending on one another, each represent hydrogen, methyl or ethyl.
  • polyamines of the formula II in the L for C2-C6-alkylene eg ethylene, 1,2-propylene or 1,2- or 1,4-butylene
  • the upper limit of the number of carbon atoms in the oxyalkylated amines to be used according to the invention depends on the number of moles of the same or different alkylene oxides of the formula I which react in the oxyalkylation. It is often not possible to specify exactly, but the upper limit of the molecular weight of the oxyalkylated is Amines usually around 30,000.
  • the process according to the invention is preferably carried out with those alkoxylated amines whose average molecular weight is 2000 to 20,000, in particular 4,000 to 15,000 and very particularly 7,000 to 13,000.
  • oxalkylated amines which derive from the reaction of C12-C25-alkylamines or C12-C25-alkenylamines with ethylene oxide and / or propylene oxide is also preferred.
  • oxyalkylated amines which are obtained by reacting polyamines of the formula II or aromatic or cycloaliphatic diamines with 3 to 50 moles of propylene oxide per equivalent of reactive amino hydrogen and subsequent reaction with 2 to 70 moles of ethylene oxide per equivalent of reactive amino hydrogen and the proportion of terminal polyethylene oxide blocks is 35 to 80% by weight, preferably 35 to 45% by weight and in particular approximately 40% by weight.
  • block copolymers generally have an average molecular weight of 4,000 to 15,000, preferably 11,000 to 15,000.
  • Suitable amines which can be reacted with alkylene oxides of the formula I are e.g. Methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, pentylamine, isopentylamine, neopentylamine, tert-pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, 2-hexadecylamine, 2-heptyldecylamine, octadecylamine, eicosylamine, 2-octyldodecylamine, docosylamine, hexacosylamine, triacontylamine, octadec
  • the amines to be used according to the invention are generally products known per se. In many cases, these products are commercially available. Amines of the type mentioned are e.g. in K. Lindner, Tenside-Textilhesstoff-Waschrohstoffe, Volume 1, p. 963 ff., 1964.
  • inorganic and organic pigments are suitable as pigments which can be used in the process according to the invention, the use of organic pigments being preferred.
  • Inorganic pigments which serve as colorants in the process according to the invention are, for example, iron oxides, titanium dioxides or carbon blacks.
  • Organic pigments which serve as colorants in the process according to the invention are, for example, those from the class of the monoazo pigments (for example products which are derived from acetoacetic acid derivatives or from ⁇ -naphthol derivatives), lacquered monoazo dyes, such as lacquered ⁇ -oxynaphthoic acid dyes, Disazo pigments, condensed disazo pigments, isoindoline derivatives, derivatives of naphthalene or perylene tetracarboxylic acid, anthraquinone pigments, thioindigo derivatives, azomethine derivatives, quinacridones, dioxazines, pyrazoloquinazolones, phthalocyanine pigments or lacquered basic dyes, such as lacquered basic dyes, such as lacquered trichloric acids, such as lacquered basic dyes.
  • lacquered monoazo dyes such as lacquered ⁇ -oxynaphtho
  • Pigment Yellow 42 examples include the inorganic pigments Pigment Yellow 42 (CI 77 492), Pigment White 6 (CI 77 891), Pigment Blue 27 (CI 77 510), Pigment Blue 29 (CI 77 007), or Pigment Black 7 (CI 77 266) , as well as the organic pigments Pigment Yellow 1 (CI 11 680), Pigment Yellow 3 (CI 11 710), Pigment Yellow 16 (CI 20 040), Pigment Yellow 17 (CI 21 705, Pigment Yellow 42 (CI 77 492), pigment Yellow 74 (CI 11 741), Pigment Yellow 83 (CI 21 108), Pigment Yellow 106, Pigment Yellow 108 (CI 68 240), Pigment Yellow 113, Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (CI 12 075), Pigment Orange 13 (CI 21 110), Pigment Orange 34 (CI 21 115), Pigment Orange 36 (CI 11 780), Pigment Orange 43 (CI 71 105), Pigment Orange 67, pigment Red
  • Pigment Red 146 (CI 12 485), Pigment Red 169 (CI 45 160: 2), Pigment Red 170, Pigment Violet 19 (CI 46 500), Pigment Violet 23 (CI 51 319), Pigment Violet 27 ( CI 42 555: 3), Pigment Blue 1 (CI 42 595: 2), Pigment Blue 15: 1 (CI 74 160), Pigment Blue 15: 3 (CI 74 160), Pigment Blue 61 (CI 42 765: 1) , Pigment Green 7 (CI 74 260), Pigment Green 8 (CI 10 008) or Pigment Green 36 (CI 74 265).
  • the oxyalkylated amines are used, for example, in an amount of 0.1 to 5%, preferably 0.3 to 3% and in particular 0.3 to 2%, in each case based on the wet weight of the leather to be dyed. An increase in the amount of amine is possible. However, it has no further advantages.
  • the pigments are used, for example, in an amount of 0.02 to 4% based on the wet weight of the leather to be dyed.
  • organic pigments preference is given to using 0.1 to 2% and in particular 0.2 to 1% pigment, based on the wet weight of the leather to be dyed.
  • inorganic pigments it is preferred to use 0.2 to 4% and in particular 0.4 to 2%, in each case based on the wet weight of the leather to be dyed.
  • mineral leather e.g. based on the metals chrome, aluminum, titanium or zirconium
  • leather to be dyed Such types of leather are e.g. used for the production of leather clothing, as upholstery leather or as upper shoe leather.
  • Oxalkylated alcohols which can be used in the process according to the invention are understood to mean those alcohols which have a hydrocarbon radical which is saturated or unsaturated and is interrupted by one or more oxygen atoms.
  • the hydrocarbon radical is straight-chain, branched or cyclic and optionally substituted by further hydroxyl groups.
  • These alcohols can e.g. are obtained when reacting C1-C30 alkanols, C3-C30 alkenols or C2-C30 alkane polyols with alkylene oxides of the formula I.
  • alkoxylated alcohols are preferred which are derived from the reaction of C10-C20 alkanols, C10-C20 alkenols or C2-C6 alkane polyols with ethylene oxide and / or propylene oxide.
  • the upper limit of the number of carbon atoms in the oxyalkylated alcohols to be used according to the invention depends on the number of moles of the same or different alkylene oxides of the formula I which react in the oxyalkylation. It is often not possible to specify exactly, but the upper limit of the molecular weight of the oxyalkylated is Alcohols usually around 10,000.
  • the process according to the invention is preferably carried out with those alkoxylated alcohols whose molecular weight is 300 to 2000 and in particular 500 to 1500.
  • Suitable alcohols which can be reacted with alkylene oxides of the formula I are, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, neopentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 2-propylheptanol , Dodecanol, 2-butyl octanol, tetradecanol, 2-pentyl nonanol, hexadecanol, octadecanol, eicosanol, Tetracosanol, hexacosanol, octacosanol, tricosanol, octadec-9 (cis) -enol, oct
  • the oxyalkylated alcohols to be used according to the invention are generally products known per se. In many cases, these products are commercially available. Alcohols of the type mentioned are e.g. in K. Lindner, Tenside-Textilwhismitte-Waschrohstoffe, Volume 1, pp. 837 ff., 1964 or in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, Volume 22, pp. 488 ff.
  • the alkoxylated alcohols are used, for example, in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight and in particular 0.2 to 2% by weight, based in each case on the leather to be dyed.
  • the pigments used as colorants in the new process can expediently be in the form of pigment preparations known per se, e.g. can be used as aqueous dispersions.
  • Those aqueous pigment preparations which contain nonionic surfactants as dispersing agents are preferred.
  • nonionic surfactants which may be mentioned are the above-mentioned components to be used according to the invention or also addition products of alkylene oxides with fatty acids, phenols, alkylphenols, acid amides or mercaptans.
  • aqueous pigment preparations which contain an oxyalkylated amine which has at least 20 carbon atoms as a dispersing aid. They are e.g. described in DE-A-2 156 603.
  • pigments which have a particle size of less than 1 ⁇ m, e.g. have from 0.01 to 0.2 ⁇ m, deliver particularly favorable results.
  • a preferred procedure is to treat the leather with an aqueous pigment preparation which contains an oxyalkylated amine which has at least 20 carbon atoms as a dispersing aid.
  • a particularly preferred procedure consists in treating the leather with an aqueous pigment preparation containing an oxyalkylated amine and additional oxyalkylated amine.
  • a procedure is very particularly preferred in which the leather is treated with an aqueous pigment preparation containing an oxyalkylated amine and additional oxyalkylated amine and an oxyalkylated alcohol which has at least 16 carbon atoms.
  • the process according to the invention is expediently carried out in such a way that a leather which has been pretreated in a customary manner is placed in an aqueous liquor in a drum and the pigment is carried out at a temperature of 20 to 60 ° C., preferably 40 to 50 ° C., preferably in the form of an aqueous one Preparation containing an oxyalkylated amine as a dispersing agent, optionally adding additional oxyalkylated amine and optionally oxyalkylated alcohol.
  • the leather is then dyed at the above-mentioned temperature and at a pH of 4 to 7, preferably 4.5 to 6, with milling. The dyeing process is generally complete after 0.5 to 2 hours. After conventional fixation with formic acid, the leather is then removed from the dyeing liquor, washed with water and worked up by methods known per se.
  • the process according to the invention can also be carried out in the presence of other auxiliaries or additives customary in leather dyeing, e.g. commercially available salts of condensation products of phenolic or naphthalenesulfonic acids with formaldehyde and urea, fat liquors based on emulsified paraffins or water-soluble polymers based on acrylates, which have a molecular weight of approx. 2000 to 5000, are operated.
  • auxiliaries or additives customary in leather dyeing e.g. commercially available salts of condensation products of phenolic or naphthalenesulfonic acids with formaldehyde and urea, fat liquors based on emulsified paraffins or water-soluble polymers based on acrylates, which have a molecular weight of approx. 2000 to 5000, are operated.
  • auxiliaries or additives can be added to the aqueous liquor either before the dyeing process or together with the pigment and the oxyalkylated amine.
  • water-soluble acid dyes are azo dyes known per se which contain sulfonic acid groups and are either metal-free or can be present as a metal complex, metal phthalocyanines containing sulfonic acid groups or anthraquinones containing sulfonic acid groups.
  • the water-soluble acid dyes are expediently added in powder form or in the form of a liquid preparation to the dyeing liquor. They are advantageously added with that of the pigment.
  • 0.1 to 6 preferably 0.5 to 5% and in particular 0.5 to 3%, in each case based on the wet weight of the leather to be dyed, of water-soluble acid dye is used.
  • the leather can be treated both with individual pigments and with mixtures of pigments. It is preferred to dye the leather with a mixture of yellow, red and blue pigments, which results in brown shades.
  • the new process leads to leather dyeing that is characterized by excellent levelness, depth of color, brilliance as well as high light fastness, wet fastness and migration fastness values. In addition, they show good coloring.
  • the percentages are percentages by weight and relate to seam-damp chrome leather.
  • the pigments used in the examples were each used in the form of an aqueous preparation, the oxyalkylated amine ethylenediamine which was first reacted with propylene oxide and then with ethylene oxide (ethylene oxide content: 40%; M 10500). Based on the weight of the pigment, the amine content was 20%.
  • the acid dyes were used in the form of an aqueous solution.
  • the oxyalkylated amine is oleylamine which has been oxethylated with about 10 moles of ethylene oxide.
  • the alkoxylated alcohol is it is tallow fatty alcohol which has been oxethylated with approx. 80 mol ethylene oxide.

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

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zum Färben von Leder mittels Pigmenten, wobei man die Färbung in Gegenwart eines oxalkylierten Amins, wobei das Amin mindestens 20 Kohlenstoffatome aufweist, vornimmt.The present invention relates to a new process for dyeing leather using pigments, the dyeing being carried out in the presence of an oxyalkylated amine, the amine having at least 20 carbon atoms.

Bei der Färbung von Leder werden üblicherweise Farbstoffe als Farbmittel verwendet. Mit Farbstoffen gefärbtes Leder weist aber häufig anwendungstechnische Mängel, z.B. eine zu geringe Lichtechtheit oder eine mangelhafte Anfärbung von Narbenbeschädigungen auf.When dyeing leather, dyes are usually used as colorants. Leather dyed with dyes, however, often has application defects, e.g. insufficient lightfastness or poor staining of scar damage.

Bei der Verwendung von Pigmenten als Farbmittel erhält man im allgemeinen Lederfärbungen, die eine gute Lichtechtheit aufweisen. Es hat sich jedoch gezeigt, daß die Verteilung der Pigmente, insbesondere auf der Oberfläche aber auch im Lederquerschnitt, bei einem solchermaßen gefärbten Leder schlecht ist. Die Pigmente lagern sich bevorzugt auf der Fleischseite und an offenen Narbenbeschädigungen des Leders ab. Die Haarlöcher bleiben oft ungefärbt.When pigments are used as colorants, leather dyeings are generally obtained which have good lightfastness. However, it has been shown that the distribution of the pigments, especially on the surface but also in the leather cross section, is poor in such a leather dyed in this way. The pigments are preferentially deposited on the meat side and on open scar damage to the leather. The hair holes often remain uncolored.

Für viele Lederarten, z.B. Polsterleder, Bekleidungsleder oder spezielle Schuhoberleder wird aber heute eine Durchfärbung verlangt.For many types of leather, e.g. Upholstery leather, clothing leather or special shoe upper leather is now required to be colored.

Aufgabe der vorliegenden Erfindung war es deshalb, ein Verfahren zum Färben von Leder mit Pigmenten als Farbmittel bereitzustellen, bei dem eine gleichmäßig gefärbte Oberfläche und bei dünnen Ledern auch eine Durchfärbung des Leders erreicht wird.The object of the present invention was therefore to provide a process for dyeing leather with pigments as colorants, in which a uniformly colored surface and, in the case of thin leathers, also a full coloration of the leather is achieved.

Es wurde nun gefunden, daß das Färben von Leder mittels Pigmenten in wäßriger Flotte vorteilhaft gelingt, wenn man das Leder mit Pigmenten in Gegenwart eines oxalkylierten Amins, das mindestens 20 Kohlenstoffatome aufweist, bei einer Temperatur von 20 bis 60°C behandelt.It has now been found that dyeing leather using pigments in an aqueous liquor is advantageously achieved if the leather is treated with pigments at from 20 to 60 ° C. in the presence of an oxyalkylated amine which has at least 20 carbon atoms.

Unter oxalkylierten Aminen, die im erfindungsgemäßen Verfahren zur Anwendung kommen können und die mindestens 20 Kohlenstoffatome aufweisen, sind sekundäre oder tertiäre Amine zu verstehen, die Kohlenwasserstoffreste aufweisen, die gesättigt oder ungesättigt sind, wobei mindestens einer dieser Reste durch ein oder mehrere Sauerstoffatome unterbrochen ist. Die Kohlenwasserstoffreste sind dabei geradkettig, verzweigt oder cyclisch und gegebenenfalls durch eine oder mehrere Iminogruppen unterbrochen und/oder durch Hydroxy substituiert.Oxalkylated amines which can be used in the process according to the invention and which have at least 20 carbon atoms are to be understood as secondary or tertiary amines which have hydrocarbon radicals which are saturated or unsaturated, at least one of these radicals being interrupted by one or more oxygen atoms. The hydrocarbon radicals are straight-chain, branched or cyclic and optionally interrupted by one or more imino groups and / or substituted by hydroxy.

Diese Amine können z.B. erhalten werden, wenn man C₁-C₃₀-Alkylamine, C₃-C₃₀-Alkenylamine oder C₂-C₃₀-Hydroxyalkylamine mit Alkylenoxiden der Formel I

Figure imgb0001

in der R¹ und R² gleich oder verschieden sind und abhängig voneinander jeweils Wasserstoff, Methyl oder Ethyl bedeuten, umsetzt.These amines can be obtained, for example, if C₁-C₃₀-alkylamines, C₃-C₃₀-alkenylamines or C₂-C₃₀-hydroxyalkylamines with alkylene oxides of the formula I.
Figure imgb0001
in which R¹ and R² are the same or different and, depending on one another, each represent hydrogen, methyl or ethyl.

Sie können außerdem beispielsweise erhalten werden, wenn man Polyamine der Formel II

Figure imgb0002

in der L für C₂-C₆-Alkylen (z.B. Ethylen, 1,2-Propylen oder 1,2- oder 1,4-Butylen), R³ für Wasserstoff oder C₁-C₆-Alkyl und n für 1 bis 5, vorzugsweise 1 bis 3 stehen, oder aromatische oder cycloaromatische Diamine mit Alkylenoxiden der obengenannten Formel I umsetzt.They can also be obtained, for example, by using polyamines of the formula II
Figure imgb0002
in the L for C₂-C₆-alkylene (eg ethylene, 1,2-propylene or 1,2- or 1,4-butylene), R³ for hydrogen or C₁-C₆-alkyl and n for 1 to 5, preferably 1 to 3 stand, or aromatic or cycloaromatic diamines with alkylene oxides of the above formula I.

Die obere Grenze der Anzahl der Kohlenstoffatome bei den erfindungsgemäß zu verwendenden oxalkylierten Aminen ist abhängig von der Molzahl der bei der Oxalkylierung zur Reaktion kommenden gleichen oder verschiedenen Alkylenoxiden der Formel I. Sie ist häufig nicht exakt anzugeben, jedoch liegt die obere Grenze des Molekulargewichts der oxalkylierten Amine üblicherweise bei ca. 30000.The upper limit of the number of carbon atoms in the oxyalkylated amines to be used according to the invention depends on the number of moles of the same or different alkylene oxides of the formula I which react in the oxyalkylation. It is often not possible to specify exactly, but the upper limit of the molecular weight of the oxyalkylated is Amines usually around 30,000.

Das erfindungsgemäße Verfahren wird vorzugsweise mit solchen oxalkylierten Aminen durchgeführt, deren mittleres Molekulargewicht 2000 bis 20000, insbesondere 4000 bis 15000 und ganz besonders 7000 bis 13000 beträgt.The process according to the invention is preferably carried out with those alkoxylated amines whose average molecular weight is 2000 to 20,000, in particular 4,000 to 15,000 and very particularly 7,000 to 13,000.

Im erfindungsgemäßen Verfahren ist weiterhin die Verwendung von solchen oxalkylierten Aminen bevorzugt, die sich aus der Umsetzung von C₁₂-C₂₅-Alkylaminen oder C₁₂-C₂₅-Alkenylaminen mit Ethylenoxid und/oder Propylenoxid ableiten.In the process according to the invention, the use of oxalkylated amines which derive from the reaction of C₁₂-C₂₅-alkylamines or C₁₂-C₂₅-alkenylamines with ethylene oxide and / or propylene oxide is also preferred.

Weiterhin bevorzugt ist die Verwendung von oxalkylierten Aminen, die durch Umsetzung von Polyaminen der Formel II oder aromatischen oder cycloaliphatischen Diaminen mit 3 bis 50 Mol Propylenoxid je Äquivalent reaktionsfähigem Aminowasserstoff und anschließender Umsetzung mit 2 bis 70 Mol Ethylenoxid je Äquivalent reaktionsfähigem Aminowasserstoff erhalten werden und wobei der Anteil an endständigen Polyethylenoxidblöcken 35 bis 80 Gew.%, vorzugsweise 35 bis 45 Gew.% und insbesondere ca. 40 Gew.% beträgt. Solche Blockcopolymeren weisen im allgemeinen ein mittleres Molekulargewicht von 4000 bis 15000, vorzugsweise 11000 bis 15000, auf.Also preferred is the use of oxyalkylated amines which are obtained by reacting polyamines of the formula II or aromatic or cycloaliphatic diamines with 3 to 50 moles of propylene oxide per equivalent of reactive amino hydrogen and subsequent reaction with 2 to 70 moles of ethylene oxide per equivalent of reactive amino hydrogen and the proportion of terminal polyethylene oxide blocks is 35 to 80% by weight, preferably 35 to 45% by weight and in particular approximately 40% by weight. Such block copolymers generally have an average molecular weight of 4,000 to 15,000, preferably 11,000 to 15,000.

Geeignete Amine, die mit Alkylenoxiden der Formel I umgesetzt werden können, sind z.B. Methylamin, Ethylamin, Propylamin, Isopropylamin, Butylamin, Isobutylamin, sec-Butylamin, Pentylamin, Isopentylamin, Neopentylamin, tert-Pentylamin, Hexylamin, Heptylamin, Octylamin, 2-Ethylhexylamin, Nonylamin, Decylamin, Dodecylamin, Tetradecylamin, Hexadecylamin, 2-Hexyldecylamin, 2-Heptyldecylamin, Octadecylamin, Eicosylamin, 2-Octyldodecylamin, Docosylamin, Hexacosylamin, Triacontylamin,Octadec-9(cis)-enylamin, Octadec-9(trans)-enylamin, Octadec-9(cis),12(cis)-dienylamin, Octadec-9(cis),12(cis),15(cis)-trienylamin, die technischen Fettamine Kokosamin, Talgamin, Oleylamin, n-Kokospropylendiamin oder n-Talgpropylendiamin, Ethanolamin, Propanolamin, Isopropanolamin, Ethylendiamin, Diethylentriamin, 1,2- oder 1,3-Proyplendiamin, Di(1,2- oder 1,3-propylen)triamin, o-, m- oder p-Phenylendiamin, Toluylendiamine, 1,1-Bis(4-aminophenyl)cyclohexan, 1,2- oder 1,4-Diaminocyclohexan oder 4,4′-Diaminodiocyclohexylmethan.Suitable amines which can be reacted with alkylene oxides of the formula I are e.g. Methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, pentylamine, isopentylamine, neopentylamine, tert-pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, 2-hexadecylamine, 2-heptyldecylamine, octadecylamine, eicosylamine, 2-octyldodecylamine, docosylamine, hexacosylamine, triacontylamine, octadec-9 (cis) -enylamine, octadec-9 (trans) -enylamine, octadec-9 (cis), 12 (cis) -dienylamine Octadec-9 (cis), 12 (cis), 15 (cis) -trienylamine, the technical fatty amines coconut amine, tallow amine, oleyl amine, n-coconut propylene diamine or n-tallow propylene diamine, ethanolamine, propanolamine, isopropanolamine, ethylene diamine, diethylene triamine, 1,2- or 1,3-propylenediamine, di (1,2- or 1,3-propylene) triamine, o-, m- or p-phenylenediamine, toluenediamines, 1,1-bis (4-aminophenyl) cyclohexane, 1,2- or 1,4-diaminocyclohexane or 4,4'-diaminodiocyclohexylmethane.

Bei den erfindungsgemäß zu verwendenden Aminen handelt es sich im allgemeinen um an sich bekannte Produkte. In vielen Fällen sind diese Produkte handelsüblich. Amine der genannten Art sind z.B. in K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, Band 1, S. 963 ff., 1964, beschrieben.The amines to be used according to the invention are generally products known per se. In many cases, these products are commercially available. Amines of the type mentioned are e.g. in K. Lindner, Tenside-Textilhilfsmittel-Waschrohstoffe, Volume 1, p. 963 ff., 1964.

Als Pigmente, die im erfindungsgemäßen Verfahren verwendet werden können, kommen sowohl anorganische wie auch organische Pigmente in Betracht, wobei die Verwendung von organischen Pigmenten bevorzugt ist.Both inorganic and organic pigments are suitable as pigments which can be used in the process according to the invention, the use of organic pigments being preferred.

Anorganische Pigmente, die im erfindungsgemäßen Verfahren als Farbmittel dienen, sind beispielsweise Eisenoxide, Titandioxide oder Ruße.Inorganic pigments which serve as colorants in the process according to the invention are, for example, iron oxides, titanium dioxides or carbon blacks.

Organische Pigmente, die im erfindungsgemäßen Verfahren als Farbmittel dienen, sind beispielsweise solche aus der Klasse der Monoazopigmente (z.B. Produkte, die sich von Acetessigarylidderivaten oder von β-Naphtholderivaten ableiten), verlackten Monoazofarbstoffe, wie verlackte β-Oxynaphthoesäurefarbstoffe, Disazopigmente, kondensierten Disazopigmente, Isoindolinderivate, Derivate der Naphthalin- oder Perylentetracarbonsäure, Anthrachinonpigmente, Thioindigoderivate, Azomethinderivate, Chinacridone, Dioxazine, Pyrazolochinazolone, Phthalocyaninpigmente oder verlackten basischen Farbstoffe, wie verlackte Triarylmethanfarbstoffe, zu nennen.Organic pigments which serve as colorants in the process according to the invention are, for example, those from the class of the monoazo pigments (for example products which are derived from acetoacetic acid derivatives or from β-naphthol derivatives), lacquered monoazo dyes, such as lacquered β-oxynaphthoic acid dyes, Disazo pigments, condensed disazo pigments, isoindoline derivatives, derivatives of naphthalene or perylene tetracarboxylic acid, anthraquinone pigments, thioindigo derivatives, azomethine derivatives, quinacridones, dioxazines, pyrazoloquinazolones, phthalocyanine pigments or lacquered basic dyes, such as lacquered basic dyes, such as lacquered trichloric acids, such as lacquered basic dyes.

Beispielhaft seien die anorganischen Pigmente Pigment Yellow 42 (C.I. 77 492), Pigment White 6 (C.I. 77 891), Pigment Blue 27 (C.I. 77 510), Pigment Blue 29 (C.I. 77 007), oder Pigment Black 7 (C.I. 77 266), sowie die organischen Pigmente Pigment Yellow 1 (C.I. 11 680), Pigment Yellow 3 (C.I. 11 710), Pigment Yellow 16 (C.I. 20 040), Pigment Yellow 17 (C.I. 21 705, Pigment Yellow 42 (C.I. 77 492), Pigment Yellow 74 (C.I. 11 741), Pigment Yellow 83 (C.I. 21 108), Pigment Yellow 106, Pigment Yellow 108 (C.I. 68 240), Pigment Yellow 113, Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (C.I. 12 075), Pigment Orange 13 (C.I. 21 110), Pigment Orange 34 (C.I. 21 115), Pigment Orange 36 (C.I. 11 780), Pigment Orange 43 (C.I. 71 105), Pigment Orange 67, Pigment Red 3 (C.I. 12 120), Pigment Red 48:1 (C.I. 15 865:1), Pigment Red 48:4 (15 865:4), Pigment Red 101 (C.I. 77 491), Pigment Red 112 (C.I. 12 370), Pigment Red 122 (C.I. 73 915), Pigment Red 123 (C.I. 71 145), Pigment Red 146 (C.I. 12 485), Pigment Red 169 (C.I. 45 160:2), Pigment Red 170, Pigment Violett 19 (C.I. 46 500), Pigment Violet 23 (C.I. 51 319), Pigment Violet 27 (C.I. 42 555:3), Pigment Blue 1 (C.I. 42 595 : 2), Pigment Blue 15 : 1 (C.I. 74 160), Pigment Blue 15 : 3 (C.I. 74 160), Pigment Blue 61 (C.I. 42 765:1), Pigment Green 7 (C.I. 74 260), Pigment Green 8 (C.I. 10 008) oder Pigment Green 36 (C.I. 74 265) genannt.Examples include the inorganic pigments Pigment Yellow 42 (CI 77 492), Pigment White 6 (CI 77 891), Pigment Blue 27 (CI 77 510), Pigment Blue 29 (CI 77 007), or Pigment Black 7 (CI 77 266) , as well as the organic pigments Pigment Yellow 1 (CI 11 680), Pigment Yellow 3 (CI 11 710), Pigment Yellow 16 (CI 20 040), Pigment Yellow 17 (CI 21 705, Pigment Yellow 42 (CI 77 492), pigment Yellow 74 (CI 11 741), Pigment Yellow 83 (CI 21 108), Pigment Yellow 106, Pigment Yellow 108 (CI 68 240), Pigment Yellow 113, Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (CI 12 075), Pigment Orange 13 (CI 21 110), Pigment Orange 34 (CI 21 115), Pigment Orange 36 (CI 11 780), Pigment Orange 43 (CI 71 105), Pigment Orange 67, pigment Red 3 (CI 12 120), Pigment Red 48: 1 (CI 15 865: 1), Pigment Red 48: 4 (15 865: 4), Pigment Red 101 (CI 77 491), Pigment Red 112 (CI 12 370) , Pigment Red 122 (CI 73 915), Pigment Red 123 (C.I. 71 145), Pigment Red 146 (CI 12 485), Pigment Red 169 (CI 45 160: 2), Pigment Red 170, Pigment Violet 19 (CI 46 500), Pigment Violet 23 (CI 51 319), Pigment Violet 27 ( CI 42 555: 3), Pigment Blue 1 (CI 42 595: 2), Pigment Blue 15: 1 (CI 74 160), Pigment Blue 15: 3 (CI 74 160), Pigment Blue 61 (CI 42 765: 1) , Pigment Green 7 (CI 74 260), Pigment Green 8 (CI 10 008) or Pigment Green 36 (CI 74 265).

Die oxalkylierten Amine werden beispielsweise in einer Menge von 0,1 bis 5 %, vorzugsweise 0,3 bis 3 % und insbesondere 0,3 bis 2 %, jeweils bezogen auf das Feuchtgewicht des zu färbenden Leders, angewendet. Eine Erhöhung der Aminmenge ist möglich. Sie bringt jedoch keine weiteren Vorteile.The oxyalkylated amines are used, for example, in an amount of 0.1 to 5%, preferably 0.3 to 3% and in particular 0.3 to 2%, in each case based on the wet weight of the leather to be dyed. An increase in the amount of amine is possible. However, it has no further advantages.

Die Pigmente werden beispielsweise in einer Menge von 0,02 bis 4 % bezogen auf das Feuchtgewicht des zu färbenden Leders, angewendet.The pigments are used, for example, in an amount of 0.02 to 4% based on the wet weight of the leather to be dyed.

Bei organischen Pigmenten verwendet man vorzugsweise 0,1 bis 2 % und insbesondere 0,2 bis 1 % Pigment, bezogen auf das Feuchtgewicht des zu färbenden Leders. Bei anorganischen Pigmenten verwendet man vorzugsweise 0,2 bis 4 % und insbesondere 0,4 bis 2 %, jeweils bezogen auf das Feuchtgewicht des zu färbenden Leders.In the case of organic pigments, preference is given to using 0.1 to 2% and in particular 0.2 to 1% pigment, based on the wet weight of the leather to be dyed. In the case of inorganic pigments, it is preferred to use 0.2 to 4% and in particular 0.4 to 2%, in each case based on the wet weight of the leather to be dyed.

Als zu färbendes Leder kommt im allgemeinen handelsübliches mineralisch (z.B. auf Basis der Metalle Chrom, Aluminium, Titan oder Zirkonium) gegerbtes Leder in Betracht. Solche Lederarten werden z.B. für die Herstellung von Lederbekleidung, als Polsterleder oder als Schuhoberleder verwendet.In general, commercially available mineral leather (e.g. based on the metals chrome, aluminum, titanium or zirconium) can be considered as leather to be dyed. Such types of leather are e.g. used for the production of leather clothing, as upholstery leather or as upper shoe leather.

Es wurde weiterhin gefunden, daß wenn man die Behandlung des Leders mit dem Pigment zusätzlich in Gegenwart eines oxalkylierten Alkohols vornimmt, der mindestens 16 Kohlenstoffatome aufweist, man zu sehr günstigen Färbeergebnissen gelangt.It has furthermore been found that if the leather is additionally treated with the pigment in the presence of an oxyalkylated alcohol which has at least 16 carbon atoms, very favorable dyeing results are obtained.

Unter oxalkylierten Alkoholen, die im erfindungsgemäßen Verfahren zur Anwendung kommen können, sind solche Alkohole zu verstehen, die einen Kohlenwasserstoffrest aufweisen, der gesättigt oder ungesättigt und durch ein oder mehrere Sauerstoffatome unterbrochen ist. Der Kohlenwasserstoffrest ist dabei geradkettig, verzweigt oder cyclisch und gegebenenfalls durch weitere Hydroxygruppen substituiert.Oxalkylated alcohols which can be used in the process according to the invention are understood to mean those alcohols which have a hydrocarbon radical which is saturated or unsaturated and is interrupted by one or more oxygen atoms. The hydrocarbon radical is straight-chain, branched or cyclic and optionally substituted by further hydroxyl groups.

Diese Alkohole können z.B. erhalten werden, wenn man C₁-C₃₀-Alkanole, C₃-C₃₀-Alkenole oder C₂-C₃₀-Alkanpolyole mit Alkylenoxiden der Formel I umsetzt.These alcohols can e.g. are obtained when reacting C₁-C₃₀ alkanols, C₃-C₃₀ alkenols or C₂-C₃₀ alkane polyols with alkylene oxides of the formula I.

Im erfindungsgemäßen Verfahren ist die Verwendung von solchen oxalkylierten Alkoholen bevorzugt, die sich aus der Umsetzung von C₁₀-C₂₀-Alkanolen, C₁₀-C₂₀-Alkenolen oder C₂-C₆-Alkanpolyolen mit Ethylenoxid und/oder Propylenoxid ableiten.In the process of the invention, the use of such alkoxylated alcohols is preferred which are derived from the reaction of C₁₀-C₂₀ alkanols, C₁₀-C₂₀ alkenols or C₂-C₆ alkane polyols with ethylene oxide and / or propylene oxide.

Die obere Grenze der Anzahl der Kohlenstoffatome bei den erfindungsgemäß zu verwendenden oxalkylierten Alkoholen ist abhängig von der Molzahl der bei der Oxalkylierung zur Reaktion kommenden gleichen oder verschiedenen Alkylenoxiden der Formel I. Sie ist häufig nicht exakt anzugeben, jedoch liegt die obere Grenze des Molekulargewichts der oxalkylierten Alkohole üblicherweise bei ca. 10000.The upper limit of the number of carbon atoms in the oxyalkylated alcohols to be used according to the invention depends on the number of moles of the same or different alkylene oxides of the formula I which react in the oxyalkylation. It is often not possible to specify exactly, but the upper limit of the molecular weight of the oxyalkylated is Alcohols usually around 10,000.

Das erfindungsgemäße Verfahren wird vorzugsweise mit solchen oxalkylierten Alkoholen durchgeführt, deren Molekulargewicht 300 bis 2000 und insbesondere 500 bis 1500 beträgt.The process according to the invention is preferably carried out with those alkoxylated alcohols whose molecular weight is 300 to 2000 and in particular 500 to 1500.

Geeignete Alkohole, die mit Alkylenoxiden der Formel I umgesetzt werden können, sind z.B. Methanol, Ethanol, Propanol, Isopropanol, Butanol, Isobutanol, Pentanol, Isopentanol, Neopentanol, Hexanol, Heptanol, Octanol, 2-Ethylhexanol, Nonanol, Decanol, 2-Propylheptanol, Dodecanol, 2-Butyloctanol, Tetradecanol, 2-Pentylnonanol, Hexadecanol, Octadecanol, Eicosanol, Tetracosanol, Hexacosanol, Octacosanol, Tricosanol, Octadec-9(cis)-enol, Octadec-9(trans)-enol, Octadec-9(cis),12(cis)-dienol, Octadec-9(cis),12(cis),15(cis)-trienol, Eicosa-5,8,11,14-tetraenol, Ethan-1,2-diol, Propan-1,2- oder 1,3-diol, Butan-1,2-1,3-, -1,4- oder -2,3-diol, Hexan-1,6-diol, Octadec-9(cis)-en-1,12-diol, Glycerin, Trimethylolethan, Trimethylolpropan, Hexan-1,2,5- oder 1,2,6-triol, 3-Hydroxymethylpentan-2,4-diol, Erythrit, Pentaerythrit, Dipentaerythrit, Mannit oder Sorbit oder technische Fettalkohole, wie Talgfettalkohol.Suitable alcohols which can be reacted with alkylene oxides of the formula I are, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, neopentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 2-propylheptanol , Dodecanol, 2-butyl octanol, tetradecanol, 2-pentyl nonanol, hexadecanol, octadecanol, eicosanol, Tetracosanol, hexacosanol, octacosanol, tricosanol, octadec-9 (cis) -enol, octadec-9 (trans) -enol, octadec-9 (cis), 12 (cis) -dienol, octadec-9 (cis), 12 (cis ), 15 (cis) -trienol, Eicosa-5,8,11,14-tetraenol, ethane-1,2-diol, propane-1,2- or 1,3-diol, butane-1,2-1, 3-, -1,4- or -2,3-diol, hexane-1,6-diol, octadec-9 (cis) -en-1,12-diol, glycerin, trimethylolethane, trimethylolpropane, hexane-1,2 , 5- or 1,2,6-triol, 3-hydroxymethylpentane-2,4-diol, erythritol, pentaerythritol, dipentaerythritol, mannitol or sorbitol or technical fatty alcohols, such as tallow fatty alcohol.

Bei den erfindungsgemäß zu verwendenden oxalkylierten Alkoholen handelt es sich im allgemeinen um an sich bekannte Produkte. In vielen Fällen sind diese Produkte handelsüblich. Alkohole der genannten Art sind z.B. in K. Lindner, Tenside-Textilhilfsmitte-Waschrohstoffe, Band 1, S. 837 ff., 1964 oder in Ullmanns Enzyklopädie der technischen Chemie, 4. Auflage, Band 22, Seite 488 ff., beschrieben.The oxyalkylated alcohols to be used according to the invention are generally products known per se. In many cases, these products are commercially available. Alcohols of the type mentioned are e.g. in K. Lindner, Tenside-Textilhilfsmitte-Waschrohstoffe, Volume 1, pp. 837 ff., 1964 or in Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, Volume 22, pp. 488 ff.

Die oxalkylierten Alkohole werden beispielsweise in einer Menge von 0,1 bis 5 Gew.%, vorzugsweise 0,3 bis 3 Gew.% und insbesondere 0,2 bis 2 Gew.%, jeweils bezogen auf das zu färbende Leder, angewendet.The alkoxylated alcohols are used, for example, in an amount of 0.1 to 5% by weight, preferably 0.3 to 3% by weight and in particular 0.2 to 2% by weight, based in each case on the leather to be dyed.

Die im neuen Verfahren als Farbmittel eingesetzten Pigmente können zweckmäßig in Form von an sich bekannten Pigmentpräparationen, z.B. als wäßrige Dispersionen verwendet werden. Dabei sind solche wäßrige Pigmentpräparationen bevorzugt, die nichtionische Tenside als Dispergierhilfsmittel enthalten. Als nichtionische Tenside sind beispielsweise die oben bezeichneten erfindungsgemäß zu verwendenden Komponenten oder auch Anlagerungsprodukte von Alkylenoxiden an Fettsäuren, Phenole, Alkylphenole, Säureamide oder Mercaptane zu nennen.The pigments used as colorants in the new process can expediently be in the form of pigment preparations known per se, e.g. can be used as aqueous dispersions. Those aqueous pigment preparations which contain nonionic surfactants as dispersing agents are preferred. Examples of nonionic surfactants which may be mentioned are the above-mentioned components to be used according to the invention or also addition products of alkylene oxides with fatty acids, phenols, alkylphenols, acid amides or mercaptans.

Besonders hervorzuheben sind solche wäßrigen Pigmentpräparationen, die als Dispergierhilfsmittel ein oxalkyliertes Amin, das mindestens 20 Kohlenstoffatome aufweist, enthalten. Sie sind z.B. in der DE-A-2 156 603 beschrieben.Particularly noteworthy are those aqueous pigment preparations which contain an oxyalkylated amine which has at least 20 carbon atoms as a dispersing aid. They are e.g. described in DE-A-2 156 603.

Es hat sich gezeigt, daß Pigmente, die eine Teilchengröße von unter 1 µm, z.B. von 0,01 bis 0,2 µm aufweisen, besonders günstige Ergebnisse liefern.It has been found that pigments which have a particle size of less than 1 µm, e.g. have from 0.01 to 0.2 µm, deliver particularly favorable results.

Eine bevorzugte Verfahrensweise besteht darin, das Leder mit einer wäßrigen Pigmentpräparation, die ein oxalkyliertes Amin, das mindestens 20 Kohlenstoffatome aufweist, als Dispergierhilfsmittel enthält, zu behandeln.A preferred procedure is to treat the leather with an aqueous pigment preparation which contains an oxyalkylated amine which has at least 20 carbon atoms as a dispersing aid.

Eine besonders bevorzugte Verfahrensweise besteht darin, die Behandlung des Leders mit einer ein oxalkyliertes Amin enthaltenden, wäßrigen Pigmentpräparation und zusätzlichem oxalkylierten Amin vorzunehmen.A particularly preferred procedure consists in treating the leather with an aqueous pigment preparation containing an oxyalkylated amine and additional oxyalkylated amine.

Ganz besonders bevorzugt ist eine Verfahrensweise, in der die Behandlung des Leders mit einer ein oxalkyliertes Amin enthaltenden, wäßrigen Pigmentpräparation und zusätzlichem oxalkylierten Amin sowie einem oxalkylierten Alkohol, der mindestens 16 Kohlenstoffatome aufweist, vorgenommen wird.A procedure is very particularly preferred in which the leather is treated with an aqueous pigment preparation containing an oxyalkylated amine and additional oxyalkylated amine and an oxyalkylated alcohol which has at least 16 carbon atoms.

Das erfindungsgemäße Verfahren wird zweckmäßig so durchgeführt, daß man ein in üblicher Weise vorbehandeltes Leder in wäßriger Flotte im Walkfaß vorlegt und bei einer Temperatur von 20 bis 60°C, vorzugsweise 40 bis 50°C das Pigment wie oben ausgeführt, vorzugsweise in Form einer wäßrigen Präparation, die ein oxalkyliertes Amin als Dispergierhilfsmittel enthält, gegebenenfalls zusätzliches oxalkyliertes Amin sowie gegebenenfalls oxalkylierten Alkohol zugibt. Danach wird die Färbung des Leders bei der obengenannten Temperatur und bei einem pH-Wert von 4 bis 7, vorzugsweise 4,5 bis 6 unter Walken vorgenommen. Der Färbeprozeß ist im allgemeinen nach 0,5 bis 2 Stunden beendet. Nach üblicher Fixierung mit Ameisensäure wird dann das Leder aus der Färbeflotte entnommen, mit Wasser gewaschen und nach an sich bekannten Verfahren aufgearbeitet.The process according to the invention is expediently carried out in such a way that a leather which has been pretreated in a customary manner is placed in an aqueous liquor in a drum and the pigment is carried out at a temperature of 20 to 60 ° C., preferably 40 to 50 ° C., preferably in the form of an aqueous one Preparation containing an oxyalkylated amine as a dispersing agent, optionally adding additional oxyalkylated amine and optionally oxyalkylated alcohol. The leather is then dyed at the above-mentioned temperature and at a pH of 4 to 7, preferably 4.5 to 6, with milling. The dyeing process is generally complete after 0.5 to 2 hours. After conventional fixation with formic acid, the leather is then removed from the dyeing liquor, washed with water and worked up by methods known per se.

Das erfindungsgemäße Verfahren kann auch in Gegenwart weiterer, bei der Lederfärbung üblicher Hilfsmittel oder Zusatzstoffe, z.B. handelsübliche Salze von Kondensationsprodukten von Phenol- oder Naphthalinsulfonsäuren mit Formaldehyd und Harnstoff, Fettlicker auf Basis emulgierter Paraffine oder wasserlösliche Polymere auf Acrylatbasis, die ein Molekulargewicht von ca. 2000 bis 5000 aufweisen, betrieben werden.The process according to the invention can also be carried out in the presence of other auxiliaries or additives customary in leather dyeing, e.g. commercially available salts of condensation products of phenolic or naphthalenesulfonic acids with formaldehyde and urea, fat liquors based on emulsified paraffins or water-soluble polymers based on acrylates, which have a molecular weight of approx. 2000 to 5000, are operated.

Diese üblichen Hilfsmittel oder Zusatzstoffe können entweder vor dem Färbeprozeß oder zusammen mit dem Pigment und dem oxalkylierten Amin der wäßrigen Flotte zugesetzt werden.These customary auxiliaries or additives can be added to the aqueous liquor either before the dyeing process or together with the pigment and the oxyalkylated amine.

Insbesondere bei der Färbung von Polsterleder kann es in manchen Fällen von Vorteil sein, den Färbeprozeß zweistufig durchzuführen, d.h. nachdem das Polsterleder einmal mit den Pigmenten behandelt wurde, wird es in einer zweiten Stufe nochmals mit Pigmenten gefärbt, wobei der Pigmentgehalt dann in der zweiten Färbeflotte im allgemeinen niedriger ist als in der ersten Flotte.In particular when dyeing upholstery leather, it can be advantageous in some cases to carry out the dyeing process in two stages, ie after the upholstery leather has been treated once with the pigments, it is dyed again with pigments in a second stage, the pigment content then being used in the second dyeing liquor is generally lower than in the first fleet.

Es hat sich gezeigt, daß man zu besonders vorteilhaften Lederfärbungen gelangt, wenn man das erfindungsgemäße Verfahren zusätzlich in Gegenwart eines oder mehrerer wasserlöslicher Säurefarbstoffe durchführt.It has been shown that particularly advantageous leather dyeings are obtained if the process according to the invention is additionally carried out in the presence of one or more water-soluble acid dyes.

Als wasserlösliche Säurefarbstoffe kommen z.B. an sich bekannte, Sulfonsäuregruppen enthaltende Azofarbstoffe, die entweder metallfrei sein oder als Metallkomplex vorliegen können, Sulfonsäuregruppen enthaltende Metallphthalocyanine oder Sulfonsäuregruppen enthaltende Anthrachinone in Betracht.Examples of water-soluble acid dyes are azo dyes known per se which contain sulfonic acid groups and are either metal-free or can be present as a metal complex, metal phthalocyanines containing sulfonic acid groups or anthraquinones containing sulfonic acid groups.

Die wasserlöslichen Säurefarbstoffe werden zweckmäßig pulverförmig oder in Form einer Flüssigpräparation zur Färbeflotte gegeben. Ihre Zugabe erfolgt vorteilhaft mit der des Pigments.The water-soluble acid dyes are expediently added in powder form or in the form of a liquid preparation to the dyeing liquor. They are advantageously added with that of the pigment.

Im allgemeinen wendet man 0,1 bis 6, vorzugsweise 0,5 bis 5 % und insbesondere 0,5 bis 3 %, jeweils bezogen auf das Feuchtgewicht des zu färbenden Leders, an wasserlöslichem Säurefarbstoff an.In general, 0.1 to 6, preferably 0.5 to 5% and in particular 0.5 to 3%, in each case based on the wet weight of the leather to be dyed, of water-soluble acid dye is used.

Im erfindungsgemäßen Verfahren kann das Leder sowohl mit einzelnen Pigmenten als auch mit Mischungen von Pigmenten behandelt werden. Bevorzugt ist dabei die Färbung des Leders mit einer Mischung aus gelben, roten und blauen Pigmenten, bei der braune Farbtöne resultieren.In the process according to the invention, the leather can be treated both with individual pigments and with mixtures of pigments. It is preferred to dye the leather with a mixture of yellow, red and blue pigments, which results in brown shades.

Mittels des neuen Verfahrens gelangt man zu Lederfärbungen, die sich durch hervorragende Egalität, Farbtiefe, Brillanz sowie durch hohe Lichtechtheits-, Naßechtheits- und Migrationsechtheitswerte auszeichnen. Darüber hinaus zeigen sie eine gute Durchfärbung.The new process leads to leather dyeing that is characterized by excellent levelness, depth of color, brilliance as well as high light fastness, wet fastness and migration fastness values. In addition, they show good coloring.

Die folgenden Beispiele sollen die Erfindung näher erläutern. Die Prozentangaben sind Gewichtsprozente und beziehen sich dabei jeweils auf falzfeuchtes Chromleder.The following examples are intended to explain the invention in more detail. The percentages are percentages by weight and relate to seam-damp chrome leather.

Die in den Beispielen verwendeten Pigmente wurden jeweils in Form einer wäßrigen Präparation eingesetzt, die als oxalkyliertes Amin Ethylendiamin, das zuerst mit Propylenoxid und dann mit Ethylenoxid umgesetzt wurde (Ethylenoxidgehalt: 40 %; M 10500), enthalten. Bezogen auf das Gewicht des Pigments, betrug der Aminanteil 20 %.The pigments used in the examples were each used in the form of an aqueous preparation, the oxyalkylated amine ethylenediamine which was first reacted with propylene oxide and then with ethylene oxide (ethylene oxide content: 40%; M 10500). Based on the weight of the pigment, the amine content was 20%.

Die Säurefarbstoffe kamen in Form einer wäßrigen Lösung zur Anwendung.The acid dyes were used in the form of an aqueous solution.

Bei dem oxalkylierten Amin handelt es sich um Oleylamin, das mit ca. 10 Mol Ethylenoxid oxethyliert wurde. Bei dem oxalkylierten Alkohol handelt es sich um Talgfettalkohol, der mit ca. 80 Mol Ethylenoxid oxethyliert wurde.The oxyalkylated amine is oleylamine which has been oxethylated with about 10 moles of ethylene oxide. The alkoxylated alcohol is it is tallow fatty alcohol which has been oxethylated with approx. 80 mol ethylene oxide.

A) Färbung von PolsterlederA) Coloring upholstery leather Allgemeine FärbevorschriftGeneral staining instructions

  • Vorbehandlung
    Polsterleder wurde nach üblichen Methoden nachgegerbt und danach ausgewaschen.    Pretreatment
    Upholstery leather was retanned using customary methods and then washed out.
  • Färbestufe 1
    Polsterleder wurde bei einer Temperatur von 50°C in 200 % einer wäßrigen Flotte, die 1 % Ammoniak enthielt, 10 Minuten behandelt. Anschließend wurde der Färbeflotte Pigment, gegebenenfalls Säurefarbstoff, oxalkyliertes Amin und oxalkylierter Alkohol zugesetzt. Das Leder wurde dann 30 Minuten gewalkt, mit 10 % eines handelsüblichen Fettlickers versetzt und weitere 60 Minuten gewalkt. Nach Zugabe von 2,5 % Ameisensäure (in 2 Portionen, in 15 Minuten Abstand) wurde weitere 30 Minuten gewalkt. Danach wurde die Färbeflotte abgelassen.    Dye level 1
    Upholstery leather was treated at a temperature of 50 ° C in 200% of an aqueous liquor containing 1% ammonia for 10 minutes. Then pigment, optionally acid dye, alkoxylated amine and alkoxylated alcohol were added to the dye liquor. The leather was then drummed for 30 minutes, 10% of a commercially available fat licker was added and the drum was drummed for a further 60 minutes. After the addition of 2.5% formic acid (in 2 portions, 15 minutes apart), the drum was drummed for a further 30 minutes. The dye liquor was then drained off.
  • Färbestufe 2
    Das Leder wurde dann bei einer Temperatur von 50°C in 200 % einer Färbeflotte, die Pigment, Säurefarbstoff, oxalkyliertes Amin und oxalkylierten Alkohol enthielt 30 Minuten gewalkt. Nach Zugabe von 1 % Ameisensäure wurde weitere 30 Minuten gewalkt.    Dye level 2
    The leather was then drummed at a temperature of 50 ° C in 200% of a dye liquor containing pigment, acid dye, oxalkylated amine and oxalkylated alcohol for 30 minutes. After the addition of 1% formic acid, it was drummed for a further 30 minutes.
  • Nachfixierung
    Danach wurde das Leder aus der Flotte entnommen und bei einer Temperatur von 40°C in 200 % einer wäßrigen Flotte, die 0,3 % Ameisensäure enthielt, 5 Minuten gewalkt. Dann wurden 0,3 % eines handelsüblichen kationischen Nachfixiermittels zugesetzt und weitere 30 Minuten gewalkt. Das Leder wurde dann nach üblichen Methoden aufgearbeitet, d.h. naß gespannt, getrocknet, angefeuchtet und gemillt.    Post-fixation
    The leather was then removed from the liquor and drummed at a temperature of 40 ° C. in 200% of an aqueous liquor which contained 0.3% formic acid for 5 minutes. Then 0.3% of a commercially available cationic post-fixing agent was added and drummed for a further 30 minutes. The leather was then worked up by customary methods, ie stretched wet, dried, moistened and milled.
Beispiel 1example 1 Färbestufe 1Dye level 1

1,0 % C.I. Pigment Red 146
1,0 % C.I. Acid Red 310
1,5 % C.I. Acid Red 282
0,3 % oxalkyiertes Amin
0,35 % oxalkylierter Alkohol1.0% CI Pigment Red 146
1.0% CI Acid Red 310
1.5% CI Acid Red 282
0.3% oxyalkylated amine
0.35% oxyalkylated alcohol

Färbestufe 2Dye level 2

0,5 % C.I. Pigment Red 146
0,5 % C.I. Acid Red 310
0,75 % C.I. Acid Red 282
0,15 % oxalkyliertes Amin
0,18 % oxalkylierter Alkohol
Farbton des gefärbten Leders: rot0.5% CI Pigment Red 146
0.5% CI Acid Red 310
0.75% CI Acid Red 282
0.15% oxyalkylated amine
0.18% oxyalkylated alcohol
Color of the dyed leather: red

Beispiel 2Example 2 Färbestufe 1Dye level 1

0,5 % Kupferphthalocyanin (α-Modifikation)
0,5 % C.I. Vat Violet 9
1,0 % C.I. Acid Blue 134
1,0 % C.I. Acid Blue 54
0,3 % oxalkyliertes Amin
0,35 oxalkylierter Alkohol0.5% copper phthalocyanine (α modification)
0.5% CI Vat Violet 9
1.0% CI Acid Blue 134
1.0% CI Acid Blue 54
0.3% oxyalkylated amine
0.35 oxyalkylated alcohol

Färbestufe 2Dye level 2

0,25 % Kupferphthalocyanin (α-Modifikation)
0,25 % C.I. Vat Violet 9
0,5 % C.I. Acid Blue 134
0,5 % C.I. Acid Blue 254
0,15 % oxalkyliertes Amin
0,18 % oxalkylierter Alkohol
Farbton des gefärbten Leders: blau.0.25% copper phthalocyanine (α-modification)
0.25% CI Vat Violet 9
0.5% CI Acid Blue 134
0.5% CI Acid Blue 254
0.15% oxyalkylated amine
0.18% oxyalkylated alcohol
Color of the dyed leather: blue.

Beispiel 3Example 3

Die Durchführung erfolgte gemäß der allgemeinen Färbevorschrift, jedoch ohne Stufe 2.
0,8 % C.I. Pigment Orange 13
3,0 % C.I. Acid Brown 422
0,3 % oxalkyliertes Amin
0,35 % oxalkylierter Alkohol
Farbton des gefärbten Leders: gelbbraun.The procedure was carried out in accordance with the general staining instructions, but without step 2.
0.8% CI Pigment Orange 13
3.0% CI Acid Brown 422
0.3% oxyalkylated amine
0.35% oxyalkylated alcohol
Color of the dyed leather: yellow-brown.

Beispiel 4Example 4

Die Durchführung erfolgte analog Beispiel 3.
1,5 % C.I. Pigment Orange 13
0,3 % oxalkyliertes Amin
0,35 % oxalkylierter Alkohol
Farbton des gefärbten Leders: braunThe procedure was analogous to Example 3.
1.5% CI Pigment Orange 13
0.3% oxyalkylated amine
0.35% oxyalkylated alcohol
Color of the dyed leather: brown

B) Färbung von OberlederB) Coloring upper leather Allgemeine FärbevorschriftGeneral staining instructions

  • Vorbehandlung
    Oberleder wurde nach üblichen Methoden mit einem Polymergerbstoff auf Basis Acrylsäure/Acrylnitril, einem amphoteren Gerbstoff auf Basis eines Kondensationsprodukts von Phenolsulfonsäure und Formaldehyd und einem Harzgerbstoff auf Basis eines Kondensationsprodukts von Melamin und Formaldehyd nachgegerbt und danach ausgewaschen.    Pretreatment
    Upper leather was retanned using customary methods with a polymer tanning agent based on acrylic acid / acrylonitrile, an amphoteric tanning agent based on a condensation product of phenolsulfonic acid and formaldehyde and a resin tanning agent based on a condensation product of melamine and formaldehyde and then washed out.
  • Färbestufe
    Das nachgegerbte Leder wurde bei einer Temperatur von 55°C in 150 % einer wäßrigen Flotte, die Pigment, Säurefarbstoff, oxalkyliertes Amin und gegebenenfalls oxalkylierten Alkohol enthielt, 40 Minuten gewalkt. Danach wurden 6 % eines handelsüblichen Fettlickers zugesetzt und 40 Minuten gewalkt. Schließlich wurde noch 1 % Ameisensäure in 2 Portionen zugegeben, wobei nach Zugabe der 1. Portion 20 Minuten und nach Zugabe der 2. Portion 30 Minuten gewalkt wurde. Danach wurde das Leder der Flotte entnommen und nach üblichen Methoden aufgearbeitet, d.h. unter vermindertem Druck getrocknet, angefeuchtet und gestollt.    Dyeing level
    The retanned leather was drummed for 40 minutes at a temperature of 55 ° C. in 150% of an aqueous liquor which contained pigment, acid dye, oxalkylated amine and optionally oxalkylated alcohol. Then 6% of a commercially available fat licker was added and the fabric was drummed for 40 minutes. Finally, 1% formic acid was added in 2 portions, followed by drumming for 20 minutes after adding the 1st portion and for 30 minutes after adding the 2nd portion. The leather was then removed from the liquor and worked up by customary methods, ie dried, moistened and stubbed under reduced pressure.
Beispiel 5Example 5

0,23 % C.I. Pigmet Yellow 83
0,2 % C.I. Pigment Red 146
0,04 % Kupferphthalocyanin (α-Modifikation)
0,04 % C.I. Vat Violet 9
2,0 % C.I. Acid Brown 434
0,1 % oxalkyliertes Amin
0,1 % oxalkylierter Alkohol
Farbton des gefärbten Leders: braun0.23% CI Pigmet Yellow 83
0.2% CI Pigment Red 146
0.04% copper phthalocyanine (α-modification)
0.04% CI Vat Violet 9
2.0% CI Acid Brown 434
0.1% oxyalkylated amine
0.1% oxyalkylated alcohol
Color of the dyed leather: brown

Beispiel 6Example 6

0,25 % C.I. Pigment Yellow 83
0,15 % C.I. Pigment Red 146
0,05 % Kupferphthalocyanin (α-Modifikation)
0,05 % C.I. Vat Violet 9
2,0 % C.I. Acid Brown 290
0,1 % oxalkyliertes Amin
0,1 % oxalkylierter Alkohol
Farbton des gefärbten Leders: braun.0.25% CI Pigment Yellow 83
0.15% CI Pigment Red 146
0.05% copper phthalocyanine (α-modification)
0.05% CI Vat Violet 9
2.0% CI Acid Brown 290
0.1% oxyalkylated amine
0.1% oxyalkylated alcohol
Color of the dyed leather: brown.

Beispiel 7Example 7

0,23 % C.I. Pigment Yellow 83
0,2 % C.I. Pigment Red 146
0,04 % Kupferphthalocyanin (α-Modifikation)
0,04 % C.I. Vat Violet 9
2,0 % C.I. Acid Brown 434
0,3 % oxalkyliertes Amin
Farbton des gefärbten Leders: braun.0.23% CI Pigment Yellow 83
0.2% CI Pigment Red 146
0.04% copper phthalocyanine (α-modification)
0.04% CI Vat Violet 9
2.0% CI Acid Brown 434
0.3% oxyalkylated amine
Color of the dyed leather: brown.

In den Beispielen 1 bis 7 wurde jeweils egal gefärbtes Leder erhalten, das eine klare Nuance und eine hohe Lichtechtheit aufweist.In Examples 1 to 7, leather of any color was obtained, which has a clear shade and a high light fastness.

Claims (5)

  1. A process for dyeing leather with a pigment in an aqueous liquor, which comprises treating the leather with a pigment at from 20 to 60°C in the presence of an alkoxylated amine of 20 or more carbon atoms.
  2. A process for dyeing leather as claimed in claim 1, wherein the leather is treated with from 0.1 to 5 %, based on the moist weight of the leather to be dyed, of an alkoxylated amine.
  3. A process for dyeing leather as claimed in claim 1, wherein the treatment is carried out in the additional presence of an alkoxylated alcohol of 16 or more carbon atoms.
  4. A process for dyeing leather as claimed in claim 1, wherein the treatment is carried out with a ready-prepared aqueous pigment preparation which contains an alkoxylated amine of 20 or more carbon atoms.
  5. A process for dyeing leather as claimed in claim 1, wherein the treatment is carried out in the additional presence of a water-soluble acid dye.
EP89109121A 1988-05-28 1989-05-20 Process for dyeing leather using pigments Expired - Lifetime EP0344555B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3818183 1988-05-28
DE3818183A DE3818183A1 (en) 1988-05-28 1988-05-28 METHOD FOR DYING LEATHER WITH PIGMENTS

Publications (3)

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EP0344555A2 EP0344555A2 (en) 1989-12-06
EP0344555A3 EP0344555A3 (en) 1991-11-06
EP0344555B1 true EP0344555B1 (en) 1993-09-08

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EP (1) EP0344555B1 (en)
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SE501132C2 (en) * 1992-11-19 1994-11-21 Berol Nobel Ab Use of alkoxylate of 2-propylheptanol in cleaning compositions
DE4244006A1 (en) * 1992-12-24 1994-06-30 Bayer Ag Cationic pigment binders
EP0889934A1 (en) * 1996-03-26 1999-01-13 Basf Aktiengesellschaft Stable dye compositions
DE60239896D1 (en) * 2002-08-07 2011-06-09 Toray Industries VELOURSKUNSTLEDER AND ITS MANUFACTURE
GB0324529D0 (en) * 2003-10-21 2003-11-26 Clariant Int Ltd Improvements in or relating to organic compounds
TWI666359B (en) * 2014-03-31 2019-07-21 日商東麗股份有限公司 Dyed artificial leather and manufacturing method thereof
CN105421108B (en) * 2015-12-14 2017-07-07 嘉兴学院 Leather levelling agent, preparation method and the method to leather coloring
US11352511B2 (en) * 2017-05-12 2022-06-07 Toyo Ink Sc Holdings Co., Ltd. Dispersant, dispersant composition, dispersion composition for batteries, electrode and battery
WO2024218124A1 (en) * 2023-04-17 2024-10-24 Basf Se Composition comprising an antimicrobial agent and an alkoxylated amine

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US2893811A (en) * 1955-12-30 1959-07-07 Gen Aniline & Film Corp Dyeing of leather
GB976529A (en) * 1961-06-09 1964-11-25 Asahi Denka Kogyo Kk An improved method for dyeing nitrogenous fibres and textiles
US4083681A (en) * 1968-06-14 1978-04-11 Sandoz Ltd. Compositions of metal complexes of disazo acid dyes stabilized with amino ethers
US3841888A (en) * 1971-11-15 1974-10-15 Basf Ag Aqueous pigment dispersions
DE2856628C2 (en) * 1978-12-29 1980-04-24 Basf Ag, 6700 Ludwigshafen Process for dyeing grain leather

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JP2783290B2 (en) 1998-08-06
US4983185A (en) 1991-01-08
JPH0219579A (en) 1990-01-23
KR900018468A (en) 1990-12-21
CA1335926C (en) 1995-06-20
EP0344555A3 (en) 1991-11-06
DE3818183A1 (en) 1989-12-07
EP0344555A2 (en) 1989-12-06
DE58905506D1 (en) 1993-10-14
ES2042875T3 (en) 1993-12-16

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