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EP0118023B1 - Process for water-proofing leather and furs - Google Patents

Process for water-proofing leather and furs Download PDF

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Publication number
EP0118023B1
EP0118023B1 EP84101000A EP84101000A EP0118023B1 EP 0118023 B1 EP0118023 B1 EP 0118023B1 EP 84101000 A EP84101000 A EP 84101000A EP 84101000 A EP84101000 A EP 84101000A EP 0118023 B1 EP0118023 B1 EP 0118023B1
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Prior art keywords
mole
acid
weight
ammonium
oxidized
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EP84101000A
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German (de)
French (fr)
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EP0118023A1 (en
Inventor
Hans-Herbert Dr. Friese
Wolfgang Prinz
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Definitions

  • the invention relates to a process for the production of waterproof leather and furs by tanning, retanning, dyeing, greasing and fixing, with the aid of copolymers containing carboxyl groups, characterized in that, after the tanning and optionally dyeing, in the same bath, one after the other as a fatliquor (A) oxidized or oxidized and partially sulfated long chain C18 - C26 hydrocarbons or C32 - C40 waxes, and as impregnating agent (B) copolymers of 60-95 mol% acrylic acid and / or methacrylic acid and 5 - 40 mol% methyl , Ethyl, propyl or butyl ester, amide or nitrile of acrylic acid or methacrylic acid with a molecular weight of 800 - 10,000, in the form of the alkali, ammonium or amine salts, and then acidified, fixed and finished.
  • A oxidized or oxidized and partially sulfated long
  • the process is carried out using raw hides or skins which are tanned and retanned in the customary manner, inorganic and / or organic, natural or synthetic tanning agents, such as chromium or aluminum salts, or phenol / naphthalene condensation products, or vegetable tanning agents, be used.
  • inorganic and / or organic, natural or synthetic tanning agents such as chromium or aluminum salts, or phenol / naphthalene condensation products, or vegetable tanning agents, be used.
  • oxidized or oxidized and partially sulfonated long-chain C18-C26 hydrocarbons or C32-C40 waxes are used as fatliquoring agents (A) in an amount of 3 - 8% by weight, based on the shaved weight of the leather.
  • the products have acid numbers of 5-100 and optionally S0 3 contents of 0.2-2.0% by weight.
  • fatliquors examples include sulfoxidized C20-C22 paraffin wax with an S0 3 content of 0.2-0.5% by weight and acid numbers of 5-15, oxidized and sulfated C24-C26 polyethylenes or paraffins with an S0 3 content of 0.3-0.8% by weight and acid numbers of 5-20, and oxidized C22-C26 paraffin with acid numbers of 60-70.
  • the products are preferably in the form of their alkali metal, ammonium or Amine salts applied.
  • the fatliquoring agents are preferably used in combination with special W / O emulsifiers such as C12-C18 - monoalkyl phosphoric acid esters, C16 - C20 - alkenyl succinic acids, fatty acid arcosides, citric acid fatty alcohol monoesters, also fatty acid monoethanolamide ether sulfates or fatty acids, in the form of the alkali metal, ammonium or amine salts .
  • W / O emulsifiers such as C12-C18 - monoalkyl phosphoric acid esters, C16 - C20 - alkenyl succinic acids, fatty acid arcosides, citric acid fatty alcohol monoesters, also fatty acid monoethanolamide ether sulfates or fatty acids, in the form of the alkali metal, ammonium or amine salts .
  • copolymer (B) After a running time of 45-60 minutes, the addition of the copolymer (B) is continued for 30 minutes in the same liquor at a pH of 5-6.
  • the copolymers used are preferably those of 70-85 mol% of acrylic acid and / or methacrylic acid with 15-30 mol% of the methyl, ethyl, propyl or butyl ester or amide or nitrile of acrylic acid or methacrylic acid in the form of the alkali metal, ammonium - or amine salts.
  • the molecular weight of the copolymers is 800-10,000. Based on the shaved weight of the leather, 0.5 - 3% by weight of copolymers are used.
  • Suitable copolymers are products based on 75 mol% of acrylic acid and 25 mol% of ethyl acrylate, Na salt, 85 mol% of acrylic acid and 15 mol% of acrylonitrile, ammonium salt and 70 mol% of acrylic acid and 30 mol% of acrylamide, Na salt.
  • soft leather After completion, soft leather is obtained, which also has a significantly better behavior towards water in case A than in case B.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Fittings On The Vehicle Exterior For Carrying Loads, And Devices For Holding Or Mounting Articles (AREA)
  • Supports For Pipes And Cables (AREA)
  • Soil Working Implements (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Escalators And Moving Walkways (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)

Abstract

This invention relates to a process for producing waterproof leathers and skins by tanning, retanning, dyeing, stuffing, and fixing which is characterized in that, after tanning and, optionally, dyeing, stuffing agents (A) in the form of oxidized or oxidized and partly sulfonated long-chain hydrocarbons of waxes and impregnating agents (B) in the form of copolymers or from 60 to 95 mol percent of (meth) acrylic acid and from 5 to 40 mol percent of an ester, amide or nitrile of (meth) acrylic acid having a molecular weight of from 800 to 10,000 in salt form are successively used in the same bath, followed by acidification, fixing and finishing. The co-use of the impregnating agents (B) with the particular stuffing agents (A) results in much greater degree of resistance to water penetration than that obtained by the use of the stuffing agent (A), alone.

Description

Zur Herstellung wasserdichter Leder und Pelze kommen insbesondere drei Verfahrensprinzipien in Betracht.

  • (1) Imprägnierung durch Einlagerung wasserunlöslicher Substanzen, z. B. feste Fette, Wachse oder spezielle Polymere,
  • (2) Imprägnierung durch Einlagerung wasserquellender Substanzen, die bei Wasseraufnahme hochviskose Emulsionen bilden und die Faserzwischenräume des Leders verstopfen, Z. B. spezielle Emulgatoren vom W/O-Typ,
  • (3) Behandlung mit hydrophobierend wirkenden Substanzen, z.B. Aluminium- und Chromkomplexe, Silikone oder organische Fluor-Verbindungen.
In particular, three process principles come into consideration for the production of waterproof leather and furs.
  • (1) Impregnation by storing water-insoluble substances, e.g. B. solid fats, waxes or special polymers,
  • (2) Impregnation by storing water-swelling substances which form highly viscous emulsions when water is absorbed and clog the interstices of the leather, eg special emulsifiers of the W / O type,
  • (3) Treatment with substances having a hydrophobic effect, for example aluminum and chromium complexes, silicones or organic fluorine compounds.

In der Praxis hat sich eine Kombination der unter (2) und (3) genannten Maßnahme bewährt, wobei bevorzugt im Walkfaß in wäßriger Flotte gearbeitet wird. Dabei erfolgt eine Umwandlung der W/O-Emulgatoren in hydrophobierend wirkende Metallkomplexsalze durch eine Fixierung mit Chrom- bzw. Aluminiumsalzen, die nach der Fettung durchgefürt wird. Dieses Verfahren weist aber Nachteile auf, da die Fettung relativ hohe pH-Werte (Über 6) erfordert, um ein oberflächliches Anfallen der Fette und damit Verschmierungen zu vermeiden. Dies führt jedoch leicht zu einer gewissen Losnarbigkeit des Leders. Außerdem zeigen die in der Praxis erhaltenen Penetrometerwerte häufig sehr starke Schwankungen, so daß eine Nachbehandlung des Leders durch Gießen, Spritzen oder Plüschen notwendig werden kann.In practice, a combination of the measures mentioned under (2) and (3) has proven its worth, preference being given to working in an aqueous liquor in a drum. The W / O emulsifiers are converted into metal complex salts with a hydrophobic effect by fixing with chromium or aluminum salts, which is carried out after the greasing. However, this method has drawbacks, since the greasing requires relatively high pH values (above 6) in order to avoid superficial accumulation of the fats and thus smearing. However, this easily leads to a certain loose grain of the leather. In addition, the penetrometer values obtained in practice often show very strong fluctuations, so that aftertreatment of the leather by casting, spraying or plushing may be necessary.

Es ist weiterhin aus der DE-Anmeldung F 10 300.28a, 9 ein Verfahren zur Verbesserung der Eigenschaften von Leder, insbesondere hinsichtlich der Wasseraufnahme und Wasserdurchlässigkeit bekannt, das dadurch gekennzeichnet ist, daß man wäßrige Lösungen oder Emulsionen von Salzen Carboxylgruppen enthaltender Polymerisate gegebenenfalls in Gegenwart von Fettungs- und Verdickungsmitteln, und/ oder von Puffersubstanzen in das Material einbringt und dieses gegebenenfalls einer Nachbehandlung unterwirft, um die Polymerisate in den unlöslichen Zustand zu überführen. Als Carboxylgruppen enthaltende Polymerisate werden u. a. Mischpolymerisate aus Acrylsäure oder Methacrylsäure und deren Estern genannt, wobei der Gehalt an Carboxylgruppen enthaltenden Komponenten zwischen 2,5 und 50 % schwankt. Es hat sich jedoch gezeigt, daß sehr hohe Mengen an Polymerisaten (> 30 % bezogen auf Falzgewicht der Leder) eingelagert werden müssen, um eine ausreichende Imprägnierwirkung zu erhalten.It is also known from DE application F 10 300.28a, 9 a process for improving the properties of leather, in particular with regard to water absorption and water permeability, which is characterized in that aqueous solutions or emulsions of salts of carboxyl group-containing polymers, if appropriate in the presence of fatliquoring and thickening agents, and / or of buffer substances in the material and optionally subjecting it to a post-treatment in order to convert the polymers into the insoluble state. As polymers containing carboxyl groups u. a. Copolymers of acrylic acid or methacrylic acid and their esters mentioned, the content of components containing carboxyl groups fluctuating between 2.5 and 50%. However, it has been shown that very high amounts of polymers (> 30% based on the shaved weight of the leather) must be stored in order to obtain a sufficient impregnation effect.

Gegenstand der Erfindung ist demgegenüber ein Verfahren zur Herstellung wasserdichter Leder und Pelze durch Gerbung, Nachgerbung, Färbung, Fettung und Fixierung, unter Zuhilfenahme von Carboxylgruppen enthaltenden Copolymeren, dadurch gekennzeichnet, daß man im Anschluß an die Gerbung und gegebenenfalls Färbung im gleichen Bad nacheinander als Fettungsmittel (A) oxidierte oder oxidierte und teilsulfierte langkettige C18 - C26 - Kohlenwasserstoffe oder C32 - C40 - Wachse, und als Imprägnierungsmittel (B) Copolymere aus 60-95 Mol-% Acrylsäure und/oder Methacrylsäure und 5 - 40 Mol-% des Methyl-, Ethyl-, Propyl- oder Butylesters, Amids oder Nitrils der Acrylsäure oder Methacrylsäure mit einem Molgewicht von 800 - 10.000, in Form der Alkali-, Anmonium- oder Aminsalze einsetzt, und danach absäuert, fixiert und fertigstellt.In contrast, the invention relates to a process for the production of waterproof leather and furs by tanning, retanning, dyeing, greasing and fixing, with the aid of copolymers containing carboxyl groups, characterized in that, after the tanning and optionally dyeing, in the same bath, one after the other as a fatliquor (A) oxidized or oxidized and partially sulfated long chain C18 - C26 hydrocarbons or C32 - C40 waxes, and as impregnating agent (B) copolymers of 60-95 mol% acrylic acid and / or methacrylic acid and 5 - 40 mol% methyl , Ethyl, propyl or butyl ester, amide or nitrile of acrylic acid or methacrylic acid with a molecular weight of 800 - 10,000, in the form of the alkali, ammonium or amine salts, and then acidified, fixed and finished.

Bei der Durchführung des Verfahrens geht man von Rohhäuten oder Fellen aus, die in üblicher Weise gegerbt und nachgegerbt werden, wobei anorganische und/oder organische, natürliche oder synthetische Gerbstoffe, wie Chrom- oder Aluminiumsalze, oder Phenol-/Naphthalinkondensationsprodukte, oder pflanzliche Gerbstoffe, eingesetzt werden.The process is carried out using raw hides or skins which are tanned and retanned in the customary manner, inorganic and / or organic, natural or synthetic tanning agents, such as chromium or aluminum salts, or phenol / naphthalene condensation products, or vegetable tanning agents, be used.

Nach Beendigung der Nachgerbung und gutem Spülen erfolgt gegebenenfalls die Färbung und anschließend die Fettung. Als Fettungsmittel (A) werden erfindungsgemäß oxidierte oder oxidierte und teilsulfierte langkettige C18- C26 - Kohlenwasserstoffe oder C32 - C40 - Wachse in einer Menge von 3 - 8 Gew.- %, bezogen auf das Falzgewicht des Leders, eingesetzt. Die Produkte weisen Säurezahlen von 5 - 100 und gegebenenfalls S03-Gehalte von 0,2 - 2,0 Gew.-% auf. Beispiele für besonders geeignete Fettungsmittel sind sulfoxidierter C20 - C22-Paraffingatsch mit einem S03-Gehalt von 0,2 - 0,5 Gew.-% und Säurezahlen von 5 - 15, oxidierte und sulfierte C24 - C26 - Polyethylene oder Paraffine mit einem S03-Gehalt von 0,3 - 0,8 Gew.-% und Säurezahlen von 5 - 20, sowie oxidiertes C22 - C 26 - Paraffin mit Säurezahlen von 60 - 70. Die Produkte werden vorzugsweise in Form ihrer Alkali-, Ammonium- oder Aminsalze angewendet. Die Fettungsmittel werden vorzugsweise in Kombination mit speziellen W/O-Emulgatoren wie C12-C18 - Monoalkylphosphorsäureester, C16 - C20 - Alkenylbernsteinsäuren, Fettsäuresarcoside, Zitronensäure-Fettalkoholmonoester, ferner Fettsäuremonoethanolamid-Ethersulfaten oder Fettsäuren, in Form der Alkali-, Ammonium- oder Aminsalze eingesetzt.After retanning and good rinsing, the coloring and then the greasing may take place. According to the invention, oxidized or oxidized and partially sulfonated long-chain C18-C26 hydrocarbons or C32-C40 waxes are used as fatliquoring agents (A) in an amount of 3 - 8% by weight, based on the shaved weight of the leather. The products have acid numbers of 5-100 and optionally S0 3 contents of 0.2-2.0% by weight. Examples of particularly suitable fatliquors are sulfoxidized C20-C22 paraffin wax with an S0 3 content of 0.2-0.5% by weight and acid numbers of 5-15, oxidized and sulfated C24-C26 polyethylenes or paraffins with an S0 3 content of 0.3-0.8% by weight and acid numbers of 5-20, and oxidized C22-C26 paraffin with acid numbers of 60-70. The products are preferably in the form of their alkali metal, ammonium or Amine salts applied. The fatliquoring agents are preferably used in combination with special W / O emulsifiers such as C12-C18 - monoalkyl phosphoric acid esters, C16 - C20 - alkenyl succinic acids, fatty acid arcosides, citric acid fatty alcohol monoesters, also fatty acid monoethanolamide ether sulfates or fatty acids, in the form of the alkali metal, ammonium or amine salts .

Nach einer Laufzeit von 45 - 60 Minuten wird unter Zusatz des Copolymerisats (B) während 30 Minuten in der gleichen Flotte bei einem pH von 5 - 6 weiterbehandelt. Als Copolymere dienen vorzugsweise solche aus 70 - 85 Mol-% Acrylsäure und/oder Methacrylsäure mit 15 - 30 Mol-% des Methyl-, Ethyl-, Propyl- oder Butylesters oder Amids oder Nitrils der Acrylsäure oder Methacrylsäure in Form der Alkali-, Ammonium- oder Aminsalze. Das Molgewicht der Copolymeren beträgt 800-10.000. Bezogen auf das Falzgewicht des Leders werden 0,5 - 3 Gew.-% an Copolymeren eingesetzt. Beispiele für geeignete Copolymere sind Produkte auf Basis 75 Mol-% Acrylsäure und 25 Mol-% Acrylsäureethylester, Na-Salz, 85 Mol-% Acrylsäure und 15 Mol-% Acrylnitril, Ammoniumsalz und 70 Mol-% Acrylsäure und 30 Mol-% Acrylamid, Na-Salz.After a running time of 45-60 minutes, the addition of the copolymer (B) is continued for 30 minutes in the same liquor at a pH of 5-6. The copolymers used are preferably those of 70-85 mol% of acrylic acid and / or methacrylic acid with 15-30 mol% of the methyl, ethyl, propyl or butyl ester or amide or nitrile of acrylic acid or methacrylic acid in the form of the alkali metal, ammonium - or amine salts. The molecular weight of the copolymers is 800-10,000. Based on the shaved weight of the leather, 0.5 - 3% by weight of copolymers are used. Examples of suitable copolymers are products based on 75 mol% of acrylic acid and 25 mol% of ethyl acrylate, Na salt, 85 mol% of acrylic acid and 15 mol% of acrylonitrile, ammonium salt and 70 mol% of acrylic acid and 30 mol% of acrylamide, Na salt.

Im Anschluß an diese Behandlung wird nachgesäuert, beispielsweise mit Ameisensäure oder Essigsäure und durch Zugabe von 2 - 4 Gew.-% eines Chrom- und/oder Aluminiumgerbstoffes fixiert und in üblicher Weise fertiggestellt. Man erhält weiche Leder oder Pelze mit guter Narbenfestigkeit. Die Wasserfestigkeit (Wasserdurchtritt und Wasseraufnahme) ist wesentlich verbessert. Die erzielten Ergebnisse sind von einer bemerkenswerten Gleichmäßigkeit und Reproduzierbarkeit.Following this treatment, acidification is carried out, for example with formic acid or acetic acid, and the mixture is fixed by adding 2-4% by weight of a chromium and / or aluminum tanning agent and finished in the customary manner. You get soft leather or furs with good scar strength. The water resistance (water penetration and water absorption) is significantly improved. The results achieved are of one remarkable uniformity and reproducibility.

Beispiel 1example 1

In üblicher Weise, jedoch ohne Emulgatorzusätze geäscherte, entkälkte, gebeizte und gepickelte Rindblößen werden chromgegerbt und auf ca. 2,8 mm gefalzt. Nach Waschen mit 200 % Wasser von 25° C wird gegen Bromkresolgrün durchneutralisiert.

  • Die Nachgerbung erfolgt mit
  • 3 Gew.-% eines Hilfsgerbstoffes auf Basis Phenol-/ Naphthalinkondensationsprodukt
  • 6 Gew.-% Mimosa
  • 6 Gew.-% Quebracho
  • 6 Gew.-% Kastanie
  • bis zur Durchgerbung durch den Lederquerschnitt. Nach gutem Spülen werden die Leder mit
  • 3 Gew.-% eines 25 %igen basischen Aluminiumgerbstoffs
  • behandelt.
  • Die Färbung und Fettung erfolgt nach folgender Arbeitsweise
  • 100 Gew.-% Wasser 65° C 15 min.
  • 1 Gew.-% saurer Farbstoff
  • 6.4 Gew.-% sulfoxidierter Paraffingatsch 60 min.
  • C20 - C22,0,2 - 0,5 Gew.-% S03
  • Säurezahl 5 -15,
  • Ammoniumsalz
  • 2 Gew.-% Ammoniak, 25 %ig
  • (pH der Flotte 5.8)
  • 2 Gew.-% Copolymerisat aus 80 Mol-% 30 min
  • Acrylsäure und 20 Mol-%
  • Acrylsäureethylester, Na-Salz
  • 2.5 Gew.-% Ameisensäure 30 min.
  • 2 Gew.-% Chromgerbstoff, 33 %ig, basisch 30 min.
  • 2 Gew.-% Aluminiumgerbstoff, 30 min.
  • 25 %ig, basisch
In the usual way, but without emulsifier additives, limed, decalcified, pickled and pickled pelts are chrome-tanned and folded to approx. 2.8 mm. After washing with 200% water at 25 ° C, neutralized against bromocresol green.
  • The retanning takes place with
  • 3% by weight of an auxiliary tanning agent based on a phenol / naphthalene condensation product
  • 6 wt% mimosa
  • 6 wt% quebracho
  • 6% by weight chestnut
  • until tanned through the leather cross-section. After a good rinse, the leathers are washed
  • 3% by weight of a 25% basic aluminum tanning agent
  • treated.
  • The coloring and greasing is done according to the following procedure
  • 100 wt .-% water 65 ° C 15 min.
  • 1% by weight acid dye
  • 6.4% by weight of sulfoxidized paraffin wax 60 min.
  • C20 - C22.0.2 - 0.5 wt% S0 3
  • Acid number 5 -15,
  • Ammonium salt
  • 2% by weight ammonia, 25%
  • (pH of the fleet 5.8)
  • 2% by weight copolymer from 80 mol% 30 min
  • Acrylic acid and 20 mol%
  • Acrylic acid ethyl ester, sodium salt
  • 2.5% by weight of formic acid for 30 min.
  • 2% by weight chrome tanning agent, 33%, basic 30 min.
  • 2% by weight aluminum tanning agent, 30 min.
  • 25%, basic

Alle Prozentangaben beziehen sich auf das Falzgewichtdes Leders.All percentages refer to the fold weight of the leather.

Nach Ausspülen und üblicher Fertigstellung erhält man weiche Leder mit deutlich verzögertem Wasserdurchtritt und geringer Wasseraufnahme (Probe A).After rinsing and completion, soft leather is obtained with significantly delayed water penetration and low water absorption (sample A).

Ein entsprechender Vergleichsversuch ohne Copolymerisatzusatz (Probe B) ergab hinsichtlich der Wasserfestigkeit wesentlich ungünstigere Werte.

Figure imgb0001
A corresponding comparative test without the addition of copolymer (sample B) gave significantly less favorable values with regard to water resistance.
Figure imgb0001

Beispiel 2Example 2

Rindoberleder wurden nach der gleichen Arbeitsweise wie im Beispiel 1 gearbeitet, jedoch wird die Fettung mit

  • 5 Gew.-% sulfoxidiertem Paraffingatsch
  • C20 - C22, 0,2 - 0,5 Gew.-% S03,
  • Säurezahl 5-15, Ammoniumsalz
  • 1.4 Gew.-% C12 - C18 - Monoalkylphosphor
  • säureester, Na-Salz
  • durchgeführt.
Cowhide leather was worked in the same way as in example 1, but the greasing is with
  • 5% by weight sulfoxidized paraffin wax
  • C20 - C22, 0.2 - 0.5% by weight S0 3 ,
  • Acid number 5-15, ammonium salt
  • 1.4% by weight of C12 - C18 monoalkyl phosphor
  • acid ester, sodium salt
  • carried out.

Nach Fertigstellung erhält man weiche Leder, dieebenfalls im Falle A ein wesentlich besseres Verhalten gegenüber Wasser als im Falle B aufweisen.

Figure imgb0002
After completion, soft leather is obtained, which also has a significantly better behavior towards water in case A than in case B.
Figure imgb0002

Beispiel 3Example 3

Rindoberleder wurden nach der gleichen Arbeitsweise wie im Beispiel 1 gearbeitet, jedoch wird die Fettung mit

  • 6,4 Gew.-% eines Gemisches aus oxidiertem und sulfiertem
  • C24 - C26 - Paraffin,
  • 0,3 - 0,8 Gew.-% SOa, Säurezahl 5 - 20, Ammoniumsalz,
  • C12 - C18 - Monoalkylphosphorsäureester, Na-Salz,
  • C16 - C18 - Alkenylbernsteinsäure, Ammoniumsalz,
  • im Gewichtsverhältnis von 6,2: 2,8: 1,3 durchgeführt.
Cowhide leather was worked in the same way as in example 1, but the greasing is with
  • 6.4% by weight of a mixture of oxidized and sulfated
  • C24 - C26 - paraffin,
  • 0.3-0.8% by weight SOa, acid number 5-20, ammonium salt,
  • C12 - C18 - monoalkyl phosphoric acid ester, sodium salt,
  • C16 - C18 - alkenyl succinic acid, ammonium salt,
  • carried out in a weight ratio of 6.2: 2.8: 1.3.

Nach Fertigstellung erhält man weiche Leder mit ausgezeichnetem Verhalten gegenüber Wasser im Falle A.

Figure imgb0003
After completion, soft leather with excellent behavior towards water is obtained in case A.
Figure imgb0003

Beispiel 4Example 4

Rindoberleder wurden nach gleicher Arbeitsweise wie im Beispiel 1 gearbeitet, jedoch wird die Fettung mit 6,4 Gew.-% eines-Gemisches aus

  • oxidiertem C22 - C26 - Paraffin,
  • Säurezahl 60 - 70,
  • C12 - C18 - Monoalkylphosphor
  • säureester, Na-Salz,
  • C16 - C18 Fettsäuremonoethanolamid-2
  • EO-sulfat, Ammoniumsalz
  • im Verhältnis 4,5:1,5: 0,4
  • durchgeführt.
  • Nach Fertigstellung erhält man weiche Leder mit gutem-Verhalten gegenüber Wasser im FallerA
Cowhide leather was worked according to the same procedure as in Example 1, but the greasing with 6.4 wt .-% of a mixture
  • oxidized C22 - C26 paraffin,
  • Acid number 60 - 70,
  • C12 - C18 - monoalkyl phosphor
  • acid ester, sodium salt,
  • C16 - C18 fatty acid monoethanolamide-2
  • EO sulfate, ammonium salt
  • in the ratio 4.5: 1.5: 0.4
  • carried out.
  • After completion, soft leather with good behavior towards water is obtained in the FallerA

Figure imgb0004
Figure imgb0004

Claims (10)

1. A process for the production of waterproof leathers and skins by tanning, retanning, dyeing, oiling and fixing using copolymers containing carboxyl groups, characterized in that, after tanning and optionally dyeing oxidized or oxidized and partially sulfonated longchain C18-C26 hydrocarbons or C32-C40 waxes as oiling agents (A) and copolymers of 60-95 mole % acrylic acid and/or methacrylic acid and 5-40 mole % of the methyl, ethyl, pronyl or butyl ester, amide or nitrile of acrylic or methacrylic acid having a molecular weight of from 800 to 10,000 in the form of the alkali, ammonium or amine salts as impregnating agents (B) are successively used in the same bath, respectively, followed by acidification, fixing and finishing.
2. A process as claimed in Claim 1, characterized by the use of oxidized or oxidized and partially sulfonated hydrocarbons or waxes having acid numbers of from 5 to 100 and, optionally, S03-contents of from 0.2 to 2.0% by weight in the form of the alkali, ammonium or amine salts as oiling agents (A) in a quantity of from 3 to 8% by weight, based on the shaved weight of the leather.
3. A process as claimed in Claims 1 and 2, characterized by the use of sulfoxidized C20-C22 paraffin wax having an S03-content of from 0.2 to 0.5% by weight and acid numbers of from 5 to 15 in the form of the alkali, ammonium or amine salts as oiling agents (A).
4. A process as claimed in Claims 1 and 2, characterized by the use of oxidized and sulfonated C24-C26 polyethylenes or paraffins having an S03-content of from 0.3 to 0.8% by weight and acid numbers of from 5 to 20 in the form of the alkali, ammonium or amine salts as oiling agents (A).
5. A process as claimed in Claims 1 and 2, characterized by the use of oxidized C22-C26 paraffin having acid numbers of from 60 to 70 in the form of the alkali, ammonium or amine salts as oiling agents (A).
6. A process as claimed in Claims 1 to 5, characterized in that the oiling agents (A) are used in combination with W/O emulsifiers or fatty acid monoethanolamide ether sulfates or fatty acids in the form of the alkali, ammonium or amine salts.
7. A process as claimed in Claim 6, characterized in that the W/O-emulsifiers are C12-C18-monoalkyl phosphoric acid esters or C16-C20-alkenyl succinic acids, fatty acid sarcosides or citric acid-fatty alcohol monoesters in the form of the alkali, ammonium or amine salts.
8. A process as claimed in Claims 1 to 7, characterized by the use of copolymers of 70-85 mole % acrylic acid and/or methacrylic acid and 15-30 mole % of the methyl, ethyl, propyl or butyl esters or amide or nitrile of acrylic acid or methacrylic acid in the form of the alkali, ammonium or amine salts as impregnating agents (B) in a quantity of from 0.5 to 3% by weight, based on the shaved weight of the leather.
9. A process as claimed in Claims 1 to 8, characterized by the use of copolymers of 75 mole % acrylic acid and 25 mole % ethyl acrylate, Na-salts, 85 mole % acrylic acid and 15 mole % acrylonitrile, ammonium salts, 70 mole % acrylic acid and 30 mole % acrylamide, Na-salts, or 80 mole % acrylic acid and 20 mole % ethyl acrylate, Na-salts, as impregnating agents (B).
10. A process as claimed in Claims 1 to 9, characterized in that, after oiling, impregnation and acidification in the same bath, the leather is fixed with from 2 to 4% by weight, based on the shaved weight of the leather, of a chromium or aluminium tanning agent.
EP84101000A 1983-02-08 1984-02-01 Process for water-proofing leather and furs Expired EP0118023B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84101000T ATE23366T1 (en) 1983-02-08 1984-02-01 PROCESS FOR THE MANUFACTURE OF WATERPROOF LEATHER AND FUR.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19833304120 DE3304120A1 (en) 1983-02-08 1983-02-08 METHOD FOR PRODUCING WATERPROOF LEATHER AND FURS
DE3304120 1983-02-08

Publications (2)

Publication Number Publication Date
EP0118023A1 EP0118023A1 (en) 1984-09-12
EP0118023B1 true EP0118023B1 (en) 1986-11-05

Family

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Application Number Title Priority Date Filing Date
EP84101000A Expired EP0118023B1 (en) 1983-02-08 1984-02-01 Process for water-proofing leather and furs

Country Status (8)

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US (1) US4527992A (en)
EP (1) EP0118023B1 (en)
AT (1) ATE23366T1 (en)
BR (1) BR8400513A (en)
CA (1) CA1207954A (en)
DE (2) DE3304120A1 (en)
ES (1) ES8501446A1 (en)
FI (1) FI840131A (en)

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Publication number Priority date Publication date Assignee Title
DE3702153A1 (en) * 1987-01-26 1988-08-04 Stockhausen Chem Fab Gmbh GIVING IN PROCESS
TNSN89128A1 (en) * 1988-12-02 1991-02-04 Rohn And Haas Company Independance Mall West LEATHER TREATMENT WITH SELECTED AMPHIPHITE COPOLYMERS
US5330537A (en) * 1990-06-07 1994-07-19 Rohm And Haas Company Leather treatment selected amphiphilic copolymer
DE4139090A1 (en) * 1991-11-28 1993-06-03 Stockhausen Chem Fab Gmbh USE OF COPOLYMERS WITH POLYSILOXANE UNITS FOR THE TREATMENT OF LEATHER AND FURS
DE4227974C2 (en) * 1992-08-26 1996-04-18 Stockhausen Chem Fab Gmbh Copolymers containing alkoxy groups, processes for their preparation and their use for retanning leather
US5417723A (en) * 1993-03-25 1995-05-23 Bayer Aktiengesellschaft Use of ester urethanes for retanning
DE4334796A1 (en) * 1993-10-13 1995-04-20 Bayer Ag Softening and hydrophobic retanning agents
DE4402029A1 (en) * 1994-01-25 1995-07-27 Basf Ag Aqueous solutions or dispersions of copolymers
DE4439990A1 (en) * 1994-11-09 1996-05-15 Bayer Ag Leather tanning agents and agents for dyes
DE19516961A1 (en) * 1995-05-12 1996-11-28 Stockhausen Chem Fab Gmbh Process for waterproofing leather at low pH values and leather produced therewith
US6211283B1 (en) * 1996-02-21 2001-04-03 Henkel Corporation Electrically insulated metallic surfaces with interior corners and methods and compositions therefor
US6479612B1 (en) 1999-08-10 2002-11-12 E. I. Du Pont De Nemours And Company Fluorochemical water and oil repellents
US20060188729A1 (en) * 2005-02-22 2006-08-24 Kai-Volker Schubert Washable leather with repellency
US7160480B2 (en) * 2005-02-22 2007-01-09 E. I. Du Pont De Nemours And Company Leather treated with fluorochemicals

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US2061618A (en) * 1936-11-24 Sulphonated hydrocarbon
DE30028C (en) * J. LESSING in Lippstadt Kober for packing and storing eggs, fruit and the like. •
US2118308A (en) * 1936-08-08 1938-05-24 American Cyanamid & Chem Corp Leather lubrication
DE896697C (en) * 1941-10-11 1953-11-16 Basf Ag Leather fatliquor
DE971898C (en) * 1943-02-02 1959-04-09 Roehm & Haas G M B H Emulsifier for emulsions of mineral, vegetable and animal fats for leather finishing
US2630408A (en) * 1948-01-30 1953-03-03 Nopco Chem Co Fat composition
DE1800244C2 (en) * 1968-10-01 1973-10-18 Roehm Gmbh, 6100 Darmstadt Process for the simultaneous greasing and impregnation of leather
US3765833A (en) * 1970-10-07 1973-10-16 Henkel & Cie Gmbh Fat-liquoring compositions
DE2538280C3 (en) * 1975-08-28 1979-03-22 Zschimmer & Schwarz Chemische Fabriken, 5420 Lahnstein Softening and / or fatliquoring agents for materials with a fibrous structure from waste materials from polyalkylene production and their use
DE2930342A1 (en) * 1979-07-26 1981-02-19 Roehm Gmbh IMPROVED METHOD FOR PRODUCING LEATHER
DE3013912A1 (en) * 1980-04-11 1981-10-29 Röhm GmbH, 6100 Darmstadt POLYMER PRODUCTS FOR TREATING BLOSSOMS AND LEATHER

Also Published As

Publication number Publication date
DE3461200D1 (en) 1986-12-11
CA1207954A (en) 1986-07-22
FI840131A (en) 1984-08-09
FI840131A0 (en) 1984-01-13
US4527992A (en) 1985-07-09
ES529550A0 (en) 1984-11-16
BR8400513A (en) 1984-09-11
ATE23366T1 (en) 1986-11-15
ES8501446A1 (en) 1984-11-16
DE3304120A1 (en) 1984-08-09
EP0118023A1 (en) 1984-09-12

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