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EP0087799A1 - Process for the liquoring and simultaneous water-proofing of leather, fur and leather substitutes - Google Patents

Process for the liquoring and simultaneous water-proofing of leather, fur and leather substitutes Download PDF

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Publication number
EP0087799A1
EP0087799A1 EP83101962A EP83101962A EP0087799A1 EP 0087799 A1 EP0087799 A1 EP 0087799A1 EP 83101962 A EP83101962 A EP 83101962A EP 83101962 A EP83101962 A EP 83101962A EP 0087799 A1 EP0087799 A1 EP 0087799A1
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Prior art keywords
saturated
fatty acid
carbon atoms
unsaturated
condensed
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EP83101962A
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German (de)
French (fr)
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EP0087799B1 (en
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Heribert Dr. Schmitz
Wolfgang Eberhardt
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Muenzing Chemie GmbH
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Muenzing Chemie GmbH
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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

Definitions

  • the invention relates to a method for greasing and simultaneously hydrophobizing leather, fur and leather substitutes, in which the material to be greased and hydrophobized is treated in an aqueous liquor which contains a lubricating and hydrophobicizing agent.
  • the first group - application from the aqueous phase - include, for example, the Metallfettklad p lexe, perfluorinated metal fatty acid complexes Phosphorklamonoester, emulsions of ZitronenTalkreestern or high molecular weight fatty acids and - Derivatives or their metal salts and hydrocarbons.
  • the second group - application from an organic phase - includes, for example, products based on Silicone oils, high molecular weight fatty acid esters, fluorine compounds and heterocyclic nitrogen compounds with a long alkyl radical.
  • the object of the invention is to improve the generic greasing and waterproofing processes based on the use of these agents.
  • phosphoric acid esters of the general formula given in claim 1 it is preferable to start in a first reaction step from phosphorus oxychloride (POC1 3 ) and a diol X, which are condensed with elimination of hydrogen chloride.
  • the molar ratio of phosphorus oxychloride to diol is 2 to 1 to 1.1 to 1, preferably 1.5 to 1.
  • the condensation gives compounds of the general formula (1) in which z is an integer from 1 to 10, preferably 1-5.
  • Suitable diol X are linear or branched, saturated or unsaturated, acyclic diols with 2-16, preferably 2-10, carbon atoms, such as, for example, 1,4-butanediol, 2.5-hexanediol, 1.6-hexanediol or 1.10 decanediol, butene-2- diol-1.4 or hexin-3-diol-2.5, or cyclic diols, such as, for example, cyclohexanediol-1.4, or aromatic diols, such as, for example, bisphenol A.
  • X can be a condensation product of ethylene oxide and / or Propylene oxide and / or butylene oxide with 2-12 mol, preferably 2-8 mol, of alkylene oxide, such as tripropylene glycol or polyethylene glycol 200.
  • the phosphorus compound of the general formula (1) is condensed (esterified) in a second reaction step with elimination of hydrogen chloride with a hydroxyl compound R.
  • Suitable hydroxyl compounds R are linear or branched, saturated or unsaturated alcohols having 4 to 22, preferably 12-18 C atoms, or the abovementioned alcohols, condensed with 1-12, preferably 1-6 mol, alkylene oxide, such as, for example, Oley alcohol, tallow fatty alcohol, synthetic Alfol alcohols, isooctadecyl alcohol or oleyl alcohol with 4 mol ethylene oxide, phenols or alkylphenols with 6 - 30 C atoms, e.g. Octylphenol, nonylphenol, di-nonylphenol, dodecylphenol, or the corresponding ethoxylated phenols and alkylphenols (1 - 12 mol EO).
  • alkylene oxide such as, for example, Oley alcohol, tallow fatty alcohol, synthetic Alfol alcohols, isooctadecyl alcohol or oleyl alcohol with 4 mol ethylene oxide, phenols or alkylphenol
  • the fatty acid polyglycol esters such as tallow fatty acid with 6 mol ethylene oxide or oleic acid esterified with polyethylene glycol 200 or the mono- or diglycerides of fatty acids such as oleic acid monoglyceride are also used as the hydroxy compound R.
  • Ethoxylated, saturated or unsaturated fatty amines, fatty acid amides and the fatty acid mono- or dialkanolamides can also be used, such as coconut fatty amine with 12 mol ethylene oxide, tallow fatty acid amide with 10 mol Ethylene oxide, oleic acid amide with 4 mol ethylene oxide and coconut fatty acid diethanolamide.
  • M stands for an alkali metal cation, for example Na + , K or for the ammonium ion or for an organic, cyclic or acyclic ammonium compound, such as for example cyclohexylammonium, triethylammonium or monoethanolammonium ion.
  • the aqueous liquor used for oiling and waterproofing can be prepared by stirring the oiling and waterproofing agent used according to the invention into warm water (approx. 50 ° C .; 3 parts water to 1 part leather treatment agent). Such a liquor is sufficiently stable and is used to lick (i.e. treat in an aqueous system) chrome-tanned or vegetable and / or synthetically retanned leathers.
  • a particular advantage of the process according to the invention is the very strong affinity of the specified fatliquoring and hydrophobicizing agents for the fiber. This can be seen e.g. during extraction with dichloromethane (according to DIN 53306), in which the leather treatment agent can practically not be extracted from the fiber.
  • the leathers that are treated according to the claimed process are characterized by good softness and suppleness and a pleasant feel.
  • the particular advantage of the leather treated by the process according to the invention lies in the unexpected, exceptionally high dynamic water resistance.
  • Chrome grain leather is retanned in the usual way with 2% of a synthetic tanning agent, dyed and Licked with 5% leather treatment agent according to the formula in claim 1.
  • the percentages above refer to the weight of the leather.
  • X ethylene glycol
  • R coconut fatty alcohol
  • M ammonium
  • z 3.
  • chrome grain leather is retanned with 20% vegetable tannins and g elickert with 6% Leather treatment agent according to formula in claim 1 in 100% float.
  • the percentages above refer to the weight of the leather.
  • X 1,4-butanediol
  • R nonylphenol polyglycol ether (5 mol EO)
  • M Na
  • z 1.
  • the usual leather additives are added to the leather greasing and waterproofing agent, for example neutral leather treatment agents such as oils, fats, chlorinated oils and Fats, chlorinated paraffins, higher molecular weight fatty alcohols, fatty acids, fatty acid esters and hydrocarbons, also anionic emulsifiers, for example sulfated hydrocarbons, sulfated native fats or oils, or sulfated fatty acids and fatty acid esters, and / or finally nonionic emulsifiers, for example fatty alcohol ethoxylates or alkylphenol ethoxylates.
  • neutral leather treatment agents such as oils, fats, chlorinated oils and Fats, chlorinated paraffins, higher molecular weight fatty alcohols, fatty acids, fatty acid esters and hydrocarbons
  • anionic emulsifiers for example sulfated hydrocarbons, sulfated native fats or oils, or sulfated fatty acids and fatty acid esters,
  • the invention relates not only to the specified methods, but also encompasses the lubricating and hydrophobicizing agents used.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

1. A method of stuffing and at the same time water-proofing leather, fleece and leather substitutes whereby the material to be stuffed and waterproofed is treated in an aqueous liquor which contains a stuffing and waterproofing agent, characterised in that the stuffing and waterproofing agent consists in a compound of general formula see diagramm : EP0087799,P4,F2 wherein X, R, M and z have the following meanings : - X is a straight or branched, saturated or unsaturated, cyclic, acyclic or aromatic, possibly also heteroatom, containing diol with 2 to 16 carbon atoms or a condensation product of ethylene oxide and/or propylene oxide and/or butylene oxide with 2 to 6 moles alkylene oxide or a mixture of said diols ; R is a hydroxy compound acting as an esterification compound, i.e. a straight or branched, saturated or unsaturated alcohol with 12 to 18 carbon atoms, or one of said alcohols, condensed with 1 to 6 mols alkylene oxide, or a phenol or alkyl phenol with 6 to 30 carbon atoms, or one of said phenols and alkyl phenols, condensed with 1 to 12 moles ethylene oxide, or a saturated or unsaturated fatty acid ester, the fatty acid radical containing 8 to 22 carbon atoms and the ester components being polyalkylene oxides with 1 to 6 mols ethylene oxide, or a saturated or unsaturated fatty acid mono- or diglyceride with 8 to 22 carbon atoms per fatty acid radical, or a saturated or unsaturated, primary or secondary fatty amine with 8 to 22 carbon atoms per alkyl radical, condensed with 1 to 24 mols alkylene oxide, or a saturated or unsaturated fatty acid amide with 8 to 22 carbon atoms, condensed with 1 to 24 mols alkylene oxide ; M is a monovalent metal cation, ammonium ion or an organic ammonium compound ; z is an integer from 1 to 5.

Description

Verfahren zum Fetten und gleichzeitigen Hydrophobieren von Leder, Pelz und LederaustauschstoffenProcess for greasing and simultaneously waterproofing leather, fur and leather substitutes

Die Erfindung betrifft ein Verfahren zum Fetten und gleichzeitigen Hydrophobieren von Leder, Pelz und Lederaustauschstoffen, bei dem das zu fettende und zu hydrophobierende Material in einer wässrigen Flotte behandelt wird, die ein Fettungs- und Hydrophobierungsmittel enthält.The invention relates to a method for greasing and simultaneously hydrophobizing leather, fur and leather substitutes, in which the material to be greased and hydrophobized is treated in an aqueous liquor which contains a lubricating and hydrophobicizing agent.

Der größte Teil der bekannten Hydrophobierungsmittel kann in zwei Gruppen eingeteilt werden, die sich durch die unterschiedliche Anwendung ergeben: zur ersten Gruppe - Anwendung aus wässriger Phase - gehören z.B. die Metallfettsäurekomplexe, perfluorierte Metallfettsäurekomplexe, Phosphorsäuremonoester, Emulsionen von Zitronensäureestern oder hochmolekularen Fettsäuren und -Derivaten bzw. deren Metallsalze und Kohlenwasserstoffen. Zur zweiten Gruppe - Anwendung aus organischer Phase - gehören z.B. Produkte auf der Basis von Siliconölen, hochmolekularen Fettsäureestern, Fluorverbindungen und heterocyclischen Stickstoffverbindungen mit langem Alkylrest.The majority of the known water repellents can be divided into two groups, which result from the different applications: the first group - application from the aqueous phase - include, for example, the Metallfettsäurekom p lexe, perfluorinated metal fatty acid complexes Phosphorsäuremonoester, emulsions of Zitronensäureestern or high molecular weight fatty acids and - Derivatives or their metal salts and hydrocarbons. The second group - application from an organic phase - includes, for example, products based on Silicone oils, high molecular weight fatty acid esters, fluorine compounds and heterocyclic nitrogen compounds with a long alkyl radical.

Aufgabe der Erfindung ist es, die auf der Verwendung dieser Mittel beruhenden, gattungsgemäßen Fettungs-und Hydrophobierungsverfahren zu verbessern.The object of the invention is to improve the generic greasing and waterproofing processes based on the use of these agents.

Die Aufgabe wird erfindungsgemäß dadurch gelöst, daß das Fettungs- und Hydrophobierungsmittel aus einer Verbindung der allgemeinen Formel

Figure imgb0001
besteht, worin X, R', M und z folgende Bedeutung haben:

  • X ist ein lineares oder verzweigtes, gesättigtes oder ungesättigtes, cyclisches, acyclisches oder aromatisches, gegebenenfalls auch Heteroatome enthaltendes Diol mit 2 bis 16 C-Atomen oder ein Kondensationsprodukt der Alkylenoxide, beispielsweise Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid mit 2 bis 12 mol Alkylenoxid oder ein Gemisch dieser Diole;
  • R ist eine als Veresterungskomponente dienende Hydroxiverbindung, nämlich ein linearer oder verzweigter, gesättigter oder ungesättigter Alkohol mit 4 bis 22 C-Atomen,
    • oder einer dieser Alkohole, kondensiert mit 1 bis 12 mol Alkylenoxid,
    • oder ein Phenol oder Alkylphenol mit 6 bis 30 C-Atomen,
    • oder eines dieser Phenole und Alkylphenole, kondensiert mit 1 bis 12 mol Alkylenoxid, oder ein gesättigter oder ungesättigter Fettsäureester, wobei der Fettsäurerest 8 bis 22 C-Atome enthält und die Esterkomponenten Polyalkylenoxide mit 1 bis 15 mol Alkylenoxid sind,
    • oder ein gesättigtes oder ungesättigtes Fettsäuremono- bzw. diglyzerid mit 8 bis 22 C-Atomen pro Fettsäurerest,
    • oder ein gesättigtes oder ungesättigtes, primäres oder sekundäres Fettamin mit 8 bis 22 C-Atomen pro Alkylrest, kondensiert mit 1 bis 24 mol Alkylenoxid,
    • oder ein gesättigtes oder ungesättigtes Fettsäureamid mit 8 bis 22 C-Atomen, kondensiert mit 1 bis 24 mol Alkylenoxid;
  • M ist ein einwertiges Metall-Kation, Ammonium-Ion oder eine organische Ammoniumverbindung;
  • z ist eine ganze Zahl von 1 bis 10.
The object is achieved in that the lubricating and hydrophobicizing agent from a compound of the general formula
Figure imgb0001
 where X, R ', M and z have the following meanings:
  • X is a linear or branched, saturated or unsaturated, cyclic, acyclic or aromatic, optionally also containing heteroatoms, diol with 2 to 16 carbon atoms or a condensation product of the alkylene oxides, for example ethylene oxide and / or propylene oxide and / or butylene oxide with 2 to 12 mol Alkylene oxide or a mixture of these diols;
  • R is a hydroxyl compound serving as an esterification component, namely a linear or branched, saturated or unsaturated alcohol having 4 to 22 carbon atoms,
    • or one of these alcohols, condensed with 1 to 12 mol of alkylene oxide,
    • or a phenol or alkylphenol with 6 to 30 C atoms,
    • or one of these phenols and alkylphenols, condensed with 1 to 12 mol alkylene oxide, or a saturated or unsaturated fatty acid ester, the fatty acid residue containing 8 to 22 C atoms and the ester components being polyalkylene oxides with 1 to 15 mol alkylene oxide,
    • or a saturated or unsaturated fatty acid mono- or diglyceride with 8 to 22 carbon atoms per fatty acid residue,
    • or a saturated or unsaturated, primary or secondary fatty amine with 8 to 22 carbon atoms per alkyl radical, condensed with 1 to 24 mol of alkylene oxide,
    • or a saturated or unsaturated fatty acid amide with 8 to 22 carbon atoms, condensed with 1 to 24 mol of alkylene oxide;
  • M is a monovalent metal cation, ammonium ion or an organic ammonium compound;
  • z is an integer from 1 to 10.

Die nachstehende Beschreibung dient im Zusammenhang mit einigen Beispielen der weiteren Erläuterung der Erfindung. "The following description is used in conjunction with some examples to further explain the invention. "

Zur Herstellung der Phosphorsäureester der allgemeinen, im Patentanspruch 1 angegebenen Formel geht man vorzugsweise in einem ersten Reaktionsschritt von Phosphoroxidchlorid (POC13) und einem Diol X aus, die unter Abspaltung von Chlorwasserstoff kondensiert werden. Das mol-Verhältnis Phosphoroxidchlorid zu Diol beträgt 2 zu 1 bis 1.1 zu 1, vorzugsweise 1.5 zu 1. Man erhält durch die Kondensation Verbindungen der allgemeinen Formel (1), worin z eine ganze Zahl von 1 bis 10, vorzugsweise 1 - 5 ist.

Figure imgb0002
To prepare the phosphoric acid esters of the general formula given in claim 1, it is preferable to start in a first reaction step from phosphorus oxychloride (POC1 3 ) and a diol X, which are condensed with elimination of hydrogen chloride. The molar ratio of phosphorus oxychloride to diol is 2 to 1 to 1.1 to 1, preferably 1.5 to 1. The condensation gives compounds of the general formula (1) in which z is an integer from 1 to 10, preferably 1-5.
Figure imgb0002

Als Diol X kommen infrage lineare oder verzweigte, gesättigte oder ungesättigte, acyclische Diole mit 2 - 16, vorzugsweise 2 - 10 C-Atomen, wie z.B. Butandiol-1.4, Hexandiol-2.5, Hexandiol-1.6 oder Decandiol-1.10, Buten-2-diol-1.4 oder Hexin-3-diol-2.5, oder cyclische Diole, wie z.B. Cyclohexandiol-1.4, oder aromatische Diole, wie z.B. Bisphenol A. Außerdem kann X sein ein Kondensationsprodukt des Ethylenoxids und/oder des Propylenoxids und/oder des Butylenoxids mit 2 - 12 mol, vorzugsweise 2 - 8 mol Alkylenoxid, wie z.B. Tripropylenglykol oder Polyethylenglykol 200.Suitable diol X are linear or branched, saturated or unsaturated, acyclic diols with 2-16, preferably 2-10, carbon atoms, such as, for example, 1,4-butanediol, 2.5-hexanediol, 1.6-hexanediol or 1.10 decanediol, butene-2- diol-1.4 or hexin-3-diol-2.5, or cyclic diols, such as, for example, cyclohexanediol-1.4, or aromatic diols, such as, for example, bisphenol A. In addition, X can be a condensation product of ethylene oxide and / or Propylene oxide and / or butylene oxide with 2-12 mol, preferably 2-8 mol, of alkylene oxide, such as tripropylene glycol or polyethylene glycol 200.

Die Phosphorverbindung der allgemeinen Formel (1) wird in einem zweiten Reaktionsschritt unter Chlorwasserstoffabspaltung mit einer Hydroxiverbindung R kondensiert (verestert).The phosphorus compound of the general formula (1) is condensed (esterified) in a second reaction step with elimination of hydrogen chloride with a hydroxyl compound R.

Als Hydroxiverbindung R kommen infrage lineare oder verzweigte, gesättigte oder ungesättigte Alkohole mit 4 bis 22, vorzugsweise 12 - 18 C-Atomen, oder die vorgenannten Alkohole, kondensiert mit 1 - 12, vorzugsweise 1 - 6 mol Alkylenoxid, wie z.B. Oleyalkohol, Talgfettalkohol, synthetische Alfol-Alkohole, Isooctadecylalkohol oder Oleylalkohol mit 4 mol Ethylenoxid, Phenole oder Alkylphenole mit 6 - 30 C-Atomen, wie z.B. Octylphenol, Nonylphenol, Di-Nonylphenol, Dodecylphenol, oder die entsprechenden ethoxilierten Phenole und Alkylphenole (1 - 12 mol EO).Suitable hydroxyl compounds R are linear or branched, saturated or unsaturated alcohols having 4 to 22, preferably 12-18 C atoms, or the abovementioned alcohols, condensed with 1-12, preferably 1-6 mol, alkylene oxide, such as, for example, Oley alcohol, tallow fatty alcohol, synthetic Alfol alcohols, isooctadecyl alcohol or oleyl alcohol with 4 mol ethylene oxide, phenols or alkylphenols with 6 - 30 C atoms, e.g. Octylphenol, nonylphenol, di-nonylphenol, dodecylphenol, or the corresponding ethoxylated phenols and alkylphenols (1 - 12 mol EO).

Als Hydroxiverbindung R finden auch die Fettsäurepolyglykolester Anwendung, wie z.B. Talgfettsäure mit 6 mol Ethylenoxid oder ölsäure, verestert mit Polyethylenglykol 200, oder die Mono- bzw. Diglyzeride von Fettsäuren, wie z.B. ölsäuremonoglyzerid. Auch ethoxilierte, gesättigte oder ungesättigte Fettamine, Fettsäureamide und die Fettsäuremono- bzw. dialkanolamide können verwendet werden, wie z.B. Kokosfettamin mit 12 mol Ethylenoxid, Talgfettsäureamid mit 10 mol Ethylenoxid, Ölsäureamid mit 4 mol Ethylenoxid und Kokosfettsäurediethanolamid.The fatty acid polyglycol esters such as tallow fatty acid with 6 mol ethylene oxide or oleic acid esterified with polyethylene glycol 200 or the mono- or diglycerides of fatty acids such as oleic acid monoglyceride are also used as the hydroxy compound R. Ethoxylated, saturated or unsaturated fatty amines, fatty acid amides and the fatty acid mono- or dialkanolamides can also be used, such as coconut fatty amine with 12 mol ethylene oxide, tallow fatty acid amide with 10 mol Ethylene oxide, oleic acid amide with 4 mol ethylene oxide and coconut fatty acid diethanolamide.

In einem dritten Reaktionsschritt werden die noch verbliebenden P-Cl-Bindungen des ursprünglichen Phosphoroxidchlorids (POC13) mit einer Base M-OH abneutralisiert.In a third reaction step, the remaining P-Cl bonds of the original phosphorus oxychloride (POC1 3 ) are neutralized with a base M-OH.

M steht für ein Alkalimetallkation, z.B. Na+, K oder für das Ammonium-Ion oder für eine organische, cyclische oder acyclische Ammoniumverbindung, wie z.B. Cyclohexylammonium-, Triethylammonium- oder Monoethanolammonium-Ion.M stands for an alkali metal cation, for example Na + , K or for the ammonium ion or for an organic, cyclic or acyclic ammonium compound, such as for example cyclohexylammonium, triethylammonium or monoethanolammonium ion.

Die zur Fettung und Hydrophobierung verwendete wässrige Flotte kann durch Einrühren des erfindungsgemäß verwendeten Fettungs- und Hydrophobierungsmittels in warmes Wasser (ca. 50°C; 3 Teile Wasser auf 1 Teil Lederbehandlungsmittel) hergestellt werden. Eine solche Flotte ist ausreichend stabil und wird zum Lickern (d.h. Behandeln in wässrigem System) von chromgegerbten oder vegetabil und/oder synthetisch nachgegerbten Ledern verwendet. Ein besonderer Vorteil des erfindungsgemäßen Verfahrens besteht in der sehr starken Affinität der angegebenen Fettungs- und Hydrophobierungsmittel zur Faser. Dies zeigt sich z.B. bei der Extraktion mit Dichlormethan (nach DIN 53306), bei der das Lederbehandlungsmittel praktisch nicht von der Faser extrahiert werden kann.The aqueous liquor used for oiling and waterproofing can be prepared by stirring the oiling and waterproofing agent used according to the invention into warm water (approx. 50 ° C .; 3 parts water to 1 part leather treatment agent). Such a liquor is sufficiently stable and is used to lick (i.e. treat in an aqueous system) chrome-tanned or vegetable and / or synthetically retanned leathers. A particular advantage of the process according to the invention is the very strong affinity of the specified fatliquoring and hydrophobicizing agents for the fiber. This can be seen e.g. during extraction with dichloromethane (according to DIN 53306), in which the leather treatment agent can practically not be extracted from the fiber.

Die Leder, die nach dem beanspruchten Verfahren behandelt werden, zeichnen sich durch gute Weichheit und Geschmeidigkeit und angenehmen Griff aus.The leathers that are treated according to the claimed process are characterized by good softness and suppleness and a pleasant feel.

Der besondere Vorteil der nach dem erfindungsgemäßen Verfahren behandelten Leder liegt in der nicht zu erwartenden, außergewöhnlich hohen dynamischen Wasserfestigkeit.The particular advantage of the leather treated by the process according to the invention lies in the unexpected, exceptionally high dynamic water resistance.

Beispiel 1:Example 1:

In üblicher Weise hergestelltes Chromnarbenleder wird mit 100% Flotte (= Wasser) , 1% Farbstoff und 5% Lederbehandlungsmittel gemäß Formel im Patentanspruch 1 praxisgerecht gelickert und aufgearbeitet. Die voranstehenden Prozentangaben beziehen sich auf das Ledergewicht. In der Formel bedeuten dabei X = Hexandiol-1.6, R = Oleylalkohol, M = Na und z = 2.Chrome grain leather produced in the usual way is licked and worked up with 100% liquor (= water), 1% dye and 5% leather treatment agent according to the formula in claim 1. The percentages above refer to the weight of the leather. In the formula, X = 1.6-hexanediol, R = oleyl alcohol, M = Na and z = 2.

Die erhaltenen Leder sind sehr weich und geschmeidig, besitzen einen trockenen seidigen Griff und zeigen eine hervorragende dynamische Wasserfestigkeit bei Prüfung auf dem "Bally-Penetrometer" (gemäß IUP/10; "Das Leder", 1961, 38).

  • Wasserdurchtritt nach Minuten: > 480 Minuten.
  • Wasseraufnahme nach 480 Minuten: 14%.
The leathers obtained are very soft and supple, have a dry silky feel and show excellent dynamic water resistance when tested on the "Bally penetrometer" (according to IUP / 10; "Das Leder", 1961, 38).
  • Water penetration after minutes:> 480 minutes.
  • Water absorption after 480 minutes: 14%.

Beispiel 2:Example 2:

Chromnarbenleder wird in üblicher Weise mit 2% eines synthetischen Gerbstoffes nachgegerbt, gefärbt und mit 5% Lederbehandlungsmittel gemäß Formel im Patentanspruch 1 gelickert. Die voranstehenden Prozentangaben beziehen sich auf das Ledergewicht. In der Formel bedeuten dabei X = Ethylenglykol, R = Kokosfettalkohol, M = Ammonium und z = 3.Chrome grain leather is retanned in the usual way with 2% of a synthetic tanning agent, dyed and Licked with 5% leather treatment agent according to the formula in claim 1. The percentages above refer to the weight of the leather. In the formula, X = ethylene glycol, R = coconut fatty alcohol, M = ammonium and z = 3.

Nach praxisgerechter Aufarbeitung wird ein weiches, gleichmäßig gefärbtes Leder mit großer Wasserfestigkeit erhalten.

  • Wasserdurchtritt nach Minuten: > 480 Minuten.
  • Wasseraufnahme nach 480 Minuten: 16%.
After practical processing, a soft, evenly colored leather with great water resistance is obtained.
  • Water penetration after minutes:> 480 minutes.
  • Water absorption after 480 minutes: 16%.

Beispiel 3:Example 3:

In bekannter Weise wird Chromnarbenleder mit 20% vegetabilischen Gerbstoffen nachgegerbt und mit 6% Lederbehandlungsmittel gemäß Formel im Patentanspruch 1 in 100% Flotte gelickert. Die voranstehenden Prozentangaben beziehen sich auf das Ledergewicht. In der Formel bedeuten dabei X = Butandiol-1.4, R = Nonylphenolpolyglykolether (5 mol EO), M = Na und z = 1.In known manner, chrome grain leather is retanned with 20% vegetable tannins and g elickert with 6% Leather treatment agent according to formula in claim 1 in 100% float. The percentages above refer to the weight of the leather. In the formula, X = 1,4-butanediol, R = nonylphenol polyglycol ether (5 mol EO), M = Na and z = 1.

Nach Aufarbeitung wird ein weiches und sehr wasserfestes Leder erhalten.

  • Wasserdurchtritt nach Minuten: > 480
  • Wasseraufnahme nach 480 Minuten: 17%.
After working up, a soft and very waterproof leather is obtained.
  • Water penetration after minutes:> 480
  • Water absorption after 480 minutes: 17%.

In allen Beispielen werden dem Lederfettungs- und Hydrophobierungsmittel je nach Bedarf übliche Lederadditive zugefügt, beispielsweise neutrale Lederbehandlungsmittel wie Öle, Fette, chlorierte Öle und Fette, Chlorparaffine, höhermolekulare Fettalkohole, Fettsäuren, Fettsäureester sowie Kohlenwasserstoffe, ferner-anionische Emulgatoren, beispielsweise sulfierte Kohlenwasserstoffe, sulfierte native Fette oder öle, oder sulfierte Fettsäuren und Fettsäureester, und/oder schließlich nichtionogene Emulgatoren, beispielsweise Fettalkoholethoxilate oder Alkylphenolethoxilate.In all examples, the usual leather additives are added to the leather greasing and waterproofing agent, for example neutral leather treatment agents such as oils, fats, chlorinated oils and Fats, chlorinated paraffins, higher molecular weight fatty alcohols, fatty acids, fatty acid esters and hydrocarbons, also anionic emulsifiers, for example sulfated hydrocarbons, sulfated native fats or oils, or sulfated fatty acids and fatty acid esters, and / or finally nonionic emulsifiers, for example fatty alcohol ethoxylates or alkylphenol ethoxylates.

Die Erfindung bezieht sich nicht nur auf die angegebenen Verfahren, sondern umfasst auch die dabei verwendeten Fettungs- und Hydrophobierungsmittel.The invention relates not only to the specified methods, but also encompasses the lubricating and hydrophobicizing agents used.

Claims (4)

1. Verfahren zum Fetten und gleichzeitigen Hydrophobieren von Leder, Pelz und Lederaustauschstoffen, bei dem das zu fettende und zu hydrophobierende Material in einer wässrigen Flotte behandelt wird, die ein Fettungs- und Hydrophobierungsmittel enthält, dadurch gekennzeich- net, daß das Fettungs- und Hydrophobierungsmittel aus einer Verbindung der allgemeinen Formel
Figure imgb0003
besteht, worin X, R, M und z folgende Bedeutung haben: X ist ein lineares oder verzweigtes, gesättigtes oder ungesättigtes, cyclisches, acyclisches oder aromatisches, gegebenenfalls auch Heteroatome enthaltendes Diol mit 2 bis 16 C-Atomen oder ein Kondensationsprodukt der Alkylenoxide, beispielsweise Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid mit 2 bis 12 mol Alkylenoxid oder ein Gemisch dieser Diole; R ist eine als Veresterungskomponente dienende Hydroxiverbindung, nämlich ein linearer oder verzweigter, gesättigter oder ungesättigter Alkohol mit 4 bis 22 C-Atomen, oder einer dieser Alkohole, kondensiert mit 1 bis 12 mol Alkylenoxid, oder ein Phenol oder Alkylphenol mit 6 bis 30 C-Atomen, oder eines dieser Phenole und Alkylphenole, kondensiert mit 1 bis 12 mol Alkylenoxid, oder ein gesättigter oder ungesättigter Fettsäureester, wobei der Fettsäurerest 8 bis 22 C-Atome enthält und die Esterkomponenten Polyalkylenoxide mit 1 bis 15 mol Alkylenoxid sind, oder ein gesättigtes oder ungesättigtes Fettsäuremono- bzw. diglyzerid mit 8 bis 22 C-Atomen pro Fettsäurerest, oder ein gesättigtes oder ungesättigtes, primäres oder sekundäres Fettamin mit 8 bis 22 C-Atomen pro Alkylrest, kondensiert mit 1 bis 24 mol Alkylenoxid, oder ein gesättigtes oder ungesättigtes Fettsäureamid mit 8 bis 22 C-Atomen, kondensiert mit 1 bis 24 mol Alkylenoxid; M ist ein einwertiges Metall-Kation, Ammonium-Ion oder eine organische Ammoniumverbindung; z ist eine ganze Zahl von 1 bis 10. 1. A process for greasing and simultaneously hydrophobizing leather, fur and leather substitutes, in which the material to be greased and hydrophobized is treated in an aqueous liquor which contains a greasing and water-repellent agent, characterized in that the greasing and water-repellent agent from a compound of the general formula
Figure imgb0003
 where X, R, M and z have the following meanings: X is a linear or branched, saturated or unsaturated, cyclic, acyclic or aromatic, optionally also containing heteroatoms, diol with 2 to 16 carbon atoms or a condensation product of the alkylene oxides, for example ethylene oxide and / or propylene oxide and / or butylene oxide with 2 to 12 mol Alkylene oxide or a mixture of these diols; R is a hydroxyl compound serving as an esterification component, namely a linear or branched, saturated or unsaturated alcohol having 4 to 22 carbon atoms, or one of these alcohols, condensed with 1 to 12 mol of alkylene oxide, or a phenol or alkylphenol with 6 to 30 C atoms, or one of these phenols and alkylphenols, condensed with 1 to 12 mol alkylene oxide, or a saturated or unsaturated fatty acid ester, the fatty acid residue containing 8 to 22 C atoms and the ester components being polyalkylene oxides with 1 to 15 mol alkylene oxide, or a saturated or unsaturated fatty acid mono- or diglyceride with 8 to 22 carbon atoms per fatty acid residue, or a saturated or unsaturated, primary or secondary fatty amine with 8 to 22 carbon atoms per alkyl radical, condensed with 1 to 24 mol of alkylene oxide, or a saturated or unsaturated fatty acid amide with 8 to 22 carbon atoms, condensed with 1 to 24 mol of alkylene oxide; M is a monovalent metal cation, ammonium ion or an organic ammonium compound; z is an integer from 1 to 10. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß dem Fettungs- und Hydrophobierungsmittel neutrale Lederbehandlungsmittel wie z.B. Öle, Fette, chlorierte Öle und Fette, Chlorparaffine, höhermolekulare Fettalkohole, Fettsäuren und Fettsäureester sowie Kohlenwasserstoffe beigegeben werden.2. The method according to claim 1, characterized in that the oiling and waterproofing agent neutral leather treatment agents such as Oils, fats, chlorinated oils and fats, chlorinated paraffins, higher molecular fatty alcohols, fatty acids and fatty acid esters and hydrocarbons are added. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß dem Fettungs- und Hydrophobierungsmittel zusätzlich anionische Emulgatoren, insbesondere sulfierte Kohlenwasserstoffe, sulfierte native Fette oder öle oder sulfierte Fettsäuren und Fettsäureester beigegeben werden.3. The method according to claim 1 or 2, characterized in that the fatliquoring and hydrophobizing agent additionally anionic emulsifiers, in particular sulfated hydrocarbons, sulfated native fats or oils or sulfated fatty acids and fatty acid esters are added. 4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß dem Fettungs- und Hydrophobierungsmittel zusätzlich nichtionogene Emulgatoren, insbesondere Fettalkoholethoxilate oder Alkyl- phenolethoxilate beigegeben werden.4. The method of claim 1, 2 or 3, characterized in that the fatliquoring agents and hydrophobizing agents in addition non-ionic emulsifiers, particularly fatty alcohol ethoxylates or alkyl are p henolethoxilate added.
EP83101962A 1982-03-03 1983-02-28 Process for the liquoring and simultaneous water-proofing of leather, fur and leather substitutes Expired EP0087799B1 (en)

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AT83101962T ATE22929T1 (en) 1982-03-03 1983-02-28 METHOD OF LUBRICATION AND SIMULTANEOUSLY HYDROPHOBIZING LEATHER, FUR AND LEATHER REPLACEMENT MATERIALS.

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DE3207562 1982-03-03
DE19823207562 DE3207562A1 (en) 1982-03-03 1982-03-03 METHOD FOR FAT AND SIMULTANEOUSLY HYDROPHOBIZING LEATHER, FUR AND LEATHER EXCHANGERS

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FR2559784A1 (en) * 1984-02-22 1985-08-23 Sandoz Sa PROCESS FOR FEEDING TANNED LEATHER AND TANNED SKINS
WO1996010651A1 (en) * 1994-10-04 1996-04-11 Henkel Kommanditgesellschaft Auf Aktien Greasing agent for leather and pelts
RU2133779C1 (en) * 1998-12-24 1999-07-27 Данелян Сергей Эдуардович Method of manufacturing heat-resistant russia upper leather from wet- saline conservation cattle skin
RU2135595C1 (en) * 1998-11-17 1999-08-27 Российский заочный институт текстильной и легкой промышленности Method of treatment of leather fabric
RU2135594C1 (en) * 1998-11-17 1999-08-27 Российский заочный институт текстильной и легкой промышленности Method of dressing skin tissue
RU2194764C1 (en) * 2002-02-18 2002-12-20 Общество с ограниченной ответственностью "Галичобувь" Method for manufacture of thermally stable russian leather
RU2228361C1 (en) * 2003-07-08 2004-05-10 Московский государственный университет дизайна и технологии Liposomal composition for treating leather and fur semifinished product and treatment processes
GB2466281A (en) * 2008-12-19 2010-06-23 3M Innovative Properties Co Composition comprising a fluorinated compound and a phosphate ester for treating surfaces
RU2748944C1 (en) * 2020-08-31 2021-06-02 Елена Николаевна Заблоцкая Method for processing hide leather fabric

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DE3504308A1 (en) * 1984-02-22 1985-08-22 Sandoz-Patent-GmbH, 7850 Lörrach Process for the simultaneous fat-liquoring and water-repellent finishing of tanned leather
DE502004001687D1 (en) * 2004-07-13 2006-11-16 Zschimmer & Schwarz Gmbh & Co Agent for the hydrophobic finishing of leather

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FR2307874A1 (en) * 1975-04-17 1976-11-12 Stockhausen & Cie Chem Fab PROCESS FOR IMPROVING THE MECHANICAL PROPERTIES AND THE HAND QUALITIES OF LEATHER, FUR AND CLOTHING OF LEATHER OR FUR

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2559784A1 (en) * 1984-02-22 1985-08-23 Sandoz Sa PROCESS FOR FEEDING TANNED LEATHER AND TANNED SKINS
US4740210A (en) * 1984-02-22 1988-04-26 Sandoz Ltd. Fatting compositions containing surface-active phosphoric acid partial esters
WO1996010651A1 (en) * 1994-10-04 1996-04-11 Henkel Kommanditgesellschaft Auf Aktien Greasing agent for leather and pelts
RU2135595C1 (en) * 1998-11-17 1999-08-27 Российский заочный институт текстильной и легкой промышленности Method of treatment of leather fabric
RU2135594C1 (en) * 1998-11-17 1999-08-27 Российский заочный институт текстильной и легкой промышленности Method of dressing skin tissue
RU2133779C1 (en) * 1998-12-24 1999-07-27 Данелян Сергей Эдуардович Method of manufacturing heat-resistant russia upper leather from wet- saline conservation cattle skin
RU2194764C1 (en) * 2002-02-18 2002-12-20 Общество с ограниченной ответственностью "Галичобувь" Method for manufacture of thermally stable russian leather
RU2228361C1 (en) * 2003-07-08 2004-05-10 Московский государственный университет дизайна и технологии Liposomal composition for treating leather and fur semifinished product and treatment processes
GB2466281A (en) * 2008-12-19 2010-06-23 3M Innovative Properties Co Composition comprising a fluorinated compound and a phosphate ester for treating surfaces
WO2010080396A2 (en) 2008-12-19 2010-07-15 3M Innovative Properties Company Composition and method to provide stain release and stain repellency properties to substrates
US20110290147A1 (en) * 2008-12-19 2011-12-01 Coppens Dirk M Composition and method to provide stain release and stain repellency properties to substrates
RU2748944C1 (en) * 2020-08-31 2021-06-02 Елена Николаевна Заблоцкая Method for processing hide leather fabric

Also Published As

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DE3207562C2 (en) 1988-06-23
EP0087799B1 (en) 1986-10-15
DE3207562A1 (en) 1983-09-15
ATE22929T1 (en) 1986-11-15

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