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EP1478785B1 - Low-voc stuffing agents, the use thereof in the production and/or treatment of leather and skins and corresponding production or treatment method - Google Patents

Low-voc stuffing agents, the use thereof in the production and/or treatment of leather and skins and corresponding production or treatment method Download PDF

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Publication number
EP1478785B1
EP1478785B1 EP03704668A EP03704668A EP1478785B1 EP 1478785 B1 EP1478785 B1 EP 1478785B1 EP 03704668 A EP03704668 A EP 03704668A EP 03704668 A EP03704668 A EP 03704668A EP 1478785 B1 EP1478785 B1 EP 1478785B1
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Prior art keywords
oil
modified
leather
weight
component
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German (de)
French (fr)
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EP1478785A1 (en
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Ralph Lunkwitz
Andreas Seitz
Gunther Pabst
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BASF SE
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BASF SE
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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

Definitions

  • the present invention relates to low-VOC fatliquoring agents, their use in the manufacture and / or treatment of leather and hides, and to processes for producing and / or treating leather and hides with the fatliquoring agents of the invention.
  • leather fatliquoring agents soften the leather, increase its fullness and firmness, and protect it against moisture, dirt, and chemical influences from the outside (see H. Herfeld, "Library of the Leather” 1985, Volume 4, p. 13 ff .).
  • Commercially available fatliquoring agents generally consist of fatty substances, such as native fats, native oils, waxes, resins and their derivatives and / or petroleum fractions and their derivatives, and waxy products such as "wool fat", in crude, purified and / or prepared (lanolin) Form (see H. Herfeld, "Library of the Leather” 1985, Volume 4, p. 59 ff .).
  • the greasing substances can - if desired - be chemically modified, ie present in a modified chemical structure.
  • the chemical modification of the fatty substances is usually that the double bonds contained in these substances are at least partially subjected to addition reactions or oxidation reactions. Frequently made modifications exist, for example, in the addition of sulfites, whereby sulfonic acid groups are introduced into the fatty substances, or in the air oxidation, whereby oxygen functions are introduced and sometimes also oligomerizations occur. But it is also possible (partial) hydrolysis of the fats, transesterifications and the like modification reactions.
  • DIN 75201 defines “fogging” as the condensation of vaporized components from the vehicle interior trim such as the car upholstery leather on the glass panes, in particular on the windshield. This can lead to a deteriorated view through the windshield, especially during night driving, and thus to a security risk.
  • the fogging behavior of leather is characterized by a gravimetric and a reflectometric method.
  • the aqueous dispersions used in the leather treatment are substantially free of organic solvents and contain an amphiphilic copolymer.
  • This copolymer consists of a predominant proportion of at least one hydrophobic monomer and a small proportion of at least one hydrophilic monomer.
  • amphiphilic copolymers are preferably carried out by emulsion polymerization in aqueous solution.
  • emulsion polymerization due to the different hydrophilicity of the monomers to be used, naturally problems arise in the copolymerization behavior. In extreme cases, this can lead to the monomers undesirably forming homopolymers each by themselves.
  • Another consequence of the unfavorable solution conditions is a complicated work-up for the destruction of unreacted monomers.
  • an emulsifier in the cited Examples used was lauryl sulfate
  • polymers containing both pendant hydrophobic groups and pendant hydrophilic alkoxylated groups are obtained by carrying out after the actual polymerization process - known in the art - derivatization reactions.
  • polymers are preferably prepared from simple monomers such as acrylamide and / or acrylic acid by conventional polymerization and then derivatized with a mixture of primary or hydrophobic amines or primary or secondary alkoxylated amines.
  • the described polymers are used as thickeners and soil release agents. Their use in leather treatment is not described.
  • Polymeric fatliquoring agents are prepared by polymerization of acrylic acid and / or methacrylic acid and / or their acid chlorides and / or their anhydrides with other copolymerizable water-soluble monomers and with copolymerizable water-insoluble monomers and subsequent reaction of the polymers thus obtained with amines.
  • DIN 75201 B gravimetric test
  • leathers treated with these polymeric fatliquoring agents have fogging values of 1.2 mg and 1.5 mg, respectively.
  • Magnopal ® SOF flaving polymer fatliquoring agent Stockhausen GmbH & Co.
  • the reflectometric values according to DIN 75201 A of the polymeric fatliquoring agents are 51% and 55% respectively, those of the comparative products 34% and 40%, respectively.
  • hydrophobic monomers which are used are longer-chain alkenes or (meth) acrylic esters of C 4 -C 12 -alkanols or vinyl esters of C 4 -C 12 -carboxylic acids.
  • the substances give good fogging values; However, there is no information about the Badauszehrung.
  • the preparation of the amphiphilic copolymers is preferably carried out by aqueous emulsion polymerization.
  • EP-B 0 753 585 describes a low-fogging surface treatment for furniture leather, in which specially treated native oils, which have less than 3% of fatty acid components with less than 16 carbon atoms, act as the basis for fatliquors.
  • Native oils used are soybean, lard, safflower and sunflower oils. The said native oils are first distilled to remove the unwanted low molecular weight components and then reacted with hydrogen sulfite or bisulfate to improve emulsifiability. Then the (partially) functionalized oils are emulsified and applied.
  • component A is a C 6 to C 14 alkanol alkoxylated with 4 to 12 AO units, or a mixture of several such alkanols
  • component B is a C 12 -C 24 fatty alcohol mixture alkoxylated with 15 to 40 AO units and component C a C 12 to C 24 fatty alcohol mixture alkoxylated with 50 to 100 AO units.
  • the AO units are expediently alkylene oxide units having 2 to 4, preferably 2 to 3, carbon atoms.
  • the building blocks of the polyether chains can all be identical or different and, if they are different, can be arranged randomly or in blocks.
  • the proportions by weight of the components in the emulsifier composition for component A are from 20 to 60, preferably from 25 to 50, in particular from 28 to 40,% by weight, for component B from 20 to 70, preferably from 25 to 60, in particular from 30 to 45,%. -% and for the component C 10 to 50, preferably 15 to 40, especially 22 to 32 wt .-% of the total weight of the composition.
  • the object of the present invention is to provide a fatliquoring agent which largely avoids the disadvantages of the prior art.
  • the with these fatliquors treated leather should be low in VOC and optionally have sufficient fastness to light and heat.
  • (hetero) cycloaliphatic C 4 - to C 30 -hydrocarbon radicals is understood as meaning saturated, mono- or polyunsaturated C 4 - to C 30 -hydrocarbon rings in which, if appropriate, methylene groups -CH 2 - denoted by -O-, - N (H) - and / or -S- are replaced, and optionally one or more linear C 1 - to C 10 alkyl radicals, linear C 1 - to C 10 alkylene bridges, branched C 3 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 -alkylene bridges carry, which are optionally mono- or polyunsaturated.
  • cycloaliphatic C 4 - to C 30 -hydrocarbon radicals are in the scope of the invention, optionally with one or more - saturated, monounsaturated or polyunsaturated - linear C 1 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 alkyl radicals substituted, lactones and lactams and urea derivatives understood.
  • the term includes both mono- and polycyclic ring systems, in particular bicyclic and tricyclic ring systems.
  • the term includes both mono- and polycyclic ring systems, in particular bicyclic and tricyclic ring systems.
  • Explicit examples which are not intended to be limiting, however, are phenyl, toluyl, cumyl, naphthyl, phenanthryl, pyridyl, indyl, optionally with one or more linear C 1 - to C 10 -alkyl radicals, linear C 1 - to C 10 -alkylene bridges , branched C 3 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 -alkylene bridges are substituted.
  • the fatliquoring agents according to the invention are particularly suitable for the fatliquoring of leathers and skins, since the leathers and skins treated in this way show low fogging.
  • the fatliquoring agents of the invention are used in Cr-free tanned leathers and skins.
  • Cr-free tanning is understood to mean all the tanning processes of leathers and skins in which no Cr (III) is used for tanning. In particular, it means processes known to the person skilled in the art, such as vegetable tanning, syntan tanning and wet-white tanning.
  • component A modified by oxidation and / or sulfitation native oils.
  • modified native oils which have a relatively high degree of oxidation and a relatively low degree of sulfitation.
  • Fats of vegetable or animal origin, in particular glycerides of natural fatty acids, with a sufficient proportion of unsaturated acids are expediently used as native oils.
  • Highly suitable native oils are those having an iodine value of about 10 to about 200. In the lower portion of this range, e.g. Stearic and tung oil, in the upper section in particular the fish oils and chaulmoogra oil.
  • Preferred are native oils with iodine numbers of about 30 to about 120, especially from 40 to 85.
  • Examples of particularly preferred native oils are fish oil, foot oil, lard oil, soybean oil, rapeseed oil, nut oil, olive oil and castor oil.
  • the sulfite products or oxidation products of the monounsaturated or polyunsaturated fats are formed by the reaction of the olefinic double bonds present in the fats with the sulfiting and / or oxidation reagents. All double bonds present in the fats or only a part of them can react.
  • oxidation reagent air at temperatures of 60 to 80 ° C is used as the oxidation reagent.
  • the oxidation can also be carried out by other methods known in the art.
  • a relatively high degree of oxidation in the sense of this invention is when ⁇ d, the difference in the specific gravity of the oil or fat before and after the oxidation, in the range of 0.01 to 0.1 g / ml, preferably from 0.03 to 0 , 05 g / ml.
  • the sulfitation is generally carried out by reaction in aqueous bisulfite. However, it can also be done by other species known in the art.
  • a relatively low degree of sulfitation in the context of this invention is present when the native oil with 2 to 8 wt .-%, preferably with 3 to 5 wt .-%, of its weight with a sulfite, calculated as sodium bisulfite (Na 2 S 2 O 5 ) has been implemented.
  • L n R are used with a total of at least 20 C-atoms, in particular with a total of at least 28 C-atoms.
  • L represents one of the following radicals: and / or n is an integer from 1 to 4.
  • Preferred monovalent radicals R are linear or branched saturated alkyl radicals and alkoxycarbonyl-substituted linear or branched alkyl radicals - (C m H 2m ) -C (O) OX 1 , where m is an integer from 0 to 28, and X 1 is a linear Alkyl radical having 1 to 28 carbon atoms or a branched alkyl radical having 3 to 28 carbon atoms.
  • Further preferred monovalent radicals R are connected via linear C 1 - to C 4 -alkylene bridges or branched C 3 - to C 4 -alkylene bridges connected with L, optionally with (un) saturated linear C 1 - to C 10 -alkanols or (un) saturated branched C 4 - to C 10 -alkanols etherified or esterified with (un) saturated linear C 1 - to C 10 -carboxylic acids or (un) saturated branched C 4 - to C 10 -carboxylic acids, phenol derivatives which am Phenyl ring with one or more linear C 1 - to C 10 - and / or branched C 3 - to C 10 -alkyl radicals and / or C 6 - to C 12 -cycloalkyl radicals may be substituted.
  • the etherified or esterified phenol derivatives are preferably those radicals L- mentioned above which are substituted by linear C 1 - to C 4 -alkylene bridges or branched C 3 - to C 4 -alkylene bridges, where the hydroxy group is substituted by (un ) saturated linear C 1 - to C 10 -alkanols or (un) saturated branched C 4 - to C 10 -alkanols or etherified with (un) saturated linear C 1 - to C 10 -carboxylic acids, or (un) saturated branched C 4 - is esterified to C 10 carboxylic acids.
  • Preferred divalent radicals R are saturated, mono- or polyunsaturated, linear C 1 - to C 18 -alkylene groups and branched C 3 - to C 18 -alkylene groups, which are optionally substituted in the hydrocarbon chain of the alkylene groups ester groups -C (O) O- and / or amide groups -C (O) N (H) and / or hydrazide groups -C (O) -N (H) -N (H) -C (O) - and / or where appropriate in the hydrocarbon chain of the alkylene groups one or more methylene groups -CH 2 - by -S-, -O- or -N (H) -park.
  • Further preferred divalent radicals R are -S-, -O- and -N (H) -.
  • Preferred trivalent radicals R are trivalent linear C 3 to C 10 or branched, (a) cyclic, (un) saturated C 4 to C 10 or aromatic C 6 to C 10 hydrocarbon radicals in which three protons are in each case represented by the Rest L are replaced.
  • preferred Hydrocarbon radicals are existing methylene groups -CH 2 - optionally substituted by - N (H) - replaced.
  • the attachment of the radical L can also take place via linear C 1 - to C 10 -alkylene bridges or branched C 3 - to C 10 -alkylene bridges to such a nitrogen atom.
  • methylene groups -CH 2 - may be replaced by -O-, -N (H) - or -S-.
  • Particularly preferred trivalent radicals R are selected from the following group:
  • Preferred R are tetravalent, substituted with alkylcarbonyloxy groups and / or O and / or N (H) units, saturated linear C 3 - to C 20 - or branched aliphatic C 4 - to C 20 hydrocarbon radicals, in which four Protons are replaced by the radicals L.
  • R C (CH 2 -OC (O) -CH 2 -CH 2 -) 4 .
  • the fatliquoring agents according to the invention preferably contain at least 40% by weight, more preferably at least 50% by weight, very preferably at least 70% by weight, of a component A or of a mixture of components A and at most 1% by weight, more preferably at most 0.5 wt .-%, most preferably at most 0.2 wt .-%, of a component B or a mixture of components B, based on the total weight of the fatliquoring agent.
  • the fatliquoring agents according to the invention can be used undiluted or, depending on the wishes of the users, in the form of aqueous dispersions (aqueous liquors), preferably with solids contents of 40 to 80% by weight, preferably with solids contents of 50 to 80% by weight, particularly preferably with solids contents of 60 to 75 wt .-% are provided.
  • aqueous dispersions aqueous liquors
  • the components of the preferred fatliquoring agents according to the invention namely the moficated native oils according to the invention and the stabilizers according to the invention, can be added to the fatliquoring liquors together or separately in any order.
  • the invention thus also relates to a process for the fatliquoring of leather and hides by treatment with the abovementioned aqueous liquors.
  • the invention further relates to the use of the described fatliquoring agent according to the invention in leather production.
  • Their use serves to soften the Leather, to increase its fullness and strength and to protect against moisture, dirt, and chemical influences from the outside.
  • the presence of the stabilizers according to the invention leads to low fogging values.
  • the composition of the conventional fatliquoring agents A1 to A5 and B1 to B5 used and the fatliquoring agents C1 to C5 and D1 to D5 used according to the invention are shown in Tables 1 and 3.
  • the proportion of the individual components is given in% by weight, based on the total fatliquoring agent, and can be found in Tables 2 and 4.
  • the non-ionic surfactant Lutensol® AT 25 from BASF AG in Ludwigshafen is a G 16 to C 18 fatty alcohol mixture which has been ethoxylated with 25 mol of ethylene oxide.
  • Acetylated lecithin is available from Compte & Rivera SA in Spain.
  • the triolein is native oleic acid triglyceride from Smit & Zoon.
  • Ebotec MO (4-octylisothiazolinone) is a biocide of Bode Chemie in Hamburg.
  • Example 1 Treatment of Cr-tanned leather with conventional fatliquoring agents (A1 to A5, B1 to B5) and fatliquoring agents (C1 to C5, D1 to D5) according to the invention
  • 100 parts by weight of chrome cattle leather with a thickness of 2.0 to 2.2 mm are placed in 100 parts by weight of water at 40 ° C. and adjusted to a pH of 4.5 by addition of sodium formate and sodium bicarbonate.
  • the leather is tumbled at 40 ° C for 60 minutes in the barrel and then washed with 200 parts by weight of water.
  • the liquor is adjusted with formic acid to a pH of 3.5 to 3.8, the leather briefly rinsed cold and further processed as usual.
  • a tanning agent such as Relugan® GTP from BASF AG in Ludwigshafen were drummed for 60 minutes.
  • an auxiliary tanning agent such as Tamol® NA BASF AG in Ludwigshafen and 30 minutes Walken 4 parts by weight of a conventional fatliquoring agent (A1 to A5, B1 to B5) or 4 parts by weight of a fatliquoring agent of the invention (C1 to C5, D1 to D5 ) was added and drummed for a further 60 minutes.
  • the fastnesses to thermal yellowing as a function of the temperature are determined on the wet blue-tanned leathers obtained after completion of the fatliquoring with the fatliquoring agents A4, B3, C4 or D3 according to Example 1.
  • the leathers were tested here 144 h after storage at 100 ° C or alternatively 4 h after storage at 120 ° C. The measurement results are shown in Table 5.
  • Db are the values for heat yellowing
  • DE is a measure of the gray values. The lower the numerical value, the better the light resistance.
  • the leathers treated with the fatliquoring agents (C4, D3) according to the invention have lower fogging values than the leathers treated with conventional fatliquoring agents (A4, B3).
  • Table 7 According to PB VWL 709 (Daimler Chrysler) certain VOC and fogging values ⁇ / u> fatliquors absolute fogging values in ppm relative fogging values in% absolute VOC values in ppm relative VOC values in% A4 - - 228 100 C4 - - 185 81.1 Blend A4 / B3 (3/1 by weight) 1389 100 - - Blend C4 / D3 (3/1 by weight) 797 57.4 - -
  • the results of the measurements show that the leathers treated with the fatliquoring agents (C4, C4 + D3) according to the invention show less fogging and also lower volatile organic compounds (VOC) values than the leathers treated with conventional fatliquoring agents (A4, A4 + B3).
  • VOC volatile organic compounds

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

Abstract

The invention relates to agents for stuffing especially Cr-free tanned leather and skins. Said agents contain A) at least one modified native oil, in addition to B) at least one stabiliser LnR, wherein L represents formula (I) and Ra = H or methyl, Rb = methyl, ethyl or tert-butyl, Rc = methyl, tert-butyl, cyclohexyl or methylcyclohexyl, R represents an n-valent, optionally substituted and/or heteroatom- containing, C3- - C30- hydrocarbon radical, and n is a whole number from 1 10. The stabiliser LnR comprises a total of at least 20 C-atoms, especially a total of at least 28 C-atoms, and in the case where n = 2: R also represents -S-, -0-, - N(H)-, -CH2-, -(CH2)2-, -CH(CH3)-, -(CH2)3 -, -CH(C2H5)- or -C(CH3)2. The invention also relates to the use of the inventive stuffing agents in the production and/or treatment of leather and to a method for producing and/or treating leather with aqueous dispersions of said stuffing agents.

Description

Die vorliegende Erfindung betrifft VOC-arme Fettungsmittel, ihre Verwendung bei der Herstellung und/oder Behandlung von Leder und Häuten sowie Verfahren zur Herstellung und/oder Behandlung von Leder und Häuten mit den erfindungsgemäßen Fettungsmitteln.The present invention relates to low-VOC fatliquoring agents, their use in the manufacture and / or treatment of leather and hides, and to processes for producing and / or treating leather and hides with the fatliquoring agents of the invention.

Fettungsmittel dienen bei der Lederherstellung zur Weichmachung des Leders, zur Steigerung seiner Fülle und Festigkeit und zur Schutzwirkung gegen Nässe, Schmutz, und chemische Einflüsse von außen (siehe H. Herfeld, "Bibliothek des Leders" 1985, Band 4, S. 13 ff .). Handelsübliche Fettungsmittel bestehen in der Regel aus fettenden Substanzen, wie nativen Fetten, nativen Ölen, Wachsen, Harzen und deren Derivaten und/oder Erdölfraktionen und deren Folgeprodukten, und wachsartigen Produkten wie "Wollfett", in roher, gereinigter und/oder zubereiteter (Lanolin) Form (siehe H. Herfeld, "Bibliothek des Leders" 1985, Band 4, S. 59 ff .). Die fettenden Substanzen können - falls gewünscht - chemisch modifiziert sein, d.h. in einer abgewandelten chemischen Struktur vorliegen.Leather fatliquoring agents soften the leather, increase its fullness and firmness, and protect it against moisture, dirt, and chemical influences from the outside (see H. Herfeld, "Library of the Leather" 1985, Volume 4, p. 13 ff .). Commercially available fatliquoring agents generally consist of fatty substances, such as native fats, native oils, waxes, resins and their derivatives and / or petroleum fractions and their derivatives, and waxy products such as "wool fat", in crude, purified and / or prepared (lanolin) Form (see H. Herfeld, "Library of the Leather" 1985, Volume 4, p. 59 ff .). The greasing substances can - if desired - be chemically modified, ie present in a modified chemical structure.

Die chemische Modifizierung der fettenden Substanzen besteht in der Regel darin, daß die in diesen Substanzen enthaltenen Doppelbindungen zumindest teilweise Additionsreaktionen oder Oxidationsreaktionen unterworfen werden. Häufig ausgeführte Modifizierungen bestehen beispielsweise in der Addition von Sulfiten, wodurch Sulfonsäuregruppen in die fettenden Substanzen eingeführt werden, oder in der Luftoxidation, wodurch Sauerstofffunktionen eingeführt werden und teilweise auch Oligomerisationen eintreten. Es sind aber auch (Teil)Hydrolyse der Fette, Umesterungen und dergleichen Modifizierungsreaktionen möglich.The chemical modification of the fatty substances is usually that the double bonds contained in these substances are at least partially subjected to addition reactions or oxidation reactions. Frequently made modifications exist, for example, in the addition of sulfites, whereby sulfonic acid groups are introduced into the fatty substances, or in the air oxidation, whereby oxygen functions are introduced and sometimes also oligomerizations occur. But it is also possible (partial) hydrolysis of the fats, transesterifications and the like modification reactions.

Diese chemischen Modifizierungen ermöglichen es, die anwendungstechnisch relevanten Eigenschaften der fettenden Substanzen wie Hydrophilie, Hydrophobie, Löslichkeit, Dispergiervermögen, Penetrations- und Verankerungseigenschaften, speziellen Einsatzzwecken bzw. den Forderungen der Anwender optimal anzupassen. Insbesondere hochwertige Autopolsterleder müssen bestimmte Kriterien erfüllen. Wesentlich ist einerseits die Weichheit des Leders, andererseits die Echtheit gegenüber Licht und Wärme und schließlich das sogenannte Fogging-Verhalten.These chemical modifications make it possible to optimally adapt the application-relevant properties of the greasing substances such as hydrophilicity, hydrophobicity, solubility, dispersibility, penetration and anchoring properties, special application purposes or the requirements of the user. In particular, high quality car upholstery leather must meet certain criteria. Essential is the one hand the Softness of the leather, on the other hand the authenticity to light and heat and finally the so-called fogging behavior.

Die DIN 75201 definiert "Fogging" als Kondensation von verdampften Bestandteilen aus der Fahrzeuginnenausstattung wie den Autopolsterledem an den Glasscheiben, insbesondere an der Windschutzscheibe. Dies kann zu einer verschlechterten Sicht durch die Windschutzscheibe, insbesondere bei Nachtfahrten, und damit zu einem Sicherheitsrisiko führen. Gemäß der DIN 75201 wird das Fogging-Verhalten von Leder durch ein gravimetrisches und ein reflektometrisches Verfahren charakterisiert.DIN 75201 defines "fogging" as the condensation of vaporized components from the vehicle interior trim such as the car upholstery leather on the glass panes, in particular on the windshield. This can lead to a deteriorated view through the windshield, especially during night driving, and thus to a security risk. According to DIN 75201, the fogging behavior of leather is characterized by a gravimetric and a reflectometric method.

Um das Fogging zu verhindern, ist es daher ein Ziel, den Anteil an organischen Verbindungen zu verringern, die nach der Bearbeitung aus dem behandelten Leder wieder austreten können ("volatile organic compounds"). Der Einsatz von organischen Verbindungen wie Lösungsmitteln läßt sich jedoch manchmal schwer vermeiden. Denn um eine gute Verteilung des Fettungsmittels auf dem Leder sicherzustellen, wird das Fettungsmittel zum Auftragen oft mit Lösungsmittel verdünnt. Aus dem Stand der Technik sind einige Möglichkeiten bekannt, um dieses Problem zu vermeiden.In order to prevent fogging, it is therefore an objective to reduce the proportion of organic compounds that can escape from the treated leather after processing ("volatile organic compounds"). However, the use of organic compounds such as solvents can sometimes be difficult to avoid. Because to ensure a good distribution of the fatliquoring agent on the leather, the fatliquor is often diluted with solvent for application. From the prior art, some ways are known to avoid this problem.

So werden in der EP-A 0 498 634 spezielle Polymere für die Herstellung von Ledern mit sogenannten "low fogging"-Eigenschaften empfohlen. Hierbei sind die in der Lederbehandlung eingesetzten wäßrigen Dispersionen im wesentlichen frei von organischen Lösungsmitteln und enthalten ein amphiphiles Copolymer. Dieses Copolymer besteht aus einem überwiegenden Anteil von mindestens einem hydrophoben Monomeren und einem geringen Anteil von mindestens einem hydrophilen Monomeren. Die Lederbehandlung mit diesen Dispersionen führt bei einem gravimetrischen Test nach DIN 75201 zu guten Resultaten. Reflektometrische Untersuchungen wurden nicht beschrieben.So be in the EP-A 0 498 634 special polymers are recommended for the production of leathers with so-called "low fogging" properties. Here, the aqueous dispersions used in the leather treatment are substantially free of organic solvents and contain an amphiphilic copolymer. This copolymer consists of a predominant proportion of at least one hydrophobic monomer and a small proportion of at least one hydrophilic monomer. The leather treatment with these dispersions leads to good results in a gravimetric test according to DIN 75201. Reflectometric studies were not described.

Die Herstellung dieser amphiphilen Copolymeren erfolgt vorzugsweise durch Emulsionspolymerisation in wäßriger Lösung. Aufgrund der unterschiedlichen Hydrophilie der einzusetzenden Monomeren ergeben sich jedoch naturgemäß Probleme beim Copolymerisationsverhalten. Im Extremfall kann dies dazu führen, dass die Monomere in unerwünschter Weise jeweils für sich Homopolymerisate bilden. Eine weitere Folge der an sich ungünstigen Lösungsverhältnisse ist eine aufwendige Aufarbeitung zur Zerstörung von nicht umgesetzten Monomeren. Zur Erzielung einer guten Emulsionsstabilität ist es außerdem erforderlich, eine ausreichende Menge eines Emulgators (in den angeführten Beispielen wurde Laurylsulfat verwendet) hinzuzufügen, was bei der Lederbearbeitung zu Abwasserproblemen führen kann.The preparation of these amphiphilic copolymers is preferably carried out by emulsion polymerization in aqueous solution. However, due to the different hydrophilicity of the monomers to be used, naturally problems arise in the copolymerization behavior. In extreme cases, this can lead to the monomers undesirably forming homopolymers each by themselves. Another consequence of the unfavorable solution conditions is a complicated work-up for the destruction of unreacted monomers. In order to achieve a good emulsion stability, it is also necessary to use a sufficient amount of an emulsifier (in the cited Examples used was lauryl sulfate), which can lead to sewage problems in leather processing.

In der EP-B 0 466 392 wird ein Verfahren zur Herstellung von Polymeren beschrieben, die sowohl seitenständige hydrophobe Gruppen als auch seitenständige hydrophile alkoxylierte Gruppen enthalten. Solche Polymere werden erhalten, indem nach dem eigentlichen Polymerisationsprozess - dem Fachmann bekannte - Derivatisierungsreaktionen durchgeführt werden. So werden bevorzugt Polymere aus einfachen Monomeren wie Acrylamid und/oder Acrylsäure durch herkömmliche Polymerisation hergestellt und danach mit einer Mischung aus primären bzw. hydrophoben Aminen bzw. primären oder sekundären alkoxylierten Aminen derivatisiert. Die beschriebenen Polymeren werden als Verdickungsmittel und Schmutzlösemittel eingesetzt. Ihr Einsatz in der Lederbehandlung wird nicht beschrieben.In the EP-B 0 466 392 describes a process for the preparation of polymers containing both pendant hydrophobic groups and pendant hydrophilic alkoxylated groups. Such polymers are obtained by carrying out after the actual polymerization process - known in the art - derivatization reactions. Thus, polymers are preferably prepared from simple monomers such as acrylamide and / or acrylic acid by conventional polymerization and then derivatized with a mixture of primary or hydrophobic amines or primary or secondary alkoxylated amines. The described polymers are used as thickeners and soil release agents. Their use in leather treatment is not described.

In den Verfahren gemäß der WO 98/10103 werden polymere Fettungsmittel durch Polymerisation von Acrylsäure und/oder Methacrylsäure und/oder deren Säurechloriden und/oder deren Anhydriden mit weiteren copolymerisierbaren wasserlöslichen Monomeren und mit copolymerisierbaren wasserunlöslichen Monomeren und anschließender Umsetzung der so erhaltenen Polymere mit Aminen hergestellt. Nach DIN 75201 B (gravimetrischer Test) werden für Leder, die mit diesen polymeren Fettungsmitteln behandelt worden sind, Fogging-Werte von 1,2 mg bzw. 1,5 mg gefunden. Die mit den Vergleichsprodukten Magnopal® SOF (foggingarmes Polymerfettungsmittel der Stockhausen GmbH & Co. KG) und Chromopol® LFC (foggingarmes Fettungsmittel auf Basis von Fischölen der Stockhausen GmbH & Co. KG) behandelten Leder erzielen Fogging-Werte von 3,9 mg bzw. 3,5 mg. Die reflektometrischen Werte nach DIN 75201 A der polymeren Fettungsmittel sind 51% bzw. 55%, die der Vergleichsprodukte 34% bzw. 40%.In the method according to the WO 98/10103 Polymeric fatliquoring agents are prepared by polymerization of acrylic acid and / or methacrylic acid and / or their acid chlorides and / or their anhydrides with other copolymerizable water-soluble monomers and with copolymerizable water-insoluble monomers and subsequent reaction of the polymers thus obtained with amines. According to DIN 75201 B (gravimetric test), leathers treated with these polymeric fatliquoring agents have fogging values of 1.2 mg and 1.5 mg, respectively. With the comparative products Magnopal ® SOF (fogging polymer fatliquoring agent Stockhausen GmbH & Co. KG) and Chromopol® ® LFC (low-fogging fatliquors based on fish oils Stockhausen GmbH & Co. KG) treated leather achieve fogging values of 3.9 mg or 3.5 mg. The reflectometric values according to DIN 75201 A of the polymeric fatliquoring agents are 51% and 55% respectively, those of the comparative products 34% and 40%, respectively.

Auch in der US 5,348,807 wird ein Verfahren beschrieben, bei dem ausgewählte amphiphile Copolymere, bestehend aus einem überwiegenden Anteil hydrophober und einem geringeren Anteil hydrophiler Baugruppen, als lösungsmittelfreie fogging-arme Fettungsmittel verwendet werden. Zur Herstellung dieser Polymere werden als hydrophile Monomere sauer oder basisch substituierte Ester ungesättigter Carbonsäuren, wie z.B. Sulfatoethyl(meth)acrylat oder Dimethylaminoethyl(meth)acrylat eingesetzt. Als hydrophobe Monomere dienen beispielsweise längerkettige Alkene oder (Meth)Acrylsäureester von C4- bis C12-Alkanolen oder Vinylester von C4- bis C12-Carbonsäuren. Die Substanzen geben gute Fogging-Werte; es fehlen jedoch Angaben über die Badauszehrung.Also in the US 5,348,807 describes a method in which selected amphiphilic copolymers, consisting of a predominant proportion of hydrophobic and a minor proportion of hydrophilic assemblies, are used as solvent-free low-fogging fatliquoring agents. For the preparation of these polymers acidic or basic substituted esters of unsaturated carboxylic acids, such as sulfatoethyl (meth) acrylate or dimethylaminoethyl (meth) acrylate are used as hydrophilic monomers. Examples of hydrophobic monomers which are used are longer-chain alkenes or (meth) acrylic esters of C 4 -C 12 -alkanols or vinyl esters of C 4 -C 12 -carboxylic acids. The substances give good fogging values; However, there is no information about the Badauszehrung.

Auch bei diesem Verfahren erfolgt die Herstellung der amphiphilen Copolymeren vorzugsweise durch wäßrige Emulsionspolymerisation. Dies führt jedoch aufgrund der unterschiedlichen Hydrophilie der einzusetzenden Monomeren wieder zu den bei der Diskussion der EP-A 0 498 634 bereits erwähnten Problemen.Also in this process, the preparation of the amphiphilic copolymers is preferably carried out by aqueous emulsion polymerization. However, this leads due to the different hydrophilicity of the monomers to be used again in the discussion of the EP-A 0 498 634 already mentioned problems.

In der EP-B 0 753 585 wird eine beschlagsarme Oberflächenbehandlung für Möbelleder beschrieben, bei der speziell behandelte native Öle, die weniger als 3% von Fettsäurekomponenten mit weniger als 16 C-Atomen aufweisen, als Basis für Fettungsmittel fungieren. Verwendete native Öle sind Sojabohnen-, Lard-, Saflor- und Sonnenblumenöl. Die besagten nativen Öle werden zunächst destilliert, um die unerwünschten niedermolekularen Bestandteile zu entfernen und anschließend mit Hydrogensulfit oder Hydrogensulfat umgesetzt, um die Emulgierbarkeit zu verbessern. Dann werden die (teil-)funktionalisierten Öle emulgiert und angewendet.In the EP-B 0 753 585 describes a low-fogging surface treatment for furniture leather, in which specially treated native oils, which have less than 3% of fatty acid components with less than 16 carbon atoms, act as the basis for fatliquors. Native oils used are soybean, lard, safflower and sunflower oils. The said native oils are first distilled to remove the unwanted low molecular weight components and then reacted with hydrogen sulfite or bisulfate to improve emulsifiability. Then the (partially) functionalized oils are emulsified and applied.

Um die Verwendung von organischen Lösungsmitteln zur Verteilung der Fettungsmittel zu vermeiden, wird nach der nicht-vorveröffentlichten DE-A 101 43 949.0 der Anmelderin eine spezielle Emulgatorzusammensetzung eingesetzt, welche drei Komponenten A, B und C umfaßt. Hierbei ist die Komponente A ein mit 4 bis 12 AO-Einheiten alkoxylierter C6 bis C14 Alkanol, oder ein Gemisch mehrerer solcher Alkanole, die Komponente B ein mit 15 bis 40 AO-Einheiten alkoxyliertes C12-C24 Fettalkoholgemisch und die Komponente C ein mit 50 bis 100 AO-Einheiten alkoxyliertes C12 bis C24 Fettalkoholgemisch. Bei den AO-Einheiten handelt es sich zweckmäßigerweise um Alkylenoxidbausteine mit 2 bis 4, vorzugsweise mit 2 bis 3 C-Atomen. Die Bausteine der Polyetherketten können alle gleich oder verschieden sein und - sofern sie verschieden sind - können sie statistisch oder blockweise angeordnet sein. Die Gewichtsanteile der Komponenten in der Emulgatorzusammensetzung betragen für die Komponente A: 20 bis 60, vorzugsweise 25 bis 50, insbesondere 28 bis 40 Gew.-%, für die Komponente B 20 bis 70, vorzugsweise 25 bis 60, insbesondere 30 bis 45 Gew.-% und für die Komponente C 10 bis 50, vorzugsweise 15 bis 40, insbesondere 22 bis 32 Gew.-% vom Gesamtgewicht der Zusammensetzung.In order to avoid the use of organic solvents for the distribution of the fatliquor, is after the non-prepublished DE-A 101 43 949.0 Applicant has used a special emulsifier composition comprising three components A, B and C. In this case, component A is a C 6 to C 14 alkanol alkoxylated with 4 to 12 AO units, or a mixture of several such alkanols, component B is a C 12 -C 24 fatty alcohol mixture alkoxylated with 15 to 40 AO units and component C a C 12 to C 24 fatty alcohol mixture alkoxylated with 50 to 100 AO units. The AO units are expediently alkylene oxide units having 2 to 4, preferably 2 to 3, carbon atoms. The building blocks of the polyether chains can all be identical or different and, if they are different, can be arranged randomly or in blocks. The proportions by weight of the components in the emulsifier composition for component A are from 20 to 60, preferably from 25 to 50, in particular from 28 to 40,% by weight, for component B from 20 to 70, preferably from 25 to 60, in particular from 30 to 45,%. -% and for the component C 10 to 50, preferably 15 to 40, especially 22 to 32 wt .-% of the total weight of the composition.

Aufgabe der vorliegende Erfindung ist es, ein Fettungsmittel bereitzustellen, welches die Nachteile des Standes der Technik weitgehend vermeidet. Die mit diesen Fettungsmitteln behandelten Leder sollen VOC-arm sein und gegebenenfalls eine ausreichende Echtheit gegenüber Licht und Wärme aufweisen.The object of the present invention is to provide a fatliquoring agent which largely avoids the disadvantages of the prior art. The with these fatliquors treated leather should be low in VOC and optionally have sufficient fastness to light and heat.

Die Aufgabe wird erfindungsgemäß gelöst durch ein Fettungsmittel umfassend

  1. A) mindestens ein modifiziertes natives Öl,
    sowie
  2. B) mindestens einen Stabilisator LnR
    wobei L- für
    Figure imgb0001
     steht,
    • mit Ra = H oder Methyl, Rb = Methyl, Ethyl oder tert-Butyl,
    • Rc = Methyl, tert-Butyl, Cyclohexyl oder Methylcyclohexyl,
    • R für einen n-wertigen, gegebenenfalls mit Carbonyl-, Alkylcarbonyloxy-, Alkylcarbamoyl- und/oder Alkoxycarbonyl-Gruppen substituierten und/oder O-, N(H)-und/oder S-Einheiten enthaltenden, gesättigten oder ungesättigten, linearen aliphatischen C3- bis C30-oder verzweigten aliphatischen C4- bis C30- oder (hetero)cycloaliphatischen C4-bis C30- oder (hetero)aromatischen C4- bis C30-Kohlenwasserstoffrest steht,
    • und n eine ganze Zahl von 1 bis 10 ist,
    • wobei der Stabilisator LnR insgesamt mindestens 20 C-Atome, insbesondere insgesamt mindestens 28 C-Atome, aufweist, und
    • im Falle von n = 2: -R- auch für -S-, -O-, -N(H)-, -CH2-, -(CH2)2-, -CH(CH3)-, - (CH2)3-, -CH(C2H5)- oder -C(CH3)2- steht.
The object is achieved according to the invention by a fatliquoring agent
  1. A) at least one modified native oil,
    such as
  2. B) at least one stabilizer L n R
    where L- for
    Figure imgb0001
     stands,
    • with R a = H or methyl, R b = methyl, ethyl or tert- butyl ,
    • R c = methyl, tert- butyl , cyclohexyl or methylcyclohexyl,
    • R is an n-valent, saturated or unsaturated, linear aliphatic C optionally substituted by carbonyl, alkylcarbonyloxy, alkylcarbamoyl and / or alkoxycarbonyl groups and / or containing O, N (H) and / or S units 3 to C 30 or branched aliphatic C 4 to C 30 or (hetero) cycloaliphatic C 4 to C 30 or (hetero) aromatic C 4 to C 30 hydrocarbon radical,
    • and n is an integer from 1 to 10,
    • wherein the stabilizer L n R has a total of at least 20 C atoms, in particular a total of at least 28 C atoms, and
    • in the case of n = 2: -R- also for -S-, -O-, -N (H) -, -CH 2 -, - (CH 2 ) 2 -, -CH (CH 3 ) -, - ( CH 2 ) 3 -, -CH (C 2 H 5 ) - or -C (CH 3 ) 2 - stands.

Unter "(hetero)cycloaliphatischen C4- bis C30-Kohlenwasserstoffresten" versteht man im Rahmen der Erfindung gesättigte, ein- oder mehrfach ungesättigte C4- bis C30-Kohlenwasserstoffringe, in denen gegebenenfalls Methylengruppen -CH2- durch -O-, - N(H)- und/oder -S- ersetzt sind, und die gegebenenfalls ein oder mehrere lineare C1- bis C10-Alkylreste, lineare C1- bis C10-Alkylenbrücken, verzweigte C3- bis C10-Alkylreste und/oder verzweigte C3- bis C10-Alkylenbrücken tragen, die gegebenenfalls ein- oder mehrfach ungesättigt sind. Unter (hetero)cycloaliphatischen C4- bis C30-Kohlenwasserstoffresten werden im Rahmen der Erfindung auch, gegebenenfalls mit einem oder mehreren - gesättigten, ein- oder mehrfach ungesättigten - linearen C1- bis C10-Alkylresten und/oder verzweigten C3- bis C10-Alkylresten substituierte, Lactone und Lactame sowie Harnstoffderivate verstanden. Von dem Begriff sind sowohl mono- als auch polycyclische Ringsysteme, insbesondere bi- und tricyclische Ringsysteme, umfaßt.In the context of the invention, "(hetero) cycloaliphatic C 4 - to C 30 -hydrocarbon radicals" is understood as meaning saturated, mono- or polyunsaturated C 4 - to C 30 -hydrocarbon rings in which, if appropriate, methylene groups -CH 2 - denoted by -O-, - N (H) - and / or -S- are replaced, and optionally one or more linear C 1 - to C 10 alkyl radicals, linear C 1 - to C 10 alkylene bridges, branched C 3 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 -alkylene bridges carry, which are optionally mono- or polyunsaturated. As (hetero) cycloaliphatic C 4 - to C 30 -hydrocarbon radicals are in the scope of the invention, optionally with one or more - saturated, monounsaturated or polyunsaturated - linear C 1 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 alkyl radicals substituted, lactones and lactams and urea derivatives understood. The term includes both mono- and polycyclic ring systems, in particular bicyclic and tricyclic ring systems.

Unter "(hetero)aromatischen C4- bis C30-Kohlenwasserstoffresten" versteht man im Rahmen der Erfindung aromatische C4- bis C30-Ringsysteme, in denen gegebenenfalls ein oder mehrere -C(H)= durch -N= ersetzt sind, und die gegebenenfalls ein oder mehrere lineare C1- bis C10-Alkylreste, lineare C1- bis C10-Alkylenbrücken, verzweigte C3- bis C10-Alkylreste und/oder verzweigte C3- bis C10-Alkylenbrücken tragen und/oder Einheiten wie -O-, -S- und/oder -N(H)- enthalten. Von dem Begriff sind sowohl mono- als auch polycyclische Ringsysteme, insbesondere bi- und tricyclische Ringsysteme, umfaßt. Explizite Beispiele, die jedoch nicht limitierend sein sollen, sind Phenyl, Toluyl, Cumyl, Naphthyl, Phenanthryl, Pyridyl, Indyl, die gegebenenfalls mit einem oder mehreren linearen C1- bis C10-Alkylresten, linearen C1- bis C10-Alkylenbrücken, verzweigten C3- bis C10-Alkylresten und/oder verzweigten C3- bis C10-Alkylenbrücken substituiert sind.In the context of the invention, "(hetero) aromatic C 4 - to C 30 -hydrocarbon radicals" is to be understood as meaning aromatic C 4 - to C 30 -ring systems in which optionally one or more -C (H) = has been replaced by -N =, and which optionally carry one or more linear C 1 - to C 10 -alkyl radicals, linear C 1 - to C 10 -alkylene bridges, branched C 3 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 -alkylene bridges and / or units such as -O-, -S- and / or -N (H) - included. The term includes both mono- and polycyclic ring systems, in particular bicyclic and tricyclic ring systems. Explicit examples, which are not intended to be limiting, however, are phenyl, toluyl, cumyl, naphthyl, phenanthryl, pyridyl, indyl, optionally with one or more linear C 1 - to C 10 -alkyl radicals, linear C 1 - to C 10 -alkylene bridges , branched C 3 - to C 10 -alkyl radicals and / or branched C 3 - to C 10 -alkylene bridges are substituted.

Die erfindungsgemäßen Fettungsmittel sind zur Fettung von Ledern und Häuten besonders geeignet, da die so behandelten Leder und Häute geringes Fogging zeigen. Insbesondere werden die erfindungsgemäßen Fettungsmittel bei Cr-frei gegerbten Ledern und Häuten eingesetzt. Unter "Cr-freier" Gerbung versteht man all die Gerbungsverfahren von Ledern und Häuten, in denen kein Cr(III) zur Gerbung eingesetzt wird. Insbesondere werden darunter dem Fachmann bekannte Verfahren wie die vegetabile Gerbung, die Syntan-Gerbung und die wet-white-Gerbung verstanden. Überraschenderweise wurde gefunden, daß mit den erfindungsgemäßen Fettungsmitteln behandelte Cr-gegerbte Leder (wet blue-Gerbung) besonders gute Echtheiten gegenüber Wärmevergilbung im Vergleich zu Cr-gegerbten Ledern zeigen, die mit herkömmlichen Fettungsmitteln behandelt wurden.The fatliquoring agents according to the invention are particularly suitable for the fatliquoring of leathers and skins, since the leathers and skins treated in this way show low fogging. In particular, the fatliquoring agents of the invention are used in Cr-free tanned leathers and skins. "Cr-free" tanning is understood to mean all the tanning processes of leathers and skins in which no Cr (III) is used for tanning. In particular, it means processes known to the person skilled in the art, such as vegetable tanning, syntan tanning and wet-white tanning. Surprisingly, it has been found that Cr tanned leathers (wet blue tanning) treated with the fatliquoring agents according to the invention show particularly good fastnesses to thermal yellowing in comparison with Cr tanned leathers which have been treated with conventional fatliquoring agents.

Besondere Vorteile ergeben sich, wenn als Komponente A) durch Oxidation und/oder Sulfitierung modifizierte native Öle eingesetzt werden.Particular advantages arise when used as component A) modified by oxidation and / or sulfitation native oils.

Besonders vorteilhaft sind modifizierte native Öle, die einen relativ hohen Oxidationsgrad und einen relativ niedrigen Sulfitierungsgrad aufweisen.Particularly advantageous are modified native oils which have a relatively high degree of oxidation and a relatively low degree of sulfitation.

Als native Öle dienen zweckmäßigerweise Fette pflanzlichen oder tierischen Ursprungs, insbesondere Glyceride natürlicher Fettsäuren, mit einem ausreichenden Anteil ungesättigter Säuren. Gut geeignete native Öle sind solche mit einer Jodzahl von ca. 10 bis ca. 200. Im unteren Abschnitt dieses Bereichs finden sich z.B. Stearin- und Tungöl, im oberen Abschnitt insbesondere die Fischöle und das Chaulmoograöl. Bevorzugt sind native Öle mit Jodzahlen von ca. 30 bis ca. 120, insbesondere von 40 bis 85.Fats of vegetable or animal origin, in particular glycerides of natural fatty acids, with a sufficient proportion of unsaturated acids are expediently used as native oils. Highly suitable native oils are those having an iodine value of about 10 to about 200. In the lower portion of this range, e.g. Stearic and tung oil, in the upper section in particular the fish oils and chaulmoogra oil. Preferred are native oils with iodine numbers of about 30 to about 120, especially from 40 to 85.

Beispiele für besonders bevorzugte native Öle sind Fischöl, Klauenöl, Lardöl, Sojaöl, Rapsöl, Nußöl, Olivenöl und Rizinusöl.Examples of particularly preferred native oils are fish oil, foot oil, lard oil, soybean oil, rapeseed oil, nut oil, olive oil and castor oil.

Die Sulfitierungsprodukte bzw. Oxidationsprodukte der ein- oder mehrfach ungesättigten Fette bilden sich durch die Reaktion der in den Fetten vorhandenen olefinischen Doppelbindungen mit den Sulfitierungs- und/oder Oxidationsreagenzien. Dabei können alle in den Fetten vorhandenen Doppelbindungen oder nur ein Teil derselben in Reaktion treten.The sulfite products or oxidation products of the monounsaturated or polyunsaturated fats are formed by the reaction of the olefinic double bonds present in the fats with the sulfiting and / or oxidation reagents. All double bonds present in the fats or only a part of them can react.

Als Oxidationsreagenz wird beispielsweise Luft bei Temperaturen von 60 bis 80°C eingesetzt. Die Oxidation kann jedoch auch nach anderen dem Fachmann bekannten Verfahren erfolgen. Ein relativ hoher Oxidationsgrad im Sinne dieser Erfmdung liegt vor, wenn Δd, der Unterschied der spezifischen Gewichte des Öls oder Fettes vor und nach der Oxidation, im Bereich von 0,01 bis 0,1 g/ml, vorzugsweise von 0,03 bis 0,05 g/ml, liegt.For example, air at temperatures of 60 to 80 ° C is used as the oxidation reagent. However, the oxidation can also be carried out by other methods known in the art. A relatively high degree of oxidation in the sense of this invention is when Δd, the difference in the specific gravity of the oil or fat before and after the oxidation, in the range of 0.01 to 0.1 g / ml, preferably from 0.03 to 0 , 05 g / ml.

Die Sulfitierung erfolgt im allgemeinen durch Umsetzung in wäßriger Bisulfitlauge. Sie kann jedoch auch nach anderen dem Fachmann bekannten Arten erfolgen. Ein relativ niedriger Sulfitierungsgrad im Sinne dieser Erfindung liegt dann vor, wenn das native Öl mit 2 bis 8 Gew.-%, vorzugsweise mit 3 bis 5 Gew.-%, seines Gewichts mit einem Sulfit, gerechnet als Natriumbisulfit (Na2S2O5), umgesetzt worden ist.The sulfitation is generally carried out by reaction in aqueous bisulfite. However, it can also be done by other species known in the art. A relatively low degree of sulfitation in the context of this invention is present when the native oil with 2 to 8 wt .-%, preferably with 3 to 5 wt .-%, of its weight with a sulfite, calculated as sodium bisulfite (Na 2 S 2 O 5 ) has been implemented.

Als Komponente B) werden Stabilisatoren LnR mit insgesamt mindestens 20 C-Atomen, insbesondere mit insgesamt mindestens 28 C-Atomen, eingesetzt. Bevorzugt steht L- für einen der nachfolgenden Reste:

Figure imgb0002
und/oder n für einen ganze Zahl von 1 bis 4.As component B) stabilizers L n R are used with a total of at least 20 C-atoms, in particular with a total of at least 28 C-atoms. Preferably, L represents one of the following radicals:
Figure imgb0002
 and / or n is an integer from 1 to 4.

Bevorzugte einwertige Reste R sind lineare oder verzweigte gesättigte Alkylreste und mit Alkoxycarbonylgruppen substituierte lineare oder verzweigte Alkylreste -(CmH2m)-C(O)OX1, wobei m eine ganze Zahl von 0 bis 28 ist, und X1 für einen linearen Alkylrest mit 1 bis 28 C-Atomen oder für einen verzweigten Alkylrest mit 3 bis 28 C-Atomen steht.Preferred monovalent radicals R are linear or branched saturated alkyl radicals and alkoxycarbonyl-substituted linear or branched alkyl radicals - (C m H 2m ) -C (O) OX 1 , where m is an integer from 0 to 28, and X 1 is a linear Alkyl radical having 1 to 28 carbon atoms or a branched alkyl radical having 3 to 28 carbon atoms.

Weitere bevorzugte einwertige Reste R sind über lineare C1- bis C4-Alkylenbrücken oder verzweigte C3- bis C4-Alkylenbrücken mit L verbundene, gegebenenfalls mit (un)gesättigten linearen C1- bis C10-Alkanolen oder (un)gesättigten verzweigten C4- bis C10-Alkanolen veretherte oder mit (un)gesättigten linearen C1- bis C10-Carbonsäuren oder (un)gesättigten verzweigten C4- bis C10-Carbonsäuren veresterte, Phenolderivate, die am Phenylring mit einem oder mehreren linearen C1- bis C10- und/oder verzweigten C3- bis C10-Alkylresten und/oder C6- bis C12-Cycloalkylresten substituiert sein können.Further preferred monovalent radicals R are connected via linear C 1 - to C 4 -alkylene bridges or branched C 3 - to C 4 -alkylene bridges connected with L, optionally with (un) saturated linear C 1 - to C 10 -alkanols or (un) saturated branched C 4 - to C 10 -alkanols etherified or esterified with (un) saturated linear C 1 - to C 10 -carboxylic acids or (un) saturated branched C 4 - to C 10 -carboxylic acids, phenol derivatives which am Phenyl ring with one or more linear C 1 - to C 10 - and / or branched C 3 - to C 10 -alkyl radicals and / or C 6 - to C 12 -cycloalkyl radicals may be substituted.

Bevorzugt handelt es sich bei den veretherten oder veresterten Phenolderivaten um die vorstehend als bevorzugt genannten Reste L-, die mit linearen C1- bis C4-Alkylenbrücken oder verzweigten C3- bis C4-Alkylenbrücken substituiert sind, wobei die Hydroxygruppe mit (un)gesättigten linearen C1- bis C10-Alkanolen oder (un)gesättigten verzweigten C4- bis C10-Alkanolen verethert oder mit (un)gesättigten linearen C1- bis C10-Carbonsäuren oder (un)gesättigten verzweigten C4- bis C10-Carbonsäuren verestert ist.The etherified or esterified phenol derivatives are preferably those radicals L- mentioned above which are substituted by linear C 1 - to C 4 -alkylene bridges or branched C 3 - to C 4 -alkylene bridges, where the hydroxy group is substituted by (un ) saturated linear C 1 - to C 10 -alkanols or (un) saturated branched C 4 - to C 10 -alkanols or etherified with (un) saturated linear C 1 - to C 10 -carboxylic acids, or (un) saturated branched C 4 - is esterified to C 10 carboxylic acids.

Ganz besonders bevorzugte einwertige Reste R sind:

  • -(CH2)9H, -CH(CH3)-(CH2)14H, -(CH2)2-C(O)OCH3, -(CH2)2-C(O)OiC8H17, -(CH2)2-C(O)O(CH2)18H, sowie
    Figure imgb0003
Very particularly preferred monovalent radicals R are:
  • - (CH 2 ) 9 H, -CH (CH 3 ) - (CH 2 ) 14 H, - (CH 2 ) 2 -C (O) OCH 3 , - (CH 2 ) 2 -C (O) OiC 8 H 17 , - (CH 2 ) 2 -C (O) O (CH 2 ) 18 H, as well as
    Figure imgb0003

Letzterer Rest R ist als L-R mit L = 3-tert-Butyl-2-hydroxy-5-methyl-phenyl unter dem Handelsnamen Irganox® 3052 der CIBA Spezialitätenchemie AG in Basel kommerziell erhältlich. Die Verbindung L-R mit L = 3,5-Di-tert-butyl-4-hydroxy-phenyl und R = - (CH2)2-C(O)OiC8H17 ist beispielsweise unter dem Handelsnamen Irganox® 1135 der CIBA Spezialitätenchemie AG in Basel kommerziell erhältlich. Die Verbindung L-R mit L = 3,5-Di-tert-butyl-4-hydroxy-phenyl und R = -(CH2)2-C(O)OC18H37 ist unter der Bezeichnung Irganox® 1076 von der CIBA Spezialitätenchemie AG in Basel, unter der Bezeichnung Dovernox® 76 der Chance & Hunt und unter der Bezeichnung Ralox® 530 der Raschig GmbH in Ludwigshafen erhältlich und zusammen mit L-R (mit L = 2-Hydroxy-3,5-dimethyl-phenyl und R = -CH(CH3)C14H29) unter der Bezeichnung Irganox 1141® der CIBA Spezialitätenchemie AG in Basel.The latter radical R is commercially available as LR with L = 3- tert- butyl-2-hydroxy-5-methylphenyl under the trade name Irganox® 3052 from CIBA Spezialitätenchemie AG in Basel. The compound LR with L = 3,5-di- tert- butyl-4-hydroxy-phenyl and R = - (CH 2 ) 2 -C (O) O i C 8 H 17 is, for example, under the trade name Irganox® 1135 of CIBA Specialty Chemicals AG in Basel commercially available. The compound LR with L = 3,5-di- tert- butyl-4-hydroxyphenyl and R = - (CH 2 ) 2 -C (O) OC 18 H 37 is sold under the name Irganox® 1076 by CIBA Spezialitätenchemie AG in Basel, under the name Dovernox® 76 of Chance & Hunt and under the name Ralox® 530 of Raschig GmbH in Ludwigshafen available and together with LR (with L = 2-hydroxy-3,5-dimethyl-phenyl and R = - CH (CH 3 ) C 14 H 29 ) under the designation Irganox 1141® of CIBA Spezialitätenchemie AG in Basel.

Bevorzugte zweiwertige Reste R sind gesättigte, ein- oder mehrfach ungesättigte, lineare C1- bis C18-Alkylengruppen und verzweigte C3- bis C18-Alkylengruppen, die gegebenenfalls in der Kohlenwasserstoffkette der Alkylengruppen Estergruppen -C(O)O- und/oder Amidgruppen -C(O)N(H)- und/oder Hydrazidgruppen -C(O)-N(H)-N(H)-C(O)- enthalten und/oder wobei gegebenenfalls in der Kohlenwasserstoffkette der Alkylengruppen ein oder mehrere Methylengruppen -CH2- durch -S-, -O- oder -N(H)-ersetzt sind. Weitere bevorzugte zweiwertige Reste R sind -S-, -O- und -N(H)-.Preferred divalent radicals R are saturated, mono- or polyunsaturated, linear C 1 - to C 18 -alkylene groups and branched C 3 - to C 18 -alkylene groups, which are optionally substituted in the hydrocarbon chain of the alkylene groups ester groups -C (O) O- and / or amide groups -C (O) N (H) and / or hydrazide groups -C (O) -N (H) -N (H) -C (O) - and / or where appropriate in the hydrocarbon chain of the alkylene groups one or more methylene groups -CH 2 - by -S-, -O- or -N (H) -setzt. Further preferred divalent radicals R are -S-, -O- and -N (H) -.

Besonders bevorzugte zweiwertige Reste R sind:

  • -S-, -O-, -N(H)-, -CH2-, -CH(CH(CH3)2)-, -CH(CH2-CH2-CH3)-,
  • -(CH2)2-C(O)-N(H)-N(H)-C(O)-(CH2)2-,
  • -(CH2)2-C(O)-O-(CH2)6-O-C(O)-(CH2)2-,
  • -(CH2)2-C(O)-N(H)-(CH2)6-N(H)C(O)-(CH2)2-,
  • -(CH2)2-C(O)-(O-CH2-CH2)3-O-C(O)-(CH2)2-, sowie
  • -(CH2)2-C(O)-O-CH2-CH2-S-CH2-CH2-O-C(O)-(CH2)2-.
Particularly preferred divalent radicals R are:
  • -S-, -O-, -N (H) -, -CH 2 -, -CH (CH (CH 3 ) 2 ) -, -CH (CH 2 -CH 2 -CH 3 ) -,
  • - (CH 2 ) 2 -C (O) -N (H) -N (H) -C (O) - (CH 2 ) 2 -,
  • - (CH 2 ) 2 -C (O) -O- (CH 2 ) 6 -OC (O) - (CH 2 ) 2 -,
  • - (CH 2 ) 2 -C (O) -N (H) - (CH 2 ) 6 -N (H) C (O) - (CH 2 ) 2 -,
  • - (CH 2 ) 2 -C (O) - (O-CH 2 -CH 2 ) 3 -OC (O) - (CH 2 ) 2 -, as well as
  • - (CH 2 ) 2 -C (O) -O-CH 2 -CH 2 -S-CH 2 -CH 2 -OC (O) - (CH 2 ) 2 -.

L2R mit L = 3-tert-Butyl-2-hydroxy-5-methyl-phenyl und R = -CH2- ist unter dem Namen Ralox® 46 von der Raschig GmbH Ludwigshafen erhältlich. L2R mit L = 3,5-Di-tert butyl-4-hydroxy-phenyl und R = -CH2- ist unter dem Namen Ralox® 02 S von der Raschig GmbH Ludwigshafen erhältlich. L2R mit L = 3-tert-Butyl-4-hydroxy-3-methylphenyl und R = -(CH2)2-C(O)-(O-CH2-CH2)3-O-C(O)-(CH2)2- ist beispielsweise unter dem Handelsnamen Irganox® 245, L2R mit L = 3,5-Di-tert-butyl-4-hydroxy-phenyl und R = -(CH2)2-C(O)-O-(CH2)6-O-C(O)-(CH2)2- unter dem Handelsnamen Irganox® 259, L2R mit L = 3,5-Di-tert-butyl-4-hydroxy-phenyl und R = -(CH2)2-C(O)-O-CH2-CH2-S-CH2-CH2-O-C(O)-(CH2)2- unter dem Handelsnamen Irganox® 1035, L2R mit L = 3,5-Di-tert-butyl-4-hydroxy-phenyl und R = -(CH2)2-C(O)-N(H)-(CH2)6-N(H)-C(O)-(CH2)2- unter dem Handelsnamen Irganox® 1098 und unter dem Handelsnamen Ralox® 198 der Raschig GmbH in Ludwigshafen und L2R mit L = 3,5-Di-tert-butyl-4-hydroxyphenyl und R = -(CH2)LC(O)-N(H)-N(H)-C(O)-(CH2)2- unter der Bezeichnung Irganox® MD 1024 erhältlich - alle von der CIBA Spezialitätenchemie AG in Basel. Unter dem Handelsnamen Santonox® R ist L2R mit L = 5-tert-Butyl-4-hydroxy-2-methylphenyl und R = -S- und unter der Bezeichnung Santowhite® powder ist L2R mit L = 5-tert-Butyl-4-hydroxy-2-methyl-phenyl und R = -CH(CH2-CH2-CH3)- erhältlich, beide von der Monsanto Company in St. Louis, USA.L 2 R with L = 3- tert- butyl-2-hydroxy-5-methylphenyl and R = -CH 2 - is available under the name Ralox® 46 from Raschig GmbH Ludwigshafen. L 2 R with L = 3,5-di- tert- butyl-4-hydroxy-phenyl and R = -CH 2 - is available under the name Ralox® 02 S from Raschig GmbH Ludwigshafen. L 2 R with L = 3- tert- butyl-4-hydroxy-3-methylphenyl and R = - (CH 2 ) 2 -C (O) - (O-CH 2 -CH 2 ) 3 -OC (O) - (CH 2 ) 2 - is, for example, under the trade name Irganox® 245, L 2 R with L = 3,5-di- tert- butyl-4-hydroxy-phenyl and R = - (CH 2 ) 2 -C (O) -O- (CH 2 ) 6 -OC (O) - (CH 2 ) 2 - under the trade name Irganox® 259, L 2 R with L = 3,5-di- tert- butyl-4-hydroxy-phenyl and R = - (CH 2 ) 2 -C (O) -O-CH 2 -CH 2 -S-CH 2 -CH 2 -OC (O) - (CH 2 ) 2 - under the trade name Irganox® 1035, L 2 R with L = 3,5-di- tert- butyl-4-hydroxyphenyl and R = - (CH 2 ) 2 -C (O) -N (H) - (CH 2 ) 6 -N (H) -C (O) - (CH 2 ) 2 - under the trade name Irganox® 1098 and under the trade name Ralox® 198 of Raschig GmbH in Ludwigshafen and L 2 R with L = 3,5-di- tert- butyl-4-hydroxyphenyl and R = - (CH 2 ) L C (O) -N (H) -N (H) -C (O) - (CH 2 ) 2 - available under the name Irganox® MD 1024 - all from CIBA Spezialitatenchemie AG in Basel , Under the trade name Santonox® R, L 2 R with L = 5- tert -butyl-4-hydroxy-2-methylphenyl and R = -S- and under the name Santowhite® powder is L 2 R with L = 5- tert - Butyl-4-hydroxy-2-methyl-phenyl and R = -CH (CH 2 -CH 2 -CH 3 ) - available, both from the Monsanto Company of St. Louis, USA.

Bevorzugte dreiwertige Reste R sind dreiwertige lineare C3- bis C10- oder verzweigte, (a)cyclische, (un)gesättigte C4- bis C10- oder aromatische C6-C10-Kohlenwasserstoffreste, bei denen drei Protonen jeweils durch den Rest L ersetzt sind. In diesen bevorzugten Kohlenwasserstoffresten sind vorhandene Methylengruppen -CH2- gegebenenfalls durch - N(H)- ersetzt.Preferred trivalent radicals R are trivalent linear C 3 to C 10 or branched, (a) cyclic, (un) saturated C 4 to C 10 or aromatic C 6 to C 10 hydrocarbon radicals in which three protons are in each case represented by the Rest L are replaced. In these preferred Hydrocarbon radicals are existing methylene groups -CH 2 - optionally substituted by - N (H) - replaced.

Hierbei können in den -N(H)- Gruppen die Wasserstoffatome am Stickstoff durch lineare C1- bis C10-Alkylreste und/oder durch verzweigte C3- bis C10-Alkylreste und/oder durch C6- bis C12-Cycloalkylreste ersetzt sein. Die Anbindung des Restes L kann auch über lineare C1- bis C10-Alkylenbrücken oder verzweigte C3- bis C10-Alkylenbrücken an ein derartiges Stickstoffatom erfolgen. Auch in diesen Alkylenbrücken können Methylengruppen -CH2- durch -O-, -N(H)- oder -S- ersetzt sein.Here, in the -N (H) - groups, the hydrogen atoms on the nitrogen by linear C 1 - to C 10 -alkyl radicals and / or by branched C 3 - to C 10 -alkyl radicals and / or by C 6 - to C 12 -cycloalkyl radicals be replaced. The attachment of the radical L can also take place via linear C 1 - to C 10 -alkylene bridges or branched C 3 - to C 10 -alkylene bridges to such a nitrogen atom. Also in these alkylene bridges, methylene groups -CH 2 - may be replaced by -O-, -N (H) - or -S-.

Besonders bevorzugte dreiwertige Reste R sind ausgewählt aus der folgenden Gruppe:

Figure imgb0004
Particularly preferred trivalent radicals R are selected from the following group:
Figure imgb0004

L3R mit L = 5-tert-Butyl-4-hydroxy-2-methyl-phenyl und R = 1,1,3-Butantriyl ist beispielsweise unter dem Handelsnamen Topanol CA der Chance & Hunt erhältlich, L3R mit L = 3,5-Di-tert-Butyl-4-hydroxy-phenyl und R = X unter den Handelsnamen Irganox® 1330 der CIBA Spezialitätenchemie AG in Basel und Ethanox® 330 der Albemarle Corporation, L3R mit L = 3,5-Di-tert-Butyl-4-hydroxy-phenyl und R = Y unter der Bezeichnung Irganox® 3114 der CIBA Spezialitätenchemie AG in Basel und unter der Bezeichnung Ralox® 3114 der Raschig GmbH in Ludwigshafen und L3R mit L = 4-tert-Butyl-3-hydroxy-2,6-dimethyl-phenyl und R = Y unter dem Handelsnamen Cyanox® 1790 der Cytec.L 3 R with L = 5- tert -butyl-4-hydroxy-2-methylphenyl and R = 1,1,3-butanetriyl is available, for example, under the trade name Topanol CA from Chance & Hunt, L 3 R where L = 3,5-di- tert- butyl-4-hydroxy-phenyl and R = X under the trade names Irganox® 1330 from CIBA Specialty Chemicals AG in Basel and Ethanox® 330 from Albemarle Corporation, L 3 R with L = 3,5-di tert -Butyl-4-hydroxy-phenyl and R = Y under the name Irganox® 3114 from CIBA Spezialitätenchemie AG in Basel and under the name Ralox® 3114 from Raschig GmbH in Ludwigshafen and L 3 R with L = 4- tert- butyl -3-hydroxy-2,6-dimethyl phenyl- and R = Y under the trade name Cyanox® 1790 from Cytec.

Bevorzugte R sind vierwertige, mit Alkylcarbonyloxy-Gruppen substituierte und/oder O- und/oder N(H)-Einheiten enthaltende, gesättigte lineare C3- bis C20- oder verzweigte aliphatische C4- bis C20-Kohlenwasserstoffreste, in denen vier Protonen durch die Reste L ersetzt sind.Preferred R are tetravalent, substituted with alkylcarbonyloxy groups and / or O and / or N (H) units, saturated linear C 3 - to C 20 - or branched aliphatic C 4 - to C 20 hydrocarbon radicals, in which four Protons are replaced by the radicals L.

Ein Beispiel für besonders bevorzugte R ist C(CH2-O-C(O)-CH2-CH2-)4. Letzterer Rest R ist als L-R mit L = 3,5-Di-tert-butyl-4-hydroxy-phenyl beispielsweise unter dem Handelsnamen Irganox® 1010 der CIBA Spezialitätenchemie AG in Basel, unter dem Namen Ralox® 630 der Raschig GmbH in Ludwigshafen und unter der Bezeichnung Ethanox® 310 der Albemarle Corporation kommerziell erhältlich.An example of particularly preferred R is C (CH 2 -OC (O) -CH 2 -CH 2 -) 4 . The latter radical R is as LR with L = 3,5-di- tert- butyl-4-hydroxy-phenyl, for example under the trade name Irganox® 1010 CIBA Specialty Chemicals in Basel, under the name Ralox® 630 Raschig GmbH in Ludwigshafen and commercially available under the name Ethanox® 310 from Albemarle Corporation.

Bevorzugt enthalten die erfindungsgemäßen Fettungsmittel mindestens 40 Gew.-%, besonders bevorzugt mindestens 50 Gew.-%, ganz besonders bevorzugt mindestens 70 Gew.-%, einer Komponente A oder einer Mischung der Komponenten A und höchstens 1 Gew.-%, besonders bevorzugt höchstens 0,5 Gew.-%, ganz besonders bevorzugt höchstens 0,2 Gew.-%, einer Komponente B oder einer Mischung der Komponenten B, bezogen auf das Gesamtgewicht des Fettungsmittels.The fatliquoring agents according to the invention preferably contain at least 40% by weight, more preferably at least 50% by weight, very preferably at least 70% by weight, of a component A or of a mixture of components A and at most 1% by weight, more preferably at most 0.5 wt .-%, most preferably at most 0.2 wt .-%, of a component B or a mixture of components B, based on the total weight of the fatliquoring agent.

Die erfindungsgemäßen Fettungsmittel können unverdünnt oder je nach den Wünschen der Anwender in Form wäßriger Dispersionen (wäßriger Flotten), zweckmäßigerweise mit Feststoffgehalten von 40 bis 80 Gew.-%, bevorzugt mit Feststoffgehalten von 50 bis 80 Gew.-%, besonders bevorzugt mit Feststoffgehalten von 60 bis 75 Gew.-% bereitgestellt werden.The fatliquoring agents according to the invention can be used undiluted or, depending on the wishes of the users, in the form of aqueous dispersions (aqueous liquors), preferably with solids contents of 40 to 80% by weight, preferably with solids contents of 50 to 80% by weight, particularly preferably with solids contents of 60 to 75 wt .-% are provided.

Die Komponenten der bevorzugten erfindungsgemäßen Fettungsmittel, nämlich die erfindungsgemäßen mofizierten nativen Öle und die erfindungsgemäßen Stabilisatoren, können den Fettungsflotten zusammen oder in beliebiger Reihenfolge getrennt zugefügt werden. Die Erfindung betrifft somit auch ein Verfahren zur Fettung von Leder und Häuten durch Behandlung mit den vorstehend genannten wäßrigen Flotten.The components of the preferred fatliquoring agents according to the invention, namely the moficated native oils according to the invention and the stabilizers according to the invention, can be added to the fatliquoring liquors together or separately in any order. The invention thus also relates to a process for the fatliquoring of leather and hides by treatment with the abovementioned aqueous liquors.

Die Erfindung betrifft ferner die Verwendung der beschriebenen erfindungsgemäßen Fettungsmittel bei der Lederherstellung. Deren Verwendung dient zur Weichmachung des Leders, zur Steigerung seiner Fülle und Festigkeit und zur Schutzwirkung gegen Nässe, Schmutz, und chemische Einflüsse von außen.The invention further relates to the use of the described fatliquoring agent according to the invention in leather production. Their use serves to soften the Leather, to increase its fullness and strength and to protect against moisture, dirt, and chemical influences from the outside.

Die Anwesenheit der erfindungsgemäßen Stabilisatoren führt zu niedrigen Fogging-Werten.The presence of the stabilizers according to the invention leads to low fogging values.

Die folgenden Ausführungsbeispiele veranschaulichen die Erfindung.The following embodiments illustrate the invention.

Ausführungsbeispieleembodiments

Die Zusammensetzung der eingesetzten herkömmlichen Fettungsmittel A1 bis A5 und B1 bis B5, sowie der eingesetzten erfindungsgemäßen Fettungsmittel C1 bis C5 und D1 bis D5 ist den Tabellen 1 und 3 zu entnehmen. Der Anteil der einzelnen Komponenten ist in Gew.-%, bezogen auf das gesamte Fettungsmittel, angegeben und den Tabellen 2 und 4 zu entnehmen. Das nicht-ionische Tensid Lutensol® AT 25 der BASF AG in Ludwigshafen ist ein G16- bis C18-Fettalkoholgemisch, welches mit 25 mol Ethylenoxid ethoxyliert wurde. Irganox® 1076 der CIBA Spezialitätenchemie AG in Basel ist LnR mit n = 1, L = 4-Hydroxy-3,5-di-tert-butyl-1-phenyl und R = -(CH2)2-C(O)O(CH2)18H. Acetyliertes Lecithin ist von der Compte & Rivera S. A. in Spanien erhältlich. Bei dem Triolein handelt es sich um natives Ölsäuretriglycerid der Smit & Zoon. Ebotec MO (4-Octylisothiazolinon) ist ein Biozid der Bode Chemie in Hamburg. Tabelle 1: Zusammensetzung der Fettungsmittel A1 bis A5 und C1 bis C5 Fettungsmittel A1 bis A5 (herkömmlich) Fettungsmittel C1 bis C5 (erfindungsgemäß) Komponente 1 90 Gew.-%ige wäßrige Lösung eines Gemisches aus Fischöl und Rapsöl 40:60 (Ölgemisch luftoxidiert bis Δd = 0,01 bis 0,1 g/ml und umgesetzt mit 4 Gew.-% Na2S2O5 - bezogen auf Ölgemisch) 90 Gew.-%ige wäßrige Lösung eines Gemisches aus Fischöl und Rapsöl 40:60 (Ölgemisch luftoxidiert bis Δd = 0,01 bis 0,1 g/ml und umgesetzt mit 4 Gew.-% Na2S2O5 - bezogen auf Ölgemisch) Komponente 2 50 Gew.-%-ige wäßrige NaOH-Lösung 50 Gew.-%-ige wäßrige NaOH-Lösung Komponente 3 Umsetzungsprodukt von Maleinsäureanhydrid mit Alkoholen und anschließender Sulfitierung und Umsetzung mit NH3 oder Amin Umsetzungsprodukt von Maleinsäureanhydrid mit Alkoholen und anschließender Sulfitierung und Umsetzung mit NH3 oder Amin Komponente 4 Lutensol® AT 25 Lutensol® AT 25 Komponente 5 3,5-Di-tert-Butyl-4-hydroxy-toluol Irganox® 1076 Tabelle 2: Mengenverhältnisse der einzelnen Komponenten in den Fettungsmitteln A1 bis A5 und C1 bis C5 Fettungsmittel A1 A2 A3 A4 A5 C1 C2 C3 C4 C5 Komponente 1 68,5 74,5 80,5 86,5 92,5 68,5 74,5 80,5 86,5 92,5 Komponente 2 2,0 2,0 2,0 2,0 2,0 2,0 2,0 2,0 2,0 2,0 Komponente 3 24,0 18,0 12,0 6,0 - 24,0 18,0 12,0 6,0 - Komponente 4 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 5,0 Komponente 5 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5 Tabelle 3: Zusammensetzung der Fettungsmittel B1 bis B5 und D1 bis D5 Fettungsmittel B1 bis B5 (herkömmlich) Fettungsmittel D1 bis D5 (erfindungsgemäß) Komponente 1 acetyliertes Lecithin acetyliertes Lecithin Komponente 2 50 Gew.-%-ige wäßrige NaOH-Lösung 50 Gew.-%-ige wäßrige NaOH-Lösung Komponente 3 Triolein Rapsöl (luftoxidiert bis Δd = 0,01 bis 0,1 g/ml und umgesetzt mit 4 Gew.-% Na2S2O5 - bezogen auf Öl) Komponente 4 Hexylenglycol Hexylenglycol Komponente 5 Wasser Wasser Komponente 6 Ebotec MO Ebotec MO Komponente 7 3,5-Di-tert-Butyl-4-hydroxy-toluol Irganox® 1076 Tabelle 4: Mengenverhältnisse der einzelnen Komponenten in den Fettungsmitteln B1 bis B5 und D1 bis D5 Fettungsmittel B1 B2 B3 B4 B5 D1 D2 D3 D4 D5 Komponente 1 63,0 68,0 73,0 78,0 83,0 63,0 68,0 73,0 78,0 83,0 Komponente 2 1,5 1,5 1,5 1,5 1,5 1,5 1,5 1,5 1,5 1,5 Komponente 3 26,0 21,0 16,0 11,0 6,0 26,0 21,0 16,0 11,0 6,0 Komponente 4 4,8 4,8 4,8 4,8 4,8 4,8 4,8 4,8 4,8 4,8 Komponente 5 4,1 4,1 4,1 4,1 4,1 4,1 4,1 4,1 4,1 4,1 Komponente 6 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 0,15 Komponente 7 0,7 0,7 0,7 0,7 0,7 0,7 0,7 0,7 0,7 0,7 The composition of the conventional fatliquoring agents A1 to A5 and B1 to B5 used and the fatliquoring agents C1 to C5 and D1 to D5 used according to the invention are shown in Tables 1 and 3. The proportion of the individual components is given in% by weight, based on the total fatliquoring agent, and can be found in Tables 2 and 4. The non-ionic surfactant Lutensol® AT 25 from BASF AG in Ludwigshafen is a G 16 to C 18 fatty alcohol mixture which has been ethoxylated with 25 mol of ethylene oxide. Irganox® 1076 from CIBA Spezialitätenchemie AG in Basel is L n R where n = 1, L = 4-hydroxy-3,5-di-tert-butyl-1-phenyl and R = - (CH 2 ) 2 -C (O ) O (CH 2 ) 18 H. Acetylated lecithin is available from Compte & Rivera SA in Spain. The triolein is native oleic acid triglyceride from Smit & Zoon. Ebotec MO (4-octylisothiazolinone) is a biocide of Bode Chemie in Hamburg. <u> Table 1: </ u> Composition of fatliquoring agents A1 to A5 and C1 to C5 Fatliquoring agent A1 to A5 (conventional) Fatliquoring agent C1 to C5 (according to the invention) Component 1 90 wt .-% aqueous solution of a mixture of fish oil and rapeseed oil 40:60 (oil mixture air-oxidized to Δd = 0.01 to 0.1 g / ml and reacted with 4 wt .-% Na 2 S 2 O 5 - based on oil mixture) 90 wt .-% aqueous solution of a mixture of fish oil and rapeseed oil 40:60 (oil mixture air-oxidized to Δd = 0.01 to 0.1 g / ml and reacted with 4 wt .-% Na 2 S 2 O 5 - based on oil mixture) Component 2 50 wt .-% - aqueous NaOH solution 50 wt .-% - aqueous NaOH solution Component 3 Reaction product of maleic anhydride with alcohols and subsequent sulfitation and reaction with NH 3 or amine Reaction product of maleic anhydride with alcohols and subsequent sulfitation and reaction with NH 3 or amine Component 4 Lutensol® AT 25 Lutensol® AT 25 Component 5 3,5-di-tert-butyl-4-hydroxy-toluene Irganox® 1076 fatliquors A1 A2 A3 A4 A5 C1 C2 C3 C4 C5 Component 1 68.5 74.5 80.5 86.5 92.5 68.5 74.5 80.5 86.5 92.5 Component 2 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Component 3 24.0 18.0 12.0 6.0 - 24.0 18.0 12.0 6.0 - Component 4 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Component 5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Fatliquoring agent B1 to B5 (conventional) Fatliquoring agent D1 to D5 (according to the invention) Component 1 acetylated lecithin acetylated lecithin Component 2 50 wt .-% - aqueous NaOH solution 50 wt .-% - aqueous NaOH solution Component 3 triolein Rapeseed oil (air-oxidised to Δd = 0.01 to 0.1 g / ml and reacted with 4 wt.% Na 2 S 2 O 5 - based on oil) Component 4 hexylene hexylene Component 5 water water Component 6 Ebotec MO Ebotec MO Component 7 3,5-di-tert-butyl-4-hydroxy-toluene Irganox® 1076 fatliquors B1 B2 B3 B4 B5 D1 D2 D3 D4 D5 Component 1 63.0 68.0 73.0 78.0 83.0 63.0 68.0 73.0 78.0 83.0 Component 2 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Component 3 26.0 21.0 16.0 11.0 6.0 26.0 21.0 16.0 11.0 6.0 Component 4 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 4.8 Component 5 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1 Component 6 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Component 7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7

Beispiel 1 Behandlung von Cr-gegerbtem Leder mit herkömmlichen Fettungsmitteln (A1 bis A5, B1 bis B5) und erfindungsgemäßen Fettungsmitteln (C1 bis C5, D1 bis D5)Example 1 Treatment of Cr-tanned leather with conventional fatliquoring agents (A1 to A5, B1 to B5) and fatliquoring agents (C1 to C5, D1 to D5) according to the invention

100 Gewichtsteile Chromrindleder der Falzstärke 2,0 bis 2,2 mm werden in 100 Gewichtsteilen Wasser von 40°C eingelegt und durch Zusatz von Natriumformiat und Natriumhydrogencarbonat auf einen pH-Wert von 4,5 eingestellt. Das Leder wird bei 40°C 60 Minuten im Fass gewalkt und dann mit 200 Gewichtsteilen Wasser gewaschen.100 parts by weight of chrome cattle leather with a thickness of 2.0 to 2.2 mm are placed in 100 parts by weight of water at 40 ° C. and adjusted to a pH of 4.5 by addition of sodium formate and sodium bicarbonate. The leather is tumbled at 40 ° C for 60 minutes in the barrel and then washed with 200 parts by weight of water.

Danach werden 100 Gewichtsteile Wasser von 40°C und 2 Gewichtsteile handelsüblicher Polymergerbstoff, 4 Gewichtsteile handelsüblicher Harzgerbstoff und 4 Gewichtsteile handelsübliche Mimosa zugesetzt. Man walkt 90 Minuten, und färbt dann das Leder in der gleichen Flotte mit 1 Gewichtsteil eines handelsüblichen Lederfarbstoffs. Dann wird die Flotte abgelassen und dem Leder 100 Gewichtsteile Wasser und entweder 4 Gewichtsteile eines handelsüblichen Fettungsmittels (A1 bis A5, B1 bis B5) oder 4 Gewichtsteile eines erfindungsgemäßen Fettungsmittels (C1 bis C5, D1 bis D5) der in den Tabellen 1 bis 4 angegebenen Zusammensetzung zugefügt, und das Leder wie üblich 60 Minuten bei 50°C in dieser Flotte gewalkt.Thereafter, 100 parts by weight of water of 40 ° C and 2 parts by weight of commercially available polymer tanning agent, 4 parts by weight of commercially available resin tanning agent and 4 parts by weight of commercial Mimosa added. It is 90 minutes, and then dyed the leather in the same liquor with 1 part by weight of a commercial leather dye. Then, the liquor is drained and the leather 100 parts by weight of water and either 4 parts by weight of a commercial fatliquoring agent (A1 to A5, B1 to B5) or 4 parts by weight of a fatliquoring agent (C1 to C5, D1 to D5) according to the invention indicated in Tables 1 to 4 Composition added, and the leather as usual for 60 minutes at 50 ° C in this liquor drummed.

Danach wird die Flotte mit Ameisensäure auf einen pH-Wert von 3,5 bis 3,8 eingestellt, das Leder kurz kalt gespült und wie allgemein üblich weiter bearbeitet.Thereafter, the liquor is adjusted with formic acid to a pH of 3.5 to 3.8, the leather briefly rinsed cold and further processed as usual.

Man erhält ein Leder mit sehr guter Färbung, guter Festnarbigkeit, bei gleichzeitig guter Fülle und mittlerer Weichheit. Die Lederoberfläche besitzt einen schmalzigen Griff.This gives a leather with very good color, good grain tightness, at the same time good body and medium softness. The leather surface has a lardy handle.

Beispiel 2 Behandlung von Cr-frei gegerbtem Leder mit herkömmlichen Fettungsmitteln (A1 bis A5, B1 bis B5) und erfindungsgemäßen Fettungsmitteln (C1 bis C5, D1 bis D5)Example 2 Treatment of Cr-Free Tanned Leather with Conventional Fatliquoring Agents (A1 to A5, B1 to B5) and Fatliquoring Agents of the Invention (C1 to C5, D1 to D5)

100 Gewichtsteile "wet white"-Rindleder der Falzstärke 2,0 bis 2,2 mm werden in 100 Gewichtsteilen Wasser eingelegt und durch Zusatz von Natriumformiat und Natriumhydrogencarbonat auf einen pH-Wert von < 3,0 eingestellt. Das Leder wird bei 30°C 60 Minuten im Fass gewalkt und dann mit 200 Gewichtsteilen Wasser gewaschen.100 parts by weight of "wet white" cowhide with a thickness of 2.0 to 2.2 mm are placed in 100 parts by weight of water and adjusted to a pH of <3.0 by addition of sodium formate and sodium bicarbonate. The leather is tumbled at 30 ° C for 60 minutes in the barrel and then washed with 200 parts by weight of water.

Danach wurde mit 4 Gewichtsteilen eines Gerbstoffs wie Relugan® GTP der BASF AG in Ludwigshafen 60 Minuten gewalkt. Nach Zugabe von 2 Gewichtsteilen eines Hilfsgerbstoffs wie Tamol® NA der BASF AG in Ludwigshafen und 30-minütigem Walken wurden 4 Gewichtsteile eines herkömmlichen Fettungsmittels (A1 bis A5, B1 bis B5) oder 4 Gewichtsteile eines erfindungsgemäßen Fettungsmittels (C1 bis C5, D1 bis D5) zugegeben und weitere 60 Minuten gewalkt. Nach Ablassen der Flotte gab man 100 Gewichtsteile Wasser von 40°C und 2 Gewichtsteile handelsüblichen Polymergerbstoff wie Relugan® SE (Polymethacrylsäure) der BASF AG in Ludwigshafen hinzu. Nach Neutralisation mit Natriumhydrogencarbonat auf pH 5 und Färbung des Leders in der gleichen Flotte mit 0,5 Gewichtsteilen eines handelsüblichen Lederfarbstoffs, beispielsweise Luganil® Light Brown NGB der BASF AG in Ludwigshafen, wurde mit 30 Gewichtsteilen handelsüblichem Sulfongerbstoff, beispielsweise Basyntan® SW flüssig der BASF AG in Ludwigshafen, und 4 Gewichtsteilen handelsübliche Vegetabilgerbstoff wie Granofin TA der Clariant GmbH (Deutschland) 2 Stunden ausgegerbt.Thereafter, 4 parts by weight of a tanning agent such as Relugan® GTP from BASF AG in Ludwigshafen were drummed for 60 minutes. After addition of 2 parts by weight of an auxiliary tanning agent such as Tamol® NA BASF AG in Ludwigshafen and 30 minutes Walken 4 parts by weight of a conventional fatliquoring agent (A1 to A5, B1 to B5) or 4 parts by weight of a fatliquoring agent of the invention (C1 to C5, D1 to D5 ) was added and drummed for a further 60 minutes. After draining the liquor, 100 parts by weight of water at 40 ° C. and 2 parts by weight of commercial polymer tanning agent such as Relugan® SE (polymethacrylic acid) from BASF AG in Ludwigshafen were added. After neutralization with sodium bicarbonate to pH 5 and dyeing of the leather in the same liquor with 0.5 part by weight of a commercially available leather dye, for example Luganil® Light Brown NGB from BASF AG in Ludwigshafen, 30 parts by weight of commercially available sulfone tanning agent, for example Basyntan® SW flüssig, BASF AG in Ludwigshafen, and 4 parts by weight of commercial vegetable tanning agent, such as Granofin TA from Clariant GmbH (Germany), aged 2 hours.

Anschließend wurde mit einem Gemisch aus 10 bis 15 Gewichtsteilen eines handelsüblichen Fettungsmittels (A1 bis A5, B1 bis B5) oder 10 bis 15 Gewichtsteilen eines erfindungsgemäßen Fettungsmittels (C1 bis C5, D1 bis D5) gefettet. Danach wurde die Flotte mit Ameisensäure auf einen pH-Wert von 3,5 bis 3,8 eingestellt, das Leder kurz kalt gespült und wie allgemein üblich weiter bearbeitet.Subsequently, greasing with a mixture of 10 to 15 parts by weight of a commercial fatliquoring agent (A1 to A5, B1 to B5) or 10 to 15 parts by weight of a fatliquoring agent (C1 to C5, D1 to D5) according to the invention. Thereafter, the liquor was adjusted to a pH of 3.5 to 3.8 with formic acid, the leather briefly rinsed cold and further processed as usual.

Man erhielt ein Leder mit sehr guter Färbung, guter Festnarbigkeit bei gleichzeitig sehr guter Fülle und exzellenter Weichheit mit elegantem Griff.The result was a leather with very good color, good grain tightness at the same time very good body and excellent softness with an elegant feel.

Bestimmung der Echtheiten gegenüber Wärmevergilbung der mit herkömmlichen Fettungsmitteln (A4, B3) und erfindungsgemäßen Fettungsmitteln (C4, D3) behandelten Cr-gegerbten (wet blue-gegerbten) LederDetermination of fastness to heat yellowing of the Cr-tanned (wet blue-tanned) leather treated with conventional fatliquoring agents (A4, B3) and fatliquoring agents (C4, D3) according to the invention

An den nach Abschluß der Fettung mit den Fettungsmitteln A4, B3, C4 oder D3 gemäß Beispiel 1 erhaltenen wet blue-gegerbten Ledern werden gemäß DIN EN 20 105-A02 die Echtheiten gegenüber Wärmevergilbung in Abhängigkeit von der Temperatur bestimmt. Die Leder wurden hier 144 h nach Lagerung bei 100°C bzw. alternativ 4 h nach Lagerung bei 120°C untersucht. Die Meßergebnisse sind Tabelle 5 zu entnehmen. Tabelle 5: Nach DIN EN 20 105-A02 bestimmte Echtheiten gegenüber Wärmevergilbung Fettungsmittel DE - -100°C Db -100°C DE - -120°C Db - 120°C A4 (herkömmlich) 6,76 5,39 9,20 7,88 C4 (erfindungsgemäß) 5,89 3,75 7,10 3,35 B3 (herkömmlich) 8,01 7,31 10,38 9,76 D3 (erfindungsgemäß) 6,97 6,40 9,09 8,16 According to DIN EN 20 105-A02, the fastnesses to thermal yellowing as a function of the temperature are determined on the wet blue-tanned leathers obtained after completion of the fatliquoring with the fatliquoring agents A4, B3, C4 or D3 according to Example 1. The leathers were tested here 144 h after storage at 100 ° C or alternatively 4 h after storage at 120 ° C. The measurement results are shown in Table 5. <u> Table 5: </ u> In accordance with DIN EN 20 105-A02 certain fastness to heat yellowing fatliquors DE - -100 ° C Db -100 ° C DE - -120 ° C Db - 120 ° C A4 (conventional) 6.76 5.39 9.20 7.88 C4 (according to the invention) 5.89 3.75 7.10 3.35 B3 (conventional) 8.01 7.31 10.38 9.76 D3 (according to the invention) 6.97 6.40 9.09 8.16

Db sind die Werte für die Wärmevergilbung, DE ist ein Maß für die Grauwerte. Je niedriger der Zahlenwert ist, desto besser ist die Lichtbeständigkeit.Db are the values for heat yellowing, DE is a measure of the gray values. The lower the numerical value, the better the light resistance.

Es zeigte sich, daß die mit den erfmdungsgemäßen Fettungsmitteln (C4, D3) behandelten Leder im Vergleich zu den mit herkömmlichen Fettungsmitteln (A4, B3) behandelten Leder bessere Echtheiten gegenüber Wärmevergilbung aufweisen.It was found that the leathers treated with the inventive fatliquoring agents (C4, D3) have better fastness to heat yellowing than the leathers treated with conventional fatliquoring agents (A4, B3).

Bestimmung der VOC- bzw. Fogging-Werte der mit herkömmlichen Fettungsmitteln (A4, B3) und erfindungsgemäßen Fettungsmitteln (C4, D3) behandelten LederDetermination of the VOC or fogging values of the leather treated with conventional fatliquoring agents (A4, B3) and fatliquoring agents (C4, D3) according to the invention

An den nach Abschluß der Fettung mit den Fettungsmitteln A4, B3, C4 oder D3 gemäß Beispiel 2 (wet white-Gerbung) erhaltenen Ledern werden gemäß DIN 75201 (Tabelle 6) und PB VWL 709 (Tabelle 7) die VOC- bzw. Fogging-Werte bestimmt. Tabelle 6: Nach DIN 75201 (gravimetrisch) bestimmte Fogging-Werte Fettungsmittel absolute Fogging-Werte in mg relative Fogging-Werte in % A4 (herkömmlich) 2,80 100 C4 (erfindungsgemäß) 2,00 71,4 B3 (herkömmlich) 3,35 100 D3 (erfindungsgemäß) 2,80 83,6 The leathers obtained after completion of the fatliquoring with the fatliquoring agents A4, B3, C4 or D3 according to Example 2 (wet white tanning) according to DIN 75201 (Table 6) and PB VWL 709 (Table 7), the VOC or fogging Values determined. <u> Table 6: </ u> According to DIN 75201 (gravimetric) certain fogging values fatliquors absolute fogging values in mg relative fogging values in% A4 (conventional) 2.80 100 C4 (according to the invention) 2.00 71.4 B3 (conventional) 3.35 100 D3 (according to the invention) 2.80 83.6

Die mit den erfindungsgemäßen Fettungsmitteln (C4, D3) behandelten Leder weisen niedrigere Fogging-Werte als die mit herkömmlichen Fettungsmitteln (A4, B3) behandelten Leder auf. Tabelle 7: Nach PB VWL 709 (Daimler Chrysler) bestimmte VOC- und Fogging-Werte Fettungsmittel absolute Fogging-Werte in ppm relative Fogging-Werte in % absolute VOC-Werte in ppm relative VOC-Werte in % A4 - - 228 100 C4 - - 185 81,1 Mischung A4/B3 (3/1- bezogen auf das Gewicht) 1389 100 - - Mischung C4/D3 (3/1- bezogen auf das Gewicht) 797 57,4 - - The leathers treated with the fatliquoring agents (C4, D3) according to the invention have lower fogging values than the leathers treated with conventional fatliquoring agents (A4, B3). <u> Table 7: According to PB VWL 709 (Daimler Chrysler) certain VOC and fogging values </ u> fatliquors absolute fogging values in ppm relative fogging values in% absolute VOC values in ppm relative VOC values in% A4 - - 228 100 C4 - - 185 81.1 Blend A4 / B3 (3/1 by weight) 1389 100 - - Blend C4 / D3 (3/1 by weight) 797 57.4 - -

Die Meßergebnisse zeigen, daß die mit den erfindungsgemäßen Fettungsmitteln (C4, C4 + D3) behandelten Leder geringeres Fogging und auch geringere VOC-Werte (VOC = volatile organic compounds) zeigen als die mit herkömmlichen Fettungsmitteln (A4, A4 + B3) behandelten Leder.The results of the measurements show that the leathers treated with the fatliquoring agents (C4, C4 + D3) according to the invention show less fogging and also lower volatile organic compounds (VOC) values than the leathers treated with conventional fatliquoring agents (A4, A4 + B3).

Claims (9)

  1. A fatliquoring agent for the production and/or treatment of leather and hides comprising
    A) at least one modified natural oil
    and
    B) at least one stabilizer LnR
    in which L- is
    Figure imgb0008
    Ra is H or methyl, Rb is methyl, ethyl or tert-butyl,
    Rc is methyl, tert-butyl, cyclohexyl or methylcyclohexyl,
    R is an n-valent, saturated or unsaturated, linear aliphatic C3- to C30- or branched aliphatic C4- to C30- or (hetero)cycloaliphatic C4- to C30- or (hetero)aromatic C4- to C30-hydrocarbon radical which is unsubstituted or substituted by carbonyl, alkylcarbonyloxy, alkylcarbamoyl and/or alkoxycarbonyl groups and/or comprises O, N(H) and/or S units,
    and n is an integer from 1 to 10,
    the stabilizer LnR having altogether at least 20 carbon atoms and
    where n is 2, -R- also being -S-, -O-, -N(H)-, - CH2-, -(CH2)2-, -CH (CH3) -, - (CH2)3-, -CH (C2H5)- or - C(CH3)2-.
  2. The fatliquoring agent according to claim 1, wherein the modified natural oil is selected from the group consisting of modified fish oil, modified neatsfoot oil, modified lard oil, modified soybean oil, modified rapeseed oil, modified walnut oil, modified olive oil and modified castor oil.
  3. The fatliquoring agent according to claim 1 or 2, which comprises at least 40, preferably at least 50, particularly preferably at least 70, % by weight of a component A or of a mixture of the components A and not more than 1, preferably not more than 0.5, particularly preferably not more than 0.2, % by weight of a component B or of a mixture of the components B, based on the total weight of the fatliquoring agent.
  4. The fatliquoring agent according to any of claims 1 to 3, wherein
    the component B comprises at least one stabilizer LR (n is 1) and R is selected from the group consisting of:
    -(CH2)9H, -CH(CH3)-(CH2)14H, -(CH2)2-C(O)OCH3,
    -(CH2)2-C(O)OiC8H17, -(CH2)2-C(O)O(CH2)18H and
    Figure imgb0009
     and/or
    the component B comprises at least one stabilizer L2R (n is 2) and R is selected from the group consisting of:
    -S-, -O-, -N(H)-, -CH2-, -CH(CH(CH3)2)-, - CH(CH2-CH2-CH3) -,
    -(CH2)2-C(O) -N (H) -N (H)-C (0) - (CH2)2-,
    - (CH2)2-C(O)-O-(CH2)6-O-C(O)-(CH2)2-,
    -(CH2)2-C(O)-N(H)-(CH2)6-N(H)-C(O)-(CH2)2-,
    -(CH2)2-C(O)-(O-CH2-CH2)3-O-C(O)-(CH2)2- and
    -(CH2)2-C(O)-O-CH2-CH2-S-CH2-CH2-O-C(O)-(CH2)2-and/or
    the component B comprises at least one stabilizer L4R (n is 4) and R is C(CH2-O-C(O)-CH2-CH2-)4.
  5. The fatliquoring agent according to any of claims 1 to 4, wherein the component B comprises at least one stabilizer L3R (n is 3) and R is selected from the group consisting of:
    Figure imgb0010
  6. The fatliquoring agent according to any of claims 1 to 5, wherein the modified natural oil is oxidized natural oil, the difference Δd between the specific gravities of the unoxidized and oxidized natural oil being from 0.01 to 0.1, preferably from 0.03 to 0.05, g/ml.
  7. The fatliquoring agent according to any of claims 1 to 6, wherein the modified natural oil is a sulfitated natural oil which is obtained by reacting the natural oil with from 2 to 8, preferably from 3 to 5, % by weight, based on its weight, of a sulfite, calculated as sodium bisulfite (Na2S2O5) .
  8. The use of a fatliquoring agent according to any of claims 1 to 7 in the production and/or treatment of leather and hides, in particular of leathers and hides tanned in the absence of chromium.
  9. A process for fatliquoring in the production and/or treatment of leather and hides with aqueous dispersions, wherein the aqueous dispersions comprise from 40 to 80, preferably from 50 to 80, particularly preferably from 60 to 75, % by weight of a fatliquoring agent according to any of claims 1 to 7.
EP03704668A 2002-02-21 2003-02-20 Low-voc stuffing agents, the use thereof in the production and/or treatment of leather and skins and corresponding production or treatment method Expired - Lifetime EP1478785B1 (en)

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DE10207277A DE10207277A1 (en) 2002-02-21 2002-02-21 Low-VOC greasing agents, their use in the production and / or treatment of leather and skins, and processes for the production and / or treatment of leather and skins with these greasing agents
PCT/EP2003/001740 WO2003070988A1 (en) 2002-02-21 2003-02-20 Low-voc stuffing agents, the use thereof in the production and/or treatment of leather and skins and corresponding production or treatment method

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CN101845525B (en) * 2010-06-09 2014-10-29 齐河力厚化工有限公司 Natural phospholipid compound greasing agent and preparation method thereof
CN102747171A (en) * 2011-04-20 2012-10-24 汤普勒化工染料(嘉兴)有限公司 Wet processing method of waterproof shoe upper leather
CN102732649B (en) * 2012-06-15 2014-08-20 海宁森德皮革有限公司 Production process of automobile interior decorative leather with ultralow total carbon emission
CN103667547B (en) * 2013-11-07 2015-07-15 山东力厚轻工新材料有限公司 Compound complex type greasing agent and preparation method thereof
CN106119441A (en) * 2016-06-28 2016-11-16 周云龙 A kind of artificial oil leather fat
KR102795960B1 (en) * 2022-11-17 2025-04-16 켐맥스 주식회사 Eco-friendly fatliquor for car seat and manufacturing method thereof

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US7192534B2 (en) 2007-03-20
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CN1636072A (en) 2005-07-06
DE10207277A1 (en) 2003-09-04
US20050224745A1 (en) 2005-10-13
AR038550A1 (en) 2005-01-19
ES2375108T3 (en) 2012-02-24
KR20040096602A (en) 2004-11-16
ATE532883T1 (en) 2011-11-15
BR0307592A (en) 2005-02-01
WO2003070988A1 (en) 2003-08-28

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