EP0564980B1 - Fat liquoring agent for leather - Google Patents

Fat liquoring agent for leather Download PDF

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Publication number
EP0564980B1
EP0564980B1 EP93105420A EP93105420A EP0564980B1 EP 0564980 B1 EP0564980 B1 EP 0564980B1 EP 93105420 A EP93105420 A EP 93105420A EP 93105420 A EP93105420 A EP 93105420A EP 0564980 B1 EP0564980 B1 EP 0564980B1
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Prior art keywords
weight
compounds
fatty substances
component
compositions
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German (de)
French (fr)
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EP0564980A1 (en
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Alberto Dr. Guerci
Donato Dipinto
Hanspeter Dr. Gethöffer
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Clariant Produkte Deutschland GmbH
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents

Definitions

  • the oiling gives leather some of its most important properties for use.
  • the following are particularly strongly influenced: elasticity, hardness, toughness, extensibility, absorbency or repellency to water and air permeability.
  • the oxidation of the oils used should be as complete as possible, with the duration of the oxidation taking as short a period as possible.
  • metal catalysts such as cobalt naphthenate, zinc sulfate, aluminum sulfate or sodium oxalate. Despite the use of catalysts, the oxidation often took several days.
  • the leather greasing agents obtained by the oxysulfitation process often showed disadvantageous properties, such as excessive viscosity, especially at low temperatures, unpleasant fish-like odor and insufficient chromium stability.
  • Inorganic peroxides and also hydrogen peroxide (DD-A-21 46 28) were usually used to reduce the odor nuisance.
  • the object of the present invention was to provide a process for the preparation of greasing compositions based on oxysulfited oils of animal and / or vegetable origin, which requires shorter oxidation times in comparison to known oxysulfitating processes and the use of metal catalysts and odor-reducing substances, such as Peroxides are not mandatory.
  • a further object of the invention was to provide compositions based on oxysulfited oils of animal and / or vegetable origin which have improved properties in use compared to the known fatty compositions, such as low viscosity, in particular at lower temperatures, and low odor, better penetration and improved stability against oxidizing compounds.
  • the invention also relates to greasing compositions obtainable by a process which comprises the above-mentioned measures.
  • compositions serve compositions based on fatty substances of animal origin and / or vegetable origin (component a).
  • fatty substances of animal origin are fish oil, oil and its transformation products, claw-claw oil, sperm oil, egg oils and tallow fat. Fish oil and cattle claw oil are preferred.
  • fatty substances of vegetable origin can also be used as starting materials.
  • fatty substances of vegetable origin are castor oil, rapeseed oil, olive oil, soybean oil, sunflower oil, palm oil, peanut oil, cotton oil and linseed oil. Rapeseed oil and sunflower oil are preferred.
  • the fatty substances of animal and vegetable origin mentioned can be used as individual substances or mixtures in the process according to the invention.
  • fatty substances of animal or vegetable origin are used as starting materials for the production of the fatty compositions according to the invention, their proportion is 70-99% by weight, based on the total weight of the mixture. If fatty substances of animal and vegetable origin are used, the starting materials have a composition in a ratio between 30 to 99.9% by weight fatty substances of animal origin and 70 to 0.1% by weight fatty substances of vegetable origin, based on the total weight of fatty substances used .
  • a preferred composition consists of approximately equal parts of fish oil, claw oil and rapeseed oil.
  • component b which differs from the compounds of component a) distinguish and in which R 1 , R 2 , R 3 are, independently of one another, straight-chain or branched, optionally substituted C 1 -C 24 -alkyl radicals, preferably straight-chain, optionally substituted C 16 -C 20 -alkyl radicals, R 4 is hydrogen or a straight-chain or branched, optionally substituted C 1 -C 6 alkyl, m is an integer greater than zero, preferably 1 to 5, particularly preferably 1 and n is an integer greater than zero, preferably 1 to 20.
  • Suitable substituents are, for example, OH, OR, NH 2 , NHR 1 , NHR 1 2 , halogen.
  • Compounds of the formula II are preferred used as component b), which differ from the compounds of component a) and in which R 1 , R 2 , R 3 , R 4 , m and n have the meaning given above.
  • R 5 - COO - R 4 are compounds of the formula III
  • R 5 is a straight-chain or branched, optionally OH-substituted C 9 -C 24 alkyl, C 9 -C 24 alkenyl or C 9 -C 24 -alkdienyl radical and R 4 has the meaning given above.
  • These compounds of the formula III are optionally present in an amount of up to 30% by weight, based on the total weight of the mixture.
  • components b) and c) find lauric acid, palmitic acid, stearic acid, margaric acid, 10-methylstearic acid, oleic acid, linoleic acid, conjugated linoleic acid, linolenic acid and their esters.
  • the compounds of the formulas I, II and optionally III can be used as individual substances or in the form of mixtures of two or more individual substances.
  • Additives for controlling the final setting can be added to the compositions according to the invention, e.g. Alkanolamines, such as diethanolamine for an optimal pH, hydrocarbons, such as paraffin oil, for the desired viscosity, low-molecular mineral oil or synthetic oils, based on chlorinated or otherwise modified paraffin derivatives, and plasticizers, such as glycerin.
  • Alkanolamines such as diethanolamine for an optimal pH
  • hydrocarbons such as paraffin oil
  • plasticizers such as glycerin.
  • additives are preferably added after the greasing compositions have been completed.
  • the starting materials located in a suitable reactor are subjected to an oxidation at a temperature above 40 ° C., preferably in the range from 40 to 90 ° C., particularly preferably 50 to 80 ° C.
  • the oxidation is preferably carried out by introducing a moderate air flow into the composition at a rate of 200 to 400 l / h.
  • the end point of the oxidation is indicated by the sufficient sulfitability of the oxidized fat.
  • a sample is taken from the reaction mixture during the oxidation and sulfited as described below.
  • Sufficient sulfitability is understood to mean that when this oxisulfited sample, preferably 10% by weight in water, is introduced, a fine emulsion is formed which is stable over a period of at least one day at room temperature and has a chromium stability of at least 5 hours . It has been shown that the end point of the oxidation and thus these properties are generally reached 10 to 30 hours earlier than in the known processes.
  • the oxidized fatty substances can be reacted with a 10 to 40% by weight, preferably 20 to 30% by weight, aqueous solution of a strong base, such as alkali metal hydroxide.
  • a strong base such as alkali metal hydroxide.
  • the solution of a sulfitizing agent is added to the oxidized starting materials.
  • a sulfitizing agent find aqueous solutions of sodium pyrosulfite, sodium bisulfite or sulfur trioxide.
  • concentration of the aqueous solutions is in the range from 5 to 50% by weight, preferably 20 to 40% by weight.
  • the reaction mixture is heated.
  • the reaction mixture is usually heated to the boiling point.
  • the reaction mixture is heated until a sample taken meets the desired requirements with regard to appearance, emulsifiability in water and resistance to electrolytes, in particular chromium.
  • the sample should be clear when it is removed, i.e. be transparent and without discoloration.
  • the sample With regard to the emulsifiability in water, the sample should form a stable, finely divided emulsion. These requirements are assessed by just looking at them.
  • the chromium stability of the sample should be given over a period of more than 5 hours, preferably at least 10 hours.
  • the chromium stability of the oxysulfited fatty substances is tested as follows. 5 ml of the oxysulfited sample are dispersed in 90 ml of distilled water in a calibrated 100 ml measuring cylinder. 5 ml of an aqueous chromium sulfate solution are added to this dispersion with vigorous shaking.
  • the chromium sulfate solution consists of a solution of 56 g of basic chromium sulfate of the formula Cr (OH) SO 4 ⁇ nH 2 O with 25% by weight Cr 2 O 3 . The time until phase separation occurs is the measure of the chromium stability.
  • the greasing compositions according to the invention are suitable as well emulsifiable electrolyte-resistant greasing agents for the greasing of demanding fur wild garments, clothing, velor, furniture, gloves and fine upper leather and are preferably used for pre-greasing and greasing after washing.
  • the greased leathers have a good grip and fullness with tight scars.
  • the greasing compositions according to the invention are preferably suitable as leather greasing agents. It has been shown that the products penetrate the leather well and give it a soft, light but full feel.
  • 323 g of fish oil, 337 g of claw oil, 300 g of rapeseed oil and 40 g of ®Prifac acid 8968 (manufacturer: Unichema, Chemie GmbH, DE) at 70 ° C with atmospheric oxygen (speed: 340 l / h) are in a 2 l reactor. oxidized. After 40 hours the mixture has a viscosity of 3 minutes 30 seconds, measured with a "Ford cup" No. 2 at 27 ° C. After the oxidation has ended, 25.6 g of a 30% strength by weight aqueous NaOH solution are added at a temperature of 40 ° C. with stirring. The solution is stirred for 30 minutes at the temperature which arises due to the occurrence of heat.
  • Example 1 323 g of fish oil, 337 g of claw oil and 300 g of rapeseed oil and 40 g of ®Prifac acid 8961 are reacted analogously to Example 1. After 60 hours, the mixture has a viscosity of 6 minutes 10 seconds, measured using a "Ford cup" No. 2 at 27 ° C. The sulfitation takes place analogously to Example 1. The viscosity of the end product is 18 minutes 25 seconds, measured with a "Ford cup" No. 2 at 27 ° C. Chromium is stable over a period of more than 5 hours.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Glass Compositions (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Fats And Perfumes (AREA)
  • Lubricants (AREA)

Description

Durch die Fettung erhält Leder einige seiner für den Gebrauch wichtigsten Eigenschaften. Besonders stark werden beeinflußt: Elastizität, Härte, Zähigkeit, Dehnbarkeit, Saugfähigkeit bzw. Abweisung gegenüber Wasser und Luftdurchlässigkeit.The oiling gives leather some of its most important properties for use. The following are particularly strongly influenced: elasticity, hardness, toughness, extensibility, absorbency or repellency to water and air permeability.

Gebräuchliche Fettungsmittel und Hilfsmittel für die Lederfettung bauen auf der Grundlage von tierischen Ölen, wie Fischöl, und/oder pflanzlichen Ölen, wie Sonnenblumenöl auf. Da Fette allein jedoch nur schwer applizierbar sind und keine Eindringtiefe in die Lederhaut besitzen, müssen sie durch chemische Modifizierung in wasseremulgierbare Fettstoffe überführt werden. Diese eigentlichen Fettungsmittel, auch Licker genannt, bestehen aus einem emulgierten Fettstoff und dem entsprechenden Emulgator. Eine gebräuchliche Möglichkeit Licker zu erhalten, besteht in der Oxidierung und nachfolgenden Sulfitierung der Fette.Common greasing agents and auxiliaries for leather greasing are based on animal oils, such as fish oil, and / or vegetable oils, such as sunflower oil. However, since fats are difficult to apply on their own and have no depth of penetration into the dermis, they have to be converted into water-emulsifiable fatty substances by chemical modification. These actual fatliquors, also called lickers, consist of an emulsified fat and the corresponding emulsifier. A common way to get licker is to oxidize and then sulfite the fats.

Sowohl an das Verfahren als auch an die damit erhaltenen Lederfettungsmittel werden, insbesondere seitens der Anwender, bestimmte Forderungen gestellt.Certain demands are made of both the method and the leather greasing agents obtained with it, in particular on the part of the users.

Bezüglich des Verfahrens soll die Oxidation der eingesetzten Öle möglichst vollständig sein, wobei die Dauer der Oxidation einen möglichst geringen Zeitraum in Anspruch nehmen soll. Um die Oxidationszeiten abzukürzen, war es bisher üblich, Metallkatalysatoren, wie Kobaltnaphthenat, Zinksulfat, Aluminiumsulfat oder Natriumoxalat, einzusetzen.
Trotz der Verwendung von Katalysatoren dauerte die Oxidation oftmals mehrere Tage.With regard to the process, the oxidation of the oils used should be as complete as possible, with the duration of the oxidation taking as short a period as possible. In order to shorten the oxidation times, it was previously customary to use metal catalysts such as cobalt naphthenate, zinc sulfate, aluminum sulfate or sodium oxalate.
Despite the use of catalysts, the oxidation often took several days.

Die nach dem Verfahren der Oxysulfitierung erhaltenen Lederfettungsmittel zeigten oftmals nachteilige Eigenschaften, wie zu hohe Viskosität, insbesondere bei niedrigen Temperaturen, unangenehmer fischartiger Geruch und zu geringe Chromstabilität.
Zur Verminderung der Geruchsbelästigung wurden üblicherweise anorganische Peroxide und auch Wasserstoffperoxid (DD-A-21 46 28) eingesetzt.The leather greasing agents obtained by the oxysulfitation process often showed disadvantageous properties, such as excessive viscosity, especially at low temperatures, unpleasant fish-like odor and insufficient chromium stability.
Inorganic peroxides and also hydrogen peroxide (DD-A-21 46 28) were usually used to reduce the odor nuisance.

Trotz der vorstehend genannten Verbesserungsmaßnahmen bestand nach wie vor der Wunsch nach fettenden Zusammensetzungen, die sich durch verbesserte Eigenschaften in der Anwendung, insbesondere im Bereich der Lederbearbeitung, auszeichnen.Despite the improvement measures mentioned above, there was still a desire for greasing compositions which have improved properties in use, in particular in the field of leather processing.

Aufgabe der vorliegenden Erfindung war es, ein Verfahren zur Herstellung von fettenden Zusammensetzungen auf der Basis von oxysulfitierten Ölen tierischer und/oder pflanzlicher Herkunft zur Verfügung zu stellen, das im Vergleich zu bekannten Oxysulfitierungsverfahren kürzere Oxidationszeiten erfordert und den Einsatz von Metallkatalysatoren und geruchsmindernden Stoffen, wie Peroxiden nicht zwingend vorschreibt.The object of the present invention was to provide a process for the preparation of greasing compositions based on oxysulfited oils of animal and / or vegetable origin, which requires shorter oxidation times in comparison to known oxysulfitating processes and the use of metal catalysts and odor-reducing substances, such as Peroxides are not mandatory.

Eine weitere Aufgabe der Erfindung war es, Zusammensetzungen auf der Basis oxysulfitierter Öle tierischer und/oder pflanzlicher Herkunft zur Verfügung zu stellen, die gegenüber den bekannten fettenden Zusammensetzungen verbesserte Eigenschaften in der Anwendung aufweisen, wie geringe Viskosität, insbesondere bei tieferen Temperaturen, geringer Eigengeruch, bessere Penetration und verbesserte Stabilität gegenüber oxidierenden Verbindungen.A further object of the invention was to provide compositions based on oxysulfited oils of animal and / or vegetable origin which have improved properties in use compared to the known fatty compositions, such as low viscosity, in particular at lower temperatures, and low odor, better penetration and improved stability against oxidizing compounds.

Überraschenderweise hat sich gezeigt, daß durch den Einsatz von konjugiertungesättigten Carbonsäuren und/oder Estern die gewünschten Verbesserungen erreicht werden.Surprisingly, it has been shown that the desired improvements are achieved by using conjugated unsaturated carboxylic acids and / or esters.

Gegenstand der Erfindung ist ein Verfahren zur Herstellung von fettenden Zusammensetzungen umfassend die Maßnahmen:

  • Oxidation von Zusammensetzungen auf der Basis von Fettstoffen enthaltend:
    • a) 70 - 99 Gew.-% Fettstoffe tierischer und/oder pflanzlicher Herkunft und
    • b) 30 - 1 Gew.-% Verbindungen der Formel I
      Figure imgb0001
       die sich von den Verbindungen der Komponente a) unterscheiden und worin
      • R1, R2, R3 unabhängig voneinander verzweigte oder geradkettige, gegebenenfalls substituierte C1-C24-Alkylreste sind,
      • R4 Wasserstoff oder ein geradkettiger oder verzweigter, gegebenenfalls substituierter C1-C6-Alkylrest ist,
      • m eine ganze Zahl größer Null ist und
      • n eine ganze Zahl größer Null ist,
      bei einer Temperatur oberhalb 40°C, bevorzugt im Bereich von 40 bis 90°C, besonders bevorzugt 50 bis 80°C,
  • gegebenenfalls Umsetzung der oxidierten Fettstoffe mit einer 10 bis 40 gew.-%igen wäßrigen Alkalihydroxidlösung und
  • anschließende Sulfitierung durch Zugabe einer 5 bis 50 gew.-%igen, bevorzugt 20 bis 40 gew.-%igen Lösung eines Sulfitierungsmittels unter gleichzeitigem oder anschließendem Erhitzen.
The invention relates to a process for the preparation of fatty compositions comprising the measures:
  • Oxidation of compositions based on fatty substances containing:
    • a) 70-99% by weight of fatty substances of animal and / or vegetable origin and
    • b) 30-1% by weight of compounds of the formula I.
      Figure imgb0001
       which differ from the compounds of component a) and in which
      • R 1 , R 2 , R 3 are independently branched or straight-chain, optionally substituted C 1 -C 24 -alkyl radicals,
      • R 4 is hydrogen or a straight-chain or branched, optionally substituted C 1 -C 6 -alkyl radical,
      • m is an integer greater than zero and
      • n is an integer greater than zero,
      at a temperature above 40 ° C, preferably in the range from 40 to 90 ° C, particularly preferably 50 to 80 ° C,
  • optionally reacting the oxidized fatty substances with a 10 to 40% by weight aqueous alkali hydroxide solution and
  • subsequent sulfitation by adding a 5 to 50% by weight, preferably 20 to 40% by weight solution of a sulfitizing agent with simultaneous or subsequent heating.

Ebenfalls Gegenstand der Erfindung sind fettenden Zusammensetzungen erhältlich durch ein Verfahren, das die obengenannten Maßnahmen umfaßt.The invention also relates to greasing compositions obtainable by a process which comprises the above-mentioned measures.

Zunächst wird das Verfahren zur Herstellung der erfindungsgemäßen fettenden Zusammensetzungen erläutert und im Anschluß daran werden die erfindungsgemäßen fettenden Zusammensetzungen beschrieben.First, the process for the preparation of the greasing compositions according to the invention is explained and then the greasing compositions according to the invention are described.

Als Ausgangsstoffe zur Herstellung der erfindungsgemäßen fettenden Zusammensetzungen dienen Zusammensetzungen auf Basis von Fettstoffen tierischer Herkunft und/oder pflanzlicher Herkunft (Komponente a). Beispiele für Fettstoffe tierischer Herkunft sind Fischöl, Tran und seine Umwandlungsprodukte, Rinderklauenöl, Spermöl, Eieröle und Talgfett. Bevorzugte Verwendung finden Fischöl und Rinderklauenöl.
Neben den Fettstoffen tierischer Herkunft können als Ausgangsstoffe auch Fettstoffe pflanzlicher Herkunft eingesetzt werden.
Beispiele für Fettstoffe pflanzlicher Herkunft sind Rizinusöl, Rapsöl, Olivenöl, Sojabohnenöl, Sonnenblumenöl, Palmöl, Erdnussöl, Baumwollöl und Leinöl. Bevorzugte Verwendung finden Rapsöl und Sonnenblumenöl.As starting materials for the production of the fatty ones according to the invention Compositions serve compositions based on fatty substances of animal origin and / or vegetable origin (component a). Examples of fatty substances of animal origin are fish oil, oil and its transformation products, claw-claw oil, sperm oil, egg oils and tallow fat. Fish oil and cattle claw oil are preferred.
In addition to fatty substances of animal origin, fatty substances of vegetable origin can also be used as starting materials.
Examples of fatty substances of vegetable origin are castor oil, rapeseed oil, olive oil, soybean oil, sunflower oil, palm oil, peanut oil, cotton oil and linseed oil. Rapeseed oil and sunflower oil are preferred.

Die genannten Fettstoffe tierischer und pflanzlicher Herkunft können als Einzelstoffe oder Mischungen in dem erfindungsgemäßen Verfahren eingesetzt werden.The fatty substances of animal and vegetable origin mentioned can be used as individual substances or mixtures in the process according to the invention.

Werden als Ausgangsstoffe zur Herstellung der erfindungsgemäßen fettenden Zusammensetzungen nur Fettstoffe tierischer oder pflanzlicher Herkunft eingesetzt, so beträgt deren Anteil 70 - 99 Gew.-%, bezogen auf das Gesamtgewicht der Mischung.
Werden Fettstoffe tierischer und pflanzlicher Herkunft eingesetzt, so besitzen die Ausgangsstoffe eine Zusammensetzung im Verhältnis zwischen 30 bis 99,9 Gew.-% Fettstoffe tierischer Herkunft und 70 bis 0,1 Gew.-% Fettstoffe pflanzlicher Herkunft, bezogen auf das Gesamtgewicht an eingesetzten Fettstoffen. Eine bevorzugte Zusammensetzung besteht aus ungefähr gleichen Teilen Fischöl, Klauenöl und Rapsöl.If only fatty substances of animal or vegetable origin are used as starting materials for the production of the fatty compositions according to the invention, their proportion is 70-99% by weight, based on the total weight of the mixture.
If fatty substances of animal and vegetable origin are used, the starting materials have a composition in a ratio between 30 to 99.9% by weight fatty substances of animal origin and 70 to 0.1% by weight fatty substances of vegetable origin, based on the total weight of fatty substances used . A preferred composition consists of approximately equal parts of fish oil, claw oil and rapeseed oil.

Neben den genannten Fettstoffen (Komponente a) werden als weitere Ausgangsstoffe Verbindungen der Formel I

Figure imgb0002
In addition to the fatty substances mentioned (component a), compounds of the formula I
Figure imgb0002

als Komponente b) eingesetzt, die sich von den Verbindungen der Komponente a) unterscheiden und worin R1, R2, R3 unabhängig voneinander geradkettige oder verzweigte, gegebenenfalls substituierte C1-C24-Alkylreste, bevorzugt geradkettige, gegebenenfalls substituierte C16-C20-Alkylreste sind, R4 Wasserstoff oder ein geradkettiger oder verzweigter, gegebenenfalls substituierter C1-C6-Alkylrest ist, m eine ganze Zahl größer Null, bevorzugt 1 bis 5, besonders bevorzugt 1 ist und n eine ganze Zahl größer Null, bevorzugt 1 bis 20 ist.
Geeignete Substituenten sind z.B. OH, OR, NH2, NHR1, NHR1 2, Halogen.used as component b), which differs from the compounds of component a) distinguish and in which R 1 , R 2 , R 3 are, independently of one another, straight-chain or branched, optionally substituted C 1 -C 24 -alkyl radicals, preferably straight-chain, optionally substituted C 16 -C 20 -alkyl radicals, R 4 is hydrogen or a straight-chain or branched, optionally substituted C 1 -C 6 alkyl, m is an integer greater than zero, preferably 1 to 5, particularly preferably 1 and n is an integer greater than zero, preferably 1 to 20.
Suitable substituents are, for example, OH, OR, NH 2 , NHR 1 , NHR 1 2 , halogen.

Bevorzugt werden Verbindungen der Formel II

Figure imgb0003
als Komponente b) eingesetzt, die sich von den Verbindungen der Komponente a) unterscheiden und worin R1, R2, R3, R4, m und n die vorstehend genannte Bedeutung besitzen.Compounds of the formula II are preferred
Figure imgb0003
 used as component b), which differ from the compounds of component a) and in which R 1 , R 2 , R 3 , R 4 , m and n have the meaning given above.

Weitere geeignete Ausgangsstoffe (Komponente c) stellen Verbindungen der Formel III

        R5 - COO - R4

dar, die sich von den Verbindungen der Komponenten a) und b) unterscheiden und worin R5 ein geradkettiger oder verzweigter, gegebenenfalls OH-substituierter C9-C24-Alkyl-, C9-C24-Alkenyl- oder C9-C24-Alkdienylrest ist und R4 die vorstehend angegebene Bedeutung hat. Diese Verbindungen der Formel III sind gegebenenfalls in einer Menge bis zu 30 Gew.-%, bezogen auf das Gesamtgewicht der Mischung enthalten.Other suitable starting materials (component c) are compounds of the formula III

R 5 - COO - R 4

are which differ from the compounds of components a) and b) and wherein R 5 is a straight-chain or branched, optionally OH-substituted C 9 -C 24 alkyl, C 9 -C 24 alkenyl or C 9 -C 24 -alkdienyl radical and R 4 has the meaning given above. These compounds of the formula III are optionally present in an amount of up to 30% by weight, based on the total weight of the mixture.

Besonders bevorzugte Verwendung als Komponenten b) und c) finden Laurinsäure, Palmitinsäure, Stearinsäure, Margarinsäure, 10-Methylstearinsäure, Ölsäure, Linolsäure, konjugierte Linolsäure, Linolensäure und deren Ester.
Die Verbindungen der Formeln I, II und gegebenenfalls III können als Einzelstoffe oder in Form von Mischungen von zwei oder mehr Einzelstoffen eingesetzt werden.Particularly preferred use as components b) and c) find lauric acid, palmitic acid, stearic acid, margaric acid, 10-methylstearic acid, oleic acid, linoleic acid, conjugated linoleic acid, linolenic acid and their esters.
The compounds of the formulas I, II and optionally III can be used as individual substances or in the form of mixtures of two or more individual substances.

Den erfindungsgemäßen Zusammensetzungen können Zusatzstoffe zur Regelung der Endeinstellung zugesetzt werden, z.B. Alkanolamine, wie Diethanolamin für einen optimalen pH-Wert, Kohlenwasserstoffe, wie Paraffinöl, für die gewünschte Viskosität, niedermolekulares Mineralöl oder synthetische Öle, auf Basis chlorierter oder anderweitig modifizierter Paraffinderivate sowie Weichmacher, wie Glycerin.Additives for controlling the final setting can be added to the compositions according to the invention, e.g. Alkanolamines, such as diethanolamine for an optimal pH, hydrocarbons, such as paraffin oil, for the desired viscosity, low-molecular mineral oil or synthetic oils, based on chlorinated or otherwise modified paraffin derivatives, and plasticizers, such as glycerin.

Diese Zusatzstoffe werden vorzugsweise nach Fertigstellung der fettenden Zusammensetzungen zugegeben.These additives are preferably added after the greasing compositions have been completed.

Die in einem geeigneten Reaktor befindlichen Ausgangsstoffe werden bei einer Temperatur oberhalb 40°C, bevorzugt im Bereich von 40 bis 90°C, besonders bevorzugt 50 bis 80°C, einer Oxidation unterzogen. Die Oxidation erfolgt vorzugsweise durch Einleiten eines gemäßigten Luftstromes mit einer Geschwindigkeit von 200 bis 400 l/h in die Zusammensetzung.The starting materials located in a suitable reactor are subjected to an oxidation at a temperature above 40 ° C., preferably in the range from 40 to 90 ° C., particularly preferably 50 to 80 ° C. The oxidation is preferably carried out by introducing a moderate air flow into the composition at a rate of 200 to 400 l / h.

Der Endpunkt der Oxidation wird durch die ausreichende Sulfitierbarkeit des oxidierten Fettstoffes angezeigt. Zu diesem Zweck wird während der Oxidation dem Reaktionsansatz eine Probe entnommen und wie nachstehend beschrieben sulfitiert. Unter einer ausreichenden Sulfitierbarkeit ist zu verstehen, daß beim Einbringen dieser oxisulfitierten Probe, bevorzugt 10 Gew.-% in Wasser, eine feine Emulsion gebildet wird, die über einen Zeitraum von mindestens einem Tag bei Raumtemperatur stabil ist und eine Chromstabilität von mindestens 5 Stunden besitzt. Es hat sich gezeigt, daß der Endpunkt der Oxidation und damit diese Eigenschaften im allgemeinen 10 bis 30 Stunden früher als bei den bekannten Verfahren erreicht werden.The end point of the oxidation is indicated by the sufficient sulfitability of the oxidized fat. For this purpose, a sample is taken from the reaction mixture during the oxidation and sulfited as described below. Sufficient sulfitability is understood to mean that when this oxisulfited sample, preferably 10% by weight in water, is introduced, a fine emulsion is formed which is stable over a period of at least one day at room temperature and has a chromium stability of at least 5 hours . It has been shown that the end point of the oxidation and thus these properties are generally reached 10 to 30 hours earlier than in the known processes.

Im Anschluß an die Oxidation und vor der Sulfitierung kann die Umsetzung der oxidierten Fettstoffe mit einer 10 bis 40 gew.-%igen, bevorzugt 20 bis 30 gew.-%igen, wäßrigen Lösung einer starken Base, wie Alkalihydroxid erfolgen.After the oxidation and before the sulfitation, the oxidized fatty substances can be reacted with a 10 to 40% by weight, preferably 20 to 30% by weight, aqueous solution of a strong base, such as alkali metal hydroxide.

Zum Zwecke der Sulfitierung werden die oxidierten Ausgangsstoffe mit der Lösung eines Sulfitierungsmittels versetzt. Bevorzugte Verwendung als Sulfitierungsmittel finden wäßrige Lösungen von Natriumpyrosulfit, Natriumhydrogensulfit oder Schwefeltrioxid. Die Konzentration der wäßrigen Lösungen liegt im Bereich von 5 bis 50 Gew.-%, bevorzugt 20 bis 40 Gew.-%.For the purpose of sulfitation, the solution of a sulfitizing agent is added to the oxidized starting materials. Preferred use as a sulfitizing agent find aqueous solutions of sodium pyrosulfite, sodium bisulfite or sulfur trioxide. The concentration of the aqueous solutions is in the range from 5 to 50% by weight, preferably 20 to 40% by weight.

Während, bevorzugt nach der Zugabe des Sulfitierungsmittels wird das Reaktionsgemisch erhitzt. Üblicherweise wird das Reaktionsgemisch bis zum Siedepunkt erhitzt. Das Reaktionsgemisch wird solange erhitzt, bis eine entnommene Probe den gewünschten Anforderungen hinsichtlich Aussehen, Emulgierbarkeit in Wasser und Elektrolytbeständigkeit, insbesondere Chromstabilität genügt. Die Probe soll bei der Entnahme klar, d.h. durchsichtig und ohne Verfärbung sein. Hinsichtlich der Emulgierbarkeit in Wasser soll die Probe eine stabile, feinverteilte Emulsion bilden. Diese Anforderungen werden durch bloßes Betrachten beurteilt. Die Chromstabilität der Probe soll über einen Zeitraum von mehr als 5 Stunden, bevorzugt mindestens 10 Stunden gegeben sein.During, preferably after the addition of the sulfitizing agent, the reaction mixture is heated. The reaction mixture is usually heated to the boiling point. The reaction mixture is heated until a sample taken meets the desired requirements with regard to appearance, emulsifiability in water and resistance to electrolytes, in particular chromium. The sample should be clear when it is removed, i.e. be transparent and without discoloration. With regard to the emulsifiability in water, the sample should form a stable, finely divided emulsion. These requirements are assessed by just looking at them. The chromium stability of the sample should be given over a period of more than 5 hours, preferably at least 10 hours.

Die Chromstabilität der oxysulfitierten Fettstoffe wird folgendermaßen geprüft. In einem geeichten 100 ml Meßzylinder werden 5 ml der oxysulfitierten Probe in 90 ml destilliertem Wasser dispergiert. Zu dieser Dispersion werden 5 ml einer wäßrigen Chromsulfatlösung unter kräftigem Schütteln hinzugefügt. Die Chromsulfatlösung besteht aus einer Lösung von 56 g basischem Chromsulfat der Formel Cr(OH)SO4 × nH2O mit 25 Gew.-% Cr2O3. Die Zeit bis zum Auftreten der Phasentrennung ist das Maß für die Chromstabilität.The chromium stability of the oxysulfited fatty substances is tested as follows. 5 ml of the oxysulfited sample are dispersed in 90 ml of distilled water in a calibrated 100 ml measuring cylinder. 5 ml of an aqueous chromium sulfate solution are added to this dispersion with vigorous shaking. The chromium sulfate solution consists of a solution of 56 g of basic chromium sulfate of the formula Cr (OH) SO 4 × nH 2 O with 25% by weight Cr 2 O 3 . The time until phase separation occurs is the measure of the chromium stability.

Eine zusätzliche Behandlung der oxidierten Ausgangsstoffe durch Waschen und/oder Neutralisation ist bei dem erfindungsgemäßen Verfahren nicht erforderlich, so daß die gesamte Reaktionsfolge in demselben Reaktor ablaufen kann.An additional treatment of the oxidized starting materials by washing and / or neutralization is not necessary in the process according to the invention, so that the entire reaction sequence can take place in the same reactor.

Als Vorteile des erfindungsgemäßen Verfahrens sind zu nennen:

  • kürzere Oxidationszeiten im Vergleich zum herkömmlichen Verfahren
  • kein notwendiger Einsatz von Metallkatalysatoren
  • kein notwendiger Einsatz von Peroxiden.
The advantages of the method according to the invention are:
  • shorter oxidation times compared to the conventional process
  • no need to use metal catalysts
  • no need to use peroxides.

Als Vorteile der erfindungsgemäßen fettenden Zusammensetzungen sind zu nennen:

  • nahezu geruchslose Produkte
  • niedrige Viskositäten, teilweise bei 0°C noch gießbar
  • hohe Chromstabilität
  • anwendungstechnische Eigenschaften ähnlich den Produkten auf reiner Fischölbasis.
Advantages of the greasing compositions according to the invention are:
  • almost odorless products
  • low viscosities, partly still pourable at 0 ° C
  • high chrome stability
  • application properties similar to products based on pure fish oil.

Die erfindungsgemäßen fettenden Zusammensetzungen eignen sich als gut emulgierbare elektrolytbeständige Fettungsmittel hervorragend für die Fettung von anspruchsvoller Pelzwildware, Bekleidungs-, Velour-, Möbel-, Handschuh- sowie feinem Oberleder und werden bevorzugt zur Vorfettung und Fettung nach dem Waschen eingestzt. Die gefetteten Leder besitzen eine gute Griffigkeit und Fülle bei anliegenden festen Narben.The greasing compositions according to the invention are suitable as well emulsifiable electrolyte-resistant greasing agents for the greasing of demanding fur wild garments, clothing, velor, furniture, gloves and fine upper leather and are preferably used for pre-greasing and greasing after washing. The greased leathers have a good grip and fullness with tight scars.

Die erfindungsgemäßen fettenden Zusammensetzungen eignen sich bevorzugt als Lederfettungsmittel. Es hat sich gezeigt, daß die Produkte das Leder gut penetrieren und einen weichen, leichten, aber vollen Griff verleihen.The greasing compositions according to the invention are preferably suitable as leather greasing agents. It has been shown that the products penetrate the leather well and give it a soft, light but full feel.

BeispieleExamples Beispiel 1example 1

In einem 2 l-Reaktor werden 323 g Fischöl, 337 g Klauenöl, 300 g Rapsöl und 40 g ®Prifac-Säure 8968 (Hersteller: Unichema, Chemie GmbH, DE) bei 70°C mit Luftsauerstoff (Geschwindigkeit: 340 l/h) oxidiert. Nach 40 Stunden besitzt die Mischung eine Viskosität von 3 Minuten 30 Sekunden, gemessen mit einem "Ford-Becher" Nr. 2 bei 27°C. Nach Beendigung der Oxidation werden 25,6 g einer 30 gew.-%igen wäßrigen NaOH-Lösung bei einer Temperatur von 40°C unter Rühren zugegeben. Die Lösung wird bei der Temperatur, die sich durch die auftretende Wärmetönung einstellt 30 Minuten gerührt. Anschließend werden 280 g einer 35 gew.-%igen Na2S2O5-Lösung nacheinander zu gleichen Teilen zugefügt. Nach der Zugabe der ersten Hälfte der Na2S2O5-Lösung wird bei der Temperatur, die sich durch die auftretende Wärmetönung einstellt 15 Minuten gerührt. Nach Beendigung der Zugabe der zweiten Hälfte wird die Temperatur bis zum Siedepunkt erhöht. Die Viskosität des Endproduktes beträgt 10 Minuten und 30 Sekunden, gemessen mit einem "Ford-Becher" Nr. 2 bei 27°C. Die Chromstabilität ist über einen Zeitraum von mehr als 5 Stunden gegeben.323 g of fish oil, 337 g of claw oil, 300 g of rapeseed oil and 40 g of ®Prifac acid 8968 (manufacturer: Unichema, Chemie GmbH, DE) at 70 ° C with atmospheric oxygen (speed: 340 l / h) are in a 2 l reactor. oxidized. After 40 hours the mixture has a viscosity of 3 minutes 30 seconds, measured with a "Ford cup" No. 2 at 27 ° C. After the oxidation has ended, 25.6 g of a 30% strength by weight aqueous NaOH solution are added at a temperature of 40 ° C. with stirring. The solution is stirred for 30 minutes at the temperature which arises due to the occurrence of heat. Then 280 g a 35 wt .-% Na 2 S 2 O 5 solution successively in equal parts. After the addition of the first half of the Na 2 S 2 O 5 solution, the mixture is stirred for 15 minutes at the temperature which arises due to the occurrence of heat. After the addition of the second half has ended, the temperature is raised to the boiling point. The viscosity of the end product is 10 minutes and 30 seconds, measured with a "Ford cup" No. 2 at 27 ° C. Chromium is stable over a period of more than 5 hours.

Zusammensetzung ®Prifac-Säure 8968

  • 23 % C18-Carbonsäure (einfach ungesättigt),
  • 9 % C18-Carbonsäure (zweifach ungesättigt),
  • 50 % C18-Carbonsäure (konjugiert ungesättigt),
  • 1 % C18-Carbonsäure (dreifach ungesättigt),
  • 1 % C20-Carbonsäure
Composition ®Prifac acid 8968
  • 23% C 18 carboxylic acid (monounsaturated),
  • 9% C 18 carboxylic acid (double unsaturated),
  • 50% C 18 carboxylic acid (conjugated unsaturated),
  • 1% C 18 carboxylic acid (triple unsaturated),
  • 1% C 20 carboxylic acid

Beispiel 2Example 2

Die Umsetzung von 323 g Fischöl, 337 g Klauenöl und 300 g Rapsöl und 40 g ®Prifac-Säure 8961 erfolgt analog Beispiel 1. Nach 60 Stunden besitzt die Mischung eine Viskosität von 6 Minuten 10 Sekunden, gemessen mit einem "Ford-Becher" Nr. 2 bei 27°C. Die Sulfitierung erfolgt analog Beispiel 1. Die Viskosität des Endproduktes beträgt 18 Minuten 25 Sekunden, gemessen mit einem "Ford-Becher" Nr. 2 bei 27°C. Die Chromstabilität ist über einen Zeitraum von mehr als 5 Stunden gegeben.323 g of fish oil, 337 g of claw oil and 300 g of rapeseed oil and 40 g of ®Prifac acid 8961 are reacted analogously to Example 1. After 60 hours, the mixture has a viscosity of 6 minutes 10 seconds, measured using a "Ford cup" No. 2 at 27 ° C. The sulfitation takes place analogously to Example 1. The viscosity of the end product is 18 minutes 25 seconds, measured with a "Ford cup" No. 2 at 27 ° C. Chromium is stable over a period of more than 5 hours.

Zusammensetzung ®Prifac-Säure 8961

  • 3 % C16-Carbonsäure,
  • 1 % C18-Carbonsäure,
  • 25 % C18-Carbonsäure (einfach ungesättigt),
  • 67 % C18-Carbonsäure (zweifach ungesättigt),
  • 1 % C18-Carbonsäure (dreifach ungesättigt)
Composition ®Prifac acid 8961
  • 3% C 16 carboxylic acid,
  • 1% C 18 carboxylic acid,
  • 25% C 18 carboxylic acid (monounsaturated),
  • 67% C 18 carboxylic acid (double unsaturated),
  • 1% C 18 carboxylic acid (triple unsaturated)

Claims (13)

  1. A process for the preparation of fat-liquoring compositions comprising the measures:
    - oxidation of compositions based on fatty substances containing:
    a) 70 - 99% by weight of fatty substances of animal and/or vegetable origin and
    b) 30 - 1% by weight of compounds of the formula I
    Figure imgb0006
     which differ from the compounds of component a) and in which
    R1, R2 and R3 independently of one another are branched or straight-chain, optionally substituted C1-C24-alkyl radicals,
    R4 is hydrogen or a straight-chain or branched, optionally substituted C1-C6-alkyl radical,
    m is an integer which is greater than zero and
    n is an integer which is greater than zero,
    at a temperature above 40°C,
    - if necessary reaction of the oxidized fatty substances with a 10 to 40% strength by weight aqueous alkali metal hydroxide solution and
    - subsequent sulfitation by addition of a 5 to 50% strength by weight solution of a sulfiting agent with simultaneous or subsequent heating.
  2. The process as claimed in claim 1, wherein compositions are oxidized which additionally contain
    - c) up to 30% by weight of compounds of the formula III

            R5 - COO - R4

    which differ from the compounds of components a) and b) and in which R5 is a straight-chain or branched, optionally OH-substituted C9-C24-alkyl, C9-C24-alkenyl or C9-C24-alkadienyl radical and R4 has the meaning shown in claim 1.
  3. The process as claimed in either of claims 1 and 2, wherein compositions containing
    30 - 99.9% by weight of fatty substances of animal origin and
    70 - 0.1 % by weight of fatty substances of vegetable origin,
    relative to the total weight of the fatty substances employed, are used as component a).
  4. The process as claimed in one of claims 1 to 3, wherein the compositions contain equal parts by weight of fish oil, neat's-foot oil and rape oil as component a).
  5. The process as claimed in one of claims 1 to 4, wherein compounds of the formula II
    Figure imgb0007
     are employed as component b), in which R1, R2, R3, R4, m and n have the meaning mentioned in claim 1, and which compounds differ from the compounds of component a).
  6. The process as claimed in one of claims 1 to 5, wherein compounds are employed as component b) in which m is an integer from 1 to 5, preferably 1, and n is an integer from 1 to 20.
  7. The process as claimed in one of claims 1 to 6, wherein compounds are employed as component b) in which R1, R2 and R3 independently of one another are a straight-chain, optionally substituted C16-C20-alkyl radical.
  8. The process as claimed in one of claims 1 to 7, wherein the oxidation is carried-out by introducing a stream of air at a temperature in the range from 40 to 90°C, preferably 50 to 80°C.
  9. The process as claimed in one of claims 1 to 8, wherein an aqueous solution of Na2S2O5, sodium hydrogensulfite or sulfur trioxide is used as the sulfiting agent.
  10. A fat-liquoring composition obtainable by a process which comprises the measures as claimed in one of claims 1 to 9.
  11. The use of the fat-liquoring compositions as claimed in claim 10 as leather fat-liquoring agents.
  12. A composition containing
    a) 70 - 99% by weight of fatty substances of animal and/or vegetable origin and
    b) 30 - 1% by weight of the compounds of the formula I mentioned in claim 1.
  13. A composition containing
    a) 70 - 99% by weight of fatty substances of animal and/or vegetable origin and
    b) 30 - 1% by weight of the compounds of the formula II mentioned in claim 5.
EP93105420A 1992-04-10 1993-04-01 Fat liquoring agent for leather Expired - Lifetime EP0564980B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4212054 1992-04-10
DE4212054 1992-04-10

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EP0564980B1 true EP0564980B1 (en) 1997-09-24

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JP (1) JPH06128600A (en)
KR (1) KR930021798A (en)
BR (1) BR9301466A (en)
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ES (1) ES2110017T3 (en)
HR (1) HRP930646A2 (en)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4405416A1 (en) * 1994-02-21 1995-10-05 Henkel Kgaa Use of sulfated substances to grease leather
DE4418943A1 (en) * 1994-05-31 1995-12-07 Henkel Kgaa Use of sulphonate(s) as dubbing agents for leather
US8062540B2 (en) * 2007-12-28 2011-11-22 Midori Hokuyo Co., Ltd Low-VOC leather
US20110064959A1 (en) * 2007-12-28 2011-03-17 Midori Hokuyo Co., Ltd. Low-voc leather
KR101315944B1 (en) * 2011-12-28 2013-10-18 김종현 Composition for self tanning using leather
CN103421912B (en) * 2013-09-04 2015-03-25 北京泛博化学股份有限公司 Fatting agent and preparing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3437443A1 (en) * 1984-10-12 1986-04-17 Henkel KGaA, 4000 Düsseldorf METHOD FOR THE PRODUCTION OF LUBRICANT FOR LEATHER AND FUR
DE3617691A1 (en) * 1986-05-26 1987-12-03 Henkel Kgaa SULFITED FATS

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EP0564980A1 (en) 1993-10-13
BR9301466A (en) 1993-10-13
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HRP930646A2 (en) 1994-10-31
JPH06128600A (en) 1994-05-10

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