EP1512759B1 - Composition for the treatment of leather - Google Patents

Composition for the treatment of leather Download PDF

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Publication number
EP1512759B1
EP1512759B1 EP03017794A EP03017794A EP1512759B1 EP 1512759 B1 EP1512759 B1 EP 1512759B1 EP 03017794 A EP03017794 A EP 03017794A EP 03017794 A EP03017794 A EP 03017794A EP 1512759 B1 EP1512759 B1 EP 1512759B1
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EP
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Prior art keywords
alcohol
composition according
leather
mpa
weight
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EP03017794A
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German (de)
French (fr)
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EP1512759A1 (en
Inventor
Michael Dr. Breitsamer
Ottmar Götz
Manfred Dr. Palissa
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Dystar Textilfarben GmbH and Co Deutschland KG
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Dystar Textilfarben GmbH and Co Deutschland KG
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Priority to AT03017794T priority Critical patent/ATE388246T1/en
Priority to EP03017794A priority patent/EP1512759B1/en
Priority to DE50309326T priority patent/DE50309326D1/en
Publication of EP1512759A1 publication Critical patent/EP1512759A1/en
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Publication of EP1512759B1 publication Critical patent/EP1512759B1/en
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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 a composition for the treatment of leather, a process for its preparation and its use for the hydrophobing and / or softening of leather.
  • Water-soluble hydrophobicizing fatliquor formulations contain the hydrophobizing components in a water phase emulsified or dispersed. Many of the emulsifiers used for this purpose counteract due to their hydrophilic parts of the molecule water repellency, resulting in insufficient hydrophobing of the leather.
  • silicone oils without or with functional groups, such as OH, carboxy and amino groups and halogen-substituted polymers, such as fluorocarbon compounds used.
  • functional groups such as OH, carboxy and amino groups
  • halogen-substituted polymers such as fluorocarbon compounds used.
  • fatty polyacrylates are used today. These cause a hydrophobic and simultaneously softening effect. Their effect is enhanced by additional use of silicone oils or functional silicone oils in the leather treatment agent (EP 1 087 021 A1 ). Disadvantage of this fatliquoring agent is that the leather produced therewith are much too soft, cause the typical "rubbery" handle acrylate-based fatliquor and thus can not or only partially used for certain applications, such as for permanent shoe upper leather.
  • the reaction product from the reaction of phosphating agent with the abovementioned OH components siloxane and furthermore alcohol and / or alcohol polyglycol ether is used, ie there is a phosphoric acid ester mixture in the composition according to the invention.
  • a phosphating agent is understood to mean any agent that is capable of forming phosphoric acid esters with the OH components.
  • the phosphating agent is P 2 O 5 , with which the phosphating reaction can be carried out in a particularly favorable, simple and rapid manner.
  • the phosphoric acid esters are in particular derived from the ortho-phosphoric acid. It can be mono-, di- and tri-esters.
  • the OH components used for the reaction with the phosphating agent are a mixture containing the siloxanes described in more detail above and also either a C 10 -C 40 alcohol or a C 10 -C 40 alcohol polyglycol ether or both a C 10 -C 40 alcohol and a C10-C40 alcohol polyglycol ether.
  • the phosphoric acid ester mixture of the composition according to the invention can, as described above, be prepared by phosphating a mixture of the abovementioned OH components. But it is also possible to use in the composition according to the invention in each case separately prepared with the respective OH components phosphoric acid ester.
  • the ⁇ , ⁇ -dihydroxypoly-C 1 -C 4 -alkylsiloxane is the compound ⁇ , ⁇ -dihydroxypolydimethylsiloxane, with which a composition according to the invention which is particularly advantageous in terms of its properties, in particular with regard to hydrophobing and plasticizing, is obtained.
  • the viscosity of the siloxane is 500 mPas. Siloxanes having this viscosity give particularly advantageous compositions according to the invention, in particular with regard to the hydrophobizing effect and the softening properties.
  • a plurality of mutually different C 10 -C 40 alcohols can be used in the phosphatization reaction.
  • they may be primary alcohols.
  • the alcohols are (i) unsaturated, in particular monounsaturated, C 12 -C 20 -fatty alcohols, in particular cetyl alcohol and oleyl alcohol, or mixtures of 2 or more of these, for example a mixture of cetyl alcohol and oleyl alcohol in the ratio 1: 1, (ii) branched or unbranched saturated C20-C40 alcohols, for example C30-C38 Guerbet alcohol, and (iii) saturated C10-C18 alcohols or mixtures of 2 or 3 of the alcohols (i) to (iii).
  • the C 10 -C 40 alcohol polyglycol ethers are preferably those derived from the C 10 -C 40 alcohols described in more detail above, in particular the alcohols (i), (ii) and (iii).
  • the alcohol polyglycol ethers used in the composition of the invention have units derived from alkylene oxide of 0.5 to 10 mol.
  • alkylene oxides ethylene oxide, propylene oxide and mixtures thereof can be used.
  • the preparation of the phosphoric acid ester mixture used in the composition according to the invention can be carried out by initially charging the abovementioned OH components in a reaction vessel. If one of the OH components is solid, it may be necessary to melt it. Optionally, the mixture of the submitted OH components can be heated to about 40 ° C.
  • the phosphating agent for example P 2 O 5 , is introduced into this mixture.
  • the phosphating reaction is exothermic, the reaction temperature can rise to 80 ° C to 85 ° C. If it rises to over 85 ° C, it is favorable to carry out a cooling.
  • the phosphating reaction can be carried out under a protective gas atmosphere, such as N 2 .
  • the reaction temperature for the phosphating may be 70 ° C to 80 ° C.
  • the reaction can be carried out with stirring. Conveniently, the reaction is stopped after completion of the phosphoric acid ester formation. This can be the case after about 5 to 6 hours.
  • the phosphating agent P 2 O 5 is favorably used based on the OH groups of the OH components in a molar ratio of 1: 2 to 1: 3 (n P 2 O 5 : n OH groups). As a result, as complete as possible conversion of the phosphating agent is achieved.
  • the amount of siloxane is desirably from 50% to 60% by weight, based on the mixture of OH components used in the phosphating reaction.
  • the remainder to 100% by weight, based on the mixture of the OH components used in the phosphating reaction, can then be formed by the C 10 -C 40 alcohol and / or C 10 -C 40 alcohol polyglycol ether.
  • the above mixture of the OH components A, B, C and D it may contain 30% by weight to 40% by weight of A, 5% by weight to 10% by weight of B, 2% by weight. % to 4 wt .-% C and 50 wt .-% to 60 wt .-% D, wherein the amounts are based on the mixture of the OH components.
  • mineral oil preferably mineral oil is used.
  • mineral oil the common mineral oils used for the leather grease can be used. These are mineral oils with predominantly paraffinic content (paraffinic mineral oils) with a viscosity of 15 mm 2 / s to 20 mm 2 / s at 40 ° C.
  • mineral oils with predominantly paraffinic content (paraffinic mineral oils) with a viscosity of 15 mm 2 / s to 20 mm 2 / s at 40 ° C.
  • other, for example naphthenic, mineral oils with other viscosities for example naphthenic, mineral oils with other viscosities.
  • synthetic oils or waxes such as paraffin oil, alkylbenzenes, paraffin waxes, polyethylene waxes but also native oils or waxes, such as wool fat, beeswax, fish oil, rapeseed oil and lecithin can be used for the composition according to the invention.
  • An emulsifier may furthermore be present in the composition according to the invention.
  • the emulsifier serves to stabilize the composition according to the invention and to improve its optical and performance properties.
  • those emulsifiers are used which do not impair the hydrophobizing effect of the composition according to the invention.
  • emulsifiers examples include those in the EP 0 213 480 A2 described salts of an ⁇ -amino acid having 2 to 6 carbon atoms and with the Akyl radical of a saturated or unsaturated fatty acid having 9 to 20 carbon atoms on the amine nitrogen, which may optionally be additionally substituted by methyl, wherein as salts alkali metal salts, in particular of sodium or of potassium, ammonium salts or salts of a mono-, di- or trialkanolamine having 2 to 4 carbon atoms in the alkanol radical, in particular mono-, di- or triethanolamine.
  • N-oleoyl sarcoside, N-stearyl sarcoside, N-lauryl sarcoside and their salts have proven particularly useful.
  • Nonionic surfactants can be used if they do not adversely affect the hydrophobic effect. These are, for example, nonionic emulsifiers (eg fatty alcohol ethoxylates) with an HLB value preferably of 3-9. It is also possible to use sorbitan esters and esters of other polyols. All surfactants from the group of anionic surfactants can also be used if they provide the required performance properties and do not impair the hydrophobic effect.
  • the amount of the emulsifier in the composition according to the invention is 0 to 5 wt .-%, preferably about 2.5 wt .-%.
  • composition according to the invention may further comprise conventional adjusting agents, in particular glycols, e.g. in an amount of from 1% to 2% by weight, based on the composition of the invention, and a biocide and / or fungicide, each e.g. in an amount of about 0.1% by weight, based on the composition of the invention.
  • conventional adjusting agents in particular glycols, e.g. in an amount of from 1% to 2% by weight, based on the composition of the invention, and a biocide and / or fungicide, each e.g. in an amount of about 0.1% by weight, based on the composition of the invention.
  • composition of the invention may be water, which also acts as an adjusting agent.
  • water causes the composition of the invention can be used immediately by the user. Distilled water or deionized water may conveniently be used as the water, thereby advantageously avoiding precipitation reactions in the composition according to the invention.
  • the composition according to the invention has a whole series of advantages.
  • the composition according to the invention is a water-emulsifiable leather treatment agent which is distinguished by an excellent hydrophobizing effect and also an excellent softening effect of leather. It is a multifunctional composition that can simultaneously achieve the hydrophobing and softening of leather.
  • the disadvantageous properties of the acrylate-based hydrophobicizing fatliquoring agent to be plasticized do not include the composition according to the invention. There is a reproducible good water repellency exercised on the leather produced, with no additional, used in the tannery aids.
  • the composition according to the invention does not adversely affect the subsequent leather treatment steps.
  • the hygienic properties of the leather produced with the composition according to the invention are outstanding.
  • the composition of the invention can be used without further use of organic solvents, whereby it proves to be advantageous in terms of toxicological and environmental aspects.
  • the composition of the invention can be easily applied to the leather in an aqueous liquor.
  • the present invention further provides a process for the preparation of the composition according to the invention, wherein the phosphoric acid ester mixture a), the Mineral oil b) and optionally the other ingredients, such as emulsifier, adjuster, biocide and fungicide are mixed and then water is added to this mixture.
  • the addition of water can be done with stirring.
  • the pH of the composition according to the invention can be adjusted to a value between 7 and 9 with a base, preferably sodium hydroxide solution or potassium hydroxide solution.
  • a base preferably sodium hydroxide solution or potassium hydroxide solution.
  • the addition of adjusting agents, such as glycols, z. B. butyglycol, fungicide and biocide can also be done only after the addition of water.
  • the composition according to the invention is ideally suited for softening and hydrophobing leather. Due to the multifunctionality of the composition according to the invention, softening and hydrophobing can be achieved simultaneously.
  • the composition according to the invention can be used in the same way as the previously used fatliquoring agents and water repellents.
  • the amount of the composition according to the invention can be 8% by weight to 15% by weight, based on the shaved weight of the leather.
  • Example 1 Preparation of a Composition According to the Invention
  • Example 2 Treatment of pure chrome leather using the agent according to the invention
  • Drum speed approx. 30 rpm for small barrels
  • Example 3 Treatment of vegetable retanned leather using a composition of the invention
  • the leathers made according to Examples 2 and 3 were full, soft, had a comfortable grip, and had no negative rubbery feel. Furthermore, they show excellent hydrophobization.

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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

A leather treating composition comprises by weight: a phosphoric acid ester mixture obtained by reaction of a phosphatizing agent with a mixture comprising (i) an alpha, omega-dihydroxypoly-1-4C-alkylsiloxane and (ii) a 10-40C alcohol optionally having 0.5-10 mols. of alkylene oxide-derived units; and an oil and/or wax (20-35%). A leather treating composition comprises by weight: (a) a phosphoric acid ester mixture obtained by reaction of a phosphatizing agent with a mixture comprising (i) an alpha, omega-dihydroxypoly-1-4C-alkylsiloxane of 25[deg]C viscosity 200-20000 mPas and/or alpha, omega-dihydroxyalkyl-poly-1-4C-alkylsiloxane of viscosity 40-300 mPas as well as (ii) a 10-40C alcohol optionally having 0.5-10 mols. of alkylene oxide-derived units; and (b) an oil and/or wax (20-35%). An independent claim is also included for production of the composition by mixing (a) with (b) and optionally also an emulsifier and then adding water.

Description

Die vorliegende Erfindung betrifft eine Zusammensetzung zur Behandlung von Leder, ein Verfahren zu deren Herstellung und deren Verwendung zum Hydrophobieren und/oder Weichmachen von Leder.The present invention relates to a composition for the treatment of leather, a process for its preparation and its use for the hydrophobing and / or softening of leather.

Es ist bekannt, daß durch das Einbringen hochmolekularer organischer Substanzen, wie z.B. Wachse, Paraffine und Fettderivate in Leder, durch Imprägnierung bzw. durch Anwendung in wäßriger Flotte, eine Hydrophobierwirkung bei Leder erreicht wird.It is known that by incorporating high molecular weight organic substances, e.g. Waxes, paraffins and fat derivatives in leather, by impregnation or by application in aqueous liquor, a hydrophobic effect is achieved in leather.

Häufig reicht die Hydrophobierwirkung herkömmlicher Hydrophobiermittel jedoch nicht aus. Nachteilig ist oft auch die Anwendung unter Mitverwendung von Lösungsmitteln, wie Chlorkohlenwasserstoffe, Butylacetat, Benzin, was aus Arbeitsschutzgründen und unter Umweltaspekten problematisch ist. Mitunter ist die Anwendung in wäßriger Flotte gar nicht möglich, z.B. bei der Walkfettung. Die Verwendung derartiger Fettgemische führt oft dazu, daß die tragehygienischen Eigenschaften, z.B. die Atmungsaktivität, der damit hergestellten Leder schlecht ist.However, the hydrophobicity of conventional water repellents is often insufficient. Another disadvantage is often the application with the concomitant use of solvents such as chlorinated hydrocarbons, butyl acetate, gasoline, which is problematic for occupational safety and environmental aspects. Sometimes the application in aqueous liquor is not possible, e.g. at the Walkfettung. The use of such fat blends often results in the wear-hygienic properties, e.g. the breathability, the leather produced with it is bad.

Wasserlösliche hydrophobierende Fettungsmittelformulierungen enthalten die hydrophobierenden Komponenten in einer Wasserphase emulgiert bzw. dispergiert. Viele der dafür verwendeten Emulgatoren wirken aufgrund ihrer hydrophilen Molekülteile einer Wasserabstoßung entgegen, was zu einer ungenügenden Hydrophobierung des Leders führt.Water-soluble hydrophobicizing fatliquor formulations contain the hydrophobizing components in a water phase emulsified or dispersed. Many of the emulsifiers used for this purpose counteract due to their hydrophilic parts of the molecule water repellency, resulting in insufficient hydrophobing of the leather.

Seit langem werden auch Silikonöle ohne bzw. mit funktionellen Gruppen, wie OH-, Carboxy- und Amino-Gruppen sowie halogensubstituierte Polymere, wie z.B. Fluorcarbonverbindungen verwendet. Diese haben den Nachteil, daß sie häufig lösungsmittelhaltig sind bzw. selbst in Lösungsmitteln appliziert werden müssen. Auch reichen die erforderlichen Wasserdichtigkeiten der damit hergestellten Leder oft nicht aus.For a long time silicone oils without or with functional groups, such as OH, carboxy and amino groups and halogen-substituted polymers, such as fluorocarbon compounds used. These have the disadvantage that they often contain solvents or must be applied even in solvents. Also, the required waterproofness of the leather produced with it is often insufficient.

Vielfach werden heute fettende Polyacrylate verwendet. Diese bewirken eine hydrophobierende und gleichzeitig weichmachende Wirkung. Gesteigert wird deren Wirkung durch zusätzliche Verwendung von Silikonölen bzw. funktionellen Silikonölen im Lederbehandlungsmittel ( EP 1 087 021 A1 ). Nachteil dieser Fettungsmittel ist, daß die damit hergestellten Leder viel zu weich sind, den typischen "gummiartigen" Griff acrylatbasierender Fettungsmittel bewirken und somit für bestimmte Anwendungsbereiche, z.B. für standige Schuhoberleder, nicht bzw. nur anteilmäßig verwendet werden können.In many cases, fatty polyacrylates are used today. These cause a hydrophobic and simultaneously softening effect. Their effect is enhanced by additional use of silicone oils or functional silicone oils in the leather treatment agent ( EP 1 087 021 A1 ). Disadvantage of this fatliquoring agent is that the leather produced therewith are much too soft, cause the typical "rubbery" handle acrylate-based fatliquor and thus can not or only partially used for certain applications, such as for permanent shoe upper leather.

Der vorliegenden Erfindung liegt somit die Aufgabe zugrunde, ein in wäßriger Flotte einsetzbares Lederbehandlungsmittel bereitzustellen, das zum Hydrophobieren und/oder Weichmachen von Leder ohne die Nachteile aus dem Stand der Technik eingesetzt werden kann.It is therefore an object of the present invention to provide a leather-treatment agent which can be used in an aqueous liquor and which can be used for hydrophobizing and / or softening leather without the disadvantages of the prior art.

Erfindungsgemäß wird dies erreicht durch eine Zusammensetzung zur Behandlung von Leder, umfaßend

  1. a) 20 Gew.-% bis 30 Gew.-%, vorzugsweise etwa 25 Gew.-%, bezogen auf die Zusammensetzung, eines Phosphorsäureestergemisches erhältlich durch Umsetzung von Phosphatierungsmittel mit einem Gemisch, enthaltend α,ω-Dihydroxypoly-C1-C4-alkylsiloxan mit einer Viskosität bei 25° C von 200 mPas bis 20 000 mPas und/oder α,ω-Dihydroxyalkyl-poly-C1-C4-alkylsiloxan mit einer Viskosität von 40 mPas bis 300 mPas sowie weiterhin C10-C40-Alkohol und/oder C10-C40-Alkohol mit 0,5 bis 10 mol, insbesondere etwa 3,5 mol, von Alkylenoxid abgeleiteten Einheiten (im weiteren als C10-C40-Alkoholpolyglykolether bezeichnet), und
  2. b) 20 Gew.-% bis 35 Gew.-%, vorzugsweise 25 Gew.-% bis 30 Gew.-%, bezogen auf die Zusammensetzung, Öl und/oder Wachs.
According to the invention this is achieved by a composition for the treatment of leather, comprising
  1. a) 20 wt .-% to 30 wt .-%, preferably about 25 wt .-%, based on the composition, of a Phosphorsäureestergemisches obtainable by reaction of phosphating agent with a mixture containing α, ω-dihydroxypoly-C1-C4-alkylsiloxane having a viscosity at 25 ° C of from 200 mPas to 20,000 mPas and / or α, ω-dihydroxyalkyl-poly-C 1 -C 4 -alkylsiloxane having a viscosity of from 40 mPas to 300 mPas and furthermore C 10 -C 40 -alcohol and / or C 10 C40 alcohol having 0.5 to 10 mol, in particular about 3.5 mol, derived from alkylene oxide units (hereinafter referred to as C10-C40 alcohol polyglycol ether), and
  2. b) 20 wt .-% to 35 wt .-%, preferably 25 wt .-% to 30 wt .-%, based on the composition, oil and / or wax.

In der erfindungsgemäßen Zusammensetzung wird das Reaktionsprodukt aus der Umsetzung von Phosphatierungsmittel mit den vorgenannten OH-Komponenten Siloxan sowie weiterhin Alkohol und/oder Alkoholpolyglykolether eingesetzt, d.h. es liegt ein Phosphorsäureestergemisch in der erfindungsgemäßen Zusammensetzung vor. Unter einem Phosphatierungsmittel im Sinne der vorliegenden Erfindung wird jedes Mittel verstanden, das mit den OH-Komponenten zur Ausbildung von Phosphorsäureestern fähig ist. Vorzugsweise ist das Phosphatierungsmittel P2O5, mit dem die Phosphatierungsreaktion in besonders günstiger, einfacher und schneller Weise durchgeführt werden kann. Die Phosphorsäureester sind insbesondere von der ortho-Phosphorsäure abgeleitet. Es kann sich um Mono-, Di- und Triester handeln.In the composition according to the invention, the reaction product from the reaction of phosphating agent with the abovementioned OH components siloxane and furthermore alcohol and / or alcohol polyglycol ether is used, ie there is a phosphoric acid ester mixture in the composition according to the invention. For the purposes of the present invention, a phosphating agent is understood to mean any agent that is capable of forming phosphoric acid esters with the OH components. Preferably, the phosphating agent is P 2 O 5 , with which the phosphating reaction can be carried out in a particularly favorable, simple and rapid manner. The phosphoric acid esters are in particular derived from the ortho-phosphoric acid. It can be mono-, di- and tri-esters.

Bei den zur Umsetzung mit dem Phosphatierungsmittel eingesetzten OH-Komponenten handelt es sich um ein Gemisch, das die vorstehend näher beschriebenen Siloxane und weiterhin entweder einen C10-C40-Alkohol oder einen C10-C40-Alkoholpolyglykolether oder sowohl einen C10-C40-Alkohol als auch einen C10-C40-Alkoholpolyglykolether aufweist.The OH components used for the reaction with the phosphating agent are a mixture containing the siloxanes described in more detail above and also either a C 10 -C 40 alcohol or a C 10 -C 40 alcohol polyglycol ether or both a C 10 -C 40 alcohol and a C10-C40 alcohol polyglycol ether.

Das Phosphorsäureestergemisch der erfindungsgemäßen Zusammensetzung kann, wie vorstehend beschrieben, durch Phosphatierung eines Gemisches der vorgenannten OH-Komponenten hergestellt werden. Es ist aber auch möglich, in der erfindungsgemäßen Zusammensetzung die jeweils mit den jeweiligen OH-Komponenten separat hergestellten Phosphorsäureester einzusetzen.The phosphoric acid ester mixture of the composition according to the invention can, as described above, be prepared by phosphating a mixture of the abovementioned OH components. But it is also possible to use in the composition according to the invention in each case separately prepared with the respective OH components phosphoric acid ester.

In einer bevorzugten Ausführungsform der erfindungsgemäßen Zusammensetzung ist das α,ω-Dihydroxypoly-C1-C4-alkylsiloxan die Verbindung α,ω-Dihydroxypolydimethylsiloxan, mit dem eine hinsichtlich ihrer Eigenschaften, insbesondere hinsichtlich des Hydrophobierens und des Weichmachens, besonders vorteilhafte erfindungsgemäße Zusammensetzung erhalten wird. Vorzugsweise beträgt die Viskosität des Siloxans 500 mPas. Siloxane mit dieser Viskosität ergeben, insbesondere hinsichtlich der Hydrophobierwirkung und den weichmachenden Eigenschaften, besonders vorteilhafte erfindungsgemäße Zusammensetzungen.In a preferred embodiment of the composition according to the invention, the α, ω-dihydroxypoly-C 1 -C 4 -alkylsiloxane is the compound α, ω-dihydroxypolydimethylsiloxane, with which a composition according to the invention which is particularly advantageous in terms of its properties, in particular with regard to hydrophobing and plasticizing, is obtained. Preferably, the viscosity of the siloxane is 500 mPas. Siloxanes having this viscosity give particularly advantageous compositions according to the invention, in particular with regard to the hydrophobizing effect and the softening properties.

Zur Herstellung des in der erfindungsgemäßen Zusammensetzung vorliegenden Phosphorsäureestergemisches können in der Phospatierungsreaktion mehrere, voneinander verschiedene C10-C40-Alkohole verwendet werden. Insbesondere kann es sich um primäre Alkohole handeln. Beispiele der Alkohole sind (i) ungesättigte, insbesondere einfach ungesättigte, C12-C20-Fettalkohole, insbesondere Cetylalkohol und Oleylalkohol, oder Gemische von 2 oder mehreren dieser, beispielsweise ein Gemisch von Cetylalkohol und Oleylalkohol in Verhältnis 1:1, (ii) verzweigte oder unverzweigte gesättigte C20-C40-Alkohole, beispielsweise C30-C38 Guerbet-Alkohol, und (iii) gesättigte C10-C18-Alkohole oder Gemische von 2 oder 3 der Alkohole (i) bis (iii).To prepare the phosphoric acid ester mixture present in the composition according to the invention, a plurality of mutually different C 10 -C 40 alcohols can be used in the phosphatization reaction. In particular, they may be primary alcohols. Examples of the alcohols are (i) unsaturated, in particular monounsaturated, C 12 -C 20 -fatty alcohols, in particular cetyl alcohol and oleyl alcohol, or mixtures of 2 or more of these, for example a mixture of cetyl alcohol and oleyl alcohol in the ratio 1: 1, (ii) branched or unbranched saturated C20-C40 alcohols, for example C30-C38 Guerbet alcohol, and (iii) saturated C10-C18 alcohols or mixtures of 2 or 3 of the alcohols (i) to (iii).

Bei den C10-C40-Alkoholpolyglykolethem handelt es sich vorzugsweise um solche, die von den vorstehend näher beschriebenen C10-C40-Alkoholen, insbesondere den Alkoholen (i), (ii) und (iii), abgeleitet sind. Die in der erfindungsgemäßen Zusammensetzung verwendeten Alkoholpolyglykolether weisen 0,5 bis 10 mol von Alkylenoxid abgeleitete Einheiten auf. Als Alkylenoxide können Ethylenoxid, Propylenoxid und Gemische davon eingesetzt werden.The C 10 -C 40 alcohol polyglycol ethers are preferably those derived from the C 10 -C 40 alcohols described in more detail above, in particular the alcohols (i), (ii) and (iii). The alcohol polyglycol ethers used in the composition of the invention have units derived from alkylene oxide of 0.5 to 10 mol. As alkylene oxides, ethylene oxide, propylene oxide and mixtures thereof can be used.

Ein besonders bevorzugtes Phosphorsäureestergemisch, das in der erfindungsgemäßen Zusammensetzung eingesetzt werden kann, ist von einem Gemisch der folgenden OH-Komponenten herstellbar:

  • A Gemisch aus ungesättigten C12-C20-Fettalkoholen, vorzugsweise Cetylalkohol/Oleylalkohol im Verhältnis 1:1, gegebenenfalls ethoxiliert mit 0,5 bis 10 mol Ethylenoxid, vorzugsweise 3,5 mol Ethylenoxid;
  • B gesättigter verzweigter bzw. unverzweigter C20-C40-Alkohol, vorzugsweise C30-C38 Guerbet-Alkohol;
  • C gesättigter Fettalkohol mit einer mittleren Kettenlänge C10-C18, und
  • D α,ω-Dihydroxypolydimethylsiloxan mit einer Viskosität bei 25°C von 200 mPas bis 20 000 mPas, vorzugsweise 500 mPas.
A particularly preferred phosphoric acid ester mixture which can be used in the composition according to the invention can be prepared from a mixture of the following OH components:
  • A mixture of unsaturated C 12 -C 20 -fatty alcohols, preferably cetyl alcohol / oleyl alcohol in the ratio 1: 1, optionally ethoxylated with 0.5 to 10 mol of ethylene oxide, preferably 3.5 mol of ethylene oxide;
  • B saturated branched or unbranched C20-C40 alcohol, preferably C30-C38 Guerbet alcohol;
  • C saturated fatty alcohol with a mean chain length C10-C18, and
  • D α, ω-dihydroxypolydimethylsiloxane having a viscosity at 25 ° C of 200 mPas to 20,000 mPas, preferably 500 mPas.

Das Gemisch dieser OH-Komponenten A, B, C und D wird mit dem Phosphatierungsmittel, insbesondere P2O5, zu dem in der erfindungsgemäßen Zusammensetzung vorliegenden Phosphorsäureestergemisch umgesetzt.The mixture of these OH components A, B, C and D is reacted with the phosphating agent, in particular P 2 O 5 , to the phosphoric acid ester mixture present in the composition according to the invention.

Die Herstellung des in der erfindungsgemäßen Zusammensetzung verwendeten Phosphorsäureestergemisches kann dadurch erfolgen, das die vorgenannten OH-Komponenten in einem Reaktionsgefäß vorgelegt werden. Sollte bei den OH-Komponenten eine fest sein, ist es gegebenenfalls erforderlich, sie zu schmelzen. Gegebenenfalls kann das Gemisch der vorgelegten OH-Komponenten auf etwa 40°C erwärmt werden. In dieses Gemisch wird das Phospatierungsmittel, beispielsweise P2O5, eingebracht. Die Phosphatierungsreaktion ist exotherm, die Reaktionstemperatur kann auf 80°C bis 85°C steigen. Steigt sie auf über 85°C, ist es günstig, eine Kühlung durchzuführen. Die Phosphatierungsreaktion kann unter Schutzgasatmosphäre, wie N2, durchgeführt werden. Die Reaktionstemperatur für die Phosphatierung kann 70°C bis 80°C betragen. Die Reaktion kann unter Rühren durchgeführt werden. Günstigerweise wird die Reaktion nach Vervollständigung der Phosphorsäureesterbildung abgebrochen. Dies kann nach etwa 5 bis 6 Stunden der Fall sein.The preparation of the phosphoric acid ester mixture used in the composition according to the invention can be carried out by initially charging the abovementioned OH components in a reaction vessel. If one of the OH components is solid, it may be necessary to melt it. Optionally, the mixture of the submitted OH components can be heated to about 40 ° C. The phosphating agent, for example P 2 O 5 , is introduced into this mixture. The phosphating reaction is exothermic, the reaction temperature can rise to 80 ° C to 85 ° C. If it rises to over 85 ° C, it is favorable to carry out a cooling. The phosphating reaction can be carried out under a protective gas atmosphere, such as N 2 . The reaction temperature for the phosphating may be 70 ° C to 80 ° C. The reaction can be carried out with stirring. Conveniently, the reaction is stopped after completion of the phosphoric acid ester formation. This can be the case after about 5 to 6 hours.

Das Phosphatierungsmittel P2O5 wird günstigerweise bezogen auf die OH-Gruppen der OH-Komponenten in einem molaren Verhältnis von 1:2 bis 1:3 (n P2O5: n OH-Gruppen) eingesetzt. Dadurch wird ein möglichst vollständiger Umsatz des Phosphatierungsmittels erreicht.The phosphating agent P 2 O 5 is favorably used based on the OH groups of the OH components in a molar ratio of 1: 2 to 1: 3 (n P 2 O 5 : n OH groups). As a result, as complete as possible conversion of the phosphating agent is achieved.

Die Menge des Siloxans beträgt günstigerweise 50 Gew.-% bis 60 Gew.-%, bezogen auf das in der Phosphatierungsreaktion eingesetzte Gemisch der OH-Komponenten. Den Rest auf 100 Gew.-%, bezogen auf das in der Phosphatierungsreaktion eingesetzte Gemisch der OH-Komponenten, kann dann der C10-C40-Alkohol und/oder C10-C40-Alkoholpolyglykolether bilden. Wird das vorstehende Gemisch aus den OH-Komponenten A, B, C und D eingesetzt, kann es 30 Gew.-% bis 40 Gew.-% A, 5 Gew.-% bis 10 Gew.-% B, 2 Gew.-% bis 4 Gew.-% C und 50 Gew.-% bis 60 Gew.-% D aufweisen, wobei die Mengenangaben auf das Gemisch der OH-Komponenten bezogen sind.The amount of siloxane is desirably from 50% to 60% by weight, based on the mixture of OH components used in the phosphating reaction. The remainder to 100% by weight, based on the mixture of the OH components used in the phosphating reaction, can then be formed by the C 10 -C 40 alcohol and / or C 10 -C 40 alcohol polyglycol ether. If the above mixture of the OH components A, B, C and D is used, it may contain 30% by weight to 40% by weight of A, 5% by weight to 10% by weight of B, 2% by weight. % to 4 wt .-% C and 50 wt .-% to 60 wt .-% D, wherein the amounts are based on the mixture of the OH components.

Als ÖI und Wachs kommt vorzugsweise Mineralöl zum Einsatz. Als Mineralöl können die gängigen für die Lederfettung verwendeten Mineralöle eingesetzt werden. Es handelt sich dabei um Mineralöle mit vorwiegend paraffinischem Anteil (paraffinbasische Mineralöle) mit einer Viskosität von 15 mm2/s bis 20 mm2/s bei 40°C. Es können aber auch andere, z.B. naphthenbasische, Mineralöle mit anderen Viskositäten verwendet werden. Weiterhin können auch synthetische Öle oder Wachse, wie Paraffinöl, Alkylbenzole, Paraffinwachse, Polyethylenwachse aber auch native Öle oder Wachse, wie Wollfett, Bienenwachs, Fischöl, Rüböl und Lecithin für die erfindungsgemäße Zusammensetzung verwendet werden.As oil and wax preferably mineral oil is used. As mineral oil, the common mineral oils used for the leather grease can be used. These are mineral oils with predominantly paraffinic content (paraffinic mineral oils) with a viscosity of 15 mm 2 / s to 20 mm 2 / s at 40 ° C. However, it is also possible to use other, for example naphthenic, mineral oils with other viscosities. Furthermore, synthetic oils or waxes, such as paraffin oil, alkylbenzenes, paraffin waxes, polyethylene waxes but also native oils or waxes, such as wool fat, beeswax, fish oil, rapeseed oil and lecithin can be used for the composition according to the invention.

In der erfindungsgemäßen Zusammensetzung kann weiterhin ein Emulgator vorliegen. Der Emulgator dient dazu, die erfindungsgemäße Zusammensetzung zu stabilisieren und hinsichtlich der optischen und anwendungstechnischen Eigenschaften zu verbessern. Es werden insbesondere solche Emulgatoren eingesetzt, die die Hydrophobierwirkung der erfindungsgemäßen Zusammensetzung nicht beeinträchtigen. Beispiele solcher Emulgatoren sind die in der EP 0 213 480 A2 beschriebenen Salze einer α-Aminosäure mit 2 bis 6 Kohlenstoffatomen und mit dem Akyl-Rest einer gesättigten oder ungesättigten Fettsäure mit 9 bis 20 C-Atomen am Aminstickstoff, das gegebenenfalls zusätzlich durch Methyl substituiert sein kann, wobei als Salze Alkalisalze, insbesondere des Natriums oder des Kaliums, die Ammoniumsalze oder Salze eines Mono-, Di- oder Trialkanolamins mit 2 bis 4 C-Atomen im Alkanolrest, insbesondere des Mono-, Di- oder Triethanolamins, in Betracht kommen. Besonders bewährt hat sich beispielsweise N-Oleoylsarkosid, N-Stearylsarkosid, N-Laurylsarkosid und deren Salze. Eingesetzt werden können nichtionische Tenside, wenn sie die Hydrophobierwirkung nicht nachteilig beeinflussen. Das sind z.B. nichtionische Emulgatoren (z.B. Fettalkoholethoxylate) mit einem HLB-Wert vorzugsweise von 3-9. Weiter eingesetzt werden können Sorbitanester und Ester anderer Polyole. Eingesetzt werden können auch alle Tenside aus der Gruppe der Aniontenside, wenn sie die geforderten anwendungstechnischen Eigenschaften erbringen und nicht zu einer Beeinträchtigung der Hydrophobierwirkung führen. Das sind z.B. niedrig ethoxylierte Phosphorsäureester auf Oleyl- oder Talgfett-Basis mit 3 bis 5 Mol Ethylenoxid oder nicht bzw. niedrig ethoxylierte Sulfosuccinate auf Kokos- oder Talgfett-Basis. Ebenso geeignet ist Laurylsulfat bzw. deren niedrig ethoxylierte Derivate.An emulsifier may furthermore be present in the composition according to the invention. The emulsifier serves to stabilize the composition according to the invention and to improve its optical and performance properties. In particular, those emulsifiers are used which do not impair the hydrophobizing effect of the composition according to the invention. Examples of such emulsifiers are those in the EP 0 213 480 A2 described salts of an α-amino acid having 2 to 6 carbon atoms and with the Akyl radical of a saturated or unsaturated fatty acid having 9 to 20 carbon atoms on the amine nitrogen, which may optionally be additionally substituted by methyl, wherein as salts alkali metal salts, in particular of sodium or of potassium, ammonium salts or salts of a mono-, di- or trialkanolamine having 2 to 4 carbon atoms in the alkanol radical, in particular mono-, di- or triethanolamine. For example, N-oleoyl sarcoside, N-stearyl sarcoside, N-lauryl sarcoside and their salts have proven particularly useful. Nonionic surfactants can be used if they do not adversely affect the hydrophobic effect. These are, for example, nonionic emulsifiers (eg fatty alcohol ethoxylates) with an HLB value preferably of 3-9. It is also possible to use sorbitan esters and esters of other polyols. All surfactants from the group of anionic surfactants can also be used if they provide the required performance properties and do not impair the hydrophobic effect. These are, for example, low-ethoxylated phosphoric esters based on oleyl or tallow with 3 to 5 Mole of ethylene oxide or non-ethoxylated sulfosuccinates based on coconut or tallow grease. Also suitable is lauryl sulfate or its low ethoxylated derivatives.

Die Menge des Emulgators in der erfindungsgemäßen Zusammensetzung beträgt 0 bis 5 Gew.-%, vorzugsweise etwa 2,5 Gew.-%.The amount of the emulsifier in the composition according to the invention is 0 to 5 wt .-%, preferably about 2.5 wt .-%.

Die erfindungsgemäße Zusammensetzung kann weiterhin übliche Stellmittel, insbesondere Glykole, z.B. in einer Menge von 1 Gew.-% bis 2 Gew.-%, bezogen auf die erfindungsgemäße Zusammensetzung, sowie ein Biozid und/oder Fungizid, jeweils z.B. in einer Menge von etwa 0,1 Gew.-%, bezogen auf die erfindungsgemäße Zusammensetzung, enthalten.The composition according to the invention may further comprise conventional adjusting agents, in particular glycols, e.g. in an amount of from 1% to 2% by weight, based on the composition of the invention, and a biocide and / or fungicide, each e.g. in an amount of about 0.1% by weight, based on the composition of the invention.

Der Rest der erfindungsgemäßen Zusammensetzung auf 100 Gew.-% kann Wasser sein, das auch als Stellmittel fungiert. Der Zusatz von Wasser bewirkt, daß die erfindungsgemäße Zusammensetzung vom Anwender sofort eingesetzt werden kann. Als Wasser kann dabei günstigerweise destilliertes Wasser oder entionisiertes Wasser verwendet werden, wodurch vorteilhafterweise Fällungsreaktionen in der erfindungsgemäßen Zusammensetzung vermieden werden.The remainder of the composition of the invention to 100 wt .-% may be water, which also acts as an adjusting agent. The addition of water causes the composition of the invention can be used immediately by the user. Distilled water or deionized water may conveniently be used as the water, thereby advantageously avoiding precipitation reactions in the composition according to the invention.

Die erfindungsgemäße Zusammensetzung, vor allem in den vorstehend näher beschriebenen bevorzugten Ausführungsformen, weist eine ganze Reihe von Vorteilen auf. Bei der erfindungsgemäßen Zusammensetzung handelt sich um ein in Wasser emulgierbares Lederbehandlungsmittel, das sich durch eine exzellente Hydrophobierwirkung und eine ebenfalls exzellente weichmachende Wirkung von Leder auszeichnet. Es handelt sich um eine multifunktionelle Zusammensetzung, mit der das Hydrophobieren und das Weichmachen von Leder gleichzeitig erreicht werden kann. Die nachteiligen Eigenschaften der zu weichmachenden acrylatbasierenden hydrophobierenden Fettungsmittel weist die erfindungsgemäße Zusammensetzung nicht auf. Es wird eine reproduzierbare gute Hydrophobierung auf die damit hergestellten Leder ausgeübt, wobei man ohne zusätzliche, in der Gerberei verwendete Hilfsmittel, auskommt. Die erfindungsgemäße Zusammensetzung beeinflußt die nachfolgenden Lederbehandlungsschritte nicht nachteilig. Die tragehygienischen Eigenschaften der mit der erfindungsgemäßen Zusammensetzung hergestellten Leder sind hervorragend. Die erfindungsgemäße Zusammensetzung kann ohne weiteren Einsatz organischer Lösungsmittel verwendet werden, wodurch sie sich hinsichtlich toxikologischer und umweltrelevanter Aspekte als vorteilhaft erweist. Die erfindungsgemäße Zusammensetzung kann einfach in wäßriger Flotte auf das Leder appliziert werden.The composition according to the invention, especially in the preferred embodiments described in more detail above, has a whole series of advantages. The composition according to the invention is a water-emulsifiable leather treatment agent which is distinguished by an excellent hydrophobizing effect and also an excellent softening effect of leather. It is a multifunctional composition that can simultaneously achieve the hydrophobing and softening of leather. The disadvantageous properties of the acrylate-based hydrophobicizing fatliquoring agent to be plasticized do not include the composition according to the invention. There is a reproducible good water repellency exercised on the leather produced, with no additional, used in the tannery aids. The composition according to the invention does not adversely affect the subsequent leather treatment steps. The hygienic properties of the leather produced with the composition according to the invention are outstanding. The composition of the invention can be used without further use of organic solvents, whereby it proves to be advantageous in terms of toxicological and environmental aspects. The composition of the invention can be easily applied to the leather in an aqueous liquor.

Gegenstand der vorliegenden Erfindung ist ferner ein Verfahren zur Herstellung der erfindungsgemäßen Zusammensetzung, wobei das Phosphorsäureestergemisch a), das Mineralöl b) und ggf. die weiteren Bestandteile, wie Emulgator, Stellmittel, Biozid und Fungizid, gemischt werden und zu diesem Gemisch dann Wasser gegeben wird.The present invention further provides a process for the preparation of the composition according to the invention, wherein the phosphoric acid ester mixture a), the Mineral oil b) and optionally the other ingredients, such as emulsifier, adjuster, biocide and fungicide are mixed and then water is added to this mixture.

Die Wasserzugabe kann unter Rühren erfolgen. Der pH-Wert der erfindungsgemäßen Zusammensetzung kann mit einer Base, vorzugsweise Natron- bzw. Kalilauge auf einen Wert zwischen 7 und 9 eingestellt werden. Die Zugabe von Stellmitteln, wie Glykole, z. B. Butyglykol, Fungizid und Biozid kann auch erst nach der Wasserzugabe erfolgen.The addition of water can be done with stirring. The pH of the composition according to the invention can be adjusted to a value between 7 and 9 with a base, preferably sodium hydroxide solution or potassium hydroxide solution. The addition of adjusting agents, such as glycols, z. B. butyglycol, fungicide and biocide can also be done only after the addition of water.

Wie bereits vorstehend ausgeführt wurde, eignet sich die erfindungsgemäße Zusammensetzung bestens zum Weichmachen und Hydrophobieren von Leder. Aufgrund der Multifunktionalität der erfindungsgemäßen Zusammensetzung kann das Weichmachen und das Hydrophobieren gleichzeitig erreicht werden. Die erfindungsgemäße Zusammensetzung kann in der prinzipiell gleichen Weise wie die bisher eingesetzten Fettungsmittel und Hydrophiermittel verwendet werden. Die Menge der erfindungsgemäßen Zusammensetzung kann dabei 8 Gew.-% bis 15 Gew.-%, bezogen auf das Falzgewicht der Leder, betragen.As already stated above, the composition according to the invention is ideally suited for softening and hydrophobing leather. Due to the multifunctionality of the composition according to the invention, softening and hydrophobing can be achieved simultaneously. The composition according to the invention can be used in the same way as the previously used fatliquoring agents and water repellents. The amount of the composition according to the invention can be 8% by weight to 15% by weight, based on the shaved weight of the leather.

Die Erfindung wird nachfolgend anhand der Beispiele näher erläutert, ohne sie jedoch darauf einzuschränken.The invention will be explained in more detail with reference to the examples, but without limiting it thereto.

Beispiel 1: Herstellung einer erfindungsgemäßen ZusammensetzungExample 1: Preparation of a Composition According to the Invention

Alle Prozentangaben beziehen sich auf das Gewicht 7,0 % Cetyl/Oleylalkohol 1:1 mit 3,5 mol Ethylenoxid und 10,2 % α, ω-Dihydroxypolydimethylsiloxan 3,0 % Guerbet-Alkohol C36 geschmolzen zusammen mit 0,9 % gesättigter Fettalkohol C 12/C 14 im Dreihalskolben vorlegen und auf 38 - 40 °C erwärmen. Dann vorsichtig 1,8 % Phosporpentoxid einstreuen. Die Reaktion verläuft exotherm, Temp. steigt auf 80 bis 85 °C. Falls Temperatur über 85 °C steigt, kühlen. Unter Stickstoff-Einleitung 5 1/2 Stunden bei 70 bis 75 °C reagieren lassen. Dann eine Mischung aus 24,3 % Mineralöl 5,0 % Wollfett 2,3 % Oleoylsarcosid und 8,8% Kalilauge 50 % in den fertigen Ester einrühren. Bei 43-47 °C verrühren bis homogen. Dann ohne Heizung 4,2 % Butylglykol einrühren. Dann mit 30,5 % deionisiertes Wasser unter intensivem Rühren eine Emulsion aufbauen (das Wasser portionsweise, langsam zugeben). Anschließend portionsweise 1,9 % Essigsäure 99,7 % techn. einrühren, dann mit 0,1 % Biozid konservieren pH im Produkt auf 7,0 - 9,0 einstellen. (Für alle Einstellmaßnahmen wurde deionisiertes Wasser verwendet) 100% All percentages are by weight 7.0% Cetyl / oleyl alcohol 1: 1 with 3.5 moles of ethylene oxide and 10.2% α, ω-dihydroxypolydimethylsiloxane 3.0% Guerbet Alcohol C36 melted together with 0.9% saturated fatty alcohol C 12 / C 14 in a three-necked flask and warm to 38 - 40 ° C. Then careful 1.8% Phosporpentoxid Sprinkle. The reaction is exothermic, Temp. Rises to 80 to 85 ° C. If temperature rises above 85 ° C, cool. React under nitrogen for 5 1/2 hours at 70 to 75 ° C. Then a mix out 24.3% mineral oil 5.0% wool grease 2.3% Oleoylsarcosid and 8.8% Potassium hydroxide solution 50% Stir into the finished ester. Stir at 43-47 ° C until homogeneous. Then without heating 4.2% butylglycol Stir. Then with 30.5% deionized water Make an emulsion with vigorous stirring (add the water in portions, slowly). Subsequently, in portions 1.9% Acetic acid 99.7% techn. stir in, then with 0.1% biocide Preserve pH in product to 7.0 - 9.0. (Deionized water was used for all adjustments) 100%

Beispiel 2: Behandlung von reinem Chromleder unter Verwendung des erfindungsgemäßen MittelsExample 2: Treatment of pure chrome leather using the agent according to the invention

Hydrophobierung    Standardrezeptur/ungefärbt
ab wet-blue    mit Chromfixierung
OriginalstärkeHydrophobing standard formulation / undyed
from wet blue with chrome fixation
original thickness

Arbeitsgang:Operation: Faßgeschwindigkeit: ca. 30 Upm für kleine FässerDrum speed: approx. 30 rpm for small barrels

Angaben: Flotte und Menge in % bezogen auf Streifengewicht Zeit in min Flotte T Menge Produkt Zeit Bemerkung OHNE NACHGERBUNG/Reine Chromleder alle Streifen in einem Faß Waschen 200 35 °C 10 Flottenwechsel Neutralisation 100 35 °C 1,0 Natriumformiat 15 1,5 Natriumbicarbonat 90 Flottenwechsel, pH ca. 6,0 Waschen 200 50 °C 10 Flottenwechsel Hydrophobierung 150 50 °C 8,0 HYDROPHOBIERUNGSMITTEL in der Gesamtflotte (150%) anlösen 0,2 Ammoniak 25 % 60 ca. 1,0 Ameisensäure 85 % 40 pH ca. 3,5 3,0 basischer Chromsulfatgerbstoff 150 Flottenwechsel Waschen 200 50 °C 10 Flottenwechsel Waschen 200 20 °C 10 Flottenwechsel Lederstreifen auf Bock,
Vacuumieren bei 65-80 °C 2 min.
Austrocknen im Trockenraum bei 35 °C.
Über Nacht im Klimaraum konditionieren bei 60 % Luftfeuchte.
Stollen 2-mal bei Stufe 12,Data: Fleet and quantity in% relative to strip weight Time in min Fleet T Quantity product Time comment WITHOUT ADVANCE / Pure chrome leather all stripes in a barrel To wash 200 35 ° C 10 fleet changes Neutralization 100 35 ° C 1.0 sodium formate 15 1.5 sodium bicarbonate 90 Fleet change, pH about 6.0 To wash 200 50 ° C 10 fleet changes waterproofing 150 50 ° C 8.0 HYDROPHOBIC EQUIPMENT in the total fleet (150%) 0.2 ammonia 25% 60 about 1.0 formic acid 85% 40 pH about 3.5 3.0 basic chromium sulfate tanning agent 150 liquor change To wash 200 50 ° C 10 fleet changes To wash 200 20 ° C 10 fleet changes Leather stripes on the buck,
Vacuum at 65-80 ° C for 2 min.
Drying in dry room at 35 ° C.
Condition overnight in a conditioning room at 60% humidity.
Stollen 2 times at level 12,

Beispiel 3: Behandlung von vegetabil nachgegerbtem Leder unter Verwendung einer erfindungsgemäßen ZusammensetzungExample 3: Treatment of vegetable retanned leather using a composition of the invention

Waschen 200 35 °C 10 Flottenwechsel Neutralisation 100 35 °C 1,0 Natriumformiat 15 1,5 Natriumbicarbonat 90 Flottenwechsel, pH ca. 6,0 Waschen 200 50 °C 10 Flottenwechsel Nachgerbung 100 45 °C 5,0 synthetischer Gerbstoff 3,0 Mimosa 2,0 Kastanie 90 0,2 Ameisensäure 85% 15 Flottenwechsel Waschen 200 50 °C 10 Flottenwechsel Streifen auf die kleinen Fässer aufteilen Hydrophobierung 150 50 °C 8,0 HYDROPHOBIERUNGSMITTEL in der Gesamtflotte (150 %) anlösen 0,2 Ammoniak 25% 60 ca. 1,0 Ameisensäure 85 % 40 pH ca. 3,5 3,0 basischer Chromsulfatgerbstoff 150 Flottenwechsel Waschen 200 50 °C 10 Flottenwechsel Waschen 200 20 °C 10 Flottenwechsel Lederstreifen auf Bock,
Vacuumieren bei 65-80 °C 2 min.
Austrocknen im Trockenraum bei 35 °C.
Über Nacht im Klimaraum konditionieren bei 60 % Luftfeuchte.
Stollen 2-mal bei Stufe 12, To wash 200 35 ° C 10 fleet changes Neutralization 100 35 ° C 1.0 sodium formate 15 1.5 sodium bicarbonate 90 Fleet change, pH about 6.0 To wash 200 50 ° C 10 fleet changes retanning 100 45 ° C 5.0 synthetic tanning agent 3.0 Mimosa 2.0 chestnut 90 0.2 formic acid 85% 15 fleet changes To wash 200 50 ° C 10 fleet changes Divide the strips on the small barrels waterproofing 150 50 ° C 8.0 HYDROPHOBIC EQUIPMENT in the total fleet (150%) 0.2 ammonia 25% 60 about 1.0 formic acid 85% 40 pH about 3.5 3.0 basic chromium sulfate tanning agent 150 fleet changes To wash 200 50 ° C 10 fleet changes To wash 200 20 ° C 10 fleet changes Leather stripes on the buck,
Vacuum at 65-80 ° C for 2 min.
Drying in dry room at 35 ° C.
Condition overnight in a conditioning room at 60% humidity.
Stollen 2 times at level 12,

EndbeurteilungFinal assessment

Die nach den Beispielen 2 und 3 hergestellte Leder waren voll, weich, hatten eine angenehmen Griff und wiesen keinen negativen gummiartigen Griff auf. Des weiteren zeigen sie eine ausgezeichnete Hydrophobierung.The leathers made according to Examples 2 and 3 were full, soft, had a comfortable grip, and had no negative rubbery feel. Furthermore, they show excellent hydrophobization.

Claims (10)

  1. Composition for the treatment of leather, comprising
    a) 20% by weight to 30% by weight, based on the composition, of a phosphoric acid ester mixture obtainable by reacting a phosphating agent with a mixture containing α,ω-dihydroxypoly-C1-C4-alkylsiloxane having a viscosity at 25°C of 200 mPa·s to 20 000 mPa·s and/or α,ω-dihydroxyalkylpoly-C1-C4-alkylsiloxane having a viscosity of 40 mPa·s to 300 mPa·s and furthermore C10-C40 alcohol and/or C10-C40 alcohol having 0.5 to 10 mol of units derived from alkylene oxide and
    b) 20% by weight to 35% by weight, based on the composition, of oil and/or wax.
  2. Composition according to Claim 1, the phosphating agent being P2O5.
  3. Composition according to either of the preceding claims, the α,ω-dihydroxypoly-C1-C4-alkylsiloxane being the compound α,ω-dihydroxypolydimethylsiloxane.
  4. Composition according to any of the preceding claims, the viscosity of the α,ω-dihydroxypoly-C1-C4-alkylsiloxane being 500 mPa·s
  5. Composition according to any of the preceding claims, the C10-C40-alcohol being selected from C12-C20 unsaturated fatty alcohol, saturated branched or straight-chain C20-C40-alcohol, saturated C10-C18-alcohol or mixtures of 2 or more thereof.
  6. Composition according to any of the preceding claims, the C10-C40-alcohol having 0.5 to 10 mol of units derived from alkylene oxide being selected from C12-C20 unsaturated fatty alcohols, saturated branched or straight-chain C20-C40-alcohol, saturated C10-C18-alcohol, which in each case have been reacted with 0.5 to 10 mol of alkylene oxide, or mixtures of 2 or more thereof.
  7. Composition according to any of the preceding claims, the phosphoric acid ester mixture being the reaction product of a phosphating agent with a mixture of
    A mixture of unsaturated C12-C20-fatty alcohols, preferably cetyl alcohol/oleyl alcohol in the ratio 1:1, optionally ethoxylated with 0.5 to 10 mol of ethylene oxide, preferably 3.5 mol of ethylene oxide;
    B saturated branched or straight-chain C20-C40-alcohol, preferably C30-C38 Guerbet alcohol;
    C saturated fatty alcohol having an average chain length of C10-C18, and
    D α,ω-dihydroxypolydimethylsiloxane having a viscosity at 25°C of 200 mPa·s to 20 000 mPa·s, preferably 500 mPa·s.
  8. Composition according to any of the preceding claims, which furthermore contains up to 5% by weight of emulsifier.
  9. Process for the preparation of a composition according to any of Claims 1 to 8, the phosphoric acid ester mixture a), the oil and/or wax b) and optionally the emulsifier being mixed and water then being added.
  10. Use of the composition according to any of Claims 1 to 8 for imparting water repellency to leather and/or softening leather.
EP03017794A 2003-08-04 2003-08-04 Composition for the treatment of leather Expired - Lifetime EP1512759B1 (en)

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EP03017794A EP1512759B1 (en) 2003-08-04 2003-08-04 Composition for the treatment of leather
DE50309326T DE50309326D1 (en) 2003-08-04 2003-08-04 Composition for the treatment of leather

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RU2043422C1 (en) * 1993-07-30 1995-09-10 Научно-производственное объединение "Центральный научно-исследовательский институт кожевенно-обувной промышленности" Fat-liquoring composition
JPH0948855A (en) * 1995-08-07 1997-02-18 Kao Corp Phosphoric acid triester-modified organo(poly)siloxane, its production, and cosmetic and preparation for external use containing the same
DE59906530D1 (en) * 1999-09-18 2003-09-11 Trumpler Gmbh & Co Chem Fab Leather treatment agent

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DE50309326D1 (en) 2008-04-17
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