EP1512759A1 - Composition for the treatment of leather - Google Patents

Composition for the treatment of leather Download PDF

Info

Publication number
EP1512759A1
EP1512759A1 EP03017794A EP03017794A EP1512759A1 EP 1512759 A1 EP1512759 A1 EP 1512759A1 EP 03017794 A EP03017794 A EP 03017794A EP 03017794 A EP03017794 A EP 03017794A EP 1512759 A1 EP1512759 A1 EP 1512759A1
Authority
EP
European Patent Office
Prior art keywords
alcohol
mpas
composition according
composition
leather
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03017794A
Other languages
German (de)
French (fr)
Other versions
EP1512759B1 (en
Inventor
Michael Dr. Breitsamer
Ottmar Götz
Manfred Dr. Palissa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dystar Textilfarben GmbH and Co Deutschland KG
Original Assignee
Dr Th Boehme KG Chemie Fabrik GmbH and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dr Th Boehme KG Chemie Fabrik GmbH and Co filed Critical Dr Th Boehme KG Chemie Fabrik GmbH and Co
Priority to DE50309326T priority Critical patent/DE50309326D1/en
Priority to AT03017794T priority patent/ATE388246T1/en
Priority to EP03017794A priority patent/EP1512759B1/en
Publication of EP1512759A1 publication Critical patent/EP1512759A1/en
Application granted granted Critical
Publication of EP1512759B1 publication Critical patent/EP1512759B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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 treating leather Process for their preparation and their use for hydrophobing and / or Softening leather.
  • Water-soluble hydrophobic fatliquoring formulations contain the hydrophobierenden components emulsified or dispersed in a water phase. Many of the Emulsifiers used for this purpose have an effect due to their hydrophilic moieties Water repellency, which leads to insufficient water repellency of the leather.
  • silicone oils without or with functional groups, such as OH, carboxy and Amino groups as well as halogen substituted polymers, e.g. Fluorocarbon compounds used. These have the disadvantage that they are often solvent-containing or even in Solvents must be applied. Also, the required waterproofness is sufficient Of the leather produced with it often not enough.
  • fatty polyacrylates are used today. These cause a hydrophobing and at the same time 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 these fatliquors is that the leather produced with it too much are soft, the typical "rubbery" handle acrylate-based fatliquor effect and thus for certain applications, e.g. for permanent shoe upper leather, not or only can be used proportionally.
  • the present invention is therefore based on the object, an aqueous liquor to provide usable leather treatment agent for hydrophobing and / or Softening leather without the disadvantages of the prior art can be used can.
  • 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
  • the ortho-phosphoric acid in particular derived from the ortho-phosphoric acid. It can be mono-, di- and triester act.
  • the OH components used for the reaction with the phosphating agent are it is a mixture containing the above-described siloxanes and further either a C10-C40 alcohol or a C10-C40 alcohol polyglycol ether or both a C10-C40 alcohol as well as a C10-C40 alcohol polyglycol ether.
  • the phosphoric acid ester mixture of the composition according to the invention can, as described above, by phosphating a mixture of the aforementioned OH components getting produced. But it is also possible in the inventive Composition each prepared separately with the respective OH components Use phosphoric acid ester.
  • composition of the invention is the ⁇ , ⁇ -dihydroxypoly-C1-C4-alkylsiloxane the compound ⁇ , ⁇ -dihydroxypolydimethylsiloxane, with the in terms of their properties, in particular with regard to the hydrophobing and the Plasticizing, particularly advantageous composition of the invention is obtained.
  • the viscosity of the siloxane is about 500 mPas. Siloxanes with this viscosity give, in particular with regard to the hydrophobic effect and the plasticizing Properties, particularly advantageous compositions according to the invention.
  • Phosphoric acid ester mixtures can in the Phospatleitersrefractress several, from each other various C10-C40 alcohols are used.
  • it may be primary Alcohols act.
  • the alcohols are (i) unsaturated, especially simple unsaturated C12-C20 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 from 2 or 3 of the alcohols (i) to (iii).
  • the C10-C40 alcohol polyglycol ethers are preferably those derived from the C10-C40 alcohols described in more detail above, in particular the alcohols (i), (ii) and (iii) are derived.
  • Alcohol polyglycol ethers have units derived from alkylene oxide of 0.5 to 10 moles. When Alkylene oxides can be used ethylene oxide, propylene oxide and mixtures thereof.
  • 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 the siloxane is desirably 50% by weight to 60% by weight, based on the the phosphating reaction used mixture of OH components.
  • the rest on 100% by weight, based on the mixture of the OH components used in the phosphating reaction, may then be the C10-C40 alcohol and / or C10-C40 alcohol polyglycol ether form.
  • the above mixture of the OH components A, B, C and D may be 30 wt .-% to 40 wt .-% A, 5 wt .-% to 10 wt .-% B, 2 wt .-% to 4 wt .-% C and 50 wt .-% to 60 wt .-% D, wherein the amounts are based on the mixture of OH components are related.
  • 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 of the invention and to improve in terms of optical and performance properties. It In particular, such emulsifiers are used, the hydrophobizing the not affect the composition of the invention.
  • emulsifiers examples include the salts of an ⁇ -amino acid having 2 to 6 described in EP 0 213 480 A2 Carbon atoms and with the acyl radical of a saturated or unsaturated fatty acid with 9 to 20 carbon atoms on the amine nitrogen, which may additionally be substituted by methyl may be, wherein as salts alkali metal salts, in particular of sodium or potassium, the Ammonium salts or salts of a mono-, di- or Trialkanolamins with 2 to 4 carbon atoms in Alkanolrest, in particular of mono-, di- or triethanolamine, come into consideration.
  • N-oleoyl sarcoside, N-stearyl sarcoside, N-lauryl sarcoside has proven particularly useful and their salts.
  • Nonionic surfactants can be used if they are Do not adversely affect the hydrophobic effect. These are e.g. nonionic emulsifiers (e.g., fatty alcohol ethoxylates) having an HLB preferably 3-9. Continue to use may be sorbitan esters and esters of other polyols. All can be used Surfactants from the group of anionic surfactants, if they meet the required performance Perform properties and do not lead to an impairment of the hydrophobic effect. These are e.g.
  • the amount of emulsifier in the composition according to the invention is 0 to 5% by weight, preferably about 2.5% by weight.
  • composition according to the invention can furthermore be customary setting agents, in particular Glycols, e.g. in an amount of 1 wt .-% to 2 wt .-%, based on the inventive Composition, as well as a biocide and / or fungicide, each e.g. in a lot of about 0.1 wt .-%, based on the composition of the invention.
  • customary setting agents in particular Glycols, e.g. in an amount of 1 wt .-% to 2 wt .-%, based on the inventive Composition, as well as a biocide and / or fungicide, each e.g. in a lot of about 0.1 wt .-%, based on the composition of the invention.
  • composition of the invention may be water, the also acts as a means of adjustment.
  • water causes the inventive Composition can be used by the user immediately.
  • distilled water or deionized water may be used, thereby advantageously avoided precipitation reactions in the composition of the invention become.
  • composition of the invention especially in those described in more detail above preferred embodiments, has a whole series of advantages.
  • the Composition according to the invention is an emulsifiable in water Leather treatment agent characterized by an excellent hydrophobicity and a also excellent softening effect of leather distinguishes. It is about a multifunctional composition with which the hydrophobing and softening of leather can be achieved at the same time.
  • the adverse properties of the too plasticizing acrylate-based hydrophobicizing fatliquoring agent has the Composition of the invention not on. It becomes a reproducible good Hydrophobization exercised on the leather produced, with no additional, in the tannery used aids, gets by.
  • the composition of the invention does not adversely affect the subsequent leather treatment steps.
  • the wearing hygienic Properties of the leather produced with the composition according to the invention outstanding.
  • the composition according to the invention can be used without further use organic solvents are used, whereby they are toxicological and environmentally relevant aspects proves beneficial.
  • the composition of the invention can be easily applied to the leather in aqueous liquor.
  • the present invention further provides a process for the preparation of Composition according to the invention, wherein the phosphoric acid ester mixture a), the Mineral oil b) and, if appropriate, the further constituents, such as emulsifier, adjuster, biocide and fungicide, be mixed and water is then added to this mixture.
  • the addition of water can be done with stirring.
  • the pH of the invention Composition can with a base, preferably sodium or potassium hydroxide solution to a value be set between 7 and 9.
  • 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 invention is suitable Composition ideal for softening and waterproofing leather. Due to the Multifunctionality of the composition of the invention can softening and Hydrophobing be achieved simultaneously.
  • the composition according to the invention can be used in in principle the same way as the previously used fatliquoring agents and water repellents be used.
  • the amount of the composition according to the invention can be 8% by weight. to 15 wt .-%, 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
  • Example 3 Treatment of vegetable retanned leather using a composition according to the invention
  • the leathers produced according to Examples 2 and 3 were full, soft, had a pleasant Handle and had no negative rubbery handle. Furthermore, they show one excellent water repellency.

Landscapes

  • 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 treating leather Process for their preparation and their use for hydrophobing and / or Softening 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. The disadvantage is often the application with the concomitant use of solvents, such as Chlorinated hydrocarbons, butyl acetate, gasoline, resulting in occupational safety and under Environmental issues is problematic. Sometimes the application in aqueous liquor is not possible, e.g. at the Walkfettung. The use of such fat mixtures often leads to the hygienic properties, e.g. the breathability, the leather produced with it bad is.

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 hydrophobic fatliquoring formulations contain the hydrophobierenden components emulsified or dispersed in a water phase. Many of the Emulsifiers used for this purpose have an effect due to their hydrophilic moieties Water repellency, which leads to insufficient water repellency of the leather.

Seit langem werden auch Silikonöle ohne bzw. mit funktionellen Gruppen, wie OH-, Carboxyund 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 as well as halogen substituted polymers, e.g. Fluorocarbon compounds used. These have the disadvantage that they are often solvent-containing or even in Solvents must be applied. Also, the required waterproofness is sufficient Of the leather produced with it often not enough.

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 hydrophobing and at the same time 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 these fatliquors is that the leather produced with it too much are soft, the typical "rubbery" handle acrylate-based fatliquor effect and thus for certain applications, e.g. for permanent shoe upper leather, not or only can be used proportionally.

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.The present invention is therefore based on the object, an aqueous liquor to provide usable leather treatment agent for hydrophobing and / or Softening leather without the disadvantages of the prior art can be used can.

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

  • 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
  • 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
  • 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
  • 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 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

    insbesondere von der ortho-Phosphorsäure abgeleitet. Es kann sich um Mono-, Di- und Triester handeln.in particular derived from the ortho-phosphoric acid. It can be mono-, di- and triester act.

    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 it is a mixture containing the above-described siloxanes and further either a C10-C40 alcohol or a C10-C40 alcohol polyglycol ether or both a C10-C40 alcohol as well as 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, by phosphating a mixture of the aforementioned OH components getting produced. But it is also possible in the inventive Composition each prepared separately with the respective OH components Use 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 etwa 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 of the invention is the α, ω-dihydroxypoly-C1-C4-alkylsiloxane the compound α, ω-dihydroxypolydimethylsiloxane, with the in terms of their properties, in particular with regard to the hydrophobing and the Plasticizing, particularly advantageous composition of the invention is obtained. Preferably, the viscosity of the siloxane is about 500 mPas. Siloxanes with this viscosity give, in particular with regard to the hydrophobic effect and the plasticizing Properties, particularly advantageous compositions according to the invention.

    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).For the preparation of the present in the composition of the invention Phosphoric acid ester mixtures can in the Phospatierungsreaktion several, from each other various C10-C40 alcohols are used. In particular, it may be primary Alcohols act. Examples of the alcohols are (i) unsaturated, especially simple unsaturated C12-C20 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 from 2 or 3 of the alcohols (i) to (iii).

    Bei den C10-C40-Alkoholpolyglykolethern 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 C10-C40 alcohol polyglycol ethers are preferably those derived from the C10-C40 alcohols described in more detail above, in particular the alcohols (i), (ii) and (iii) are derived. Those used in the composition of the invention Alcohol polyglycol ethers have units derived from alkylene oxide of 0.5 to 10 moles. When Alkylene oxides can be used ethylene oxide, propylene oxide and mixtures thereof.

    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-Dihydroxypolydimethylsiloxan having a viscosity at 25 ° C from 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 the siloxane is desirably 50% by weight to 60% by weight, based on the the phosphating reaction used mixture of OH components. The rest on 100% by weight, based on the mixture of the OH components used in the phosphating reaction, may then be the C10-C40 alcohol and / or C10-C40 alcohol polyglycol ether form. When the above mixture of the OH components A, B, C and D is used, It may be 30 wt .-% to 40 wt .-% A, 5 wt .-% to 10 wt .-% B, 2 wt .-% to 4 wt .-% C and 50 wt .-% to 60 wt .-% D, wherein the amounts are based on the mixture of OH components are related.

    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. Of the Emulsifier serves to stabilize the composition of the invention and to improve in terms of optical and performance properties. It In particular, such emulsifiers are used, the hydrophobizing the not affect the composition of the invention. Examples of such emulsifiers are the salts of an α-amino acid having 2 to 6 described in EP 0 213 480 A2 Carbon atoms and with the acyl radical of a saturated or unsaturated fatty acid with 9 to 20 carbon atoms on the amine nitrogen, which may additionally be substituted by methyl may be, wherein as salts alkali metal salts, in particular of sodium or potassium, the Ammonium salts or salts of a mono-, di- or Trialkanolamins with 2 to 4 carbon atoms in Alkanolrest, in particular of mono-, di- or triethanolamine, come into consideration. For example, N-oleoyl sarcoside, N-stearyl sarcoside, N-lauryl sarcoside has proven particularly useful and their salts. Nonionic surfactants can be used if they are Do not adversely affect the hydrophobic effect. These are e.g. nonionic emulsifiers (e.g., fatty alcohol ethoxylates) having an HLB preferably 3-9. Continue to use may be sorbitan esters and esters of other polyols. All can be used Surfactants from the group of anionic surfactants, if they meet the required performance Perform properties and do not lead to an impairment of the hydrophobic effect. These are e.g. low ethoxylated phosphoric acid 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 emulsifier in the composition according to the invention is 0 to 5% by weight, preferably about 2.5% by weight.

    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 can furthermore be customary setting agents, in particular Glycols, e.g. in an amount of 1 wt .-% to 2 wt .-%, based on the inventive Composition, as well as a biocide and / or fungicide, each e.g. in a lot of about 0.1 wt .-%, 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, the also acts as a means of adjustment. The addition of water causes the inventive Composition can be used by the user immediately. As water can do it Conveniently, distilled water or deionized water may be used, thereby advantageously avoided precipitation reactions in the composition of the invention become.

    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 hergesellten 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 of the invention, especially in those described in more detail above preferred embodiments, has a whole series of advantages. In the Composition according to the invention is an emulsifiable in water Leather treatment agent characterized by an excellent hydrophobicity and a also excellent softening effect of leather distinguishes. It is about a multifunctional composition with which the hydrophobing and softening of Leather can be achieved at the same time. The adverse properties of the too plasticizing acrylate-based hydrophobicizing fatliquoring agent has the Composition of the invention not on. It becomes a reproducible good Hydrophobization exercised on the leather produced, with no additional, in the tannery used aids, gets by. The composition of the invention does not adversely affect the subsequent leather treatment steps. The wearing hygienic Properties of the leather produced with the composition according to the invention outstanding. The composition according to the invention can be used without further use organic solvents are used, whereby they are toxicological and environmentally relevant aspects proves beneficial. The composition of the invention can be easily applied to the leather in 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 Composition according to the invention, wherein the phosphoric acid ester mixture a), the Mineral oil b) and, if appropriate, the further constituents, such as emulsifier, adjuster, biocide and fungicide, be mixed and water is then 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 invention Composition can with a base, preferably sodium or potassium hydroxide solution to a value be set between 7 and 9. 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 invention is suitable Composition ideal for softening and waterproofing leather. Due to the Multifunctionality of the composition of the invention can softening and Hydrophobing be achieved simultaneously. The composition according to the invention can be used in in principle the same way as the previously used fatliquoring agents and water repellents be used. The amount of the composition according to the invention can be 8% by weight. to 15 wt .-%, based on the shaved weight of the leather.

    Die Erfindung wird nachfolgend anhand der Beispiele näher erläutert, ohne sie jedoch darauf einzuschränken.The invention is explained in more detail below with reference to the examples, but without them limit.

    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 ca. 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 about 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

    Hydrophobierungwaterproofing Standardrezeptur/ungefärbtStandard recipe / undyed ab wet-bluefrom wet-blue mit Chromfixierungwith chrome fixation Originalstärkeoriginal thickness

    Arbeitsgang:Operation:

    Figure 00090001
    Figure 00100001
    Figure 00090001
    Figure 00100001

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

    Figure 00100002
    Figure 00110001
    Figure 00100002
    Figure 00110001

    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 produced according to Examples 2 and 3 were full, soft, had a pleasant Handle and had no negative rubbery handle. Furthermore, they show one excellent water repellency.

    Claims (10)

    Zusammensetzung zur Behandlung von Leder, umfassend a) 20 Gew.-% bis 30 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 von Alkylenoxid abgeleiteten Einheiten und b) 20 Gew.-% bis 35 Gew.-%, bezogen auf die Zusammensetzung, ÖI und/oder Wachs. A composition for the treatment of leather, comprising a) 20 wt .-% to 30 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. 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 also C 10 -C 40 -alcohol and / or C 10 -C 40 -alcohol having 0, 5 to 10 mol of alkylene oxide derived units and b) 20 wt .-% to 35 wt .-%, based on the composition, oil and / or wax. Zusammensetzung nach Anspruch 1, wobei das Phosphatierungsmittel P2 O5 ist.A composition according to claim 1, wherein the phosphating agent is P 2 O 5 . Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das α,ω-Dihydroxypoly-C1-C4-alkylsiloxan die Verbindung α,ω-Dihydroxypolydimethylsiloxan ist.A composition according to any one of the preceding claims, wherein the α, ω-dihydroxypoly-C 1 -C 4 -alkylsiloxane the compound is α, ω-dihydroxypolydimethylsiloxane. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Viskosität des α,ω-Dihydroxypoly-C1-C4-alkylsiloxans etwa 500 mPas beträgt.Composition according to any one of the preceding claims, wherein the viscosity of the α, ω-dihydroxypoly-C1-C4-alkylsiloxane is about 500 mPas. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei der C10-C40 Alkohol ausgewählt ist unter C12-C20 ungesättigtem Fettalkohol, gesättigtem verzweigten oder unverzweigten C20-C40 Alkohol, gesättigtem C10-C18 Alkohol oder Gemischen von 2 oder mehreren davon.A composition according to any one of the preceding claims, wherein the C10-C40 Alcohol is selected from C12-C20 unsaturated fatty alcohol, saturated branched or unbranched C20-C40 alcohol, saturated C10-C18 alcohol or mixtures of 2 or several of them. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei der C10-C40-Alkohol mit 0,5 bis 10 mol von Alkylenoxid abgeleitete Einheiten ausgewählt ist unter C12-C20 ungesättigten Fettalkoholen, gesättigtem verzweigten oder unverzweigten C20-C40 Alkohol, gesättigtem C10-C18 Alkohol, die jeweils mit 0,5 bis 10 mol Alkylenoxid umgesetzt sind, oder Gemische von 2 oder mehreren davon.A composition according to any one of the preceding claims, wherein the C10-C40 alcohol with units derived from 0.5 to 10 moles of alkylene oxide is selected from C12-C20 unsaturated fatty alcohols, saturated branched or unbranched C20-C40 alcohol, saturated C10-C18 alcohol, each reacted with 0.5 to 10 moles of alkylene oxide, or Mixtures of 2 or more of them. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Phosphorsäureestergemisch das Umsetzungsprodukt von Phosphatierungsmittel mit einem Gemisch von 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 gesättigten verzweigten bzw. unverzweigten C20-C40-Alkohol, vorzugsweise C30-C38 Guerbet-Alkohol; C gesättigtem 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 ist.A composition according to any one of the preceding claims, wherein the phosphoric acid ester mixture comprises the reaction product of phosphating agent with a mixture of 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 is. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei sie weiterhin bis zu 5 Gew.-% Emulgator enthält.A composition according to any one of the preceding claims, wherein it further comprises to 5 wt .-% emulsifier. Verfahren zur Herstellung einer Zusammensetzung nach einem der Ansprüche 1 bis 8, wobei das Phosphorsäureestergemisch a) das ÖI und/oder Wachs b) und gegebenenfalls der Emulgator gemischt und dann Wasser zugegeben wird.Process for the preparation of a composition according to any one of claims 1 to 8, wherein the phosphoric acid ester mixture a) the oil and / or wax b) and optionally the Emulsifier mixed and then water is added. Verwendung der Zusammensetzung nach einem der Ansprüche 1 bis 8 zum Hydrophobieren und/oder Weichmachen von Leder.Use of the composition according to any one of claims 1 to 8 for Hydrophobing and / or softening leather.
    EP03017794A 2003-08-04 2003-08-04 Composition for the treatment of leather Expired - Lifetime EP1512759B1 (en)

    Priority Applications (3)

    Application Number Priority Date Filing Date Title
    DE50309326T DE50309326D1 (en) 2003-08-04 2003-08-04 Composition for the treatment of leather
    AT03017794T ATE388246T1 (en) 2003-08-04 2003-08-04 COMPOSITION FOR TREATING LEATHER
    EP03017794A EP1512759B1 (en) 2003-08-04 2003-08-04 Composition for the treatment of leather

    Applications Claiming Priority (1)

    Application Number Priority Date Filing Date Title
    EP03017794A EP1512759B1 (en) 2003-08-04 2003-08-04 Composition for the treatment of leather

    Publications (2)

    Publication Number Publication Date
    EP1512759A1 true EP1512759A1 (en) 2005-03-09
    EP1512759B1 EP1512759B1 (en) 2008-03-05

    Family

    ID=34130069

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP03017794A Expired - Lifetime EP1512759B1 (en) 2003-08-04 2003-08-04 Composition for the treatment of leather

    Country Status (3)

    Country Link
    EP (1) EP1512759B1 (en)
    AT (1) ATE388246T1 (en)
    DE (1) DE50309326D1 (en)

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CN102190606A (en) * 2010-03-19 2011-09-21 广州市浪奇实业股份有限公司 Preparation method of novel sulfonated grease

    Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    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
    EP1087021A1 (en) * 1999-09-18 2001-03-28 Trumpler GmbH & Co. Chemische Fabrik Leather-treatment agent

    Patent Citations (3)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    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
    EP1087021A1 (en) * 1999-09-18 2001-03-28 Trumpler GmbH & Co. Chemische Fabrik Leather-treatment agent

    Non-Patent Citations (2)

    * Cited by examiner, † Cited by third party
    Title
    BASKAR G ET AL: "DEVELOPMENT OF PHOSPHORYLATED FATLIQUORS AND THEIR APPLICATION IN THE MANUFACTURE OF SOPHISTICATED LEATHERS", JOURNAL OF THE AMERICAN LEATHER CHEMISTS ASSOCIATION, AMERICAN LEATHER CHEMISTS ASSOCIATION. CINCINNATI, US, vol. 86, no. 4, 1 April 1991 (1991-04-01), pages 159 - 165, XP000236734, ISSN: 0002-9726 *
    DATABASE WPI Section Ch Week 199621, Derwent World Patents Index; Class A97, AN 1996-207771, XP002262486 *

    Cited By (1)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    CN102190606A (en) * 2010-03-19 2011-09-21 广州市浪奇实业股份有限公司 Preparation method of novel sulfonated grease

    Also Published As

    Publication number Publication date
    DE50309326D1 (en) 2008-04-17
    EP1512759B1 (en) 2008-03-05
    ATE388246T1 (en) 2008-03-15

    Similar Documents

    Publication Publication Date Title
    EP0213480B1 (en) Method of water-proofing leather and furs
    DE4415062B4 (en) Means and processes for waterproofing leather and furs
    DE1594503A1 (en) Tools for the cold working of metals
    EP0353704B1 (en) Liquid or fluid derivatives of natural fats and oils and process for their preparation and use
    EP1512759B1 (en) Composition for the treatment of leather
    EP1427862A1 (en) Polyisobutene as substitute for wool fat in stuffing agents for the production of leather, the stuffing agent, the use thereof and the produced leather
    EP0760015B1 (en) Cationic agents for stuffing leather and hides
    EP0265818A2 (en) Process for the preparation of N,N-disubstituted beta-aminoacids and their use in water-proofing leather and skins
    DE3230925A1 (en) Partial phosphoric esters, preparation thereof and use thereof as leather fatliquoring agents, and also formulations containing same
    CH665426A5 (en) METHOD FOR FAT AND WATER REPELLENT EQUIPMENT OF TANED LEATHER.
    EP0763139B1 (en) Stuffing agents for leathers and fur-skins
    EP0670828B1 (en) Sulphited fats with a reduced free-bisulphite content
    EP1597402B1 (en) Method for hydrophobing leather and furskins
    EP0784707B1 (en) Process for producing leather greasing agents
    EP1621640B1 (en) Agent for the hydrophobic treatment of leather
    DE10306748A1 (en) Rendering leather and pelts hydrophobic, useful in preparation of e.g. clothes and furniture, by treatment with mixture containing carboxylated and non-carboxylated polysiloxanes
    EP0280152B1 (en) Water-proofing agent for leather
    WO2005113839A2 (en) Aqueous compositions containing alkoxylated alcohols and hydrophobic components, method for the production and use thereof
    EP0746629B1 (en) Use of sulfonated substances for stuffing leather
    WO2003060167A1 (en) Cationic-emulsified greasing agents
    DE3504308A1 (en) Process for the simultaneous fat-liquoring and water-repellent finishing of tanned leather
    DE2819937A1 (en) PREPARATION FOR GREASING LEATHER
    WO1996025523A1 (en) Treatment agents for leathers and hides
    DE10332991A1 (en) Rendering leather and pelts hydrophobic, useful in preparation of e.g. clothes and furniture, by treatment with mixture containing carboxylated and non-carboxylated polysiloxanes
    DE10111196A1 (en) New composition useful for leather treatment and as an emulsifier comprises sulfo-functional di- or tribasic carboxylic acid esters and nonhydroxylic ethers and esters

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 20040218

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

    AX Request for extension of the european patent

    Extension state: AL LT LV MK

    AKX Designation fees paid

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    RAP1 Party data changed (applicant data changed or rights of an application transferred)

    Owner name: DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

    REF Corresponds to:

    Ref document number: 50309326

    Country of ref document: DE

    Date of ref document: 20080417

    Kind code of ref document: P

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080616

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080605

    Ref country code: SK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    Ref country code: CZ

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080805

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: RO

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    EN Fr: translation not filed
    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    26N No opposition filed

    Effective date: 20081208

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080831

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20080804

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20081226

    Ref country code: BG

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080605

    Ref country code: EE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080831

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080831

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080831

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080305

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080804

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: HU

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080906

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20080804

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20080606

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R081

    Ref document number: 50309326

    Country of ref document: DE

    Owner name: DYSTAR COLOURS DISTRIBUTION GMBH, DE

    Free format text: FORMER OWNER: DYSTAR COLOURS DEUTSCHLAND GMBH, 65929 FRANKFURT, DE

    Effective date: 20111216

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R081

    Ref document number: 50309326

    Country of ref document: DE

    Owner name: DYSTAR COLOURS DISTRIBUTION GMBH, DE

    Free format text: FORMER OWNER: DYSTAR COLOURS DISTRIBUTION GMBH, 65929 FRANKFURT, DE

    Effective date: 20130709

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20130924

    Year of fee payment: 11

    Ref country code: AT

    Payment date: 20130726

    Year of fee payment: 11

    REG Reference to a national code

    Ref country code: AT

    Ref legal event code: PC

    Ref document number: 388246

    Country of ref document: AT

    Kind code of ref document: T

    Owner name: DYSTAR COLOURS DISTRIBUTION GMBH, DE

    Effective date: 20131009

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: TR

    Payment date: 20130703

    Year of fee payment: 11

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20130821

    Year of fee payment: 11

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 50309326

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: AT

    Ref legal event code: MM01

    Ref document number: 388246

    Country of ref document: AT

    Kind code of ref document: T

    Effective date: 20140804

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20140804

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 50309326

    Country of ref document: DE

    Effective date: 20150303

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20140804

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20150303

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: TR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20140804