EP3402905A1 - Method for hydrophobising leather and leather produced by means of same - Google Patents

Method for hydrophobising leather and leather produced by means of same

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Publication number
EP3402905A1
EP3402905A1 EP17700338.1A EP17700338A EP3402905A1 EP 3402905 A1 EP3402905 A1 EP 3402905A1 EP 17700338 A EP17700338 A EP 17700338A EP 3402905 A1 EP3402905 A1 EP 3402905A1
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EP
European Patent Office
Prior art keywords
leather
pressure
pressure vessel
compressed gas
process according
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
EP17700338.1A
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German (de)
French (fr)
Other versions
EP3402905B1 (en
Inventor
Manfred Renner
Andreas Sengespeick
Michael Prokein
Eckhard Weidner
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Ruhr Universitaet Bochum
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Ruhr Universitaet Bochum
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Priority to PL17700338T priority Critical patent/PL3402905T3/en
Publication of EP3402905A1 publication Critical patent/EP3402905A1/en
Application granted granted Critical
Publication of EP3402905B1 publication Critical patent/EP3402905B1/en
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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

Definitions

  • the present invention relates to a leather hydrophobization process and leather made therewith.
  • the term “leather” is understood to mean tanned collagen-containing material, with and without hair, which has been obtained by a preceding tanning process.
  • the term “leather” therefore includes not only leather as such, but also furs and skins made from animal hides or skins.
  • the leather can be derived from any animal such as cattle, sheep, goats, pigs, buffalos, birds, reptiles, etc.
  • the tanning process by which the leather is obtained may be a mineral, vegetable or synthetic tanning process, according to the type of Tanning used tannins (mineral salts, vegetable tannins, synthetic tanning agents).
  • the term “leather” further includes leather of any thickness, for example, very thin bag leather, but also very thick sole leather.
  • Conventional tanning processes for the manufacture of leather include a series of aqueous baths in which the raw material is treated to become leather. These aqueous baths are divided into the works in the so-called water workshop, the actual tanning and retanning.
  • the aqueous baths therefore comprise all operations which are carried out in an aqueous medium for the production of leather. These include, for example, weeping, dehairing (ashening), pimpling, tanning, retanning, fatting, dyeing, etc.
  • the individual treatment processes in this leather production are well known to those skilled in the art and therefore need not be further explained.
  • the present disclosure is “leather”. Also tanned, treated and dried collagen-containing material before the state “crust” is thus “leather”.
  • the term “crust” refers to the condition of an animal's skin before the so-called finishing, that is to say before the final surface appearance applied to the surface.
  • finishing that is to say before the final surface appearance applied to the surface.
  • tanned, treated and dried collagen-containing material which, after drying, has not been subjected to any mechanical work such as, for example, the tunnel or millen.
  • Freshly tanned leather is wet or at least moist and needs to be dried.
  • so-called tunnel dryers are used, in which the leather is dried by means of elevated temperature, or so-called vacuum dryer, in which the leather is dried by applying a vacuum at optionally also elevated temperature.
  • leather Even when dried, however, leather contains bound water. Excessive drying, with which the water bound in the leather would be partially or even completely removed, is undesirable because this would cause embrittlement and degeneration of the leather. Overly dried leather becomes brittle and therefore unusable.
  • dry leather is therefore understood to mean tanned collagen-containing material which has been dried for at least 48 hours at 50 ° C.
  • dry leather in the context of this disclosure, by definition, this dry leather has a water content of 0% by weight, although it still contains water bound in the leather. "Increased water content” is used in the context of this disclosure if the leather contains more water than the water which is bound in the leather after the described drying, i. if there is free water in the leather.
  • Collagen-containing material and thus the hides used as the raw material for leather production, naturally has a certain proportion of ionizable and non-ionizable functional groups.
  • the proportion of these groups varies depending on the chemicals used. For example, in chrome tanning, the proportion of acidic carboxy groups is reduced. If vegetable tanning agents are used for tanning, the proportion of OH groups increases significantly due to the hydroxyl groups present in the vegetable tannins. Due to the natural origin of collagen-containing material and a large number of different leather chemicals that can be used in the leather manufacturing process, a general statement about the shares of the existing functional groups and thus also on the later bound in the leather after drying water is not possible.
  • leather is mainly used in the footwear and clothing industry, in the automotive industry and in the furniture industry. In the mentioned fields of application it is increasingly required that the leather is water-repellent, ie has a high resistance to water penetration. Unfortunately, leather is hydrophilic, especially vegetable tanned leather, which is why the required water-repellent properties represent a major challenge for the leather industry.
  • hydrophobic substances such as oils, fats, waxes, paraffins, fluorocarbons and hydrophobized polymers in the leather structure. This is usually done in an aqueous medium before, during or after retanning using emulsifiers which allow a sufficiently fine distribution of the water-insoluble hydrophobizing agents in the aqueous phase.
  • the emulsions must be in a subsequent process step
  • known leather hydrophobization methods not only improve the water-repellent properties of the leather but also increase its softness. Sometimes this is a positive side-effect, but in other cases this is disadvantageous, for example for products requiring special strength, such as shoe soles. Furthermore, especially leather products which require high strength are produced using a high proportion of hydrophilic vegetable tanning agents which embed themselves in the leather and prevent or at least greatly hinder a water-repellent finish by means of conventional hydrophobization processes. A permanent and complete, ie continuous hydrophobing especially of vegetable and / or synthetic tanned leather is therefore not yet known. Only superficially applied systems for hydrophobing fail at higher mechanical stress, such as occurs in the area of shoe leather, quickly and therefore do not represent a satisfactory solution.
  • the present invention has set itself the goal of providing a Lederhydrophobi mecanicsclar which allows a long-term stable, complete and process technically well reproducible hydrophobing of vegetable and / or synthetic tanned leather in particular, so that by means of this method also deep hydrophobized leather can be produced, which for example as Shoe leather can be used.
  • the mixture used to treat the leather does not have to be supplied to the pressure vessel as such, but only has to be produced during treatment.
  • the hydrophobizing agent can be supplied to the pressure vessel before a pressure build-up, during a pressure build-up, during a pressure hold time or even during the relaxation of the pressure vessel.
  • the water repellent can already be brought into contact with the leather to be treated before the leather is introduced into the pressure vessel. It is only important that during the treatment of the leather, a mixture of the compressed gas and the hydrophobing agent is formed. In other words, the hydrophobing agent used must be at least partially soluble in the compressed gas.
  • compressed C0 2 is preferably used as the compressed gas.
  • other compressed gases may also be used, for example carbon monoxide, ethane, propane, pentane, ammonia, fluorine-chlorine-alkanes and mixtures of these substances.
  • the hydrophobizing agent dissolved in the compressed gas can also completely penetrate thick leathers due to the low viscosity and excellent diffusion properties of the compressed gas, and thus achieve deep hydrophobization.
  • the penetration of the In particular, the hydrophobizing agent dissolved in the compressed gas can be controlled over the duration of the treatment, so that only shallow layers of the leather can be rendered hydrophobic by means of a suitable, relatively short treatment time, if so desired.
  • Hydrophobizing agents which can be used are reactive polymers, hydrocarbons, silanes, silanols and siloxanes, which preferably have one or more epoxide, ester, carboxyl, anhydride, amine, hydroxide and / or halide functional groups.
  • Particularly preferred according to the present invention is the use of a hydrophobing agent which consists of at least one silane and / or silanol and / or siloxane.
  • a hydrophobing agent which consists of at least one silane and / or silanol and / or siloxane.
  • compounds of the type alkylsilanol, alkoxysilane, alkylchlorosilane and organofunctionalized silanes are outstandingly suitable as water repellents in the process according to the invention.
  • These may be monofunctional, difunctional and / or trifunctional compounds.
  • these compounds have the general form Ri (i-3) R2 (o-2) -SiX (i -3 ), wherein Ri denotes a hydrophobic group, R 2 denotes an organically functionalized radical and X a hydrolyzable group, usually one Alkoxy, more rarely a chlorine group represents.
  • Ri denotes a hydrophobic group
  • R 2 denotes an organically functionalized radical
  • X a hydrolyzable group, usually one Alkoxy, more rarely a chlorine group represents.
  • the organically functionalized R 2 groups may additionally have functional groups capable of forming covalent bonds with the hydroxyl and the hydroxyl groups
  • Such additional functional groups can be amino, epoxide, ester and carboxy groups.
  • Examples of compounds having such additional functional groups are 3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.
  • alkoxysilanes are particularly preferred as water repellents Al kylmethoxysilane, wherein alkyl is Ci to C 2 o-alkyl.
  • alkylmethoxysilanes are dialkylmethoxysilane, alkyltrimethoxysilane and mixtures of these substances.
  • Very particular preference is given to hexadecyltrimethoxysilane, isooctyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane or mixtures of the abovementioned substances.
  • alkylalkoxysilanes but also alkylchlorosilanes, hydrolyze to give alkylsilanols which can polymerize with elimination of water or react with nucleophilic reagents such as, for example, hydroxyl groups, carboxyl groups and / or amines. no tendency can bind.
  • nucleophilic reagents such as, for example, hydroxyl groups, carboxyl groups and / or amines. no tendency can bind.
  • the hydrophobizing agent is fixed in the leather or incorporated into the leather, whereby the desired long-term stable and insensitive to mechanical stress hydrophobing of the leather is achieved.
  • silanols are used as hydrophobing agents
  • alkyl silanols such as, for example, Methylsilanoltriol, diphenylsilanediol and / or trimethylsilanol
  • silanols in particular alkyl silanols, therefore leather with little or no residual water content can be well hydrophobed.
  • the compressed gas After treating the leather with the mixture of compressed gas and hydrophobizing agent, the compressed gas is depressurized to ambient pressure and non-leather-fixed hydrophobing agent is separated.
  • the gas used as well as the excess hydrophobizing agent separated from the gas can be reused.
  • a wastewater treatment is not necessary because in principle no wastewater is obtained in the leather hydrophobization process according to the invention.
  • the main advantage of the process according to the invention is the possibility of long-term stable hydrophobing of a large variety of collagenous materials regardless of the nature of the starting material and regardless of the nature of the leather production process.
  • the hydrophobing process according to the invention for example, both soft chrome leather and vegetable and / or synthetically tanned leather of high strength can be rendered hydrophobic.
  • the hydrophobizing agent specifically contains solid chemical binders. fertilize with the collagen and / or the substances bound in the collagen. Furthermore, according to the invention, the hydrophobizing agent can crosslink with itself and thus form a hydrophobic network in the leather.
  • the hydrophobic treatment according to the process of the invention is not carried out during the working steps which occur in conventional leather production in aqueous baths.
  • the intermediate "leather” is hydrophobicized, which has been obtained from a kind of leather manufacturing process of any kind.
  • the water content of the leather i. the content of free water, between 0 wt .-% and 25 wt .-% amount.
  • the specification of a water content of 0% by weight does not mean that no water is present in the leather at all, but this indication means that exclusively bound water is present in the leather, but no free water.
  • the term "25% by weight of water content” therefore means that in addition to the bound water, free water is still present in the leather in a proportion which corresponds to one quarter of the total weight of the dry leather.
  • the quality of the hydrophobing can be improved if not only bound water is contained in the leather provided, but also a certain proportion of free water, but should not exceed 25 wt .-% , Accordingly, in the inventive method of
  • Water content of the leather before introducing the leather into the pressure vessel or after the treatment in the pressure vessel to a value between 0 and 25 % By weight.
  • the water content of the leather in the pressure vessel to a value between 0 and 25 wt .-% can be adjusted.
  • the possibilities for setting an increased water content in leather are many.
  • a desired, increased water content of the leather can already be achieved in that the leather is not dried in the drying process until there is only bound water in the leather. Instead, the drying process of the leather can be terminated when the desired, increased water content between 0 and 25 wt .-% is reached.
  • the starting product is leather with a water content of 0% by weight and an increased water content is desired
  • the increase in the water content can be achieved, for example, by treating the dry leather in a climate chamber in which sufficient air humidity is present, which causes the dry leather to absorb moisture from the air.
  • the dry leather can be sprayed or dripped with water. Another option is to add steam or saturated steam to a container containing the dry leather.
  • the adjustment of the desired, increased water content during the supply of the compressed gas can be carried out in the pressure vessel, either by dissolving water in the supplied compressed gas or by separately introducing water into the pressure vessel during a supply of the compressed gas.
  • the setting of an increased water content can also be done after the introduction of the compressed gas into the pressure vessel, either during a pressure holding period or during the relaxation of the pressure vessel or only after the expansion of the pressure vessel.
  • the hydrophobizing agent used in the process according to the invention is preferably supplied to the pressure vessel before a pressure build-up, during the pressure build-up, during a pressure hold time or during the relaxation of the pressure vessel.
  • the feeding can be done for example by presenting the hydrophobizing agent in an associated with the pressure vessel feed chamber, by pumping, by spraying and / or by previously dissolving the hydrophobizing agent in the compressed gas. It is also possible, although not preferred, to apply the hydrophobing agent prior to introduction of the leather into the pressure vessel by, for example, pouring on the leather or spraying the leather. It is also possible to add different water repellents in succession.
  • the mixture of compressed gas and the hydrophobing agent used i. the dissolution of the hydrophobizing agent in the compressed gas takes place independently of the desired type of hydrophobing alone
  • the parameters pressure and temperature, which influence a solution of the hydrophobizing agent in the compressed gas vary depending on the hydrophobing agent used.
  • the treatment of the leather takes place advantageously at a pressure of 30 to 300 bar, preferably at a pressure of 50 to 250 bar and more preferably at a pressure of 70 to 200 bar.
  • the most suitable pressure for a given hydrophobing agent and a given hydrophobing task may need to be determined by series of tests.
  • the treatment of the leather is advantageously carried out at a temperature of 10 ° C to 150 ° C, preferably at a temperature of 20 ° C to 130 ° C and more preferably at a temperature of 30 ° C to 110 ° C, in particular the temperature range of 60 ° C to 80 ° C has been found to be particularly suitable.
  • a most suitable temperature is optionally determined by experiment.
  • the penetration depth of the hydrophobing agent can be controlled above all over the treatment time. It is obvious that thin leather requires a shorter treatment time to complete penetration with hydrophobing agent than thick leather. According to the invention, the treatment of the leather takes place advantageously for a period of 5 minutes to 10 hours, preferably for 10 minutes to 5 hours and more preferably for 30 minutes to 4 hours.

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

Abstract

The invention relates to a method for hydrophobising leather, comprising the steps: providing tanned and at least partially dried leather, the free-water content of which is in the range from 0 to 25 wt.% with respect to the weight of the dried leather; treating the leather with a mixture of compressed gas and a hydrophobising agent at a pressure of at least 30 bar in a pressure vessel; and relieving the pressure of the pressure vessel to ambient pressure. Leathers with a hydrophobic surface, as well as thick and firm, deep hydrophobised leathers can be obtained by applying the claimed method, which can be used, for example, for the soles of shoes.

Description

Lederhydrophobierungsverfahren und damit hergestelltes Leder  Leather hydrophobization process and leather produced therewith
Die vorliegende Erfindung betrifft ein Lederhydrophobierungsverfahren und damit hergestelltes Leder. The present invention relates to a leather hydrophobization process and leather made therewith.
Im Rahmen der folgenden Offenbarung wird unter dem Begriff "Leder" gegerbtes kollagenhaltiges Material mit und ohne Haar verstanden, das durch ein vorangegangenes Gerbverfahren erhalten worden ist. Der Begriff "Leder" umfasst demnach nicht nur Leder als solches, sondern auch aus Tierhäuten oder Fellen hergestellte Pelze und Felle. Das Leder kann von beliebigen Tieren stammen, beispielsweise von Rindern, Schafen, Ziegen, Schweinen, Büffeln, Vögeln, Reptilien etc. Das Gerbverfahren, mit dem das Leder erhalten wird, kann ein mineralisches, vegetabiles oder synthetisches Gerbverfahren sein, entsprechend der Art der zur Gerbung verwendeten Gerbstoffe (Mineralsalze, pflanzliche Gerbstoffe, synthetische Gerbstoffe). Der Begriff "Leder" umfasst des Weiteren Leder jeglicher Dicke, beispielsweise besonders dünnes Täschnerleder, aber auch sehr dickes Sohlenleder. In the context of the following disclosure, the term "leather" is understood to mean tanned collagen-containing material, with and without hair, which has been obtained by a preceding tanning process. The term "leather" therefore includes not only leather as such, but also furs and skins made from animal hides or skins. The leather can be derived from any animal such as cattle, sheep, goats, pigs, buffalos, birds, reptiles, etc. The tanning process by which the leather is obtained may be a mineral, vegetable or synthetic tanning process, according to the type of Tanning used tannins (mineral salts, vegetable tannins, synthetic tanning agents). The term "leather" further includes leather of any thickness, for example, very thin bag leather, but also very thick sole leather.
Herkömmliche Gerbverfahren zur Herstellung von Leder umfassen eine Reihe wässri- ger Bäder, in denen das Rohmaterial behandelt wird, um zu Leder zu werden. Diese wässrigen Bäder gliedern sich in die Arbeiten in der sogenannten Wasserwerkstatt, die eigentliche Gerbung sowie die Nachgerbung. Die wässrigen Bäder umfassen demnach alle Arbeitsschritte, die in einem wässrigen Medium zur Herstellung von Leder durchgeführt werden. Dazu gehören beispielsweise das Weichen, das Enthaaren (Äschern), das Pickeln, das Gerben, das Nachgerben, das Fetten, das Färben etc. Die einzelnen Behandlungsprozesse im Rahmen dieser Lederherstellung sind Fachleuten auf dem Gebiet wohlbekannt und brauchen daher nicht weiter erläutert zu werden. Conventional tanning processes for the manufacture of leather include a series of aqueous baths in which the raw material is treated to become leather. These aqueous baths are divided into the works in the so-called water workshop, the actual tanning and retanning. The aqueous baths therefore comprise all operations which are carried out in an aqueous medium for the production of leather. These include, for example, weeping, dehairing (ashening), pimpling, tanning, retanning, fatting, dyeing, etc. The individual treatment processes in this leather production are well known to those skilled in the art and therefore need not be further explained.
Sobald die mittels der verschiedenen Behandlungsschritte gegerbten Häute getrocknet werden, handelt es sich im Rahmen der vorliegenden Offenbarung um "Leder". Auch gegerbtes, behandeltes und getrocknetes kollagenhaltiges Material vor dem Zustand "Crust" ist somit "Leder". Als "Crust" wird in der Gerbereiindustrie der Zustand einer tierischen Haut vor dem sogenannten Finishing, d.h. vor der auf die Oberfläche aufgebrachten, endgültigen Oberflächenoptik bezeichnet. Als "Leder" im Rahmen dieser Erfindung wird demnach insbesondere auch gegerbtes, behandeltes und getrocknetes kollagenhaltiges Material angesehen, welches nach der Trocknung noch keinen mechanischen Arbeiten wie beispielsweise dem Stollen oder dem Millen unterzogen worden ist. Once the skins tanned by the various treatment steps are dried, the present disclosure is "leather". Also tanned, treated and dried collagen-containing material before the state "crust" is thus "leather". In the tanning industry, the term "crust" refers to the condition of an animal's skin before the so-called finishing, that is to say before the final surface appearance applied to the surface. As "leather" in the context of this invention, therefore, especially tanned, treated and dried collagen-containing material which, after drying, has not been subjected to any mechanical work such as, for example, the tunnel or millen.
Frisch gegerbtes Leder ist nass oder zumindest feucht und muss getrocknet werden. Hierzu werden beispielsweise sogenannte Tunneltrockner verwendet, in denen das Leder mittels erhöhter Temperatur getrocknet wird, oder auch sogenannte Vakuumtrockner, in denen das Leder durch Aufbringen von Unterdruck bei gegebenenfalls ebenfalls erhöhter Temperatur getrocknet wird. Selbst in getrocknetem Zustand enthält Leder jedoch gebundenes Wasser. Eine übermäßige Trocknung, mit der auch das im Leder gebundene Wasser teilweise oder sogar vollständig entfernt werden würde, ist unerwünscht, denn dies hätte eine Versprödung und Degeneration des Leders zur Folge. Übermäßig getrocknetes Leder wird brüchig und damit unbrauchbar. Im Rahmen der vorliegenden Offenbarung wird unter "trockenem Leder" deshalb gegerbtes kollagenhaltiges Material verstanden, das mindestens 48 Stunden lang bei 50°C getrocknet worden ist und somit kein freies Wasser mehr enthält, sondern ausschließlich im Leder gebundenes Wasser. Wenn im Rahmen dieser Offenbarung von "trockenem Leder" die Rede ist, dann hat dieses trockene Leder definitionsgemäß einen Wassergehalt von 0 Gew.-%, obwohl es noch im Leder gebundenes Wasser enthält. Von "erhöhtem Wassergehalt" wird im Rahmen dieser Offenbarung gesprochen, wenn das Leder mehr Wasser enthält als dasjenige Wasser, welches nach der beschriebenen Trocknung im Leder gebunden vorliegt, d.h. wenn im Leder freies Wasser vorliegt. Freshly tanned leather is wet or at least moist and needs to be dried. For this purpose, for example, so-called tunnel dryers are used, in which the leather is dried by means of elevated temperature, or so-called vacuum dryer, in which the leather is dried by applying a vacuum at optionally also elevated temperature. Even when dried, however, leather contains bound water. Excessive drying, with which the water bound in the leather would be partially or even completely removed, is undesirable because this would cause embrittlement and degeneration of the leather. Overly dried leather becomes brittle and therefore unusable. In the context of the present disclosure, "dry leather" is therefore understood to mean tanned collagen-containing material which has been dried for at least 48 hours at 50 ° C. and thus no longer contains free water, but exclusively water bound in the leather. By "dry leather" in the context of this disclosure, by definition, this dry leather has a water content of 0% by weight, although it still contains water bound in the leather. "Increased water content" is used in the context of this disclosure if the leather contains more water than the water which is bound in the leather after the described drying, i. if there is free water in the leather.
Kollagenhaltiges Material und damit die als Rohmaterial für die Lederherstellung eingesetzten Häute verfügt von Natur aus über einen bestimmten Anteil an ionisierbaren und nicht ionisierbaren funktionellen Gruppen. Im Laufe des Lederherstellungsprozesses verändert sich der Anteil dieser Gruppen in Abhängigkeit der eingesetzten Chemikalien. Zum Beispiel wird bei der Chromgerbung der Anteil an sauren Carboxygruppen verringert. Werden zum Gerben vegetabile Gerbstoffe eingesetzt, so erhöht sich der Anteil von OH-Gruppen aufgrund der in den vegetabilen Gerbstoffen vorhandenen Hydroxylgruppen signifikant. Aufgrund des natürlichen Ursprungs kollagenhaltigen Materials sowie einer Vielzahl verschiedener Lederchemikalien, die im Rahmen des Lederherstellungsprozesses Verwendung finden können, ist eine allgemeingültige Angabe über die Anteile der vorhandenen funktionellen Gruppen und damit auch über das später im Leder nach der Trocknung noch gebundene Wasser nicht möglich. Leder findet heutzutage hauptsächlich Anwendung in der Schuh- und Bekleidungsindustrie, in der Automobilindustrie und in der Möbelindustrie. In den genannten Anwendungsgebieten wird zunehmend gefordert, dass das Leder wasserabweisend ist, d.h. eine hohe Resistenz gegen ein Eindringen von Wasser hat. Leider ist Leder hydrophil, insbesondere vegetabil gegerbtes Leder, weshalb die geforderten wasserabweisenden Eigenschaften eine große Herausforderung für die Lederindustrie darstellen. Collagen-containing material, and thus the hides used as the raw material for leather production, naturally has a certain proportion of ionizable and non-ionizable functional groups. During the leather manufacturing process, the proportion of these groups varies depending on the chemicals used. For example, in chrome tanning, the proportion of acidic carboxy groups is reduced. If vegetable tanning agents are used for tanning, the proportion of OH groups increases significantly due to the hydroxyl groups present in the vegetable tannins. Due to the natural origin of collagen-containing material and a large number of different leather chemicals that can be used in the leather manufacturing process, a general statement about the shares of the existing functional groups and thus also on the later bound in the leather after drying water is not possible. Today, leather is mainly used in the footwear and clothing industry, in the automotive industry and in the furniture industry. In the mentioned fields of application it is increasingly required that the leather is water-repellent, ie has a high resistance to water penetration. Unfortunately, leather is hydrophilic, especially vegetable tanned leather, which is why the required water-repellent properties represent a major challenge for the leather industry.
Um die wasserabweisenden Eigenschaften von kollagenhaltigen Materialien zu verbessern, ist es bereits bekannt, hydrophobe Substanzen wie Öle, Fette, Wachse, Paraffine, Fluorcarbone und hydrophobierte Polymere in die Lederstruktur einzubringen. Üblicherweise geschieht dies im wässrigen Medium vor, während oder nach der Nachgerbung unter Verwendung von Emulgatoren, die eine ausreichend feine Verteilung der wasserunlöslichen Hydrophobierungsmittel in der wässrigen Phase ermöglichen. Die Emulsionen müssen in einem anschließenden Verfahrensschritt In order to improve the water-repellent properties of collagen-containing materials, it is already known to incorporate hydrophobic substances such as oils, fats, waxes, paraffins, fluorocarbons and hydrophobized polymers in the leather structure. This is usually done in an aqueous medium before, during or after retanning using emulsifiers which allow a sufficiently fine distribution of the water-insoluble hydrophobizing agents in the aqueous phase. The emulsions must be in a subsequent process step
aufgebrochen werden, um eine Einlagerung der wasserunlöslichen Hydrophobierungsmittel in das Leder zu gestatten. Bei diesen bekannten Verfahren wird ein signifikanter Anteil der verwendeten Chemikalien nicht im Kollagen fixiert oder eingelagert und verbleibt somit im Abwasser. Dies belastet nicht nur die Umwelt, sondern führt auch zu erhöhten Kosten für überschüssig einzusetzende Chemikalien und anschließende Verfahrensschritte zur Abwasseraufbereitung. are broken up to allow the inclusion of the water-insoluble hydrophobing agents in the leather. In these known methods, a significant proportion of the chemicals used is not fixed or stored in the collagen and thus remains in the wastewater. This not only pollutes the environment, but also leads to increased costs for excessively used chemicals and subsequent process steps for wastewater treatment.
Bekannte Lederhydrophobierungsverfahren verbessern darüber hinaus nicht nur die wasserabweisenden Eigenschaften des Leders, sondern erhöhen auch dessen Weichheit. Manchmal ist dies ein positiver Nebeneffekt, in anderen Fällen ist dies jedoch nachteilig, beispielsweise bei Produkten, die eine besondere Festigkeit benötigen wie z.B. Schuhsohlen. Ferner werden insbesondere Lederprodukte, die eine hohe Festigkeit benötigen, unter Verwendung eines hohen Anteils an hydrophilen vegetabilen Gerbstoffen hergestellt, die sich im Leder einlagern und eine wasserabweisende Ausrüstung mittels konventioneller Hydrophobierungsverfahren verhindern oder zumindest stark erschweren. Eine dauerhafte und vollständige, d.h. durchgehende Hydrophobierung insbesondere von vegetabil und/oder synthetisch gegerbtem Leder ist deshalb bisher nicht bekannt. Lediglich oberflächig aufgebrachte Systeme zur Hydrophobierung versagen bei höherer mechanischer Belastung, wie sie etwa im Bereich von Schuhleder vorkommt, schnell und stellen daher keine zufriedenstellende Lösung dar. Die vorliegende Erfindung hat sich zum Ziel gesetzt, ein Lederhydrophobierungsverfahren anzugeben, welches eine langzeitstabile, vollständige und prozesstechnisch gut reproduzierbare Hydrophobierung von insbesondere vegetabil und/oder synthetisch gegerbtem Leder ermöglicht, so dass mittels dieses Verfahrens auch tiefenhyd- rophobiertes Leder herstellbar ist, welches beispielsweise als Schuhsohlenleder Verwendung finden kann. In addition, known leather hydrophobization methods not only improve the water-repellent properties of the leather but also increase its softness. Sometimes this is a positive side-effect, but in other cases this is disadvantageous, for example for products requiring special strength, such as shoe soles. Furthermore, especially leather products which require high strength are produced using a high proportion of hydrophilic vegetable tanning agents which embed themselves in the leather and prevent or at least greatly hinder a water-repellent finish by means of conventional hydrophobization processes. A permanent and complete, ie continuous hydrophobing especially of vegetable and / or synthetic tanned leather is therefore not yet known. Only superficially applied systems for hydrophobing fail at higher mechanical stress, such as occurs in the area of shoe leather, quickly and therefore do not represent a satisfactory solution. The present invention has set itself the goal of providing a Lederhydrophobierungsverfahren which allows a long-term stable, complete and process technically well reproducible hydrophobing of vegetable and / or synthetic tanned leather in particular, so that by means of this method also deep hydrophobized leather can be produced, which for example as Shoe leather can be used.
Diese Aufgabe ist erfindungsgemäß gelöst durch ein Lederhydrophobierungsverfahren, welches die folgenden Schritte aufweist: This object is achieved according to the invention by a leather hydrophobization process, which comprises the following steps:
Bereitstellen von gegerbtem, zumindest teilweise getrocknetem Leder, dessen Gehalt an freiem Wasser im Bereich von 0 bis 25 Gew.-% bezogen auf das Gewicht des getrockneten Leders liegt,  Providing tanned, at least partially dried leather whose free water content ranges from 0 to 25% by weight, based on the weight of the dried leather,
Behandeln des Leders mit einer Mischung aus komprimiertem Gas und einem Hydrophobierungsmittel bei einem Druck von mindestens 30 bar in einem Druckbehälter, und  Treating the leather with a mixture of compressed gas and a hydrophobing agent at a pressure of at least 30 bar in a pressure vessel, and
Entspannen des Druckbehälters auf Umgebungsdruck.  Relax the pressure vessel to ambient pressure.
Die zum Behandeln des Leders verwendete Mischung muss dem Druckbehälter nicht als solche zugeführt werden, sondern muss lediglich beim Behandeln entstehen. Das Hydrophobierungsmittel kann dem Druckbehälter vor einem Druckaufbau, während eines Druckaufbaus, während einer Druckhaltezeit oder auch während des Entspannens des Druckbehälters zugeführt werden. Auch kann das Hydrophobierungsmittel mit dem zu behandelnden Leder bereits in Kontakt gebracht werden, bevor das Leder in den Druckbehälter eingebracht wird. Wichtig ist lediglich, dass während des Behandeins des Leders eine Mischung aus dem komprimierten Gas und dem Hydrophobierungsmittel entsteht. Mit anderen Worten muss das verwendete Hydrophobierungsmittel in dem komprimierten Gas zumindest teilweise löslich sein. The mixture used to treat the leather does not have to be supplied to the pressure vessel as such, but only has to be produced during treatment. The hydrophobizing agent can be supplied to the pressure vessel before a pressure build-up, during a pressure build-up, during a pressure hold time or even during the relaxation of the pressure vessel. Also, the water repellent can already be brought into contact with the leather to be treated before the leather is introduced into the pressure vessel. It is only important that during the treatment of the leather, a mixture of the compressed gas and the hydrophobing agent is formed. In other words, the hydrophobing agent used must be at least partially soluble in the compressed gas.
In dem erfindungsgemäßen Lederhydrophobierungsverfahren wird als komprimiertes Gas vorzugsweise komprimiertes C02 eingesetzt. Jedoch können im Rahmen der Erfindung alternativ oder zusätzlich auch andere komprimierte Gase zum Einsatz kommen, beispielsweise Kohlenmonoxid, Ethan, Propan, Pentan, Ammoniak, Fluor- Chlor-Alkane und Mischungen dieser Stoffe. Das in dem komprimierten Gas gelöste Hydrophobierungsmittel kann aufgrund der geringen Viskosität und hervorragenden Diffusionseigenschaft des komprimierten Gases auch dicke Leder vollständig durchdringen und damit eine Tiefenhydrophobierung erzielen. Das Eindringverhalten des im komprimierten Gas gelösten Hydrophobierungsmittels kann vor allem über die Behandlungsdauer gesteuert werden, so dass mittels einer geeigneten, relativ kurzen Behandlungsdauer auch nur oberflächennahe Schichten des Leders hydrophobiert werden können, falls dies so gewünscht ist. In the leather hydrophobization process according to the invention, compressed C0 2 is preferably used as the compressed gas. However, in the context of the invention, alternatively or additionally, other compressed gases may also be used, for example carbon monoxide, ethane, propane, pentane, ammonia, fluorine-chlorine-alkanes and mixtures of these substances. The hydrophobizing agent dissolved in the compressed gas can also completely penetrate thick leathers due to the low viscosity and excellent diffusion properties of the compressed gas, and thus achieve deep hydrophobization. The penetration of the In particular, the hydrophobizing agent dissolved in the compressed gas can be controlled over the duration of the treatment, so that only shallow layers of the leather can be rendered hydrophobic by means of a suitable, relatively short treatment time, if so desired.
Als Hydrophobierungsmittel können reaktive Polymere, Kohlenwasserstoffe, Silane, Silanole und Siloxane verwendet werden, die vorzugsweise ein oder mehrere funktionelle Gruppen vom Typ Epoxid, Ester, Carboxyl, Anhydrid, Amin, Hydroxid und/oder Halogenid aufweisen. Besonders bevorzugt ist gemäß der vorliegenden Erfindung der Einsatz eines Hydrophobierungsmittels, welches aus wenigstens einem Silan und/oder Silanol und/oder Siloxan besteht. Speziell wurde gefunden, dass Verbindungen vom Typ Alkylsilanol, Alkoxysilan, Alkylchlorsilan und organofunktionalisierte Silane hervorragend als Hydrophobierungsmittel im erfindungsgemäßen Verfahren geeignet sind. Hierbei kann es sich um monofunktionale, difunktionale und/oder trifunktionale Verbindungen handeln. In der Regel haben diese Verbindungen die allgemeine Form Ri(i-3)R2(o-2)-SiX(i-3), wobei Ri eine hydrophobe Gruppe bezeichnet, R2 einen organisch funktionalisierten Rest und X eine hydrolysierbare Gruppe, meist eine Alkoxygruppe, seltener auch eine Chlor-Gruppe, darstellt. Durch Hydrolysereaktionen mit Wasser bilden solche Verbindungen Silanole der Form R(i-3)-Si(OH)(i-3). Die organisch funktionalisierten R2-Gruppen können zusätzlich funktionelle Gruppen aufweisen, die in der Lage sind, kovalente Bindungen mit den Hydroxyl- sowie den Hydrophobizing agents which can be used are reactive polymers, hydrocarbons, silanes, silanols and siloxanes, which preferably have one or more epoxide, ester, carboxyl, anhydride, amine, hydroxide and / or halide functional groups. Particularly preferred according to the present invention is the use of a hydrophobing agent which consists of at least one silane and / or silanol and / or siloxane. In particular, it has been found that compounds of the type alkylsilanol, alkoxysilane, alkylchlorosilane and organofunctionalized silanes are outstandingly suitable as water repellents in the process according to the invention. These may be monofunctional, difunctional and / or trifunctional compounds. In general, these compounds have the general form Ri (i-3) R2 (o-2) -SiX (i -3 ), wherein Ri denotes a hydrophobic group, R 2 denotes an organically functionalized radical and X a hydrolyzable group, usually one Alkoxy, more rarely a chlorine group represents. By hydrolysis reactions with water such compounds form silanols of the form R (i -3 ) -Si (OH) (i -3 ). The organically functionalized R 2 groups may additionally have functional groups capable of forming covalent bonds with the hydroxyl and the hydroxyl groups
Carboxyl- und Amino-Gruppen des Leders auszubilden. Solche zusätzlichen funktionellen Gruppen können Amino-, Epoxid-, Ester- und Carboxy-Gruppen sein. Beispiele für Verbindungen mit solchen zusätzlichen funktionellen Gruppen sind 3-Amino- propyltrimethoxysilan, 3-Ureidopropyltrimethoxysilan und 3-Glycidoxypropyltri- methoxysilan. Form carboxyl and amino groups of the leather. Such additional functional groups can be amino, epoxide, ester and carboxy groups. Examples of compounds having such additional functional groups are 3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.
Unter den Alkoxysilanen sind als Hydrophobierungsmittel besonders bevorzugt Al- kylmethoxysilane, wobei Alkyl für Ci bis C2o-Alkyl steht. Beispiele für solche besonders bevorzugten Alkylmethoxysilane sind Dialkylmethoxysilan, Alkyltrimethoxysilan und Mischungen dieser Stoffe. Ganz besonders bevorzugt sind Hexadecyltrimethoxysilan, Isooctyltrimethoxysilan, Dimethyldiethoxysilan, Phenyltriethoxysilan oder Mischungen der vorgenannten Stoffe. Among the alkoxysilanes are particularly preferred as water repellents Al kylmethoxysilane, wherein alkyl is Ci to C 2 o-alkyl. Examples of such particularly preferred alkylmethoxysilanes are dialkylmethoxysilane, alkyltrimethoxysilane and mixtures of these substances. Very particular preference is given to hexadecyltrimethoxysilane, isooctyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane or mixtures of the abovementioned substances.
In Gegenwart von Wasser hydrolysieren Alkylalkoxysilane, aber auch Alkylchlorsilane zu Alkylsilanolen, die unter Wasserabspaltung polymerisieren können oder sich an nukleophile Reagenzien wie z.B. Hydroxylgruppen, Carboxylgruppen und/oder Ami- nogruppen binden können. Auf diese Weise wird das Hydrophobierungsmittel im Leder fixiert bzw. in das Leder eingelagert, wodurch die erwünschte langzeitstabile und gegenüber mechanischer Beanspruchung unempfindliche Hydrophobierung des Leders erreicht wird. In the presence of water, alkylalkoxysilanes, but also alkylchlorosilanes, hydrolyze to give alkylsilanols which can polymerize with elimination of water or react with nucleophilic reagents such as, for example, hydroxyl groups, carboxyl groups and / or amines. nogruppen can bind. In this way, the hydrophobizing agent is fixed in the leather or incorporated into the leather, whereby the desired long-term stable and insensitive to mechanical stress hydrophobing of the leather is achieved.
Wenn als Hydrophobierungsmittel Silanole zum Einsatz kommen, insbesondere Alkyl- silanole wie z.B. Methylsilanoltriol, Diphenylsilandiol und/oder Trimethylsilanol, kann auf den zuvor beschriebenen Hydrolyseschritt verzichtet werden. Mit Silanolen, insbesondere Alkylsilanolen, kann deshalb Leder mit wenig oder gar keinem Restwassergehalt gut hydrophobiert werden. When silanols are used as hydrophobing agents, in particular alkyl silanols, such as, for example, Methylsilanoltriol, diphenylsilanediol and / or trimethylsilanol, can be dispensed with the hydrolysis step described above. With silanols, in particular alkyl silanols, therefore leather with little or no residual water content can be well hydrophobed.
Nach dem Behandeln des Leders mit der Mischung aus komprimiertem Gas und Hydrophobierungsmittel wird das verdichtete Gas auf Umgebungsdruck entspannt und nicht im Leder fixiertes Hydrophobierungsmittel wird abgeschieden. Das verwendete Gas sowie das aus dem Gas abgetrennte, überschüssige Hydrophobierungsmittel können wieder verwendet werden. Eine Abwasserreinigung ist nicht notwendig, da beim erfindungsgemäßen Lederhydrophobierungsverfahren grundsätzlich kein Abwasser anfällt. After treating the leather with the mixture of compressed gas and hydrophobizing agent, the compressed gas is depressurized to ambient pressure and non-leather-fixed hydrophobing agent is separated. The gas used as well as the excess hydrophobizing agent separated from the gas can be reused. A wastewater treatment is not necessary because in principle no wastewater is obtained in the leather hydrophobization process according to the invention.
Der Hauptvorteil des erfindungsgemäßen Verfahrens ist in der Möglichkeit der lang- zeitstabilen Hydrophobierung einer großen Produktvielfalt kollagener Materialien unabhängig von der Art des Ausgangsmaterials und unabhängig von der Art des Lederherstellungsverfahrens zu sehen. Mit dem erfindungsgemäßen Hydrophobierungsverfahren kann zum Beispiel sowohl weiches Chromleder als auch vegetabil und/oder synthetisch gegerbtes Leder hoher Festigkeit hydrophobiert werden. The main advantage of the process according to the invention is the possibility of long-term stable hydrophobing of a large variety of collagenous materials regardless of the nature of the starting material and regardless of the nature of the leather production process. With the hydrophobing process according to the invention, for example, both soft chrome leather and vegetable and / or synthetically tanned leather of high strength can be rendered hydrophobic.
Konventionelle Hydrophobierungsverfahren hingegen funktionieren nur für spezielle Produktgruppen. Zusätzliche Hilfschemikalien, die bei konventionellen Hydrophobierungsverfahren notwendig sind, werden bei dem erfindungsgemäßen Verfahren nicht benötigt. Ferner sind die durch Anwendung des erfindungsgemäßen Verfahrens erhaltenen Ergebnisse sehr gut reproduzierbar, wohingegen selbst etablierte Hydrophobierungsverfahren für Chromleder unter einer eingeschränkten Reproduzierbarkeit leiden. Conventional hydrophobing processes, however, only work for special product groups. Additional auxiliary chemicals which are necessary in conventional hydrophobization processes are not required in the process according to the invention. Furthermore, the results obtained by applying the method according to the invention are very well reproducible, whereas even established hydrophobing processes for chrome leather suffer from a limited reproducibility.
Im Gegensatz zu konventionellen geschlossenen Systemen zur Hydrophobierung wird durch eine Anwendung des erfindungsgemäßen Verfahrens die Dampfdurchlässigkeit der hydrophobierten Produkte nicht beeinträchtigt, weil Faserzwischenräume nicht verstopft werden, sondern das Hydrophobierungsmittel gezielt feste chemische Bin- düngen mit dem Kollagen und/oder den im Kollagen gebundenen Substanzen eingeht. Ferner kann sich erfindungsgemäß das Hydrophobierungsmittel mit sich selbst vernetzen und somit ein hydrophobes Netzwerk im Leder bilden. In contrast to conventional closed systems for hydrophobing, application of the process according to the invention does not impair the vapor permeability of the hydrophobicized products because fiber interspaces are not clogged, but rather the hydrophobizing agent specifically contains solid chemical binders. fertilize with the collagen and / or the substances bound in the collagen. Furthermore, according to the invention, the hydrophobizing agent can crosslink with itself and thus form a hydrophobic network in the leather.
Im Unterschied zu herkömmlichen Lederhydrophobierungsverfahren wird die Hydrophobierung nach dem erfindungsgemäßen Verfahren nicht während der Arbeitsschritte durchgeführt, die bei der konventionellen Lederherstellung in wässrigen Bädern erfolgen. Erfindungsgemäß wird vielmehr das Zwischenprodukt "Leder" hydropho- biert, welches aus einem wie auch immer gearteten Lederherstellungsprozess erhalten worden ist. In contrast to conventional leather hydrophobization processes, the hydrophobic treatment according to the process of the invention is not carried out during the working steps which occur in conventional leather production in aqueous baths. According to the invention, instead, the intermediate "leather" is hydrophobicized, which has been obtained from a kind of leather manufacturing process of any kind.
Damit sich das Hydrophobierungsmittel im erfindungsgemäßen Verfahren wie beschrieben in das Leder einlagern kann, muss der Wassergehalt des Leders, d.h. der Gehalt an freiem Wasser, zwischen 0 Gew.-% und 25 Gew.-% betragen. Wie bereits ausgeführt, bedeutet die Angabe eines Wassergehalts von 0 Gew.-% nicht, dass im Leder überhaupt kein Wasser mehr vorhanden ist, sondern diese Angabe bedeutet, dass im Leder ausschließlich gebundenes Wasser vorliegt, jedoch kein freies Wasser. Die Angabe "25 Gew.-% Wassergehalt" bedeutet demnach, dass im Leder zusätzlich zum gebundenen Wasser noch freies Wasser in einem Anteil vorhanden ist, der einem Viertel des Gesamtgewichts des trockenen Leders entspricht. Wiegt beispielsweise ein Lederstück im trockenen Zustand (Wassergehalt 0 Gew.-%) 1 kg, so wiegt dasselbe Lederstück mit einem Wassergehalt von 25 Gew.-% 1,25 kg. Ein größerer Wasseranteil ist nicht vorteilhaft, denn er verringert die Fähigkeit des komprimierten Gases, in das Leder einzudringen. Bei Wassergehalten über 25 Gew.-% spielt zunehmend die Löslichkeit des komprimierten Gases in Wasser eine entscheidende Rolle, denn das komprimierte Gas muss sich dann zunächst in dem im Leder befindlichen Wasser lösen, um in das Leder eindringen zu können. Dieser Prozess findet aufgrund der natürlichen Struktur von Leder jedoch nur langsam und begrenzt statt, wodurch eine Tiefenhydrophobierung verhindert wird. In order for the hydrophobizing agent in the process according to the invention to be able to be incorporated into the leather as described, the water content of the leather, i. the content of free water, between 0 wt .-% and 25 wt .-% amount. As already stated, the specification of a water content of 0% by weight does not mean that no water is present in the leather at all, but this indication means that exclusively bound water is present in the leather, but no free water. The term "25% by weight of water content" therefore means that in addition to the bound water, free water is still present in the leather in a proportion which corresponds to one quarter of the total weight of the dry leather. For example, if a piece of leather weighs 1 kg in the dry state (water content 0% by weight), the same piece of leather with a water content of 25% by weight weighs 1.25 kg. A greater proportion of water is not advantageous because it reduces the ability of the compressed gas to penetrate the leather. At water contents above 25 wt .-% increasingly plays the solubility of the compressed gas in water a crucial role, because the compressed gas must then first dissolve in the water in the leather in order to penetrate into the leather can. However, due to the natural structure of leather, this process is slow and limited, preventing deep hydrophobization.
Je nach dem als Ausgangsmaterial verwendeten Leder und dem eingesetzten Hydrophobierungsmittel kann die Qualität der Hydrophobierung verbessert werden, wenn im bereitgestellten Leder nicht nur gebundenes Wasser enthalten ist, sondern darüber hinaus ein gewisser Anteil an freiem Wasser, der jedoch 25 Gew.-% nicht übersteigen soll. Entsprechend kann beim erfindungsgemäßen Verfahren der Depending on the leather used as the starting material and the hydrophobing agent used, the quality of the hydrophobing can be improved if not only bound water is contained in the leather provided, but also a certain proportion of free water, but should not exceed 25 wt .-% , Accordingly, in the inventive method of
Wassergehalt des Leders vor einem Einbringen des Leders in den Druckbehälter oder im Anschluss an die Behandlung im Druckbehälter auf einen Wert zwischen 0 und 25 Gew.-% eingestellt werden. Alternativ kann der Wassergehalt des Leders auch im Druckbehälter auf einen Wert zwischen 0 und 25 Gew.-% eingestellt werden. Water content of the leather before introducing the leather into the pressure vessel or after the treatment in the pressure vessel to a value between 0 and 25 % By weight. Alternatively, the water content of the leather in the pressure vessel to a value between 0 and 25 wt .-% can be adjusted.
Die Möglichkeiten zur Einstellung eines erhöhten Wassergehaltes im Leder sind vielfältig. Beispielsweise kann ein gewünschter, erhöhter Wassergehalt des Leders bereits dadurch erreicht werden, dass das Leder im Trocknungsvorgang nicht so weit getrocknet wird, bis nur noch gebundenes Wasser im Leder vorliegt. Stattdessen kann der Trocknungsprozess des Leders beendet werden, wenn der gewünschte, erhöhte Wassergehalt zwischen 0 und 25 Gew.-% erreicht ist. Wenn es sich bei dem Ausgangsprodukt um Leder mit einem Wassergehalt von 0 Gew.-% handelt und ein erhöhter Wassergehalt gewünscht ist, kann die Steigerung des Wassergehalts beispielsweise durch Behandeln des trockenen Leders in einer Klimakammer erzielt werden, in der eine ausreichende Luftfeuchtigkeit vorhanden ist, die dazu führt, dass das trockene Leder Feuchtigkeit aus der Luft aufnimmt. Auch kann das trockene Leder mit Wasser besprüht oder betropft werden. Eine weitere Möglichkeit besteht im Zuführen von Dampf oder Sattdampf in einen Behälter, in dem sich das trockene Leder befindet. Eine noch weitere Möglichkeit besteht darin, Wasser in dem komprimierten Gas zu lösen, welches zum Behandeln des Leders verwendet wird. Demnach kann die Einstellung des gewünschten, erhöhten Wassergehalts während der Zuführung des komprimierten Gases in den Druckbehälter erfolgen, entweder durch Auflösen von Wasser in das zuzuführende, komprimierte Gas oder durch separates Einbringen von Wasser in den Druckbehälter während einer Zuführung des komprimierten Gases. Die Einstellung eines erhöhten Wassergehalts kann jedoch auch nach der Einbringung des komprimierten Gases in den Druckbehälter erfolgen, entweder während einer Druckhaltedauer oder während des Entspannens des Druckbehälters oder erst nach dem Entspannen des Druckbehälters. The possibilities for setting an increased water content in leather are many. For example, a desired, increased water content of the leather can already be achieved in that the leather is not dried in the drying process until there is only bound water in the leather. Instead, the drying process of the leather can be terminated when the desired, increased water content between 0 and 25 wt .-% is reached. If the starting product is leather with a water content of 0% by weight and an increased water content is desired, the increase in the water content can be achieved, for example, by treating the dry leather in a climate chamber in which sufficient air humidity is present, which causes the dry leather to absorb moisture from the air. Also, the dry leather can be sprayed or dripped with water. Another option is to add steam or saturated steam to a container containing the dry leather. Yet another possibility is to dissolve water in the compressed gas used to treat the leather. Accordingly, the adjustment of the desired, increased water content during the supply of the compressed gas can be carried out in the pressure vessel, either by dissolving water in the supplied compressed gas or by separately introducing water into the pressure vessel during a supply of the compressed gas. However, the setting of an increased water content can also be done after the introduction of the compressed gas into the pressure vessel, either during a pressure holding period or during the relaxation of the pressure vessel or only after the expansion of the pressure vessel.
Das im erfindungsgemäßen Verfahren verwendete Hydrophobierungsmittel wird dem Druckbehälter vorzugsweise vor einem Druckaufbau, während des Druckaufbaus, während einer Druckhaltezeit oder während des Entspannens des Druckbehälters zugeführt. Das Zuführen kann beispielsweise durch Vorlegen des Hydrophobierungsmittels in einer mit dem Druckbehälter verbundenen Vorlagekammer, durch Einpumpen, durch Versprühen und/oder durch vorheriges Lösen des Hydrophobierungsmittels im komprimierten Gas geschehen. Es ist auch möglich, obgleich nicht bevorzugt, das Hydrophobierungsmittel vor einer Einbringung des Leders in den Druckbehälter durch beispielsweise Gießen auf das Leder oder Besprühen des Leders aufzubringen. Es ist ebenfalls möglich, verschiedene Hydrophobierungsmittel nacheinander zuzuführen. The hydrophobizing agent used in the process according to the invention is preferably supplied to the pressure vessel before a pressure build-up, during the pressure build-up, during a pressure hold time or during the relaxation of the pressure vessel. The feeding can be done for example by presenting the hydrophobizing agent in an associated with the pressure vessel feed chamber, by pumping, by spraying and / or by previously dissolving the hydrophobizing agent in the compressed gas. It is also possible, although not preferred, to apply the hydrophobing agent prior to introduction of the leather into the pressure vessel by, for example, pouring on the leather or spraying the leather. It is also possible to add different water repellents in succession.
Die Mischung aus komprimiertem Gas und dem verwendeten Hydrophobierungsmittel, d.h. das Lösen des Hydrophobierungsmittels im komprimierten Gas, erfolgt unabhängig von der gewünschten Art der Hydrophobierung allein durch die The mixture of compressed gas and the hydrophobing agent used, i. the dissolution of the hydrophobizing agent in the compressed gas takes place independently of the desired type of hydrophobing alone
Anwesenheit des komprimierten Gases. Die Parameter Druck und Temperatur, die eine Lösung des Hydrophobierungsmittels im komprimierten Gas beeinflussen, variieren je nach verwendetem Hydrophobierungsmittel. Erfindungsgemäß findet das Behandeln des Leders vorteilhaft bei einem Druck von 30 bis 300 bar statt, vorzugsweise bei einem Druck von 50 bis 250 bar und besonders bevorzugt bei einem Druck von 70 bis 200 bar. Der für ein gegebenes Hydrophobierungsmittel und eine gegebene Hydrophobierungsaufgabe am besten geeignete Druck ist gegebenenfalls durch Versuchsreihen zu ermitteln. Presence of compressed gas. The parameters pressure and temperature, which influence a solution of the hydrophobizing agent in the compressed gas, vary depending on the hydrophobing agent used. According to the invention, the treatment of the leather takes place advantageously at a pressure of 30 to 300 bar, preferably at a pressure of 50 to 250 bar and more preferably at a pressure of 70 to 200 bar. The most suitable pressure for a given hydrophobing agent and a given hydrophobing task may need to be determined by series of tests.
Erfindungsgemäß findet das Behandeln des Leders vorteilhaft bei einer Temperatur von 10°C bis 150°C, vorzugsweise bei einer Temperatur von 20°C bis 130°C und besonders bevorzugt bei einer Temperatur von 30°C bis 110°C statt, wobei sich insbesondere der Temperaturbereich von 60°C bis 80°C als besonders geeignet erwiesen hat. Auch hier gilt, dass bei vorgegebenem Hydrophobierungsmittel und einer gegebenen Hydrophobierungsaufgabe eine am besten geeignete Temperatur gegebenenfalls durch Versuche zu ermitteln ist. According to the invention, the treatment of the leather is advantageously carried out at a temperature of 10 ° C to 150 ° C, preferably at a temperature of 20 ° C to 130 ° C and more preferably at a temperature of 30 ° C to 110 ° C, in particular the temperature range of 60 ° C to 80 ° C has been found to be particularly suitable. Again, for a given hydrophobing agent and given hydrophobing task, a most suitable temperature is optionally determined by experiment.
Wie bereits erläutert, lässt sich die Eindringtiefe des Hydrophobierungsmittels vor allem über die Behandlungszeit steuern. Es liegt dabei auf der Hand, dass dünne Leder eine kürzere Behandlungszeit bis zur vollständigen Durchdringung mit Hydrophobierungsmittel benötigen als dicke Leder. Erfindungsgemäß findet das Behandeln des Leders vorteilhaft für einen Zeitraum von 5 Minuten bis 10 Stunden statt, vorzugsweise für 10 Minuten bis 5 Stunden und besonders bevorzugt für 30 Minuten bis 4 Stunden. As already explained, the penetration depth of the hydrophobing agent can be controlled above all over the treatment time. It is obvious that thin leather requires a shorter treatment time to complete penetration with hydrophobing agent than thick leather. According to the invention, the treatment of the leather takes place advantageously for a period of 5 minutes to 10 hours, preferably for 10 minutes to 5 hours and more preferably for 30 minutes to 4 hours.
Durch Anwendung des erfindungsgemäßen Verfahrens kann oberflächenhydropho- biertes Leder, aber auch dickes und festes, tiefenhydrophobiertes Leder erhalten werden, wie es beispielsweise für Schuhsohlen Verwendung findet. By applying the method according to the invention it is possible to obtain surface-hydrophobized leather, but also thick and firm, deep-hydrophobized leather, as used for example for shoe soles.

Claims

Patentansprüche claims
1. Lederhydrophobierungsverfahren, mit den Schritten: 1. Leather hydrophobization process, with the steps:
Bereitstellen von gegerbtem, zumindest teilweise getrocknetem Leder, dessen Gehalt an freiem Wasser im Bereich von 0 bis 25 Gew.-% bezogen auf das Gewicht des getrockneten Leders liegt,  Providing tanned, at least partially dried leather whose free water content ranges from 0 to 25% by weight, based on the weight of the dried leather,
Behandeln des Leders mit einer Mischung aus komprimiertem Gas und einem Hydrophobierungsmittel bei einem Druck von mindestens 30 bar in einem Druckbehälter, und  Treating the leather with a mixture of compressed gas and a hydrophobing agent at a pressure of at least 30 bar in a pressure vessel, and
Entspannen des Druckbehälters auf Umgebungsdruck.  Relax the pressure vessel to ambient pressure.
2. Lederhydrophobierungsverfahren nach Anspruch 1, 2. leather hydrophobization process according to claim 1,
dadurch gekennzeichnet, dass der Gehalt an freiem Wasser vor einem Einbringen des Leders in den Druckbehälter oder im Anschluss an die Behandlung im Druckbehälter auf einen Wert zwischen 0 und 25 Gew.-% eingestellt wird. characterized in that the content of free water is adjusted to a value between 0 and 25 wt .-% before introducing the leather into the pressure vessel or after the treatment in the pressure vessel.
3. Lederhydrophobierungsverfahren nach Anspruch 1, 3. leather hydrophobization process according to claim 1,
dadurch gekennzeichnet, dass der Gehalt an freiem Wasser im Druckbehälter auf einen Wert zwischen 0 und 25 Gew.-% eingestellt wird. characterized in that the content of free water in the pressure vessel is set to a value between 0 and 25 wt .-%.
4. Lederhydrophobierungsverfahren nach Anspruch 3, 4. leather hydrophobization process according to claim 3,
dadurch gekennzeichnet, dass die Einstellung des Gehalts an freiem Wasser vor einer Zuführung des komprimierten Gases, während der Zuführung des komprimierten Gases oder nach der Zuführung des komprimierten Gases in den Druckbehälter erfolgt. characterized in that the adjustment of the content of free water before a supply of the compressed gas, during the supply of the compressed gas or after the supply of the compressed gas into the pressure vessel.
5. Lederhydrophobierungsverfahren nach Anspruch 4, 5. leather hydrophobization process according to claim 4,
dadurch gekennzeichnet, dass dann, wenn die Einstellung des Gehalts an freiem Wasser während oder nach der Zuführung des komprimierten Gases in den Druckbehälter erfolgt, diese Einstellung zusammen mit einer Einbringung des komprimierten Gases oder nach der Einbringung des komprimierten Gases in den Druckbehälter erfolgt, entweder während einer Druckhaltedauer oder während des Entspannens des Druckbehälters oder nach dem Entspannen des Druckbehälters. characterized in that, when the adjustment of the free water content occurs during or after the supply of the compressed gas to the pressure vessel, this adjustment takes place together with introduction of the compressed gas or after introduction of the compressed gas into the pressure vessel, either during a pressure holding period or during the relaxation of the pressure vessel or after the expansion of the pressure vessel.
6. Lederhydrophobierungsverfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass eine Zuführung des wenigstens einen Hydrophobierungsmittels in den Druckbehälter vor einem Druckaufbau, während des Druckaufbaus, während einer Druckhaltezeit oder während des Entspannens des 6. leather hydrophobization process according to any one of the preceding claims, characterized in that a supply of the at least one hydrophobing agent in the pressure vessel before a pressure build-up, during the pressure build-up, during a pressure-holding time or during the relaxation of the
Druckbehälters erfolgt. Pressure vessel takes place.
7. Lederhydrophobierungsverfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Hydrophobierungsmittel wenigstens ein Silan und/oder Silanol und/oder Siloxan ist. 7. leather hydrophobization process according to any one of the preceding claims, characterized in that the hydrophobizing agent is at least one silane and / or silanol and / or siloxane.
8. Lederhydrophobierungsverfahren nach Anspruch 7, 8. leather hydrophobization process according to claim 7,
dadurch gekennzeichnet, dass das wenigstens eine Silan ausgewählt ist aus der Gruppe der Alkoxysilane, der Alkylchlorsilane oder der organofunktionalisierten Sila- ne. characterized in that the at least one silane is selected from the group of alkoxysilanes, alkylchlorosilanes or organofunctionalized silanes.
9. Lederhydrophobierungsverfahren nach Anspruch 8, 9. leather hydrophobization process according to claim 8,
dadurch gekennzeichnet, dass das wenigstens eine Silan ein Dialkyldimethoxysilan oder ein Alkyltrimethoxysilan oder eine Mischung daraus ist, vorzugsweise Hexa- decyltrimethoxysilan, Isooctyltrimethoxysilan, Dimethyldiethoxysilan, Phenyl- triethoxysilan oder eine Mischung daraus. characterized in that the at least one silane is a dialkyldimethoxysilane or an alkyltrimethoxysilane or a mixture thereof, preferably hexadecyltrimethoxysilane, isooctyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane or a mixture thereof.
10. Lederhydrophobierungsverfahren nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, dass das wenigstens eine Silanol ein Alkylsilanol ist, vorzugsweise Methylsilantriol, Diphenylsilandiol, Trimethylsilanol oder eine Mischung daraus. 10. Lederhydrophobierungsverfahren according to any one of claims 7 to 9, characterized in that the at least one silanol is an alkylsilanol, preferably methylsilane triol, diphenylsilanediol, trimethylsilanol or a mixture thereof.
11. Lederhydrophobierungsverfahren nach einen der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das komprimierte Gas CO, CO2, Ethan, Propan, Pen- tan, Ammoniak, ein Fluor-Chlor-Alkan oder eine Mischung zweier oder mehrerer dieser Stoffe ist. 11. leather hydrophobization process according to any one of the preceding claims, characterized in that the compressed gas is CO, CO 2 , ethane, propane, pentane, ammonia, a fluorine-chlorine alkane or a mixture of two or more of these substances.
12. Lederhydrophobierungsverfahren nach einen der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Behandeln des Leders bei einem Druck von 30 bis 300 bar, vorzugsweise bei einem Druck von 50 bis 250 bar und besonders bevorzugt bei einem Druck von 70 bis 200 bar stattfindet. 12. Lederhydrophobierungsverfahren according to any one of the preceding claims, characterized in that the treatment of the leather takes place at a pressure of 30 to 300 bar, preferably at a pressure of 50 to 250 bar and more preferably at a pressure of 70 to 200 bar.
13. Lederhydrophobierungsverfahren nach einen der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Behandeln des Leders bei einer Temperatur von 10°C bis 150°C, vorzugsweise bei einer Temperatur von 20°C bis 130°C und besonders bevorzugt bei einer Temperatur von 30°C bis 110°C, insbesondere bei 60°C bis 80°C stattfindet. 13. Lederhydrophobierungsverfahren according to any one of the preceding claims, characterized in that the treatment of the leather at a temperature of 10 ° C to 150 ° C, preferably at a temperature of 20 ° C to 130 ° C and particularly preferably at a temperature of 30 ° C to 110 ° C, especially at 60 ° C to 80 ° C takes place.
14. Lederhydrophobierungsverfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Behandeln des Leders für einen Zeitraum von 5 Minuten bis 10 Stunden, vorzugsweise für 10 Minuten bis 5 Stunden und besonders bevorzugt für 30 Minuten bis 4 Stunden erfolgt. 14 leather hydrophobization method according to any one of the preceding claims, characterized in that the treatment of the leather for a period of 5 minutes to 10 hours, preferably for 10 minutes to 5 hours and more preferably for 30 minutes to 4 hours.
15. Tiefenhydrophobiertes Leder, erhalten durch Anwendung des Verfahrens nach einem der Ansprüche 1 bis 14. 15. Deep hydrophobized leather obtained by using the method according to any one of claims 1 to 14.
EP17700338.1A 2016-01-12 2017-01-12 Process for waterproofing leather and corresponding leather Active EP3402905B1 (en)

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DE102016000243.3A DE102016000243A1 (en) 2016-01-12 2016-01-12 Leather hydrophobization process and leather produced therewith
PCT/EP2017/050548 WO2017121789A1 (en) 2016-01-12 2017-01-12 Method for hydrophobising leather and leather produced by means of same

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DE102019109425B4 (en) 2019-04-10 2022-01-05 Uvex Safety Gloves Gmbh & Co. Kg Process for the production of an impregnated polymer substrate, Process for the production of chemical protective gloves and Use of an impregnated polymer substrate for protective clothing
IT201900017942A1 (en) * 2019-10-04 2021-04-04 Leather Plus S R L Functionalizing treatment method for leathers and the like.
CN113061670B (en) * 2021-03-31 2022-05-03 四川大学 Method for modifying superhydrophobicity of substance containing collagen fibers, method for tanning without tanning agent, and leather product

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PL3402905T3 (en) 2020-06-15
DK3402905T3 (en) 2020-03-16
DE102016000243A1 (en) 2017-07-13
US10947605B2 (en) 2021-03-16
US20190017129A1 (en) 2019-01-17
WO2017121789A1 (en) 2017-07-20
CN108779503A (en) 2018-11-09
EP3402905B1 (en) 2019-12-18

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