EP3402905B1 - Process for waterproofing leather and corresponding leather - Google Patents

Process for waterproofing leather and corresponding leather Download PDF

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Publication number
EP3402905B1
EP3402905B1 EP17700338.1A EP17700338A EP3402905B1 EP 3402905 B1 EP3402905 B1 EP 3402905B1 EP 17700338 A EP17700338 A EP 17700338A EP 3402905 B1 EP3402905 B1 EP 3402905B1
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EP
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Prior art keywords
leather
pressure
hydrophobising
pressure vessel
compressed gas
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German (de)
French (fr)
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EP3402905A1 (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
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Ruhr Universitaet Bochum
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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 waterproofing process and leather produced therewith.
  • the term “leather” is understood to mean tanned collagen-containing material with and without hair, which has been obtained by a previous tanning process.
  • the term “leather” therefore includes not only leather as such, but also furs and skins made from animal skins or furs.
  • the leather can come from any animal, for example from cattle, sheep, goats, pigs, buffalos, birds, reptiles etc.
  • the tanning process with which the leather is obtained can be a mineral, vegetable or synthetic tanning process, depending on the type of Tanning uses tanning agents (mineral salts, vegetable tanning agents, synthetic tanning agents).
  • the term “leather” also encompasses leather of any thickness, for example particularly thin leather made from baggage, but also very thick sole leather.
  • Conventional tanning processes for the production of leather include a series of aqueous baths in which the raw material is treated to become leather (see e.g. DE 195 07 572 A1 ). These watery baths are divided into the work in the so-called water workshop, the actual tanning and the retanning.
  • the aqueous baths therefore include all work steps that are carried out in an aqueous medium for the production of leather. These include, for example, softening, dehairing (liming), pickling, tanning, retanning, greasing, dyeing etc.
  • the individual treatment processes in the context of this leather production are well known to experts in the field and therefore do not need to be explained further.
  • Freshly tanned leather is wet or at least damp and needs to be dried.
  • so-called tunnel dryers are used, in which the leather is dried by means of an elevated temperature, or so-called vacuum dryers, in which the leather is dried by applying a vacuum at an optionally likewise elevated temperature.
  • leather contains bound water. Excessive drying, which would also partially or even completely remove the water bound in the leather, is undesirable, since this would result in embrittlement and degeneration of the leather. Excessively dried leather becomes brittle and therefore unusable.
  • dry leather is therefore understood to mean tanned collagen-containing material which has been dried at 50 ° C.
  • dry leather is mentioned in the context of this disclosure, then this dry leather by definition 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 present in the leather after the drying described, i.e. if there is free water in the leather.
  • Material containing collagen and thus the hides used as raw material for leather production naturally have a certain proportion of ionizable and non-ionizable functional groups.
  • the proportion of these groups changes depending on the chemicals used. For example, the amount of acidic carboxy groups is reduced in chrome tanning. If vegetable tanning agents are used for tanning, the proportion of OH groups increases significantly due to the hydroxyl groups present in the vegetable tanning agents. 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, it is not possible to give a general statement about the proportions of the functional groups present and therefore also about the water that is later bound in the leather after drying.
  • Today leather is mainly used in the shoe and clothing industry, in the automotive industry and in the furniture industry. In the fields of application mentioned, it is increasingly required that the leather is water-repellent, i.e. has a high resistance to water ingress. Unfortunately, leather is hydrophilic, especially vegetable-tanned leather, which is why the required water-repellent properties represent a major challenge for the leather industry.
  • the present invention has set itself the goal of specifying a leather waterproofing process which enables long-term stable, complete and process-technically reproducible waterproofing of in particular vegetable tanned and / or synthetically tanned leather, so that this process can also be used to produce deeply waterproofed leather which is used, for example, as shoe sole leather Can be found.
  • 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 the treatment.
  • the hydrophobizing agent can be supplied to the pressure vessel before a pressure build-up, during a pressure build-up, during a pressure-holding time or even while the pressure vessel is being released.
  • the waterproofing agent can also be brought into contact with the leather to be treated before the leather is introduced into the pressure vessel. It is only important that a mixture of the compressed gas and the water repellent is formed during the treatment of the leather. In other words, the hydrophobizing agent used must be at least partially soluble in the compressed gas.
  • compressed CO 2 is preferably used as the compressed gas.
  • other compressed gases can also be used within the scope of the invention, for example carbon monoxide, ethane, propane, pentane, ammonia, fluorine-chloroalkanes and mixtures of these substances. Due to the low viscosity and excellent diffusion properties of the compressed gas, the waterproofing agent dissolved in the compressed gas can also penetrate completely through thick leather and thus achieve a deep hydrophobization.
  • the penetration behavior of the Hydrophobing agent dissolved in the compressed gas can be controlled above all by the duration of the treatment, so that only a layer of the leather close to the surface can be made hydrophobic by means of a suitable, relatively short duration of treatment, if so desired.
  • Reactive polymers, hydrocarbons, silanes, silanols and siloxanes which preferably have one or more functional groups of the epoxy, ester, carboxyl, anhydride, amine, hydroxide and / or halide type can be used as the hydrophobizing agent.
  • a hydrophobizing agent which consists of at least one silane and / or silanol and / or siloxane.
  • compounds of the alkylsilanol, alkoxysilane, alkylchlorosilane and organofunctionalized silane type are outstandingly suitable as water repellents in the process according to the invention.
  • R 1 (1-3) R 2 (0-2) -SiX (1-3) R 1 denotes a hydrophobic group
  • R 2 denotes an organically functionalized residue
  • X a hydrolyzable group , usually an alkoxy group, more rarely a chlorine group.
  • the organically functionalized R 2 groups can additionally have functional groups which are able to form covalent bonds with the hydroxyl and carboxyl and amino groups of the leather.
  • Such additional functional groups can be amino, epoxy, ester and carboxy groups. Examples of compounds with such additional functional groups are 3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.
  • alkyl methoxysilanes are particularly preferred as hydrophobizing agents, alkyl being C 1 to C 20 alkyl.
  • alkyl methoxysilanes are dialkyl methoxysilane, alkyl trimethoxysilane and mixtures of these substances.
  • Hexadecyltrimethoxysilane, isooctyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane or mixtures of the aforementioned substances are very particularly preferred.
  • alkylalkoxysilanes but also alkylchlorosilanes, hydrolyze to alkylsilanols, which can polymerize with elimination of water, or which bind to nucleophilic reagents such as hydroxyl groups, carboxyl groups and / or amino groups can bind.
  • the hydrophobizing agent is fixed in the leather or stored in the leather, as a result of which the desired long-term stability of the leather, which is insensitive to mechanical stress, is achieved.
  • silanols are used as water repellents, especially alkyl silanols such as e.g. Methylsilanoltriol, diphenylsilanediol and / or trimethylsilanol can be dispensed with the hydrolysis step described above.
  • alkyl silanols especially alkyl silanols, leather with little or no residual water content can therefore be well hydrophobized.
  • the compressed gas After treating the leather with the mixture of compressed gas and water repellent, the compressed gas is released to ambient pressure and water repellent not fixed in the leather is separated.
  • the gas used as well as the excess hydrophobing agent separated from the gas can be reused. Wastewater treatment is not necessary since no wastewater is produced in the leather hydrophobization process according to the invention.
  • the main advantage of the process according to the invention can be seen in the possibility of the long-term stable hydrophobization of a large variety of collagen materials, regardless of the type of starting material and regardless of the type of leather production process.
  • the hydrophobization process according to the invention for example, both soft chrome leather and vegetable and / or synthetically tanned leather of high strength can be made hydrophobic.
  • Conventional waterproofing 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.
  • the results obtained by using the method according to the invention are very reproducible, whereas even established hydrophobization methods for chrome leather suffer from a limited reproducibility.
  • the vapor permeability of the hydrophobized products is not impaired by using the method according to the invention, because the interstices of the fibers are not clogged, but rather the hydrophobizing agent deliberately forms firm chemical bonds 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 hydrophobization by the process according to the invention is not carried out during the work steps which take place in conventional leather production in aqueous baths. Rather, according to the invention, the intermediate product "leather” is hydrophobized, which has been obtained from a leather manufacturing process of whatever type.
  • the water content of the leather i.e. the free water content is between 0% by weight and 25% by weight.
  • the specification of a water content of 0% by weight does not mean that there is no longer any water at all in the leather, but rather this specification means that only bound water is present in the leather, but no free water.
  • the statement "25% by weight water content” therefore means that in addition to the bound water, there is free water in the leather in a proportion which corresponds to a quarter of the total weight of the dry leather.
  • the quality of the hydrophobicizing can be improved if the leather provided does not only contain bound water, but also a certain proportion of free water, which should not, however, exceed 25% by weight .
  • the water content of the leather can be between 0 and 25 before the leather is introduced into the pressure vessel or after the treatment in the pressure vessel % By weight can be set.
  • the water content of the leather in the pressure vessel can be set to a value between 0 and 25% by weight.
  • an increased water content in the leather there are many ways to set an increased water content in the leather.
  • a desired, increased water content of the leather can already be achieved in that the leather is not dried in the drying process until only bound water is present in the leather.
  • the drying process of the leather can be ended when the desired, increased water content between 0 and 25% by weight has been 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 climatic chamber in which there is sufficient air humidity, which causes the dry leather to absorb moisture from the air.
  • the dry leather can also be sprayed or dripped with water. Another possibility is to supply steam or saturated steam to a container in which the dry leather is located.
  • Yet another option is to dissolve water in the compressed gas that is used to treat the leather. Accordingly, the setting of the desired, increased water content can take place during the supply of the compressed gas into the pressure container, either by dissolving water in the compressed gas to be supplied or by separately introducing water into the pressure container during a supply of the compressed gas. However, an increased water content can also be set after the compressed gas has been introduced into the pressure vessel, either during a pressure-holding period or while the pressure vessel is being released or only after the pressure vessel has been released.
  • the hydrophobizing agent used in the process according to the invention is preferably fed to the pressure vessel before a pressure build-up, during the pressure build-up, during a pressure-holding time or while the pressure vessel is being released.
  • the supply can take place, for example, by placing the hydrophobizing agent in a supply chamber connected to the pressure container, by pumping in, by spraying and / or by previously dissolving the hydrophobizing agent in the compressed gas. It is also possible, although not preferred, to apply the hydrophobizing agent, for example by pouring onto the leather or spraying the leather, before introducing the leather into the pressure vessel.
  • the mixture of compressed gas and the hydrophobizing agent used i.e. the dissolving of the hydrophobizing agent in the compressed gas takes place independently of the desired type of hydrophobization solely through the presence of the compressed gas.
  • the parameters pressure and temperature, which influence a solution of the hydrophobizing agent in the compressed gas vary depending on the hydrophobizing agent used.
  • the treatment of the leather advantageously takes place at a pressure of 30 to 300 bar, preferably at a pressure of 50 to 250 bar and particularly preferably at a pressure of 70 to 200 bar.
  • the pressure most suitable for a given hydrophobizing agent and a given hydrophobizing task may have to be determined by a series of tests.
  • the treatment of the leather advantageously takes place 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., in particular the temperature range from 60 ° C to 80 ° C has proven to be particularly suitable.
  • a most suitable temperature can be determined by tests, if necessary.
  • the penetration depth of the hydrophobizing agent can be controlled primarily via the treatment time. It is obvious that thin leather needs a shorter treatment time to completely penetrate with water repellent than thick leather. According to the invention, the treatment of the leather advantageously takes place for a period of 5 minutes to 10 hours, preferably for 10 minutes to 5 hours and particularly 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)

Description

Die vorliegende Erfindung betrifft ein Lederhydrophobierungsverfahren und damit hergestelltes Leder.The present invention relates to a leather waterproofing process and leather produced 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 previous tanning process. The term "leather" therefore includes not only leather as such, but also furs and skins made from animal skins or furs. The leather can come from any animal, for example from cattle, sheep, goats, pigs, buffalos, birds, reptiles etc. The tanning process with which the leather is obtained can be a mineral, vegetable or synthetic tanning process, depending on the type of Tanning uses tanning agents (mineral salts, vegetable tanning agents, synthetic tanning agents). The term "leather" also encompasses leather of any thickness, for example particularly thin leather made from baggage, but also very thick sole leather.

Herkömmliche Gerbverfahren zur Herstellung von Leder umfassen eine Reihe wässriger Bäder, in denen das Rohmaterial behandelt wird, um zu Leder zu werden (siehe z. B. DE 195 07 572 A1 ). 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 production of leather include a series of aqueous baths in which the raw material is treated to become leather (see e.g. DE 195 07 572 A1 ). These watery baths are divided into the work in the so-called water workshop, the actual tanning and the retanning. The aqueous baths therefore include all work steps that are carried out in an aqueous medium for the production of leather. These include, for example, softening, dehairing (liming), pickling, tanning, retanning, greasing, dyeing etc. The individual treatment processes in the context of this leather production are well known to experts in the field and therefore do not need to be explained further.

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.As soon as the skins tanned by means of the various treatment steps are dried, it is "leather" within the scope of the present disclosure. Even tanned, treated and dried collagen-containing material before the "crust" condition is therefore "leather". In the tannery industry, the condition of an animal skin before the so-called finishing, ie before the final surface appearance applied to the surface, is referred to as a "crust". Accordingly, "leather" in the context of this invention is in particular also tanned, treated and dried collagen-containing material, which has not been subjected to any mechanical work, such as the tunnel or mill, after drying.

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 damp 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 an elevated temperature, or so-called vacuum dryers, in which the leather is dried by applying a vacuum at an optionally likewise elevated temperature. However, even in the dried state, leather contains bound water. Excessive drying, which would also partially or even completely remove the water bound in the leather, is undesirable, since this would result in embrittlement and degeneration of the leather. Excessively 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 at 50 ° C. for at least 48 hours and thus no longer contains free water, but only water bound in the leather. If "dry leather" is mentioned in the context of this disclosure, then this dry leather by definition has a water content of 0% by weight, although it still contains water bound in the leather. The term "increased water content" is used in the context of this disclosure if the leather contains more water than the water which is present in the leather after the drying described, i.e. 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.Material containing collagen and thus the hides used as raw material for leather production naturally have a certain proportion of ionizable and non-ionizable functional groups. In the course of the leather manufacturing process, the proportion of these groups changes depending on the chemicals used. For example, the amount of acidic carboxy groups is reduced in chrome tanning. If vegetable tanning agents are used for tanning, the proportion of OH groups increases significantly due to the hydroxyl groups present in the vegetable tanning agents. 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, it is not possible to give a general statement about the proportions of the functional groups present and therefore also about the water that is later bound in the leather after drying.

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.Today leather is mainly used in the shoe and clothing industry, in the automotive industry and in the furniture industry. In the fields of application mentioned, it is increasingly required that the leather is water-repellent, i.e. has a high resistance to water ingress. 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 (siehe z. B. DE 44 04 890 A1 ). Die Emulsionen müssen in einem anschließenden Verfahrensschritt 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.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 into the leather structure. This usually takes place in the aqueous medium before, during or after retanning using emulsifiers which enable the water-insoluble hydrophobicizing agents to be distributed sufficiently finely in the aqueous phase (see, e.g. DE 44 04 890 A1 ). The emulsions must be broken up in a subsequent process step in order to allow the water-insoluble hydrophobing agents to be incorporated into the leather. In these known processes, a significant proportion of the chemicals used are not fixed or stored in the collagen and therefore remain in the waste water. This not only pollutes the environment, but also leads to increased costs for excess 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.Known leather waterproofing processes 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 it is disadvantageous, for example for products that require special strength, such as shoe soles. Furthermore, leather products in particular, which require high strength, are produced using a high proportion of hydrophilic vegetable tannins, which are embedded in the leather and prevent or at least greatly complicate a water-repellent finish by means of conventional hydrophobization processes. A permanent and complete, ie continuous hydrophobization, in particular of vegetable and / or synthetically tanned leather, is therefore not known to date. Only surface-applied systems for waterproofing fail quickly under higher mechanical loads, such as those found in the area of shoe leather, and therefore do not represent a satisfactory solution.

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 tiefenhydrophobiertes Leder herstellbar ist, welches beispielsweise als Schuhsohlenleder Verwendung finden kann.The present invention has set itself the goal of specifying a leather waterproofing process which enables long-term stable, complete and process-technically reproducible waterproofing of in particular vegetable tanned and / or synthetically tanned leather, so that this process can also be used to produce deeply waterproofed leather which is used, for example, as shoe sole leather Can be found.

Diese Aufgabe ist erfindungsgemäß gelöst durch ein Lederhydrophobierungsverfahren, welches die folgenden Schritte aufweist:

  • 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,
  • Behandeln des Leders mit einer Mischung aus komprimiertem Gas und einem Hydrophobierungsmittel bei einem Druck von mindestens 30 bar in einem Druckbehälter, und
  • Entspannen des Druckbehälters auf Umgebungsdruck.
According to the invention, this object is achieved by a leather hydrophobization process which has the following steps:
  • Providing tanned, at least partially dried leather, the free water content of which is in the range from 0 to 25% by weight, based on the weight of the dried leather,
  • Treating the leather with a mixture of compressed gas and a water repellent at a pressure of at least 30 bar in a pressure vessel, and
  • 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 Behandelns 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 the treatment. The hydrophobizing agent can be supplied to the pressure vessel before a pressure build-up, during a pressure build-up, during a pressure-holding time or even while the pressure vessel is being released. The waterproofing agent can also be brought into contact with the leather to be treated before the leather is introduced into the pressure vessel. It is only important that a mixture of the compressed gas and the water repellent is formed during the treatment of the leather. In other words, the hydrophobizing agent used must be at least partially soluble in the compressed gas.

In dem erfindungsgemäßen Lederhydrophobierungsverfahren wird als komprimiertes Gas vorzugsweise komprimiertes CO2 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 waterproofing process according to the invention, compressed CO 2 is preferably used as the compressed gas. However, alternatively or additionally, other compressed gases can also be used within the scope of the invention, for example carbon monoxide, ethane, propane, pentane, ammonia, fluorine-chloroalkanes and mixtures of these substances. Due to the low viscosity and excellent diffusion properties of the compressed gas, the waterproofing agent dissolved in the compressed gas can also penetrate completely through thick leather and thus achieve a deep hydrophobization. The penetration behavior of the Hydrophobing agent dissolved in the compressed gas can be controlled above all by the duration of the treatment, so that only a layer of the leather close to the surface can be made hydrophobic by means of a suitable, relatively short duration of treatment, 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 R1(1-3)R2(0-2)-SiX(1-3), wobei R1 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(1-3)-Si(OH)(1-3). Die organisch funktionalisierten R2-Gruppen können zusätzlich funktionelle Gruppen aufweisen, die in der Lage sind, kovalente Bindungen mit den Hydroxyl- sowie den 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-Aminopropyltrimethoxysilan, 3-Ureidopropyltrimethoxysilan und 3-Glycidoxypropyltrimethoxysilan.Reactive polymers, hydrocarbons, silanes, silanols and siloxanes which preferably have one or more functional groups of the epoxy, ester, carboxyl, anhydride, amine, hydroxide and / or halide type can be used as the hydrophobizing agent. According to the present invention, it is particularly preferred to use a hydrophobizing agent which consists of at least one silane and / or silanol and / or siloxane. In particular, it has been found that compounds of the alkylsilanol, alkoxysilane, alkylchlorosilane and organofunctionalized silane type are outstandingly suitable as water repellents in the process according to the invention. These can be monofunctional, difunctional and / or trifunctional compounds. As a rule, these compounds have the general form R 1 (1-3) R 2 (0-2) -SiX (1-3) , where R 1 denotes a hydrophobic group, R 2 denotes an organically functionalized residue and X a hydrolyzable group , usually an alkoxy group, more rarely a chlorine group. By hydrolysis reactions with water, such compounds form silanols of the form R (1-3) -Si (OH) (1-3) . The organically functionalized R 2 groups can additionally have functional groups which are able to form covalent bonds with the hydroxyl and carboxyl and amino groups of the leather. Such additional functional groups can be amino, epoxy, ester and carboxy groups. Examples of compounds with such additional functional groups are 3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.

Unter den Alkoxysilanen sind als Hydrophobierungsmittel besonders bevorzugt Alkylmethoxysilane, wobei Alkyl für C1 bis C20-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, alkyl methoxysilanes are particularly preferred as hydrophobizing agents, alkyl being C 1 to C 20 alkyl. Examples of such particularly preferred alkyl methoxysilanes are dialkyl methoxysilane, alkyl trimethoxysilane and mixtures of these substances. Hexadecyltrimethoxysilane, isooctyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane or mixtures of the aforementioned substances are very particularly preferred.

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 Aminogruppen 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 alkylsilanols, which can polymerize with elimination of water, or which bind to nucleophilic reagents such as hydroxyl groups, carboxyl groups and / or amino groups can bind. In this way, the hydrophobizing agent is fixed in the leather or stored in the leather, as a result of which the desired long-term stability of the leather, which is insensitive to mechanical stress, is achieved.

Wenn als Hydrophobierungsmittel Silanole zum Einsatz kommen, insbesondere Alkylsilanole 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.If silanols are used as water repellents, especially alkyl silanols such as e.g. Methylsilanoltriol, diphenylsilanediol and / or trimethylsilanol can be dispensed with the hydrolysis step described above. With silanols, especially alkyl silanols, leather with little or no residual water content can therefore be well hydrophobized.

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 water repellent, the compressed gas is released to ambient pressure and water repellent not fixed in the leather is separated. The gas used as well as the excess hydrophobing agent separated from the gas can be reused. Wastewater treatment is not necessary since no wastewater is produced in the leather hydrophobization process according to the invention.

Der Hauptvorteil des erfindungsgemäßen Verfahrens ist in der Möglichkeit der langzeitstabilen 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. 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.The main advantage of the process according to the invention can be seen in the possibility of the long-term stable hydrophobization of a large variety of collagen materials, regardless of the type of starting material and regardless of the type of leather production process. With the hydrophobization process according to the invention, for example, both soft chrome leather and vegetable and / or synthetically tanned leather of high strength can be made hydrophobic. Conventional waterproofing 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 using the method according to the invention are very reproducible, whereas even established hydrophobization methods 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 Bindungen 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 hydrophobization, the vapor permeability of the hydrophobized products is not impaired by using the method according to the invention, because the interstices of the fibers are not clogged, but rather the hydrophobizing agent deliberately forms firm chemical bonds 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" hydrophobiert, welches aus einem wie auch immer gearteten Lederherstellungsprozess erhalten worden ist.In contrast to conventional leather hydrophobization processes, the hydrophobization by the process according to the invention is not carried out during the work steps which take place in conventional leather production in aqueous baths. Rather, according to the invention, the intermediate product "leather" is hydrophobized, which has been obtained from a leather manufacturing process of whatever type.

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 to be incorporated into the leather as described in the process according to the invention, the water content of the leather, i.e. the free water content is between 0% by weight and 25% by weight. As already stated, the specification of a water content of 0% by weight does not mean that there is no longer any water at all in the leather, but rather this specification means that only bound water is present in the leather, but no free water. The statement "25% by weight water content" therefore means that in addition to the bound water, there is free water in the leather in a proportion which corresponds to a quarter of the total weight of the dry leather. For example, if a piece of leather weighs 1 kg when dry (water content 0% by weight), the same piece of leather with a water content of 25% by weight weighs 1.25 kg. A larger proportion of water is not advantageous because it reduces the ability of the compressed gas to penetrate the leather. At water contents of more than 25% by weight, the solubility of the compressed gas in water plays an increasingly important role, because the compressed gas must first dissolve in the water in the leather in order to be able to penetrate the leather. However, due to the natural structure of leather, this process is slow and limited, which prevents deep water repellency.

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 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.Depending on the leather used as the starting material and the hydrophobicizing agent used, the quality of the hydrophobicizing can be improved if the leather provided does not only contain bound water, but also a certain proportion of free water, which should not, however, exceed 25% by weight , Accordingly, in the method according to the invention, the water content of the leather can be between 0 and 25 before the leather is introduced into the pressure vessel or after the treatment in the pressure vessel % By weight can be set. Alternatively, the water content of the leather in the pressure vessel can be set to a value between 0 and 25% by weight.

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.There are many ways to set an increased water content in the leather. 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 only bound water is present in the leather. Instead, the drying process of the leather can be ended when the desired, increased water content between 0 and 25% by weight has been 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 climatic chamber in which there is sufficient air humidity, which causes the dry leather to absorb moisture from the air. The dry leather can also be sprayed or dripped with water. Another possibility is to supply steam or saturated steam to a container in which the dry leather is located. Yet another option is to dissolve water in the compressed gas that is used to treat the leather. Accordingly, the setting of the desired, increased water content can take place during the supply of the compressed gas into the pressure container, either by dissolving water in the compressed gas to be supplied or by separately introducing water into the pressure container during a supply of the compressed gas. However, an increased water content can also be set after the compressed gas has been introduced into the pressure vessel, either during a pressure-holding period or while the pressure vessel is being released or only after the pressure vessel has been released.

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.The hydrophobizing agent used in the process according to the invention is preferably fed to the pressure vessel before a pressure build-up, during the pressure build-up, during a pressure-holding time or while the pressure vessel is being released. The supply can take place, for example, by placing the hydrophobizing agent in a supply chamber connected to the pressure container, by pumping in, by spraying and / or by previously dissolving the hydrophobizing agent in the compressed gas. It is also possible, although not preferred, to apply the hydrophobizing agent, for example by pouring onto the leather or spraying the leather, before introducing the leather into the pressure vessel.

Es ist ebenfalls möglich, verschiedene Hydrophobierungsmittel nacheinander zuzuführen.It is also possible to add different hydrophobizing agents 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 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.The mixture of compressed gas and the hydrophobizing agent used, i.e. the dissolving of the hydrophobizing agent in the compressed gas takes place independently of the desired type of hydrophobization solely through the presence of the compressed gas. The parameters pressure and temperature, which influence a solution of the hydrophobizing agent in the compressed gas, vary depending on the hydrophobizing agent used. According to the invention, the treatment of the leather advantageously takes place at a pressure of 30 to 300 bar, preferably at a pressure of 50 to 250 bar and particularly preferably at a pressure of 70 to 200 bar. The pressure most suitable for a given hydrophobizing agent and a given hydrophobizing task may have to be determined by a 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 advantageously takes place 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., in particular the temperature range from 60 ° C to 80 ° C has proven to be particularly suitable. Here, too, it is true that with a given hydrophobizing agent and a given hydrophobization task, a most suitable temperature can be determined by tests, if necessary.

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 hydrophobizing agent can be controlled primarily via the treatment time. It is obvious that thin leather needs a shorter treatment time to completely penetrate with water repellent than thick leather. According to the invention, the treatment of the leather advantageously takes place for a period of 5 minutes to 10 hours, preferably for 10 minutes to 5 hours and particularly preferably for 30 minutes to 4 hours.

Durch Anwendung des erfindungsgemäßen Verfahrens kann oberflächenhydrophobiertes Leder, aber auch dickes und festes, tiefenhydrophobiertes Leder erhalten werden, wie es beispielsweise für Schuhsohlen Verwendung findet.By using the method according to the invention, surface-hydrophobicized leather, but also thick and strong, deeply hydrophobicized leather can be obtained, as is used for example for shoe soles.

Claims (14)

  1. Method for hydrophobising leather, comprising the steps:
    - providing tanned, at least partly dried leather whose content of free water is in the range of from 0 to 25 wt.%, based on 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.
  2. Method for hydrophobising leather according to claim 1,
    characterised in that the content of free water is adjusted to a value between 0 and 25 wt.% before the leather is introduced into the pressure vessel or following treatment in the pressure vessel.
  3. Method for hydrophobising leather according to claim 1,
    characterised in that the content of free water is adjusted to a value between 0 and 25 wt.% in the pressure vessel.
  4. Method for hydrophobising leather according to claim 3,
    characterised in that the adjustment of the content of free water takes place before the compressed gas is fed into the pressure vessel, during feeding of the compressed gas into the pressure vessel or after the compressed gas has been fed into the pressure vessel.
  5. Method for hydrophobising leather according to claim 4,
    characterised in that, when the adjustment of the content of free water takes place during or after the feeding of the compressed gas into the pressure vessel, the adjustment takes place together with the introduction of the compressed gas or after the introduction of the compressed gas into the pressure vessel, either during a pressure holding time or during pressure relief of the pressure vessel or after pressure relief of the pressure vessel.
  6. Method for hydrophobising leather according to any one of the preceding claims,
    characterised in that the feeding of the at least one hydrophobising agent into the pressure vessel takes place before a pressure build-up, during pressure build-up, during a pressure holding time or during pressure relief of the pressure vessel.
  7. Method for hydrophobising leather according to any one of the preceding claims,
    characterised in that the hydrophobising agent is at least one silane and/or silanol and/or siloxane.
  8. Method for hydrophobising leather according to claim 7,
    characterised in that the at least one silane is selected from the group of alkoxysilanes, alkylchlorosilanes or organofunctionalised silanes.
  9. Method for hydrophobising leather according to claim 8,
    characterised 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. Method for hydrophobising leather according to any one of claims 7 to 9,
    characterised in that the at least one silanol is an alkylsilanol, preferably methylsilanetriol, diphenylsilanediol, trimethylsilanol or a mixture thereof.
  11. Method for hydrophobising leather according to any one of the preceding claims,
    characterised in that the compressed gas is CO, CO2, ethane, propane, pentane, ammonia, a fluoro-chloro-alkane or a mixture of two or more of these substances.
  12. Method for hydrophobising leather according to any one of the preceding claims,
    characterised in that the treatment of the leather takes place at a pressure of from 30 to 300 bar, preferably at a pressure of from 50 to 250 bar and particularly preferably at a pressure of from 70 to 200 bar.
  13. Method for hydrophobising leather according to any one of the preceding claims,
    characterised in that the treatment of the leather takes place at a temperature of from 10°C to 150°C, preferably at a temperature of from 20°C to 130°C and particularly preferably at a temperature of from 30°C to 110°C, in particular at from 60°C to 80°C.
  14. Method for hydrophobising leather according to any one of the preceding claims,
    characterised in that the treatment of the leather takes place for a period of from 5 minutes to 10 hours, preferably for from 10 minutes to 5 hours and particularly preferably for from 30 minutes to 4 hours.
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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EP3402905B1 true EP3402905B1 (en) 2019-12-18

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EP (1) EP3402905B1 (en)
CN (1) CN108779503B (en)
DE (1) DE102016000243A1 (en)
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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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DK3402905T3 (en) 2020-03-16
EP3402905A1 (en) 2018-11-21
US10947605B2 (en) 2021-03-16
DE102016000243A1 (en) 2017-07-13
CN108779503B (en) 2021-11-02
US20190017129A1 (en) 2019-01-17
WO2017121789A1 (en) 2017-07-20
PL3402905T3 (en) 2020-06-15
CN108779503A (en) 2018-11-09

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