EP3440227B1 - Composition and process for tanning based on acetal of aldehydic tanning agent - Google Patents

Composition and process for tanning based on acetal of aldehydic tanning agent Download PDF

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Publication number
EP3440227B1
EP3440227B1 EP17715042.2A EP17715042A EP3440227B1 EP 3440227 B1 EP3440227 B1 EP 3440227B1 EP 17715042 A EP17715042 A EP 17715042A EP 3440227 B1 EP3440227 B1 EP 3440227B1
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EP
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Prior art keywords
acetal
weight
tanning
leather
aldehydic
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EP17715042.2A
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German (de)
French (fr)
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EP3440227A1 (en
Inventor
Catherine Gabagnou
Nina SCHULTE
Grigore Daniel HERTA
Jens Fennen
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TFL Ledertechnik GmbH and Co KG
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TFL Ledertechnik GmbH and Co KG
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Priority to EP19167730.1A priority Critical patent/EP3561081A1/en
Publication of EP3440227A1 publication Critical patent/EP3440227A1/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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes

Definitions

  • the invention relates to a composition containing a tanning agent for tanning hides and / or pelts.
  • the invention also relates to a method for tanning hides and / or pelts for the production of leather.
  • the invention relates to a composition and a method for pretanning and / or retanning, preferably for pretanning.
  • the tanning and, in particular, the pretanning of hides and / or pelts by aldehyde tanning agents is generally known and is used commercially, for example in the so-called "wet white” process.
  • the main aldehydic tanning agents used are formaldehyde, propionaldehyde, glyoxal and, in the most common cases, glutaraldehyde.
  • a major disadvantage of these previously known compositions and methods which are based on the use of the tanning agents mentioned is, however, that the tanning agents have too high a reactivity towards the proteins of the skin to be tanned. Frequently, therefore, particularly in the case of relatively thick hides and / or pelts, insufficient penetration of the tanning agents into deeper layers of the skin to be tanned and / or of the hide to be tanned can occur. This can lead to inhomogeneous tanning, which can negatively affect the quality of the leather produced.
  • aldehydic tanning agents generally have a very high toxicity and a pungent odor. Inhaling aldehydic vapors and direct contact with these aldehydic tanning agents are, however, often unavoidable with known compositions and processes based on them, so that people who use them for tanning hides and / or pelts are exposed to an increased health risk. In this context, there is therefore a need to improve occupational safety when tanning with aldehydic tanning agents.
  • the object is therefore to create a composition and / or a method of the type mentioned at the outset in which the aforementioned disadvantages do not occur.
  • composition according to the invention has the advantage over previously known compositions based on aldehydic tanning agents that acetals of aldehydic tanning agents are not or hardly reactive towards the proteins of the hide and / or pelts to be tanned. Such acetals are particularly stable in a neutral and alkaline medium and for this reason do not react with the proteins mentioned when the composition according to the invention is applied to the skin and / or the fur at this pH value. In addition, acetals from aldehydic tanning agents are less toxic than the aldehydic tanning agent itself, i.e. the aldehyde.
  • composition according to the invention Another hitherto completely unknown, surprising effect is shown in the composition according to the invention in that when the composition according to the invention is used for tanning, improved penetration into deeper layers of the skin to be tanned and / or of the fur to be tanned can be achieved.
  • a more homogeneous tanning can thereby be achieved compared with previously known compositions which are based on aldehydic tanning agents.
  • the pH value can be lowered after an exposure time in such a way that the aldehydic tanning agent is released and becomes reactive as a result.
  • the composition according to the invention is applied in non-reactive form to a skin and / or a fur, which can be made available, for example, in a closable container.
  • the aldehydic tanning agent of the composition can be activated by subsequent acidification, that is to say lowering the pH value, this being possible, for example, within the closed vessel by adding an acid.
  • composition according to the invention can also be applied to a pickled pelt.
  • the acetal of an aldehyde tanning agent is an acetal of formaldehyde, propionaldehyde, glutaraldehyde and / or glyoxal.
  • the composition contains two or more of the acetals mentioned.
  • the acetal is glutaraldehyde.
  • the acetals mentioned of aldehydic tanning agents have a particularly good tanning effect.
  • an alcohol component of the acetal of an aldehyde tanning agent is methanol, ethanol, diethylene glycol and / or triethylene glycol.
  • the alcohol component of the acetal is preferably methanol.
  • the acetal of an aldehydic produced with previously known processes can also be purified by using other previously known purification processes, such as, for example, column chromatography, in particular flash chromatography, in order to obtain an even purer acetal.
  • the composition according to the invention has at least one saccharide, in particular a reducing saccharide.
  • the composition according to the invention contains at least one saccharide with a dextrose equivalent of 10 to 100.
  • the proportion of the at least one saccharide in the composition is 0.1% by weight to 30% by weight, in particular 2.5% by weight to 15% by weight , amounts to. This allows the reactivity of the released aldehydic tanning agent to be further reduced and thus a slower and gentler tanning process due to improved penetration (also during the actual tanning process) into the deeper layers of the skin.
  • the composition has at least one or the at least one previously mentioned saccharide which is selected from the group of glucose, sucrose or a mixture of glucose and sucrose.
  • saccharide which is selected from the group of glucose, sucrose or a mixture of glucose and sucrose.
  • the composition contains a proportion of polyoxaalkylene glycol.
  • the proportion of polyoxaalkylene glycol is selected from the group of polyoxaethylene diol, polyoxa-1,2-propylene diol or a mixture of polyoxaethylene diol and polyoxa-1,2-propylene diol.
  • the composition contains two or more of the polyoxaalkylene glycols mentioned.
  • one or the aforementioned proportion of polyoxaalkylene glycol in the composition contains one or more polyoxaalkylene glycols with a molecular weight M R of 120 to 1,000. It can be particularly expedient here if one or the aforementioned proportion of polyoxaalkylene glycol / s in the composition is 2.5 to 15% by weight.
  • composition according to the invention additionally contains an aldehyde, in particular where a proportion of the aldehyde in the composition is 0.1% by weight to 50% by weight, in particular 5% by weight to 50% by weight , in particular 10% by weight to 40% by weight, in particular 20% by weight to 30% by weight.
  • the solvent of the composition according to the invention can have one selected from the group consisting of water, water-soluble organic solvents or a mixture of water and water-soluble organic solvents.
  • Glycerol and / or a monoetherified polyoxaalkylene glycol for example, can be suitable as water-soluble organic solvents.
  • the water-soluble organic solvent has a molecular weight M R of greater than or equal to 100 and / or of less than or equal to 2,000.
  • the pH-regulating buffer component can set a pH of 7.5 to 10.5 for the composition.
  • the aldehydic tanning agent is stable and therefore not reactive with the proteins of the hide to be tanned and / or of the fur to be tanned. In this way, particularly good penetration of the composition into deeper layers can be achieved.
  • Suitable pH-regulating buffer components can be, for example, one or more selected from the group consisting of carbonate buffer, borate buffer and / or phosphate buffer.
  • the same advantages apply as have already been explained above for the composition according to the invention.
  • the method according to the invention can be used for tanning, pretanning and / or retanning of pelts.
  • a skin that has been fleshed and / or depilated after the pimple and / or the stain can be defined as nakedness, but which has not yet been tanned.
  • an acetal of formaldehyde, propionaldehyde, glutaraldehyde, glyoxal and / or one according to formula A and / or formula B can be used as the acetal of an aldehyde tanning agent.
  • it can be useful if two or more of the aforementioned acetals are used. It can be particularly useful if at least one acetal of glutaraldehyde is used.
  • Particularly good tanning can be achieved by using methanol, ethanol, diethylene glycol and / or triethylene glycol or two or more of the alcohol components mentioned as an alcohol component of the acetal.
  • methanol can be provided as an alcohol component.
  • the acetal is added with a composition which comprises further components.
  • the acetal is added with the composition according to the invention, as described and claimed herein.
  • a particularly good tanning effect can be achieved if a proportion of the added acetal based on the total weight of the fur and / or hide is 0.25% by weight to 10% by weight, in particular 1.0% by weight to 6 , 0% by weight, in particular 1.5% by weight to 5% by weight, preferably 2.0% by weight or 4.5% by weight.
  • the pH is adjusted to 6 to 9, in particular to 7.5 to 8.5, before the addition of the acetal.
  • the aldehydic tanning agent is not released, so that the acetal remains stable. Therefore, the aldehydic tanning agent cannot (yet) react with the proteins of the skin and / or the fur.
  • the acetal is added after a pickling process has been carried out and / or after a pickling step has been carried out.
  • the skin and / or the fur can be treated with an acid and / or with common salt.
  • the aldehydic tanning agent can be provided that after the addition of the acetal into the liquor, the pH of the liquor is set to 1 to 2.5, in particular to 1.8 to 2.5, is set. After the aldehydic tanning agent has been released, it can react with the proteins of the hide to be tanned and / or of the hide to be tanned.
  • a temperature of the liquor at least during the tanning step i.e. after activation of the aldehyde tanning agent, is between 10 ° C and 50 ° C, in particular between 20 ° C and 30 °, in particular 25 ° C.
  • Particularly good tanning can be achieved at the temperatures mentioned.
  • acetals provided for tanning are provided in combination with other tanning agents in the composition according to the invention and / or the method according to the invention. Further suitable tanning agents for this purpose are given below in the examples.
  • the invention also relates to a leather which is produced by the method according to the invention, as described and claimed herein and / or by using the composition according to the invention, as described and claimed here.
  • the leather according to the invention can be a pretanned leather.
  • the invention also relates to the use of the aforementioned leather according to the invention for producing a sanded and / or full-grain crust leather by one or more steps selected from the group of retanning, fatliquoring, filling and / or dyeing.
  • the invention therefore also relates to a crust leather, in particular a sanded and / or full-grain crust leather, produced by the treatment according to the invention of the leather, as mentioned above, by one or more of the steps selected from the group consisting of retanning, fatliquoring, filling and / or dyeing.
  • the invention also relates to the use of the leather according to the invention, as described and claimed herein and / or the crust leather according to the invention, as described and claimed herein, for the production of finished leather, in particular for the production of an automobile, furniture, clothing, glove , Leather goods, aircraft, lining and / or shoe upper leather articles.
  • the invention thus relates to a composition containing an acetal of an aldehydic tanning agent for tanning hides and / or hides and a method for tanning hides and / or hides for producing leather, an acetal of an aldehydic tanning agent being used.
  • the aldehydic tanning agent can be released by lowering the pH value, which initiates a tanning step.
  • the composition according to the invention and the method according to the invention are distinguished by a lower toxicity compared to conventional compositions and tanning processes which are based on aldehydic tanning agents. Furthermore, an improved penetration of the tanning agents into deeper layers of the hide and / or the fur is possible, so that a particularly homogeneous tanning is achieved.
  • Acetals of aldehydic tanning agents can, as described and claimed herein, be used for pretanning and / or retanning of hides, in particular animal hides, and / or pelts can, for example, come from an animal from the group consisting of cattle, pigs, goats, deer, sheep and / or deer.
  • acetals of aldehydic tanning agents mentioned and their use, as described and claimed herein, can also be used for pretanning and / or retanning of hides, in particular animal hides, and / or pelts which have been pretreated by known, conventional methods.
  • Suitable methods for pretreatment can be, for example, liming, deliming, bating, pickling and / or mechanical treatment.
  • the method according to the invention for pretanning, (main) tanning and / or retanning of hides, in particular animal hides, and / or pelts, as described and claimed herein, can be carried out in an aqueous medium, in particular in an aqueous liquor.
  • the pH can be adjusted to values from 1 to 10.
  • a suitable temperature for carrying out the process according to the invention can be between 10.degree. C. and 50.degree.
  • the temperature is preferably between 15 ° C and 35 ° C, in particular 25 ° C.
  • a suitable duration of the actual tanning step that is to say an incubation time of the hides and / or the pelts with the released aldehyde (corresponds to the aldehydic tanning agent), can be from 10 minutes to 12 hours.
  • a hide to be tanned and / or a hide to be tanned can be provided in a conventional tanning vessel. All further steps of the method according to the invention can then be carried out, for example, in this vessel and / or a drum.
  • tanning agents for pretanning and / or retanning of hides, in particular animal hides, and / or pelts .
  • suitable further tanning agents can be mineral tanning agents such as chromium, aluminum, zirconium, titanium and iron salts, synthetic tanning agents (syntans), polymer tanning agents and / or vegetable tanning agents (vegetable tanning agents).
  • the percentages by weight in the specific examples below relate to a total weight of the hide to be tanned and / or of the fur to be tanned.
  • the skin to be tanned and / or the fur to be tanned are provided in 3000 mL of water (hereinafter referred to as aqueous liquor) with a set pH of 7.5 to 8.5 and a temperature of 25 ° C in a suitable vessel .
  • an acetal of an aldehydic tanning agent for example acetal of glutaraldehyde
  • the acetal was here, as it is in U.S. 2,885,443 and or U.S. 4,448,977 is described.
  • the liquor with the acetal is allowed to act on the skin and / or the fur, for example in a rotatable drum provided for this purpose.
  • An exposure time can be freely selected, for example, depending on the thickness of the skin and / or the fur. The thicker the skin and / or fur, the longer the exposure time should be selected in order to achieve adequate penetration of the acetal into deeper skin layers.
  • the exposure time can be between 2 hours and 7 hours.
  • a preferred exposure time here is 5 hours.
  • the aldehydic tannin for example in the form of glutaraldehyde, is released.
  • the released aldehydic tanning agent can then react with the proteins of the skin and / or the fur, in particular with collagen. This initiates the actual tanning process.
  • the released aldehyde is then allowed to act on the skin and / or the hide in a tanning step, for example in the rotating drum.
  • a suitable exposure time here can be between 1.5 hours and 5 hours, preferably 3 hours.
  • 2% by weight of sodium hydrogen carbonate are added.
  • the aqueous liquor is then allowed to act on the pretanned skin and / or the pretanned hide in order to fix the aldehyde as completely as possible.
  • An exposure time can be, for example, between 1.5 and 4.5 hours, in particular 3 hours.
  • the pH is then adjusted to 4.0 to 4.2.
  • the liquor is discarded and the pre-tanned skin and / or the pre-tanned hide is washed with water, in particular with approx. 3000 ml of water.
  • the pretanned hide and / or the pretanned hide can then be dried and, for example, brought to a thickness of 1.1 to 1.3 mm.
  • the skin to be tanned and / or the fur to be tanned are provided in 3000 mL water (hereinafter referred to as aqueous liquor) with a set pH of 3.0 to 3.2 and a temperature of 25 ° C in a suitable vessel .
  • aqueous liquor 3000 mL water
  • no penetration step is provided in which the aldehydic tanning agent in the form of acetal first acts on the skin and / or the fur without reacting with proteins.
  • an acetal of an aldehydic tanning agent for example acetal of glutaraldehyde
  • an aldehydic tanning agent for example acetal of glutaraldehyde
  • 1% by weight of a mixture, in particular a 1: 1 mixture, of sodium formate and sodium hydrogen carbonate is added.
  • the pH is then adjusted to 4.0 to 4.2.
  • the liquor is then left to act for 1.5 hours to 4.5 hours, in particular for 3 hours.
  • 2% by weight of sodium hydrogen carbonate are then added, the liquor again being allowed to act for 2 hours to 6 hours, in particular for 4 hours.
  • the pH is then readjusted to 4.0 to 4.2.
  • the liquor is discarded and the pre-tanned skin and / or the pre-tanned hide is washed with water, in particular with approx. 3000 ml of water.
  • the pretanned hide and / or the pretanned hide can then be dried and, for example, brought to a thickness of 1.1 to 1.3 mm.

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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 Erfindung betrifft eine Zusammensetzung enthaltend einen Gerbstoff zum Gerben von Häuten und/oder Fellen. Ferner betrifft die Erfindung auch ein Verfahren zur Gerbung von Häuten und/oder Fellen zur Herstellung von Leder. Insbesondere betrifft die Erfindung eine Zusammensetzung und ein Verfahren zur Vorgerbung und/oder Nachgerbung, vorzugsweise zur Vorgerbung.The invention relates to a composition containing a tanning agent for tanning hides and / or pelts. The invention also relates to a method for tanning hides and / or pelts for the production of leather. In particular, the invention relates to a composition and a method for pretanning and / or retanning, preferably for pretanning.

Es sind bereits mehrere Zusammensetzungen und Verfahren der eingangs erwähnten Art bekannt. Die Gerbung und insbesondere die Vorgerbung von Häuten und/oder Fellen durch aldehydische Gerbstoffe ist allgemein bekannt und wird kommerziell beispielsweise im sogenannten "wet white"-Verfahren genutzt. Als aldehydische Gerbstoffe kommen hierbei vorwiegend Formaldehyd, Propionaldehyd, Glyoxal und in den häufigsten Fällen Glutaraldehyd zum Einsatz.Several compositions and methods of the type mentioned at the beginning are already known. The tanning and, in particular, the pretanning of hides and / or pelts by aldehyde tanning agents is generally known and is used commercially, for example in the so-called "wet white" process. The main aldehydic tanning agents used are formaldehyde, propionaldehyde, glyoxal and, in the most common cases, glutaraldehyde.

Ein wesentlicher Nachteil dieser vorbekannten Zusammensetzungen und Verfahren, die auf der Verwendung der genannten Gerbstoffe beruhen, besteht allerdings darin, dass die Gerbstoffe eine zu hohe Reaktivität gegenüber den Proteinen der zu gerbenden Haut aufweisen. Häufig kann es daher, insbesondere bei relativ dicken Häuten und/oder Fellen, zu einer unzureichenden Penetration der Gerbstoffe in tiefergelegene Hautschichten der zu gerbenden Haut und/oder des zu gerbenden Fells kommen. Dies kann zu einer inhomogenen Gerbung führen, was die Qualität des hergestellten Leders negativ beeinträchtigen kann.A major disadvantage of these previously known compositions and methods which are based on the use of the tanning agents mentioned is, however, that the tanning agents have too high a reactivity towards the proteins of the skin to be tanned. Frequently, therefore, particularly in the case of relatively thick hides and / or pelts, insufficient penetration of the tanning agents into deeper layers of the skin to be tanned and / or of the hide to be tanned can occur. This can lead to inhomogeneous tanning, which can negatively affect the quality of the leather produced.

Ein weiterer Nachteil vorbekannter Zusammensetzungen und Verfahren der eingangs erwähnten Art, die auf der Verwendung dieser Gerbstoffe basieren, besteht darin, dass aldehydische Gerbstoffe grundsätzlich eine sehr hohe Toxizität und einen stechenden Geruch aufweisen. Das Einatmen von aldehydischen Dämpfen und direkter Kontakt mit diesen aldehydischen Gerbstoffen sind bei vorbekannten Zusammensetzungen und darauf basierenden Verfahren allerdings häufig nicht vermeidbar, so dass für Personen, die diese zum Gerben von Häuten und/oder Fellen einsetzen, einer erhöhten Gesundheitsgefahr ausgesetzt sind. In diesem Zusammenhang besteht daher ein Bedarf, um die Arbeitssicherheit beim Gerben mit aldehydischen Gerbstoffen zu verbessern.Another disadvantage of previously known compositions and methods of the type mentioned at the outset which are based on the use of these tanning agents is that aldehydic tanning agents generally have a very high toxicity and a pungent odor. Inhaling aldehydic vapors and direct contact with these aldehydic tanning agents are, however, often unavoidable with known compositions and processes based on them, so that people who use them for tanning hides and / or pelts are exposed to an increased health risk. In this context, there is therefore a need to improve occupational safety when tanning with aldehydic tanning agents.

Es besteht also die Aufgabe, eine Zusammensetzung und/oder ein Verfahren der eingangs erwähnten Art zu schaffen, bei welcher/n/m die zuvor genannten Nachteile nicht auftreten.The object is therefore to create a composition and / or a method of the type mentioned at the outset in which the aforementioned disadvantages do not occur.

Bei der erfindungsgemäßen Zusammensetzung ist zur Lösung der genannten Aufgabe die Kombination der Merkmale gemäß des Anspruchs 1 vorgesehen. Insbesondere wird somit erfindungsgemäß zur Lösung der genannten Aufgabe eine Zusammensetzung vorgeschlagen, die zum Gerben von Häuten und/oder Fellen vorgesehen ist, umfassend:

  • 5 Gew.-% bis 95 Gew.-% eines Acetals eines aldehydischen Gerbstoffes,
  • 1 Gew.-% bis 5 Gew.-% einer pH-regulierenden Pufferkomponente und
  • 4 Gew.-% bis 90 Gew.-% eines Lösungsmittels, wobei durch die pH-regulierende Pufferkomponente ein pH-Wert der Zusammensetzung von 7,5 bis 10,5 eingestellt ist.
In the case of the composition according to the invention, the combination of the features according to claim 1 is provided in order to achieve the stated object. In particular, according to the invention, in order to achieve the stated object, a composition is proposed which is intended for tanning hides and / or pelts, comprising:
  • 5% by weight to 95% by weight of an acetal of an aldehydic tanning agent,
  • 1% by weight to 5% by weight of a pH-regulating buffer component and
  • 4% by weight to 90% by weight of a solvent, the pH-regulating buffer component setting the composition to a pH of 7.5 to 10.5.

Die erfindungsgemäße Zusammensetzung hat gegenüber vorbekannten Zusammensetzungen, welche auf aldehydischen Gerbstoffen basieren, den Vorteil, dass Acetale von aldehydischen Gerbstoffen gegenüber den Proteinen der zu gerbenden Haut und/oder Felle nicht oder kaum reaktiv sind. Derartige Acetale sind insbesondere im neutralen und alkalischen Medium stabil und reagieren aus diesem Grund nicht mit den genannten Proteinen, wenn die erfindungsgemäße Zusammensetzung bei diesem pH-Wert auf die Haut und/oder das Fell aufgebracht wird. Darüber hinaus weisen Acetale von aldehydischen Gerbstoffen eine geringere Toxizität als der aldehydische Gerbstoff selbst, also das Aldehyd, auf. Ein weiterer bis dato vollkommen unbekannter, überraschender Effekt zeigt sich bei der erfindungsgemäßen Zusammensetzung dadurch, dass bei einer Verwendung der erfindungsgemäßen Zusammensetzung zum Gerben eine verbesserte Penetration in tiefere Schichten der zu gerbenden Haut und/oder des zu gerbenden Fells erreichbar ist. Insbesondere bei relativ dicken Häuten und Fellen kann dadurch eine homogenere Gerbung verglichen mit vorbekannten Zusammensetzungen, die auf aldehydischen Gerbstoffen basieren, erreicht werden. Nachdem die erfindungsgemäße Zusammensetzung auf eine zu gerbende Haut und/oder ein Fell aufgetragen ist, kann nach einer Einwirkzeit der pH-Wert derart abgesenkt werden, dass der aldehydische Gerbstoff freigesetzt wird und dadurch reaktiv wird. Durch das Einwirken des Acetals auf die Haut und/oder das Fell kann es also in tiefere Schichten eindringen und dort anschließend der Gerbstoff freigesetzt werden. Nach einer vorgenommenen Gerbung kann durch Erhöhung
des pH-Wertes der aldehydische Gerbstoff fixiert und die Gerbung beendet werden. Ferner wird die erfindungsgemäße Zusammensetzung in nicht reaktiver Form auf eine Haut und/oder ein Fell aufgetragen, welches beispielsweise in einem verschließbaren Behälter bereitstellbar ist/sind. Durch eine anschließende Ansäuerung, das heißt ein Absenken des pH-Wertes, kann der aldehydische Gerbstoff der Zusammensetzung aktiviert werden, wobei dies beispielsweise innerhalb des geschlossenen Gefäßes durch eine Zugabe einer Säure möglich ist. Dadurch kann ein Einatmen von Aldehyddämpfen und ein Kontakt mit der Zusammensetzung durch einen Benutzer besser vermieden werden, wodurch die Arbeitssicherheit beim Gerben signifikant erhöht wird. Alternativ oder ergänzend kann die erfindungsgemäße Zusammensetzung auch auf eine gebeizte Blöße angewandt werden.The composition according to the invention has the advantage over previously known compositions based on aldehydic tanning agents that acetals of aldehydic tanning agents are not or hardly reactive towards the proteins of the hide and / or pelts to be tanned. Such acetals are particularly stable in a neutral and alkaline medium and for this reason do not react with the proteins mentioned when the composition according to the invention is applied to the skin and / or the fur at this pH value. In addition, acetals from aldehydic tanning agents are less toxic than the aldehydic tanning agent itself, i.e. the aldehyde. Another hitherto completely unknown, surprising effect is shown in the composition according to the invention in that when the composition according to the invention is used for tanning, improved penetration into deeper layers of the skin to be tanned and / or of the fur to be tanned can be achieved. In particular in the case of relatively thick hides and skins, a more homogeneous tanning can thereby be achieved compared with previously known compositions which are based on aldehydic tanning agents. After the composition according to the invention has been applied to a skin and / or a fur to be tanned, the pH value can be lowered after an exposure time in such a way that the aldehydic tanning agent is released and becomes reactive as a result. Through the action of the acetal on the skin and / or the fur, it can penetrate deeper layers and the tannin can then be released there. After a tanning process, it can be increased
the pH of the aldehydic tanning agent is fixed and the tanning is ended. Furthermore, the composition according to the invention is applied in non-reactive form to a skin and / or a fur, which can be made available, for example, in a closable container. The aldehydic tanning agent of the composition can be activated by subsequent acidification, that is to say lowering the pH value, this being possible, for example, within the closed vessel by adding an acid. In this way, inhalation of aldehyde vapors and contact with the composition by a user can be better avoided, as a result of which work safety during tanning is significantly increased. As an alternative or in addition, the composition according to the invention can also be applied to a pickled pelt.

Gemäß einer bevorzugten Weiterbildung der erfindungsgemäßen Zusammensetzung ist das Acetal eines aldehydischen Gerbstoffes ein Acetal von Formaldehyd, Propionaldehyd, Glutaraldehyd und/oder Glyoxal. Insbesondere kann es vorgesehen sein, dass die Zusammensetzung zwei oder mehr der genannten Acetale enthält. Gemäß einer bevorzugten Ausgestaltung ist das Acetal von Glutaraldehyd. Die genannten Acetale aldehydischer Gerbstoffe weisen eine besonders gute Gerbwirkung auf.According to a preferred development of the composition according to the invention, the acetal of an aldehyde tanning agent is an acetal of formaldehyde, propionaldehyde, glutaraldehyde and / or glyoxal. In particular, it can be provided that the composition contains two or more of the acetals mentioned. According to a preferred embodiment, the acetal is glutaraldehyde. The acetals mentioned of aldehydic tanning agents have a particularly good tanning effect.

Es kann weiter zweckmäßig sein, wenn eine Alkoholkomponente des Acetals eines aldehydischen Gerbstoffes Methanol, Ethanol, Diethylenglykol und/oder Triethylenglykol ist. Vorzugsweise ist die Alkoholkomponente des Acetals Methanol. Verfahren zur Herstellung von Acetalen eines aldehydischen Gerbstoffes sind bereits aus dem Stand der Technik bekannt. Beispielsweise sind in der US 2,885,443 und der US 4,448,977 Verfahren zur Herstellung eines Acetals, insbesondere von Glutaraldehyd, beschrieben. Das mit vorbekannten Verfahren hergestellte Acetal eines aldehydischen Gerbstoffes kann zudem durch die Anwendung weiterer vorbekannter Reinigungsverfahren, wie beispielsweise durch Säulenchromatographie, insbesondere durch Flash-Chromatographie, aufgereinigt werden, um ein noch reineres Acetal zu erhalten.It can also be useful if an alcohol component of the acetal of an aldehyde tanning agent is methanol, ethanol, diethylene glycol and / or triethylene glycol. The alcohol component of the acetal is preferably methanol. Processes for the production of acetals of an aldehydic tanning agent are already known from the prior art. For example, in the U.S. 2,885,443 and the U.S. 4,448,977 Process for the production of an acetal, in particular glutaraldehyde, is described. The acetal of an aldehydic produced with previously known processes The tanning agent can also be purified by using other previously known purification processes, such as, for example, column chromatography, in particular flash chromatography, in order to obtain an even purer acetal.

Um die Reaktivität eines durch Absenken des pH-Wertes freigesetzten aldehydischen Gerbstoffes während eines Gerbschrittes weiter reduzieren zu können, kann es zweckmäßig sein, wenn die erfindungsgemäße Zusammensetzung zumindest ein Saccharid, insbesondere ein reduzierendes Saccharid, aufweist. Alternativ oder ergänzend dazu kann es zweckmäßig sein, wenn die erfindungsgemäße Zusammensetzung zumindest ein Saccharid mit einem Dextroseäquivalent von 10 bis 100 enthält. Gemäß einer bevorzugten Ausgestaltung der erfindungsgemäßen Zusammensetzung kann es vorgesehen sein, dass der Anteil des zumindest einen Saccharids an der Zusammensetzung 0,1 Gew.-% bis 30 Gew.-%, insbesondere 2,5 Gew.-% bis 15 Gew.-%, beträgt. Damit lässt sich die Reaktivität des freigesetzten aldehydischen Gerbstoffes weiter verringern und somit eine langsamere und schonendere Gerbung aufgrund einer verbesserten Penetration (auch während der eigentlichen Gerbung) in tiefere Hautschichten erreichen.In order to be able to further reduce the reactivity of an aldehydic tanning agent released by lowering the pH during a tanning step, it can be useful if the composition according to the invention has at least one saccharide, in particular a reducing saccharide. As an alternative or in addition to this, it can be expedient if the composition according to the invention contains at least one saccharide with a dextrose equivalent of 10 to 100. According to a preferred embodiment of the composition according to the invention, it can be provided that the proportion of the at least one saccharide in the composition is 0.1% by weight to 30% by weight, in particular 2.5% by weight to 15% by weight , amounts to. This allows the reactivity of the released aldehydic tanning agent to be further reduced and thus a slower and gentler tanning process due to improved penetration (also during the actual tanning process) into the deeper layers of the skin.

Besonders zweckmäßig kann es dabei sein, wenn die Zusammensetzung zumindest ein oder das zumindest eine, bereits zuvor genannte Saccharid aufweist, welches aus der Gruppe aus Glucose, Sucrose oder einer Mischung aus Glucose und Sucrose ausgewählt ist. Hierbei handelt es sich um für die Gerbung besonders gut geeignete reduzierende Saccharide, die zu einer verbesserten Gerbung einer Haut und/oder eines Fells führen.It can be particularly expedient if the composition has at least one or the at least one previously mentioned saccharide which is selected from the group of glucose, sucrose or a mixture of glucose and sucrose. These are reducing saccharides which are particularly well suited for tanning and lead to improved tanning of a hide and / or a fur.

Gemäß einer vorteilhaften Weiterentwicklung der erfindungsgemäßen Zusammensetzung kann es zweckmäßig sein, wenn die Zusammensetzung einen Anteil an Polyoxaalkylenglycol enthält. Insbesondere kann es erfindungsgemäß vorgesehen sein, dass der Anteil an Polyoxaalkylenglycol ausgewählt aus der Gruppe aus Polyoxaethylendiol, Polyoxa-1,2-propylendiol oder einer Mischung aus Polyoxaethylendiol und Polyoxa-1,2-propylendiol ist. Insbesondere kann es vorgesehen sein, dass die Zusammensetzung zwei oder mehr der genannten Polyoxaalkylenglycole enthält.According to an advantageous further development of the composition according to the invention, it can be expedient if the composition contains a proportion of polyoxaalkylene glycol. In particular it can be provided according to the invention that the proportion of polyoxaalkylene glycol is selected from the group of polyoxaethylene diol, polyoxa-1,2-propylene diol or a mixture of polyoxaethylene diol and polyoxa-1,2-propylene diol. In particular, it can be provided that the composition contains two or more of the polyoxaalkylene glycols mentioned.

Um die Lederqualität weiter zu verbessern, kann es weiter besonders zweckmäßig sein, wenn ein oder der bereits zuvor genannte Anteil an Polyoxaalkylenglycol an der Zusammensetzung ein oder mehrere Polyoxaalkylenglycole mit einer Molekülmasse MR von 120 bis 1.000 enthält. Dabei kann es besonders zweckmäßig sein, wenn ein oder der bereits zuvor genannte Anteil an Polyoxaalkylenglycol/en an der Zusammensetzung 2,5 bis 15 Gew.-% beträgt.In order to further improve the leather quality, it can also be particularly expedient if one or the aforementioned proportion of polyoxaalkylene glycol in the composition contains one or more polyoxaalkylene glycols with a molecular weight M R of 120 to 1,000. It can be particularly expedient here if one or the aforementioned proportion of polyoxaalkylene glycol / s in the composition is 2.5 to 15% by weight.

Gemäß einer bevorzugten Ausgestaltung der erfindungsgemäßen Zusammensetzung und/oder des erfindungsgemäßen Verfahrens, wie hierin ebenfalls beschrieben und beansprucht, kann es vorgesehen sein, dass das Acetal eines aldehydischen Gerbstoffes das Acetal nach Formel A und/oder Formel B ist, wobei:

Figure imgb0001
und
Figure imgb0002
 ist, wobei

  • x = 0 bis 8,
    • y = 2 bis 6,
    • R1 = -H, -CH2, -CHO,
    Figure imgb0003
     ist, und
    wobei z = 2 bis 6 und
    R2, R3, R4 und R5 unabhängig voneinander je eines ausgewählt aus
Figure imgb0004
 und wobei
  • m = 0 bis 8,
  • n = 0 bis 8,
  • o = 0 bis 8
ist/sind. Die Acetale gemäß Formel A und B liefern ein besonders gutes Ergebnis bei der Herstellung von Leder.According to a preferred embodiment of the composition according to the invention and / or the method according to the invention, as also described and claimed herein, it can be provided that the acetal of an aldehydic tanning agent is the acetal according to formula A and / or formula B, where:
Figure imgb0001
 and
Figure imgb0002
 is, where
  • x = 0 to 8,
    • y = 2 to 6,
    • R 1 = -H, -CH 2 , -CHO,
    Figure imgb0003
     is and
    where z = 2 to 6 and
    R 2 , R 3 , R 4 and R 5 are each independently selected from
Figure imgb0004
 and where
  • m = 0 to 8,
  • n = 0 to 8,
  • o = 0 to 8
is / are. The acetals according to formula A and B give a particularly good result in the production of leather.

Es kann weiter zweckmäßig sein, wenn die erfindungsgemäße Zusammensetzung zusätzlich ein Aldehyd enthält, insbesondere wobei ein Anteil des Aldehyds an der Zusammensetzung 0,1 Gew.-% bis 50 Gew.-%, insbesondere 5 Gew.-% bis 50 Gew.-%, insbesondere 10 Gew.-% bis 40 Gew.-%, insbesondere 20 Gew.-% bis 30 Gew.-%, beträgt.It can also be useful if the composition according to the invention additionally contains an aldehyde, in particular where a proportion of the aldehyde in the composition is 0.1% by weight to 50% by weight, in particular 5% by weight to 50% by weight , in particular 10% by weight to 40% by weight, in particular 20% by weight to 30% by weight.

Das Lösungsmittel der erfindungsgemäßen Zusammensetzung kann eines ausgewählt aus der Gruppe bestehend aus Wasser, wasserlöslichen organischen Lösungsmitteln oder eine Mischung von Wasser und wasserlöslichen organischen Lösungsmitteln aufweisen. Als wasserlösliche organische Lösungsmittel können sich beispielsweise Glycerin und/oder ein monoverethertes Polyoxaalkylenglycol eignen. Alternativ oder ergänzend dazu kann es auch vorgesehen sein, dass das wasserlösliche organische Lösungsmittel eine Molekülmasse MR von größer oder gleich 100 und/oder von kleiner oder gleich 2.000 hat.The solvent of the composition according to the invention can have one selected from the group consisting of water, water-soluble organic solvents or a mixture of water and water-soluble organic solvents. Glycerol and / or a monoetherified polyoxaalkylene glycol, for example, can be suitable as water-soluble organic solvents. As an alternative or in addition to this, it can also be provided that the water-soluble organic solvent has a molecular weight M R of greater than or equal to 100 and / or of less than or equal to 2,000.

Gemäß einer weiteren bevorzugten Ausgestaltung der erfindungsgemäßen Zusammensetzung kann durch die pH-regulierende Pufferkomponente ein pH-Wert der Zusammensetzung von 7,5 bis 10,5 eingestellt sein. In diesem pH-Bereich ist der aldehydische Gerbstoff stabil und daher nicht reaktiv mit den Proteinen der zu gerbenden Haut und/oder des zu gerbenden Fells. Dadurch kann eine besonders gute Penetration der Zusammensetzung in tiefere Schichten erreicht werden.According to a further preferred embodiment of the composition according to the invention, the pH-regulating buffer component can set a pH of 7.5 to 10.5 for the composition. In this pH range, the aldehydic tanning agent is stable and therefore not reactive with the proteins of the hide to be tanned and / or of the fur to be tanned. In this way, particularly good penetration of the composition into deeper layers can be achieved.

Geeignete pH-regulierende Pufferkomponenten können beispielsweise eine oder mehrere ausgewählt aus der Gruppe bestehend aus Carbonatpuffer, Boratpuffer und/oder Phosphatpuffer sein.Suitable pH-regulating buffer components can be, for example, one or more selected from the group consisting of carbonate buffer, borate buffer and / or phosphate buffer.

Ferner wird zur Lösung der oben genannten Aufgabe ein Verfahren gemäß den Merkmalen des unabhängigen Verfahrensanspruchs 8 bereitgestellt. Insbesondere wird zur Lösung der zuvor genannten Aufgabe ein Verfahren der eingangs erwähnten Art vorgeschlagen, welches die folgenden Schritte umfasst:

  • Bereitstellen einer Haut und/oder eines Fells in einer Flotte mit einem pH-Wert zwischen 1 und 10,
  • Einstellen des pH-Wertes auf 6 bis 9 vor Zugabe eines Acetals eines aldehydischen Gerbstoffes,
  • Zugabe des Acetals eines aldehydischen Gerbstoffes auf die Haut und/oder das Fell in der Flotte,
  • Einwirken des in die Flotte zugegebenen Acetals auf die Haut und/oder das Fell in einem Penetrations¬schritt,
  • Einstellen des pH-Wertes der Flotte zwischen 1 und 3,6 in einem Aktivierungsschritt, wobei der aldehydi¬sche Gerbstoff freigesetzt wird,
  • Einwirken des in der Flotte freigesetzten aldehydi¬schen Gerbstoffs auf die Haut und/oder das Fell in einem Gerbungsschritt,
  • Einstellen des pH-Wertes der Flotte zwischen 3,8 und 5 zum Fixieren des aldehydischen Gerbstoffs in einem Fixierungsschritt.
Furthermore, a method is used to achieve the above-mentioned object according to the features of independent method claim 8 provided. In particular, a method of the type mentioned at the beginning is proposed for solving the aforementioned object, which comprises the following steps:
  • Providing a skin and / or a fur in a liquor with a pH value between 1 and 10,
  • Adjusting the pH value to 6 to 9 before adding an acetal of an aldehydic tanning agent,
  • Adding the acetal of an aldehydic tanning agent to the skin and / or the fur in the liquor,
  • Action of the acetal added to the liquor on the skin and / or the fur in a penetration step,
  • Adjustment of the pH value of the liquor between 1 and 3.6 in an activation step, whereby the aldehydic tannin is released,
  • Action of the aldehydic tanning agent released in the liquor on the skin and / or the hide in one tanning step,
  • Adjusting the pH of the liquor between 3.8 and 5 to fix the aldehydic tanning agent in one fixation step.

Das Verfahren kann mit den weiteren im Folgenden beschriebenen vorteilhaften Ausgestaltungen erweitert werden.The method can be expanded with the further advantageous refinements described below.

Für das erfindungsgemäße Verfahren, wie dies hierin beschrieben und beansprucht ist, gelten die gleichen Vorteile wie sie bereits zuvor für die erfindungsgemäße Zusammensetzung erläutert wurden. Ferner kann das erfindungsgemäße Verfahren, wie auch die erfindungsgemäße Zusammensetzung, zur Gerbung, Vorgerbung und/oder Nachgerbung einer Blöße eingesetzt werden. Als Blöße kann eine entfleischte und/oder enthaarte Haut nach dem Pickel und/oder der Beize definiert sein, die jedoch noch nicht gegerbt wurde.For the method according to the invention, as described and claimed herein, the same advantages apply as have already been explained above for the composition according to the invention. Furthermore, the method according to the invention, like the composition according to the invention, can be used for tanning, pretanning and / or retanning of pelts. A skin that has been fleshed and / or depilated after the pimple and / or the stain can be defined as nakedness, but which has not yet been tanned.

Gemäß einer bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens kann als Acetal eines aldehydischen Gerbstoffes ein Acetal von Formaldehyd, Propionaldehyd, Glutaraldehyd, Glyoxal und/oder eines gemäß Formel A und/oder Formel B, verwendet werden. Insbesondere kann es zweckmäßig sein, wenn zwei oder mehr der zuvor genannten Acetale verwendet werden. Besonders zweckmäßig kann es sein, wenn zumindest ein Acetal von Glutaraldehyd verwendet wird.According to a preferred embodiment of the process according to the invention, an acetal of formaldehyde, propionaldehyde, glutaraldehyde, glyoxal and / or one according to formula A and / or formula B can be used as the acetal of an aldehyde tanning agent. In particular, it can be useful if two or more of the aforementioned acetals are used. It can be particularly useful if at least one acetal of glutaraldehyde is used.

Dabei kann es zweckmäßig sein, wenn als Flotte eine wässrige Flotte verwendet wird.It can be useful if an aqueous liquor is used as the liquor.

Eine besonders gute Gerbung kann dadurch erreicht werden, dass als eine Alkoholkomponente des Acetals Methanol, Ethanol, Diethylenglykol und/oder Triethylenglykol verwendet wird oder zwei oder mehr der genannten Alkoholkomponenten. Gemäß einer besonders vorteilhaften Ausgestaltung des erfindungsgemäßen Verfahrens kann als eine Alkoholkomponente Methanol vorgesehen sein.Particularly good tanning can be achieved by using methanol, ethanol, diethylene glycol and / or triethylene glycol or two or more of the alcohol components mentioned as an alcohol component of the acetal. According to a particularly advantageous embodiment of the method according to the invention, methanol can be provided as an alcohol component.

Es kann besonders zweckmäßig sein, wenn bei dem erfindungsgemäßen Verfahren das Acetal mit einer Zusammensetzung zugegeben wird, die weitere Komponenten umfasst. Alternativ oder ergänzend kann es besonders zweckmäßig sein, wenn das Acetal mit der erfindungsgemäßen Zusammensetzung, wie hierin beschrieben und beansprucht ist, zugegeben wird.It can be particularly expedient if, in the process according to the invention, the acetal is added with a composition which comprises further components. Alternatively or in addition, it can be particularly expedient if the acetal is added with the composition according to the invention, as described and claimed herein.

Eine besonders gute Gerbwirkung kann dadurch erreichbar sein, wenn ein Anteil des zugegebenen Acetals bezogen auf ein Gesamtgewicht des Felles und/oder der Haut 0,25 Gew.-% bis 10 Gew.-%, insbesondere 1,0 Gew.-% bis 6,0 Gew.-%, insbesondere 1,5 Gew.-% bis 5 Gew.-%, vorzugsweise 2,0 Gew.-% oder 4,5 Gew.-%, beträgt.A particularly good tanning effect can be achieved if a proportion of the added acetal based on the total weight of the fur and / or hide is 0.25% by weight to 10% by weight, in particular 1.0% by weight to 6 , 0% by weight, in particular 1.5% by weight to 5% by weight, preferably 2.0% by weight or 4.5% by weight.

Besonders zweckmäßig kann es sein, wenn bei dem erfindungsgemäßen Verfahren vor der Zugabe des Acetals der pH-Wert auf 6 bis 9, insbesondere auf 7,5 bis 8,5, eingestellt wird. Bei einem derartigen pH-Wert wird der aldehydische Gerbstoff nicht freigesetzt, so dass das Acetal stabil bleibt. Daher kann der aldehydische Gerbstoff (noch) nicht mit den Proteinen der Haut und/oder des Felles reagieren.It can be particularly useful if, in the process according to the invention, the pH is adjusted to 6 to 9, in particular to 7.5 to 8.5, before the addition of the acetal. At such a pH value, the aldehydic tanning agent is not released, so that the acetal remains stable. Therefore, the aldehydic tanning agent cannot (yet) react with the proteins of the skin and / or the fur.

Es kann erfindungsgemäß vorgesehen sein, dass die Zugabe des Acetals nach einer Durchführung eines Beizverfahrens und/oder nach einer Durchführung eines Pickelschrittes vorgenommen wird. Während eines solchen Pickelschrittes kann die Haut und/oder das Fell mit einer Säure und/oder mit Kochsalz behandelt werden. Eine Vielzahl von Beizverfahren und Pickelschritte sind bereits aus dem Stand der Technik vorbekannt.According to the invention, it can be provided that the acetal is added after a pickling process has been carried out and / or after a pickling step has been carried out. During such a pimple step, the skin and / or the fur can be treated with an acid and / or with common salt. A large number of pickling processes and pickling steps are already known from the prior art.

Zur Freisetzung des aldehydischen Gerbstoffes kann es vorgesehen sein, dass nach der Zugabe des Acetals in die Flotte der pH-Wert der Flotte auf 1 bis 2,5, insbesondere auf 1,8 bis 2,5, eingestellt wird. Nach Freisetzung des aldehydischen Gerbstoffes kann dieser mit den Proteinen der zu gerbenden Haut und/oder des zu gerbenden Felles reagieren.To release the aldehydic tanning agent, it can be provided that after the addition of the acetal into the liquor, the pH of the liquor is set to 1 to 2.5, in particular to 1.8 to 2.5, is set. After the aldehydic tanning agent has been released, it can react with the proteins of the hide to be tanned and / or of the hide to be tanned.

Gemäß einer bevorzugten Ausgestaltung des erfindungsgemäßen Verfahrens kann es zweckmäßig sein, wenn eine Temperatur der Flotte zumindest während des Gerbungsschrittes, das heißt nach Aktivierung des aldehydischen Gerbstoffes, zwischen 10°C und 50°C, insbesondere zwischen 20°C und 30°, insbesondere 25°C, beträgt. Bei den genannten Temperaturen ist eine besonders gute Gerbung erreichbar.According to a preferred embodiment of the process according to the invention, it can be useful if a temperature of the liquor at least during the tanning step, i.e. after activation of the aldehyde tanning agent, is between 10 ° C and 50 ° C, in particular between 20 ° C and 30 °, in particular 25 ° C. Particularly good tanning can be achieved at the temperatures mentioned.

Weiter ist es denkbar, dass die zur Gerbung vorgesehenen Acetale bei der erfindungsgemäßen Zusammensetzung und/oder dem erfindungsgemäßen Verfahren in Kombination mit anderen Gerbstoffen vorgesehen ist. Geeignete weitere Gerbstoffe hierfür sind nachfolgend in den Beispielen genannt.It is also conceivable that the acetals provided for tanning are provided in combination with other tanning agents in the composition according to the invention and / or the method according to the invention. Further suitable tanning agents for this purpose are given below in the examples.

Ferner betrifft die Erfindung auch ein Leder, welches nach dem erfindungsgemäßen Verfahren, wie hierin beschrieben und beansprucht und/oder durch die Verwendung der erfindungsgemäßen Zusammensetzung, wie hierin beschrieben und beansprucht ist, hergestellt ist. Insbesondere kann es sich bei dem erfindungsgemäßen Leder um ein vorgegerbtes Leder handeln.Furthermore, the invention also relates to a leather which is produced by the method according to the invention, as described and claimed herein and / or by using the composition according to the invention, as described and claimed here. In particular, the leather according to the invention can be a pretanned leather.

Des Weiteren betrifft die Erfindung auch die Verwendung des zuvor genannten erfindungsgemäßen Leders zur Herstellung eines geschliffenen und/oder vollnarbigen Crust-Leders durch einen oder mehrere Schritte ausgewählt aus der Gruppe aus Nachgerbung, Fettung, Füllung und/oder Färbung.Furthermore, the invention also relates to the use of the aforementioned leather according to the invention for producing a sanded and / or full-grain crust leather by one or more steps selected from the group of retanning, fatliquoring, filling and / or dyeing.

Daher betrifft die Erfindung also auch ein Crust-Leder, insbesondere eines geschliffenes und/oder vollnarbiges Crust-Leders, hergestellt durch die erfindungsgemäße Behandlung des Leders, wie zuvor genannt, durch einen oder mehrere der Schritte ausgewählt aus der Gruppe aus Nachgerbung, Fettung, Füllung und/oder Färbung.The invention therefore also relates to a crust leather, in particular a sanded and / or full-grain crust leather, produced by the treatment according to the invention of the leather, as mentioned above, by one or more of the steps selected from the group consisting of retanning, fatliquoring, filling and / or dyeing.

Die Erfindung betrifft außerdem die Verwendung des erfindungsgemäßen Leders, wie hierin beschrieben und beansprucht und/oder des erfindungsgemäßen Crust-Leders, wie hierin beschrieben und beansprucht, zur Herstellung zugerichteter Leder, insbesondere zur Herstellung eines Automobil-, Möbel-, Bekleidungs-, Handschuh-, Lederwaren-, Flugzeug-, Futter- und/oder Schuhoberleder-Artikels.The invention also relates to the use of the leather according to the invention, as described and claimed herein and / or the crust leather according to the invention, as described and claimed herein, for the production of finished leather, in particular for the production of an automobile, furniture, clothing, glove , Leather goods, aircraft, lining and / or shoe upper leather articles.

Die Erfindung betrifft also eine Zusammensetzung enthaltend ein Acetal eines aldehydischen Gerbstoffs zum Gerben von Häuten und/oder Fellen sowie ein Verfahren zur Gerbung von Häuten und/oder Fellen zur Herstellung von Leder, wobei ein Acetal eines aldehydischen Gerbstoffes verwendet wird. Durch Absenken des pH-Wertes kann der aldehydische Gerbstoff freigesetzt werden, wodurch ein Gerbungsschritt eingeleitet wird. Die erfindungsgemäße Zusammensetzung und das erfindungsgemäße Verfahren zeichnen sich durch eine geringere Toxizität gegenüber konventionellen Zusammensetzungen und Gerbungsverfahren aus, die auf aldehydischen Gerbstoffen beruhen. Ferner ist eine verbesserte Penetration der Gerbstoffe in tiefere Schichten der Haut und/oder des Felles möglich, so dass eine besonders homogene Gerbung erreicht wird.The invention thus relates to a composition containing an acetal of an aldehydic tanning agent for tanning hides and / or hides and a method for tanning hides and / or hides for producing leather, an acetal of an aldehydic tanning agent being used. The aldehydic tanning agent can be released by lowering the pH value, which initiates a tanning step. The composition according to the invention and the method according to the invention are distinguished by a lower toxicity compared to conventional compositions and tanning processes which are based on aldehydic tanning agents. Furthermore, an improved penetration of the tanning agents into deeper layers of the hide and / or the fur is possible, so that a particularly homogeneous tanning is achieved.

BeispieleExamples

Acetale von aldehydischen Gerbstoffen können, wie hierin beschrieben und beansprucht, zur Vorgerbung und/oder Nachgerbung von Häuten, insbesondere von Tierhäuten, und/oder Fellen verwendet werden, wobei diese beispielsweise von einem Tier aus der Gruppe aus Rind, Schwein, Ziege, Reh, Schaf und/oder Hirsch stammen können.Acetals of aldehydic tanning agents can, as described and claimed herein, be used for pretanning and / or retanning of hides, in particular animal hides, and / or pelts can, for example, come from an animal from the group consisting of cattle, pigs, goats, deer, sheep and / or deer.

Die genannten Acetale von aldehydischen Gerbstoffen und deren Verwendung, wie hierin beschrieben und beansprucht, können auch zur Vorgerbung und/oder Nachgerbung von Häuten, insbesondere von Tierhäuten, und/oder Fellen eingesetzt werden, die durch vorbekannte, konventionelle Verfahren vorbehandelt sind. Geeignete Verfahren zur Vorbehandlung können dabei beispielsweise Äschern (engl. liming), Entkälkung (engl. deliming), Beizen (engl. bating), Pickel (engl. pickling) und/oder eine mechanische Behandlung sein.The acetals of aldehydic tanning agents mentioned and their use, as described and claimed herein, can also be used for pretanning and / or retanning of hides, in particular animal hides, and / or pelts which have been pretreated by known, conventional methods. Suitable methods for pretreatment can be, for example, liming, deliming, bating, pickling and / or mechanical treatment.

Das erfindungsgemäße Verfahren zur Vorgerbung, (Haupt)Gerbung und/oder Nachgerbung von Häuten, insbesondere von Tierhäuten, und/oder Fellen, wie hierin beschrieben und beansprucht, kann in einem wässrigen Milieu, insbesondere in einer wässrigen Flotte, durchgeführt werden. Der pH-Wert kann dabei auf Werte von 1 bis 10 eingestellt werden.The method according to the invention for pretanning, (main) tanning and / or retanning of hides, in particular animal hides, and / or pelts, as described and claimed herein, can be carried out in an aqueous medium, in particular in an aqueous liquor. The pH can be adjusted to values from 1 to 10.

Eine geeignete Temperatur zur Durchführung des erfindungsgemäßen Verfahrens kann zwischen 10°C und 50°C liegen. Bevorzugt liegt die Temperatur bei einem Wert zwischen 15°C und 35°C, insbesondere bei 25°C.A suitable temperature for carrying out the process according to the invention can be between 10.degree. C. and 50.degree. The temperature is preferably between 15 ° C and 35 ° C, in particular 25 ° C.

Eine geeignete Dauer des eigentlichen Gerbungsschrittes, das heißt eine Inkubationszeit der Häute und/oder der Felle mit dem freigesetzten Aldehyd (entspricht dem aldehydischen Gerbstoff) kann von 10 Minuten bis zu 12 Stunden sein.A suitable duration of the actual tanning step, that is to say an incubation time of the hides and / or the pelts with the released aldehyde (corresponds to the aldehydic tanning agent), can be from 10 minutes to 12 hours.

Das erfindungsgemäße Verfahren, wie hierin beschrieben und beansprucht, eignet sich hervorragend dazu, um in bestehenden Gerbereien durchgeführt zu werden. Insbesondere kann eine zu gerbende Haut und/oder ein zu gerbendes Fell in einem üblichen Gerbungsgefäß bereitgestellt werden. Alle weiteren Schritte des erfindungsgemäßen Verfahrens können anschließend beispielsweise in diesem Gefäß und/oder einer Trommel durchgeführt werden.The method according to the invention, as described and claimed herein, is eminently suitable for use in existing Tanneries to be carried out. In particular, a hide to be tanned and / or a hide to be tanned can be provided in a conventional tanning vessel. All further steps of the method according to the invention can then be carried out, for example, in this vessel and / or a drum.

Des Weiteren ist es möglich, dass das erfindungsgemäße Verfahren, wie hierin beschrieben und beansprucht, neben dem Acetal von Aldehyden und/oder Aldehyden in Kombination mit weiteren Gerbstoffen zur Vorgerbung und/oder Nachgerbung von Häuten, insbesondere von Tierhäuten, und/oder Fellen eingesetzt wird. Beispiele für geeignete weitere Gerbstoffe können mineralische Gerbstoffe, wie Chrom-, Aluminium-, Zirkon-, Titan- und Eisensalze, synthetische Gerbstoffe (Syntane), Polymer-Gerbstoffe und/oder vegetabile Gerbstoffe (Pflanzen-Gerbstoffe) sein.Furthermore, it is possible that the method according to the invention, as described and claimed herein, is used in addition to the acetal of aldehydes and / or aldehydes in combination with other tanning agents for pretanning and / or retanning of hides, in particular animal hides, and / or pelts . Examples of suitable further tanning agents can be mineral tanning agents such as chromium, aluminum, zirconium, titanium and iron salts, synthetic tanning agents (syntans), polymer tanning agents and / or vegetable tanning agents (vegetable tanning agents).

Die Gew.-%-Angaben in den nachfolgenden spezifischen Beispielen beziehen sich auf ein Gesamtgewicht der zu gerbenden Haut und/oder des zu gerbenden Fells.The percentages by weight in the specific examples below relate to a total weight of the hide to be tanned and / or of the fur to be tanned.

Beispiel 1example 1

Die zu gerbende Haut und/oder das zu gerbende Fell werden in 3000 mL Wasser (im Folgenden als wässrige Flotte bezeichnet) mit einem eingestellten pH-Wert von 7,5 bis 8,5 und einer Temperatur von 25°C in einem geeigneten Gefäß bereitgestellt.The skin to be tanned and / or the fur to be tanned are provided in 3000 mL of water (hereinafter referred to as aqueous liquor) with a set pH of 7.5 to 8.5 and a temperature of 25 ° C in a suitable vessel .

Zu der wässrigen Flotte werden dann 4,5 Gew.-% eines Acetals eines aldehydischen Gerbstoffes, beispielsweise Acetal von Glutaraldehyd, zugegeben. Das Acetal wurde hierbei, wie es in US 2,885,443 und/oder US 4,448,977 beschrieben ist, hergestellt.4.5% by weight of an acetal of an aldehydic tanning agent, for example acetal of glutaraldehyde, is then added to the aqueous liquor. The acetal was here, as it is in U.S. 2,885,443 and or U.S. 4,448,977 is described.

In einem Penetrationsschritt lässt man die Flotte mit dem Acetal auf die Haut und/oder das Fell beispielsweise in einer dafür vorgesehenen drehbaren Trommel einwirken. Eine Einwirkzeit kann beispielsweise je nach Dicke der Haut und/oder des Fells frei gewählt werden. Je dicker eine Haut und/oder ein Fell ist, desto länger sollte die Einwirkzeit gewählt werden, um eine adäquate Penetration des Acetals in tiefere Hautschichten zu erreichen. Beispielsweise kann die Einwirkzeit zwischen 2 Stunden und 7 Stunden betragen. Eine bevorzugte Einwirkzeit beträgt hier 5 Stunden.In a penetration step, the liquor with the acetal is allowed to act on the skin and / or the fur, for example in a rotatable drum provided for this purpose. An exposure time can be freely selected, for example, depending on the thickness of the skin and / or the fur. The thicker the skin and / or fur, the longer the exposure time should be selected in order to achieve adequate penetration of the acetal into deeper skin layers. For example, the exposure time can be between 2 hours and 7 hours. A preferred exposure time here is 5 hours.

Nach dem Ende des Penetrationsschritts werden 2 Gew.-% Ameisensäure zugegeben und der pH-Wert auf 1,8 bis 2,5 eingestellt. Durch das Absenken des pH-Wertes wird der aldehydische Gerbstoff, beispielsweise in Form von Glutaraldehyd, freigesetzt. Der freigesetzte aldehydische Gerbstoff kann dann mit den Proteinen der Haut und/oder des Fells, insbesondere mit Kollagen, reagieren. Dadurch wird die eigentliche Gerbung eingeleitet.After the end of the penetration step, 2% by weight of formic acid are added and the pH is adjusted to 1.8 to 2.5. By lowering the pH, the aldehydic tannin, for example in the form of glutaraldehyde, is released. The released aldehydic tanning agent can then react with the proteins of the skin and / or the fur, in particular with collagen. This initiates the actual tanning process.

Anschließend lässt man das freigesetzte Aldehyd auf die Haut und/oder das Fell in einem Gerbungsschritt beispielsweise in der drehbaren Trommel einwirken. Eine geeignete Einwirkzeit kann hier zwischen 1,5 Stunden und 5 Stunden, vorzugsweise 3 Stunden, betragen.The released aldehyde is then allowed to act on the skin and / or the hide in a tanning step, for example in the rotating drum. A suitable exposure time here can be between 1.5 hours and 5 hours, preferably 3 hours.

Nach dem Ende der Einwirkzeit des Gerbungsschritts werden 2 Gew.-% Natriumhydrogencarbonat zugegeben. Anschließend lässt man die wässrige Flotte auf die vorgegerbte Haut und/oder das vorgegerbte Fell einwirken, um das Aldehyd möglichst vollständig zu fixieren. Eine Einwirkzeit kann beispielsweise zwischen 1,5 und 4,5 Stunden, insbesondere 3 Stunden betragen. Der pH-Wert wir dann auf 4,0 bis 4,2 eingestellt.After the end of the exposure time of the tanning step, 2% by weight of sodium hydrogen carbonate are added. The aqueous liquor is then allowed to act on the pretanned skin and / or the pretanned hide in order to fix the aldehyde as completely as possible. An exposure time can be, for example, between 1.5 and 4.5 hours, in particular 3 hours. The pH is then adjusted to 4.0 to 4.2.

Nach der Fixierung der vorgegerbten Haut und/oder des vorgegerbten Fells wird die Flotte verworfen und die vorgegerbte Haut und/oder das vorgegerbten Fell mit Wasser, insbesondere mit ca. 3000 mL Wasser, gewaschen.After the pre-tanned skin and / or the pre-tanned fur has been fixed, the liquor is discarded and the pre-tanned skin and / or the pre-tanned hide is washed with water, in particular with approx. 3000 ml of water.

Anschließend kann die vorgegerbte Haut und/oder das vorgegerbten Fell getrocknet und beispielsweise auf eine Dicke von 1,1 bis 1,3 mm gebracht werden.The pretanned hide and / or the pretanned hide can then be dried and, for example, brought to a thickness of 1.1 to 1.3 mm.

Beispiel 2Example 2

Die zu gerbende Haut und/oder das zu gerbende Fell werden in 3000 mL Wasser (im Folgenden als wässrige Flotte bezeichnet) mit einem eingestellten pH-Wert von 3,0 bis 3,2 und einer Temperatur von 25°C in einem geeigneten Gefäß bereitgestellt. Bei dem Verfahren nach Beispiel 2 ist im Gegensatz zu Beispiel 1 kein Penetrationsschritt vorgesehen, in welchem der aldehydische Gerbstoff in Form des Acetals zunächst auf die Haut und/oder das Fell einwirkt, ohne dabei mit Proteinen zu reagieren.The skin to be tanned and / or the fur to be tanned are provided in 3000 mL water (hereinafter referred to as aqueous liquor) with a set pH of 3.0 to 3.2 and a temperature of 25 ° C in a suitable vessel . In the method according to example 2, in contrast to example 1, no penetration step is provided in which the aldehydic tanning agent in the form of acetal first acts on the skin and / or the fur without reacting with proteins.

Zu der wässrigen Flotte werden dann 2,1 Gew.-% eines Acetals eines aldehydischen Gerbstoffes, beispielsweise Acetal von Glutaraldehyd, zugegeben. Durch den niedrigen pH-Wert der Flotte wird das Aldehyd, beispielsweise in Form von Glutaraldehyd, direkt freigesetzt und kann mit den Proteinen der Haut und/oder des Fells reagieren. Dieser Schritt entspricht daher dem eigentlichen Gerbungsschritt. Anschließend lässt man das freigesetzte Aldehyd auf die Haut und/oder das Fell beispielsweise in der drehbaren Trommel einwirken. Eine geeignete Einwirkzeit kann hier zwischen 3 Stunden und 7 Stunden, vorzugsweise 5 Stunden, betragen.2.1% by weight of an acetal of an aldehydic tanning agent, for example acetal of glutaraldehyde, is then added to the aqueous liquor. Due to the low pH value of the liquor, the aldehyde, for example in the form of glutaraldehyde, is released directly and can react with the proteins of the skin and / or the fur. This step therefore corresponds to the actual tanning step. The released aldehyde is then allowed to act on the skin and / or the fur, for example in the rotating drum. A suitable exposure time here can be between 3 hours and 7 hours, preferably 5 hours.

Nach dem Ende der Einwirkzeit des Gerbungsschritts wird 1 Gew.-% einer Mischung, insbesondere einer 1:1 Mischung, aus Natriumformiat und Natriumhydrogencarbonat zugegeben. Anschließend wird der pH-Wert auf 4,0 bis 4,2 eingestellt. Man lässt die Flotte dann für 1,5 Stunden bis 4,5 Stunden, insbesondere für 3 Stunden, einwirken. Anschließend werden 2 Gew.-% Natriumhydrogencarbonat zugegeben, wobei man die Flotte erneut für 2 Stunden bis 6 Stunden, insbesondere für 4 Stunden, einwirken lässt. Anschließend wird der pH-Wert erneut auf 4,0 bis 4,2 eingestellt. Durch diese Schritte wird das Aldehyd fixiert.After the end of the exposure time of the tanning step, 1% by weight of a mixture, in particular a 1: 1 mixture, of sodium formate and sodium hydrogen carbonate is added. The pH is then adjusted to 4.0 to 4.2. The liquor is then left to act for 1.5 hours to 4.5 hours, in particular for 3 hours. 2% by weight of sodium hydrogen carbonate are then added, the liquor again being allowed to act for 2 hours to 6 hours, in particular for 4 hours. The pH is then readjusted to 4.0 to 4.2. These steps fix the aldehyde.

Nach der Fixierung der vorgegerbten Haut und/oder des vorgegerbten Fells wird die Flotte verworfen und die vorgegerbte Haut und/oder das vorgegerbten Fell mit Wasser, insbesondere mit ca. 3000 mL Wasser, gewaschen.After the pre-tanned skin and / or the pre-tanned fur has been fixed, the liquor is discarded and the pre-tanned skin and / or the pre-tanned hide is washed with water, in particular with approx. 3000 ml of water.

Anschließend kann die vorgegerbte Haut und/oder das vorgegerbten Fell getrocknet und beispielsweise auf eine Dicke von 1,1 bis 1,3 mm gebracht werden.The pretanned hide and / or the pretanned hide can then be dried and, for example, brought to a thickness of 1.1 to 1.3 mm.

VergleichsversucheComparative experiments

Um die Qualität des hergestellten Leders im Vergleich zu Leder zu testen, das mittels einer konventionellen Methode mit dem Gerbstoff Glutaraldehyd (GA) hergestellt wurde, wurden Vergleichsversuche angestellt.In order to test the quality of the leather produced in comparison with leather produced by means of a conventional method with the tanning agent glutaraldehyde (GA), comparative tests were carried out.

Die Verfahren wurden dabei analog zu den Beispielen 1 und 2 durchgeführt, mit der Ausnahme, dass das Acetal durch 4,5 Gew.-% Glutaraldehyd durch Zugabe einer wässrigen 20%igen GA-Lösung ersetzt wurde. Anschließend wurde die Farbe, Schrumpftemperatur und Spaltbarkeit (engl. shavability) nach ISO ermittelt. Ergebnisse Spaltbarkeit Schrumpf temperatur Farbe Beispiel 1 2 78 2 Beispiel 2 3 76 2 GA Referenzprobe 3 75 2 (dabei bedeutet: 1 = sehr gut, 2 = gut, 3 = befriedigend, 4 = ausreichend) The processes were carried out analogously to Examples 1 and 2, with the exception that the acetal was replaced by 4.5% by weight glutaraldehyde by adding an aqueous 20% GA solution. The color, shrinkage temperature and shavability were then determined according to ISO. <u> Results </u> Cleavage Shrinkage temperature colour example 1 2 78 2 Example 2 3 76 2 GA reference sample 3 75 2 (means: 1 = very good, 2 = good, 3 = satisfactory, 4 = sufficient)

Alle drei hergestellten Lederproben wurden zusammen mit einer Mischung aus folgenden Bestandteilen in einer drehbaren Trommel behandelt (Gew.-% bezogen auf Gewicht der Lederproben):

  • 100 Gew.-% Wasser, 28 Gew.-% Sulfon Gerbstoff SELLATAN MBS gran und 12 Gew.-% Sulfon Gerbstoff SELLATAN HAT liq., 3 Gew.-% des Harzgebstoffes MAGNOPAL DP und jeweils 2 Gew.-% der Fettungs-Komponenten CORIPOL ALF und 2 Gew.-% CORIPOL ESA wurden hinzugegeben und in der Trommel inkubiert. Nach 3 Stunden wurde der pH auf 4,6 eingestellt. 2 Gew.-% des Farbstoffes SELLA FAST Orange 2GC wurde hinzugegeben und für 8 Stunden inkubiert. Anschließend wurde der pH-Wert durch Zugabe von Ameisensäure auf 4,0 eingestellt. Die Flüssigkeit wurde dann verworfen und das Leder einmal mit 300 Gew.-% Wasser gewaschen.
  • 100 Gew.-% Wasser wurden auf eine Temperatur von 45°C eingestellt und 4 Gew.-% CORIPOL ALF und 8 Gew.-% CORIPOL ESA als Fettungs-Komponenten hinzugegeben.
All three leather samples produced were treated together with a mixture of the following ingredients in a rotating drum (% by weight based on the weight of the leather samples):
  • 100% by weight of water, 28% by weight of sulphone tanning agent SELLATAN MBS gran and 12% by weight sulphone tanning agent SELLATAN HAT liq., 3% by weight of the resinous material MAGNOPAL DP and 2% by weight of each of the fatliquoring components CORIPOL ALF and 2% by weight CORIPOL ESA were added and incubated in the drum. After 3 hours the pH was adjusted to 4.6. 2% by weight of the dye SELLA FAST Orange 2GC was added and incubated for 8 hours. The pH was then adjusted to 4.0 by adding formic acid. The liquid was then discarded and the leather washed once with 300% by weight water.
  • 100% by weight of water were adjusted to a temperature of 45 ° C. and 4% by weight of CORIPOL ALF and 8% by weight of CORIPOL ESA were added as fatliquoring components.

Nach 60 Minuten Einwirkzeit wurde der pH-Wert auf 3,5 durch Zugabe von Ameisensäure eingestellt. Anschließend wurde das Leder zweimal mit 100 Gew.-% Wasser gewaschen und feucht über Nacht gelagert. Danach wurde das Leder vakuumgetrocknet. Nachdem das Leder dann gespannt wurde, wurde es wie nachfolgend aufgelistet bewertet: GA Referenzprobe Beispiel 1 Beispiel 2 Fülle 0 0 0 Fülle im Bauchbereich 0 0 0 Weichheit 0 -0,5 -0,5 Millkorn 0 0 0 Farbe des crust 0 +0,5 +0,5 Gleichmäßigkeit 0 0 0 Griff seidig seidig trocken (dabei bedeutet: +2/-2 = signifikante Abweichung, +1/-1 = Abweichung, 0 = keine Abweichung) After a contact time of 60 minutes, the pH was adjusted to 3.5 by adding formic acid. The leather was then washed twice with 100% by weight of water and stored moist overnight. The leather was then vacuum dried. After that Leather was then stretched, it was rated as listed below: GA reference sample example 1 Example 2 Abundance 0 0 0 Fullness in the abdominal area 0 0 0 Softness 0 -0.5 -0.5 Millkorn 0 0 0 Color of the crust 0 +0.5 +0.5 uniformity 0 0 0 handle silky silky dry (means: + 2 / -2 = significant deviation, + 1 / -1 = deviation, 0 = no deviation)

Claims (18)

  1. Composition for tanning hides and/or skins, comprising:
    5% by weight to 95% by weight of an acetal of an aldehydic tanning agent,
    1% by weight to 5% by weight of a pH-regulating buffer component and
    4% by weight to 90% by weight of a solvent, a pH of the composition of 7.5 to 10.5 being set by the pH-regulating buffer component.
  2. Composition according to Claim 1, characterized in that the acetal of an aldehydic tanning agent is an acetal of formaldehyde, propionaldehyde, glutaraldehyde and/or glyoxal, in particular of glutaraldehyde.
  3. Composition according to Claim 1 or 2, characterized in that an alcohol component of the acetal of an aldehydic tanning agent is methanol, ethanol, diethylene glycol and/or triethylene glycol, and preferably is methanol.
  4. Composition according to any of Claims 1 to 3, characterized in that the composition contains a proportion of polyoxaalkylene glycol, in particular selected from the group consisting of polyoxaethylenediol, polyoxa-1,2-propylenediol or a mixture of polyoxaethylenediol and polyoxa-1,2-propylenediol.
  5. Composition according to any of Claims 1 to 4, characterized in that the acetal of an aldehydic tanning agent is the acetal of formula A and/or formula B,
    wherein
    formula A is:
    Figure imgb0009
     and
    Figure imgb0010
     wherein
    x = 0 to 8,
    y = 2 to 6,
    R1 = -H, -CH2, -CHO,
    Figure imgb0011
     and
    wherein
    z = 2 to 6 and
    R2, R3, R4 and R5 each independently of one another are one selected from
    Figure imgb0012
     and wherein
    m = 0 to 8,
    n = 0 to 8,
    o = 0 to 8.
  6. Composition according to any of Claims 1 to 5, characterized in that the solvent is one selected formula B is: from the group consisting of water, water-soluble organic solvents or a mixture of water and water-soluble organic solvents, in particular wherein the water-soluble organic solvent is glycerol and/or a monoetherified polyoxaalkylene glycol, preferably having a molecular mass MR of greater than or equal to 100 and/or of less than or equal to 2000.
  7. Composition according to any of Claims 1 to 6, characterized in that the pH-regulating buffer component is one or more selected from the group consisting of carbonate buffer, borate buffer and/or phosphate buffer.
  8. Process for the pre-tanning and/or retanning of hides and/or skins, especially pelts, in a float, comprising the steps:
    - provision of a hide and/or skin in a float having a pH of between 1 and 10,
    - adjustment of the pH to 6 to 9 prior to addition of an acetal of an aldehydic tanning agent,
    - addition of the acetal of an aldehydic tanning agent to the hide and/or skin in the float,
    - action of the acetal added to the float on the hide and/or skin in a penetration step,
    - adjustment of the pH of the float to between 1 and 3.6 in an activation step, wherein the aldehydic tanning agent is released,
    - action of the aldehydic tanning agent released in the float on the hide and/or skin in a tanning step,
    - adjustment of the pH of the float to between 3.8 and 5 for fixing the aldehydic tanning agent in a fixing step.
  9. Process according to Claim 8, characterized in that the acetal of an aldehydic tanning agent used is an acetal of formaldehyde, propionaldehyde, glutaraldehyde, glyoxal and/or one according to formula A and/or formula B, in particular of glutaraldehyde, and/or in that the float used is an aqueous float.
  10. Process according to any of the preceding claims, characterized in that, as an alcohol component of the acetal, methanol, ethanol, diethylene glycol and/or triethylene glycol, preferably methanol, is used.
  11. Process according to any of the preceding claims, characterized in that the acetal is added with a composition comprising further components and/or with a composition according to any of Claims 1 to 11.
  12. Process according to any of the preceding claims, characterized in that a proportion of the acetal added based on a total weight of the skin and/or the hide is 0.25% by weight to 10% by weight.
  13. Process according to any of the preceding claims, characterized in that the pH is adjusted to 7.5 to 8.5 prior to addition of the acetal.
  14. Process according to any of the preceding claims, characterized in that the pH of the float is adjusted to 1 to 2.5 after addition of the acetal.
  15. Process according to any of the preceding claims, characterized in that a temperature of the float during the tanning is between 10°C and 50°C, in particular between 20°C and 30°C, especially 25°C.
  16. Leather, in particular pretanned leather, produced by a process according to any of Claims 8 to 15 and/or by using the composition according to any of Claims 1 to 7.
  17. Crust leather, in particular a buffed and/or full grain crust leather, produced by treating the leather according to Claim 16 by one or more of the steps selected from the group consisting of retanning, fatliquoring, filling and/or dyeing.
  18. Use of the leather according to Claim 16 and/or of the crust leather according to Claim 17 for the production of dressed leather, in particular for the production of an automobile, furniture, clothing, glove, leather goods, aircraft, lining and/or shoe leather upper article.
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US20190106758A1 (en) 2019-04-11
EP3440227A1 (en) 2019-02-13
WO2017174181A1 (en) 2017-10-12
DE102016004192A1 (en) 2017-10-12
EP3561081A1 (en) 2019-10-30
BR112018067719A2 (en) 2019-01-08
US10604813B2 (en) 2020-03-31
PT3440227T (en) 2022-03-03
CN108884500A (en) 2018-11-23
ES2906793T3 (en) 2022-04-20
MX2018011665A (en) 2019-01-10
CN108884500B (en) 2022-08-19
BR112018067719B1 (en) 2022-11-29

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