EP2956558B1 - Method for the production of leather - Google Patents

Method for the production of leather Download PDF

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Publication number
EP2956558B1
EP2956558B1 EP14703867.3A EP14703867A EP2956558B1 EP 2956558 B1 EP2956558 B1 EP 2956558B1 EP 14703867 A EP14703867 A EP 14703867A EP 2956558 B1 EP2956558 B1 EP 2956558B1
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EP
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Prior art keywords
leather
acid
methanesulfonic acid
deliming
salts
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EP14703867.3A
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German (de)
French (fr)
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EP2956558A1 (en
Inventor
Robert Orth
Yu Mei
Walter Bertkau
Thomas Schneider
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • 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
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring

Definitions

  • the present invention relates to a process for the production of leather comprising a plurality of steps, characterized in that methanesulfonic acid is used in at least one step selected from deliming and fatliquoring.
  • Processes for making leather typically involve a variety of steps. Many leather making steps are carried out in the aqueous medium at a certain pH. The adjustment of the optimum pH is of great importance and influences the properties of the produced leather.
  • the choice of a suitable acid to neutralize the leather has a significant influence on the quality of the leather produced. This is the case, for example, in the deliming step. For example, using too much acid can negatively affect the optical and physical properties of the leather, possibly because the raw hides swell too much. If one chooses a too weak acid, this can mean that the adjustment of the pH is slow or the acid or other substances needed for the production of the leather do not completely penetrate the rawhide. In addition to the pH, the properties of the leather are often influenced by the materials used and the manufacturing process in a way that is not always predictable.
  • conventional leather production methods in the deliming step remove the lime residues adhering to the liming, for example with about 1% lactic acid, dilute acetic acid, formic acid or other organic acids.
  • suitable acids are, for example, ammonium salts such as ammonium sulfate or ammonium chloride, boric acid, phosphoric acid or carbonic acid.
  • hydrochloric acid or sulfuric acid is also possible.
  • the use of these acids in leather production has long been known to the person skilled in the art and is described, for example, in Römpp's Chemie Lexikon under the heading "Tannery”. For a subsequent Mineralgerbung the nakedness is adjusted sour by pimples, whereby as pimples usually inorganic acids and common salt, if necessary also with additions of organic acids serve.
  • EP 563,139 describes the use of methanesulfonic acid for pimpling leather.
  • the object of the present invention was to provide a process for producing leather which does not have the disadvantages of the prior art which gives soft and attractive leather and is efficient to perform.
  • the object has been achieved by a process for producing leather comprising a plurality of steps, characterized in that methanesulfonic acid is used in at least one step selected from deliming and fatliquoring.
  • Animal skins are the skins of any dead animals such as beef, veal, pork, goat, sheep, kangaroo, fish, ostrich or game. It is irrelevant to the present invention whether the animals whose hides one wishes to treat were slaughtered, were huntmännisch killed or have died from natural causes.
  • Processes for making leather typically involve a variety of steps.
  • the hair is removed from the animal skin.
  • This step is also referred to as a shearing step.
  • the animal skin is usually treated with basic substances such as lime. Frequently, sodium hydroxide, sodium carbonate, sulfides or organic sulfur compounds are also added.
  • the deboning step for example, meat remnants and subcutaneous connective tissue are mechanically removed from the animal skin.
  • the deliming step also: descaling, English: deliming
  • the basic components from the depilatory step are partially or completely neutralized.
  • the animal skin is loosened and prepared for the absorption of tannin and thus on the actual tanning.
  • Suitable tanning methods include the use of mineral salts (chromium III, aluminum, zirconium or iron salts), vegetable tanning with vegetable tannins (tannins in leaves, barks, woods and fruits), tanning (synonymously tanning) with fish and marine oils (Trane) or with fats of the brain, synthetic tanning with synthetically produced tannins (syntans, resin tanning agents, polymer tanning agents, polyphosphates, paraffinsulfochloride), aldehyde tanning (formerly formaldehyde, today mainly glutaraldehyde). It is also possible to combine different tanning procedures.
  • the leather After tanning, the leather is usually mechanically dehydrated (withering) and brought to a uniform thickness with folding machines.
  • the final leather properties become such as softness, color, fullness, texture, ductility, water absorption, etc., determined by the wet finish. Further steps are often the retannage, deacidification or neutralization, dyeing, fatliquoring and fixation of dyes and fatty substances.
  • all tanning agent groups which have been described in the main tanning can be used for retanning.
  • synthetic tanning agents, vegetable tanning agents and resin and polymer tanning agents are of particular importance in the retanning, since they often have a particularly favorable influence on the fullness and structure of the leather.
  • the acid residues of strong acids are often neutralized, as a result of which, as a rule, a better resistance of the leather is obtained.
  • the coloring is often done with dyes that form a chemical bond with the leather fiber.
  • Advantageous dyes are distinguished not only by the good dyeing properties (for example, tacking properties on the leather, combinability, large color palette) and fastness properties, but also by low environmental impact.
  • the natural leather color depends, among other things, on the tanning agent used. Chrome tannins often give a light, greyish-green intrinsic color, vegetable oils can, for example, yellow-brown - reddish brown.
  • Aluminum salts and synthetic tannins often yield white to light beige leather. Glutaraldehyde and fatty tanning agents usually color the leathers yellowish.
  • a pH of 4 to 6.5 is usually set, preferably from 4.5 to 6.
  • a more acidic pH is set to ensure uniform fixation of the fatliquoring agent through the leather cross section to reach.
  • a pH of from 2 to 6, preferably from 2.5 to 5, particularly preferably from 3 to 4 and especially preferably from 3.2 to 3.5 is set towards the end of the fatliquoring step.
  • steps are often carried out in the order given for preparation. However, within limits, it is also possible to execute them in other orders or to execute and combine steps together. Not all of the above steps need to be performed to produce leather. In addition, processes for producing leather may include other steps in addition to the aforementioned steps.
  • methanesulfonic acid is used in the deliming step or in the fatliquoring step for the production of leather.
  • Methanesulfonic acid serves primarily to adjust the pH.
  • Methanesulfonic acid is preferably added to the animal skin at the beginning of the actual working step.
  • the operation consists essentially of the neutralization of basic components with acids, which according to the invention methanesulfonic acid include.
  • the use of methanesulfonic acid in a particular step is also understood to mean the addition of methanesulfonic acid before the actual working step or after the preceding working step, if this serves to prepare the actual working step.
  • methanesulfonic acid is used at least in the deliming step.
  • methanesulfonic acid is used at least in the fatliquoring step.
  • Methanesulfonic acid is used according to the invention usually as an aqueous solution.
  • methanesulfonic acid is used as 0.05 to 0.5% strength by weight aqueous solution, preferably 0.07 to 0.2% by weight and particularly preferably 0.08 to 0.15% by weight.
  • methanesulfonic acid is used together with salts and / or other acids and / or acid derivatives. Suitable acid derivatives are, for example, esters or acid anhydrides.
  • methanesulfonic acid is used with salts of methanesulfonic acid.
  • Suitable salts of methanesulfonic acid include, for example, alkali metal or alkaline earth metal salts such as sodium, potassium, magnesium or calcium salts of methanesulfonic acid.
  • methanesulfonic acid is used together with inorganic salts.
  • Suitable inorganic salts are, for example, salts of sulfuric acid, hydrohalic acids, phosphoric acid, boric acid, carbonic acid, nitric acid.
  • suitable inorganic salts are, for example, ammonium sulfate, sodium sulfate, sodium chloride, ammonium chloride.
  • methanesulfonic acid is used together with salts of organic acids.
  • Suitable salts of organic acids are, for example, ammonium, alkali metal or alkaline earth metal salts of organic acids, such as ammonium, sodium, potassium or magnesium salts of organic acids.
  • Suitable salts of organic acids are, for example, salts of monocarboxylic acids or dicarboxylic acids. Examples of suitable salts of organic acids are, for example, salts of formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, lactic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid.
  • methanesulfonic acid is used together with other acids.
  • Suitable other acids may be inorganic acids or organic acids.
  • Suitable inorganic acids are, for example, sulfuric acid, hydrochloric acid, boric acid, carbonic acid, phosphoric acid.
  • Suitable organic acids are, for example, monocarboxylic acids or dicarboxylic acids. Examples of suitable organic acids are formic, acetic, lactic, formic, propionic, oxalic, malonic, succinic, glutaric, adipic, tartaric, lactic, phthalic, terephthalic, maleic and fumaric acids.
  • methanesulfonic acid is used in combination with ammonium sulfate. In another embodiment, methanesulfonic acid is used in combination with formic acid. In another embodiment, methanesulfonic acid is used in combination with one or more ammonium salts of dicarboxylic acids. In another embodiment, methanesulfonic acid is used in combination with one or more aliphatic dicarboxylic acids. In another preferred embodiment, methanesulfonic acid is used in combination with one or more carboxylic acid esters.
  • the amount of Saizen, other acids or acid derivatives can vary widely.
  • an aqueous solution containing 0.05 to 0.2% by weight of methanesulfonic acid and 0.5 to 2% by weight of ammonium sulfate is used.
  • a pH of 4 to 9, preferably 6 to 8.5 and particularly preferably 7.5 to 8.5 is set.
  • the deliming step lasts from 30 minutes to 4 hours, in exceptional cases shorter or longer.
  • the deliming step is completed in 45 to 90 minutes.
  • Processes according to the invention are characterized in that they are simple to carry out and permit an efficient and rapid adjustment of the pH in the individual process steps. Furthermore, inventive methods allow the production of leather, which are characterized by advantageous optical and haptic properties. In particular, they are characterized by pleasant softness and do not swell so much, do not swell so much as leather, which are produced by conventional methods.
  • the leathers produced according to the invention are characterized by a good softness and have a pleasant, appealing, fine and clean grain. In addition, they have good dyeing properties such as high uniformity and color brilliance.
  • the physical properties such as tensile strength, tear strength, elongation at break or scar extensibility of the leather produced by the process according to the invention are comparable or better than those of leather, which have been prepared according to the prior art.
  • leather produced according to the invention which has been produced using methanesulfonic acid in the deliming step, is distinguished, in addition to the advantages described above, by the fact that calcium ions can be removed from the leather very efficiently. As a result, in particular the softness and tear strength of the leather is advantageously influenced.
  • Another object of the present invention is leather, which has been produced by the process according to the invention.
  • a rawhide of beef was depilated and fleshed. The depilation took place with the addition of quick lime and sodium sulfide.
  • the leathers were treated with decalcifier according to Example I.1 to I.6 to adjust a pH of 8. The skins were first treated at room temperature for 20 minutes with a mixture A and then for 60 minutes with a mixture B. Subsequently, the skins were subjected to tanning and retanning with identical chromium-tanning formulations.
  • methanesulfonic acid made it possible to adjust the pH in a shorter time and gave clean and flat raw skins which were not so much swollen as skins which were subjected to deliming without methanesulfonic acid.
  • the leathers made using methanesulfonic acid in the deleting step are softer than leathers made according to the prior art and have them nice, fine and clean scars.
  • the physical properties are comparable to or better than those of leathers made according to the prior art.
  • cowhide rawhide Four pieces of cowhide rawhide were depilated and fleshed. The depilation took place with the addition of quick lime and sodium sulfide. For deliming, the skins were first washed at room temperature for 20 minutes with water and then first treated with a 1.2 wt% solution of ammonium sulfate and then with a 3.5 wt% solution of ammonium sulfate and allowed to act for 10 minutes to a pH from 8.3 to 8.5.
  • the pH of the deliming solutions for Examples II.1 and II.2 was between 8.3 and 8.43 in both cases and was very similar.
  • the content of free calcium ions in the decalcification solution to Example II.1 and II.2 was significantly higher with the addition of methanesulfonic acid than without the addition of methanesulfonic acid.
  • the following procedure was performed on different pieces before the start of the deliming process and after completion of the deliming process.
  • the leathers of Examples II.1 and II.2 were dried before or after completion of the deliming. 0.15 g of leather was placed in a 50 ml Erlenmeyer flask and 4 ml of a mixture of nitric acid and hydrochloric acid (mass ratio 1.3) were added. As soon as the mixture was cooled back to room temperature, to this was added 1 ml of hydrogen peroxide (32 wt% in water). The mixture was heated to 120 ° C for 180 min. The mixture was cooled to room temperature and made up to 50 ml volume with water. The content of calcium ions in the leather was determined by determining the concentration of calcium ions in the solution by atomic absorption spectrometry.
  • the leathers of Examples II.1 and II.2 were washed twice with water for 10 minutes. Subsequently, the skins were subjected to tanning and retanning with identical chromium-tanning formulations.
  • the leathers of Example II.2 (with the addition of methanesulfonic acid) were less swollen and softer than the leathers of Example II.1 (without methanesulfonic acid).
  • Chromium-tanned wet-blue leather (beef) was cut into 1-by-1 cm pieces and 25 g each was placed in a 250-ml glass flask.
  • 25 g each was placed in a 250-ml glass flask.
  • 5 g of fatliquoring agent according to Table 2 were given and in each case so much fully desalted (VE) water that the amount of liquid in the flask including fatliquoring agent was 75 ml.
  • the flasks were heated to 40 ° C for three hours.
  • Table 2 Chromium content of the wastewater of various wet-blue leathers with addition of formic acid or MSA in the fatliquoring step; fatliquoring agents used: SS: sulfonated rapeseed oil, SIM: sulfite fish oil, OSL: sulfite fish oil, SXL / N: composite fatliquor, sulfate castor oil; Quantities of acid in% by weight relative to the leather used.

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

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Leder umfassend mehrere Schritte, dadurch gekennzeichnet, dass in mindestens einem Schritt ausgewählt aus Entkälkung und Fettung Methansulfonsäure verwendet wird.The present invention relates to a process for the production of leather comprising a plurality of steps, characterized in that methanesulfonic acid is used in at least one step selected from deliming and fatliquoring.

Leder ist einer der ältesten Werkstoffe, an den in der heutigen Zeit sehr hohe Ansprüche im Bezug unter anderem auf die Haltbarkeit und die optischen und haptischen Eigenschaften gestellt werden.Leather is one of the oldest materials to which today's demands are very high in terms of durability and optical and tactile properties, among other things.

Prozesse zur Herstellung von Leder umfassen in der Regel eine Vielzahl von Schritten. Viele Schritte der Lederherstellung werden im wässrigen Medium bei einem bestimmten pH durchgeführt. Die Einstellung des optimalen pH ist dabei von großer Bedeutung und beeinflusst die Eigenschaften des hergestellten Leders.Processes for making leather typically involve a variety of steps. Many leather making steps are carried out in the aqueous medium at a certain pH. The adjustment of the optimum pH is of great importance and influences the properties of the produced leather.

Insbesondere wenn im vorhergehenden Schritt im alkalischen Medium gearbeitet wurde, hat die Wahl einer geeigneten Säure zur Neutralisation des Leders einen deutlichen Einfluss auf die Qualität des hergestellten Leders. Dieses ist zum Beispiel im Entkälkungsschritt der Fall. Verwendet man zum Beispiel eine zu starke Säure, so kann dies die optischen und physikalischen Eigenschaften des Leders negativ beeinflussen, möglicherweise, weil die Rohhäute zu stark anschwellen. Wählt man eine zu schwache Säure kann dies dazu führen, dass die Einstellung des pH nur langsam geschieht oder die Säure oder andere für die Herstellung des Leders benötigte Substanzen die Rohhaut nicht vollständig penetrieren. Neben dem pH werden die Eigenschaften des Leders durch die verwendeten Stoffe und den Herstellungsprozess oft auf eine Art und Weise beeinflusst, die sich nicht immer vorhersagen lässt.In particular, when working in the alkaline medium in the previous step, the choice of a suitable acid to neutralize the leather has a significant influence on the quality of the leather produced. This is the case, for example, in the deliming step. For example, using too much acid can negatively affect the optical and physical properties of the leather, possibly because the raw hides swell too much. If one chooses a too weak acid, this can mean that the adjustment of the pH is slow or the acid or other substances needed for the production of the leather do not completely penetrate the rawhide. In addition to the pH, the properties of the leather are often influenced by the materials used and the manufacturing process in a way that is not always predictable.

Herkömmliche Herstellverfahren für Leder lösen vor dem eigentlichen Gerben im Entkälkungsschritt (auch als Entkalkungsschritt bezeichnet, englisch: deliming) die vom Äschern anhaftenden Kalkreste zum Beispiel mit etwa 1 %iger Milchsäure, verdünnter Essigsäure, Ameisensäure oder anderen organischen Säuren heraus. Andere geeignete Säuren sind zum Beispiel Ammoniumsalze wie Ammoniumsulfat oder Ammoniumchlorid, Borsäure, Phosphorsäure oder Kohlensäure. Ebenfalls möglich ist die Verwendung von Salzsäure oder Schwefelsäure. Die Verwendung dieser Säuren in der Lederherstellung ist dem Fachmann seit langem bekannt und zum Beispiel beschrieben in Römpp's Chemie Lexikon unter dem Stichwort "Gerberei". Für eine nachfolgende Mineralgerbung wird die Blöße durch Pickeln sauer eingestellt, wobei als Pickel meist anorganische Säuren und Kochsalz, ggf. auch mit Zusätzen von organischen Säuren, dienen.Prior to the actual tanning process, conventional leather production methods in the deliming step (also referred to as deliming step) remove the lime residues adhering to the liming, for example with about 1% lactic acid, dilute acetic acid, formic acid or other organic acids. Other suitable acids are, for example, ammonium salts such as ammonium sulfate or ammonium chloride, boric acid, phosphoric acid or carbonic acid. Also possible is the use of hydrochloric acid or sulfuric acid. The use of these acids in leather production has long been known to the person skilled in the art and is described, for example, in Römpp's Chemie Lexikon under the heading "Tannery". For a subsequent Mineralgerbung the nakedness is adjusted sour by pimples, whereby as pimples usually inorganic acids and common salt, if necessary also with additions of organic acids serve.

EP 563 139 beschreibt die Verwendung von Methansulfonsäure zum Pickeln von Leder. EP 563,139 describes the use of methanesulfonic acid for pimpling leather.

Aufgabe der vorliegende Erfindung war es, ein Verfahren zur Herstellung von Leder bereit zu stellen, das nicht die Nachteile des Standes der Technik aufweist, weiche und ansprechende Leder ergibt und effizient auszuführen ist.The object of the present invention was to provide a process for producing leather which does not have the disadvantages of the prior art which gives soft and attractive leather and is efficient to perform.

Die Aufgabe wurde gelöst durch ein Verfahren zur Herstellung von Leder umfassend mehrere Schritte, dadurch gekennzeichnet, dass in mindestens einem Schritt ausgewählt aus Entkälkung und Fettung Methansulfonsäure verwendet wird.The object has been achieved by a process for producing leather comprising a plurality of steps, characterized in that methanesulfonic acid is used in at least one step selected from deliming and fatliquoring.

Zur Durchführung des erfindungsgemäßen Verfahrens geht man aus von Tierhäuten oder Halbzeugen. Bei Tierhäuten handelt es sich dabei um die Häute von beliebigen toten Tieren, beispielsweise Rind, Kalb, Schwein, Ziege, Schaf, Känguru, Fisch, Strauß oder Wild. Dabei ist es für die vorliegende Erfindung unerheblich, ob die Tiere, dessen Häute man zu behandeln wünscht, geschlachtet wurden, waidmännisch erlegt wurden oder an natürlichen Ursachen zugrunde gegangen sind.To carry out the method according to the invention is based on animal hides or semi-finished products. Animal skins are the skins of any dead animals such as beef, veal, pork, goat, sheep, kangaroo, fish, ostrich or game. It is irrelevant to the present invention whether the animals whose hides one wishes to treat were slaughtered, were huntmännisch killed or have died from natural causes.

Prozesse zur Herstellung von Leder umfassen in der Regel eine Vielzahl von Schritten. Im Enthaarungsschritt werden die Haare aus der Tierhaut entfernt. Dieser Schritt wird auch als Äscherungsschritt bezeichnet. Zum Enthaaren wird die Tierhaut in der Regel mit basischen Substanzen wie Kalk behandelt. Häufig werden ebenfalls Natriumhydroxid, Natriumcarbonat, Sulfide oder organische Schwefelverbindungen zugesetzt. Im Entfleischungsschritt werden zum Beispiel auf mechanischem Wege Fleischreste und Unterhautbindegewebe von der Tierhaut entfernt. Im Entkälkungsschritt (Auch: Entkalkung, Englisch: deliming) werden die basischen Komponenten aus dem Enthaarungsschritt teilweise oder vollständig neutralisiert. In der Beize wird die Tierhaut aufgelockert und für die Aufnahme des Gerbstoffes und damit auf die eigentliche Gerbung vorbereitet. Für eine eventuelle nachfolgende Mineralgerbung wird die Blöße durch Pickeln sauer eingestellt, wobei als Pickel meist anorganische Säuren und Kochsalz, ggf. auch mit Zusätzen von organischen Säuren, dienen. In der Oberhaut verbliebene Haarwurzeln, Haarpigmente, Grundhaare und Fettstoffe lassen sich oft durch Auswaschen oder Spülen allein nicht entfernen. Besonders im Handwerksbetrieb wird daher ein Schritt des Streichens durchgeführt, in dem das Streichen der Häute zum Beispiel mittels Streicheisen auf dem Gerberbaum erfolgt.Processes for making leather typically involve a variety of steps. In the depilation step, the hair is removed from the animal skin. This step is also referred to as a shearing step. For dehairing the animal skin is usually treated with basic substances such as lime. Frequently, sodium hydroxide, sodium carbonate, sulfides or organic sulfur compounds are also added. In the deboning step, for example, meat remnants and subcutaneous connective tissue are mechanically removed from the animal skin. In the deliming step (also: descaling, English: deliming), the basic components from the depilatory step are partially or completely neutralized. In the stain, the animal skin is loosened and prepared for the absorption of tannin and thus on the actual tanning. For a possible subsequent Mineralgerbung the nakedness is adjusted sour by pimples, whereby as pimples usually inorganic acids and common salt, if necessary also with additions of organic acids serve. Hair roots, hair pigments, ground hair and fatty substances remaining in the epidermis can often not be removed by washing out or rinsing alone. Especially in the craft business, therefore, a step of stroking is performed, in which the stroking of the skins, for example, by means of chisel on the tanner tree.

Die eigentlichen Gerbungsschritte geschehen unter Zusatz eines Gerbungsmittels. Geeignete Gerbverfahren umfassen die Verwendung von Mineralsalzen (Chrom-III-, Aluminium-, Zirkonoder Eisensalze), Vegetabilgerbung mit pflanzlichen Gerbstoffen (Tannine in Blättern, Rinden, Hölzern und Früchten), Fettgerbung (synonym Sämischgerbung) mit Fisch-, und Seetierölen (Trane) oder mit Fetten des Gehirns, Synthetische Gerbung mit synthetisch hergestellten Gerbstoffen (Syntane, Harzgerbstoffe, Polymergerbstoffe, Polyphosphate, Paraffinsulfochlorid), Aldehydgerbung (früher Formaldehyd, heute hauptsächlich Glutaraldehyd). Es ist auch möglich verschiedene Gerbverfahren miteinander zu kombinieren.The actual tanning steps are done with the addition of a tanning agent. Suitable tanning methods include the use of mineral salts (chromium III, aluminum, zirconium or iron salts), vegetable tanning with vegetable tannins (tannins in leaves, barks, woods and fruits), tanning (synonymously tanning) with fish and marine oils (Trane) or with fats of the brain, synthetic tanning with synthetically produced tannins (syntans, resin tanning agents, polymer tanning agents, polyphosphates, paraffinsulfochloride), aldehyde tanning (formerly formaldehyde, today mainly glutaraldehyde). It is also possible to combine different tanning procedures.

Nach der Gerbung wird das Leder in der Regel mechanisch entwässert (Abwelken) und mit Falzmaschinen auf eine gleichmäßige Stärke gebracht.After tanning, the leather is usually mechanically dehydrated (withering) and brought to a uniform thickness with folding machines.

Vor allem bei der Chromgerbung und bei Herstellung chromfreier Leder durch eine kombinierte Vorgerbung mit Aldehyden und synthetischen Gerbstoffen, werden die endgültigen Ledereigenschaften wie Weichheit, Farbe, Fülle, Struktur, Dehnbarkeit, Wasseraufnahme etc. durch die Nasszurichtung bestimmt.
Weitere Arbeitsschritte sind häufig die Nachgerbung, Entsäuerung oder Neutralisation, Färbung, Fettung und Fixierung der Farb- und Fettstoffe. Grundsätzlich können zur Nachgerbung alle Gerbstoffgruppen, die bei der Hauptgerbung beschrieben wurden, verwendet werden. Besondere Bedeutung bei der Nachgerbung haben aber synthetische Gerbstoffe, Vegetabilgerbstoffe und Harz- und Polymergerbstoffe, da diese häufig einen besonders günstigen Einfluss auf die Fülle und Struktur des Leders nehmen.
Bei der Entsäuerung werden häufig die Säurereste starker Säuren neutralisiert, wodurch in der Regel eine bessere Beständigkeit der Leder erhalten wird.
Die Färbung erfolgt häufig mit Farbstoffen die mit der Lederfaser eine chemische Bindung eingehen. Vorteilhafte Farbstoffe zeichnen sich neben den guten Färbeigenschaften (zum Beispiel Aufziehverhalten auf das Leder, Kombinierbarkeit, große Farbpalette) und Echtheiten durch eine geringe Umweltbelastung aus.
Die natürliche Lederfarbe hängt unter anderem vom verwendeten Gerbstoff ab. Chromgerbungen geben häufig eine helle, grau-grüne Eigenfarbe, Vegetabilleder können zum Beispiel gelbbraun - rotbraun sein. Aluminiumsalze und synthetische Gerbstoffe ergeben häufig weiße bis hellbeige Leder. Glutaraldehyd und Fettgerbstoffe färben die Leder in der Regel gelblich.Especially in chrome tanning and in the production of chromium-free leather by a combined pretanning with aldehydes and synthetic tanning agents, the final leather properties become such as softness, color, fullness, texture, ductility, water absorption, etc., determined by the wet finish.
Further steps are often the retannage, deacidification or neutralization, dyeing, fatliquoring and fixation of dyes and fatty substances. In principle, all tanning agent groups which have been described in the main tanning can be used for retanning. However, synthetic tanning agents, vegetable tanning agents and resin and polymer tanning agents are of particular importance in the retanning, since they often have a particularly favorable influence on the fullness and structure of the leather.
During deacidification, the acid residues of strong acids are often neutralized, as a result of which, as a rule, a better resistance of the leather is obtained.
The coloring is often done with dyes that form a chemical bond with the leather fiber. Advantageous dyes are distinguished not only by the good dyeing properties (for example, tacking properties on the leather, combinability, large color palette) and fastness properties, but also by low environmental impact.
The natural leather color depends, among other things, on the tanning agent used. Chrome tannins often give a light, greyish-green intrinsic color, vegetable oils can, for example, yellow-brown - reddish brown. Aluminum salts and synthetic tannins often yield white to light beige leather. Glutaraldehyde and fatty tanning agents usually color the leathers yellowish.

Die Fettung bewirkt eine bessere Weichheit und Geschmeidigkeit. Die Fettungsmittel umhüllen die Lederfasern mit einem dünnen Fettfilm. Die Fasern verkleben dadurch bei der Trocknung nicht so stark und können sich leichter gegeneinander verschieben. Vor der Fettung wird in der Regel ein pH von 4 bis 6,5 eingestellt, bevorzugt von 4,5 bis 6. Während des Fettungsschrittes, insbesondere am Ende des Fettungsschrittes wird ein stärker saurer pH eingestellt, um eine gleichmäßige Fixierung des Fettungsmittels durch den Lederquerschnitt zu erreichen. In der Regel wird gegen Ende des Fettungsschrittes ein pH von 2 bis 6 bevorzugt 2,5 bis 5, besonders bevorzugt von 3 bis 4 und insbesondere bevorzugt von 3,2 bis 3,5 eingestellt. Durch den Einsatz von Hydrophobierungsmitteln können Leder schmutz- und wasserabweisend, bis wasserdicht ausgerüstet werden.Greasing results in better softness and smoothness. The fatliquors envelop the leather fibers with a thin film of grease. As a result, the fibers do not stick together so much during drying and can shift more easily against each other. Prior to fatliquoring, a pH of 4 to 6.5 is usually set, preferably from 4.5 to 6. During the fatliquoring step, especially at the end of the fatliquoring step, a more acidic pH is set to ensure uniform fixation of the fatliquoring agent through the leather cross section to reach. As a rule, a pH of from 2 to 6, preferably from 2.5 to 5, particularly preferably from 3 to 4 and especially preferably from 3.2 to 3.5, is set towards the end of the fatliquoring step. Through the use of water repellents leather can be dirt and water repellent, equipped to waterproof.

Die oben genannten Schritte werden zur Herstellung häufig in der angegebenen Reihenfolge ausgeführt. Es ist jedoch in Grenzen auch möglich, diese in anderen Reihenfolgen auszuführen oder Schritte gemeinsam auszuführen und zu kombinieren.
Nicht alle der zuvor genannten Schritte müssen zur Herstellung von Leder ausgeführt werden. Außerdem können Verfahren zur Herstellung von Leder neben den zuvor genannten Schritte auch noch weitere Schritte umfassen.The above steps are often carried out in the order given for preparation. However, within limits, it is also possible to execute them in other orders or to execute and combine steps together.
Not all of the above steps need to be performed to produce leather. In addition, processes for producing leather may include other steps in addition to the aforementioned steps.

Erfindungsgemäß wird im Entkälkungsschritt oder im Fettungsschritt zur Herstellung von Leder Methansulfonsäure verwendet. Methansulfonsäure dient dabei in erster Linie zur Einstellung des pH Wertes. Bevorzugt wird Methansulfonsäure dabei zu Beginn des eigentlichen Arbeitsschrittes zu der Tierhaut gegeben. Im Fall der Entkälkung besteht der Arbeitsschritt im Wesentlichen aus der Neutralisation basischer Komponenten mit Säuren, die erfindungsgemäß Methansulfonsäure umfassen. Erfindungsgemäß wird unter der Verwendung von Methansulfonsäure in einem bestimmten Arbeitsschritt auch die Zugabe von Methansulfonsäure vor dem eigentlichen Arbeitsschritt oder nach dem vorhergehenden Arbeitsschritt verstanden, wenn dieses der Vorbereitung des eigentlichen Arbeitsschrittes dient.According to the invention, methanesulfonic acid is used in the deliming step or in the fatliquoring step for the production of leather. Methanesulfonic acid serves primarily to adjust the pH. Methanesulfonic acid is preferably added to the animal skin at the beginning of the actual working step. In the case of deliming, the operation consists essentially of the neutralization of basic components with acids, which according to the invention methanesulfonic acid include. According to the invention, the use of methanesulfonic acid in a particular step is also understood to mean the addition of methanesulfonic acid before the actual working step or after the preceding working step, if this serves to prepare the actual working step.

In einer bevorzugten Ausführungsform wird Methansulfonsäure mindestens im Entkälkungsschritt verwendet.In a preferred embodiment, methanesulfonic acid is used at least in the deliming step.

In einer anderen bevorzugten Ausführungsform wird Methansulfonsäure mindestens im Fettungsschritt verwendet.In another preferred embodiment, methanesulfonic acid is used at least in the fatliquoring step.

Methansulfonsäure wird erfindungsgemäß in der Regel als wässrige Lösung eingesetzt. In der Regel wird Methansulfonsäure als 0,05 bis 0,5 gew%ige wässrige Lösung eingesetzt, bevorzugt 0,07 bis 0,2 gew%ig und besonders bevorzugt 0,08 bis 0,15 gew%ig.
In einer Ausführungsform wird Methansulfonsäure zusammen mit Salzen und/oder anderen Säuren und/oder Säurederivaten eingesetzt. Geeignete Säurederivate sind zum Beispiel Ester oder Säureanhydride.Methanesulfonic acid is used according to the invention usually as an aqueous solution. As a rule, methanesulfonic acid is used as 0.05 to 0.5% strength by weight aqueous solution, preferably 0.07 to 0.2% by weight and particularly preferably 0.08 to 0.15% by weight.
In one embodiment, methanesulfonic acid is used together with salts and / or other acids and / or acid derivatives. Suitable acid derivatives are, for example, esters or acid anhydrides.

In einer Ausführungsform wird Methansulfonsäure mit Salzen von Methansulfonsäure eingesetzt. Geeignete Salze von Methansulfonsäure sind zum Beispiele Alkalimetall- oder Erdalkalimetallsalze wie zum Beispiel Natrium, Kalium, Magnesium oder Calciumsalze der Methansulfonsäure.
In einer anderen Ausführungsform wird Methansulfonsäure zusammen mit anorganischen Salzen eingesetzt. Geeignete anorganische Salze sind zum Beispiel Salze der Schwefelsäure, Halogenwasserstoffsäuren, Phosphorsäure, Borsäure, Kohlensäure, Salpetersäure. Beispiele für geeignete anorganische Salze sind zum Beispiel Ammoniumsulfat, Natriumsulfat, Natriumchlorid, Ammoniumchlorid.
In einer anderen Ausführungsform wird Methansulfonsäure zusammen mit Salzen von organischen Säuren eingesetzt. Geeignete Salze organischer Säuren sind zum Beispiel Ammonium-, Alkalimetall- oder Erdalkalimetallsalze von organischen Säuren wie Ammonium-, Natrium-, Kalium- oder Magnesiumsalze organischer Säuren. Geeignete Salze organischer Säuren sind zum Beispiel Salze von Monocarbonsäuren oder Dicarbonsäuren. Beispiel für geeignete Salze organischer Säuren sind zum Beispiel Salze von Ameisensäure, Essigsäure, Propionsäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Weinsäure, Milchsäure, Phthalsäure, Terephthalsäure, Maleinsäure, Fumarsäure.
In einer anderen Ausführungsform wird Methansulfonsäure zusammen mit anderen Säuren eingesetzt. Geeignete andere Säuren können anorganische Säuren oder organische Säuren sein. Geeignete anorganische Säuren sind zum Beispiel Schwefelsäure, Salzsäure, Borsäure, Kohlensäure, Phosphorsäure. Geeignete organische Säuren sind zum Beispiel Monocarbonsäuren oder Dicarbonsäuren. Beispiele für geeignete organische Säuren sind Ameisensäure, Essigsäure, Milchsäure, Ameisensäure, Propionsäure, Oxalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Weinsäure, Milchsäure, Phthalsäure, Terephthalsäure, Maleinsäure, Fumarsäure.In one embodiment, methanesulfonic acid is used with salts of methanesulfonic acid. Suitable salts of methanesulfonic acid include, for example, alkali metal or alkaline earth metal salts such as sodium, potassium, magnesium or calcium salts of methanesulfonic acid.
In another embodiment, methanesulfonic acid is used together with inorganic salts. Suitable inorganic salts are, for example, salts of sulfuric acid, hydrohalic acids, phosphoric acid, boric acid, carbonic acid, nitric acid. Examples of suitable inorganic salts are, for example, ammonium sulfate, sodium sulfate, sodium chloride, ammonium chloride.
In another embodiment, methanesulfonic acid is used together with salts of organic acids. Suitable salts of organic acids are, for example, ammonium, alkali metal or alkaline earth metal salts of organic acids, such as ammonium, sodium, potassium or magnesium salts of organic acids. Suitable salts of organic acids are, for example, salts of monocarboxylic acids or dicarboxylic acids. Examples of suitable salts of organic acids are, for example, salts of formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, tartaric acid, lactic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid.
In another embodiment, methanesulfonic acid is used together with other acids. Suitable other acids may be inorganic acids or organic acids. Suitable inorganic acids are, for example, sulfuric acid, hydrochloric acid, boric acid, carbonic acid, phosphoric acid. Suitable organic acids are, for example, monocarboxylic acids or dicarboxylic acids. Examples of suitable organic acids are formic, acetic, lactic, formic, propionic, oxalic, malonic, succinic, glutaric, adipic, tartaric, lactic, phthalic, terephthalic, maleic and fumaric acids.

In einer Ausführungsform wird Methansulfonsäure in Kombination mit Ammoniumsulfat eingesetzt.
In einer anderen Ausführungsform wird Methansulfonsäure in Kombination mit Ameisensäure eingesetzt.
In einer anderen Ausführungsform wird Methansulfonsäure in Kombination mit einer oder mehreren Ammoniumsalzen von Dicarbonsäuren eingesetzt.
In einer anderen Ausführungsform wird Methansulfonsäure in Kombination mit einer oder mehreren aliphatischen Dicarbonsäuren eingesetzt.
In einer anderen bevorzugten Ausführungsform wird Methansulfonsäure in Kombination mit einem oder mehreren Carbonsäureestern eingesetzt.In one embodiment, methanesulfonic acid is used in combination with ammonium sulfate.
In another embodiment, methanesulfonic acid is used in combination with formic acid.
In another embodiment, methanesulfonic acid is used in combination with one or more ammonium salts of dicarboxylic acids.
In another embodiment, methanesulfonic acid is used in combination with one or more aliphatic dicarboxylic acids.
In another preferred embodiment, methanesulfonic acid is used in combination with one or more carboxylic acid esters.

Die Menge an Saizen, anderen Säuren oder Säurederivaten kann breit variieren. In einer Ausführungsform wird eine wässrige Lösung enthaltend 0,05 bis 0,2 gew% Methansulfonsäure und 0,5 bis 2 gew% Ammoniumsulfat eingesetzt.The amount of Saizen, other acids or acid derivatives can vary widely. In one embodiment, an aqueous solution containing 0.05 to 0.2% by weight of methanesulfonic acid and 0.5 to 2% by weight of ammonium sulfate is used.

Üblicherweise wird bei der Entkälkung in erfindungsgemäßen Verfahren ein pH von 4 bis 9, bevorzugt 6 bis 8,5 und besonders bevorzugt 7,5 bis 8,5 eingestellt.Usually, in the deliming process according to the invention, a pH of 4 to 9, preferably 6 to 8.5 and particularly preferably 7.5 to 8.5 is set.

In der Regel dauert der Entkälkungsschritt von 30 Minuten bis 4 Stunden, in Ausnahmefällen auch kürzer oder länger. Bevorzugt ist der Entkälkungsschritt in 45 bis 90 Minuten abgeschlossen.In general, the deliming step lasts from 30 minutes to 4 hours, in exceptional cases shorter or longer. Preferably, the deliming step is completed in 45 to 90 minutes.

Erfindungsgemäße Verfahren zeichnen sich dadurch aus, dass sie einfach durchzuführen sind und eine effiziente und schnelle Einstellung des pH in den einzelnen Verfahrensschritten ermöglichen.
Weiterhin ermöglichen erfindungsgemäße Verfahren die Herstellung von Leder, die sich durch vorteilhafte optische und haptische Eigenschaften auszeichnen. Insbesondere zeichnen sie sich unter anderem durch angenehme Weichheit aus und schwellen nicht so sehr auf, quellen nicht so sehr auf wie Leder, die nach herkömmlichen Verfahren hergestellt werden.Processes according to the invention are characterized in that they are simple to carry out and permit an efficient and rapid adjustment of the pH in the individual process steps.
Furthermore, inventive methods allow the production of leather, which are characterized by advantageous optical and haptic properties. In particular, they are characterized by pleasant softness and do not swell so much, do not swell so much as leather, which are produced by conventional methods.

Die erfindungsgemäß hergestellten Leder zeichnen sich durch eine gute Weichheit aus und haben eine angenehme, ansprechende, feine und saubere Narbung. Außerdem weisen sie gute Färbeeigenschaften auf wie hohe Gleichmäßigkeit und Farbbrillianz.The leathers produced according to the invention are characterized by a good softness and have a pleasant, appealing, fine and clean grain. In addition, they have good dyeing properties such as high uniformity and color brilliance.

Die physikalischen Eigenschaften wie Zugfestigkeit, Reißfestigkeit, Bruchdehnung oder Narbendehnfähigkeit der nach dem erfindungsgemäßen Verfahren hergestellten Leder sind vergleichbar oder besser als die von Leder, die gemäß dem Stand der Technik hergestellt worden sind.The physical properties such as tensile strength, tear strength, elongation at break or scar extensibility of the leather produced by the process according to the invention are comparable or better than those of leather, which have been prepared according to the prior art.

Insbesondere erfindungsgemäß hergestelltes Leder, das unter Verwendung von Methansulfonsäure im Entkälkungsschritt hergestellt worden ist, zeichnet sich neben den oben beschriebenen Vorteilen dadurch aus, dass Calciumionen sehr effizient aus dem Leder entfernt werden können. Dadurch wird insbesondere die Weichheit und die Reißfestigkeit des Leders vorteilhaft beeinflusst.In particular, leather produced according to the invention, which has been produced using methanesulfonic acid in the deliming step, is distinguished, in addition to the advantages described above, by the fact that calcium ions can be removed from the leather very efficiently. As a result, in particular the softness and tear strength of the leather is advantageously influenced.

Erfindungsgemäß hergestelltes Leder, das unter Verwendung von Methansulfonsäure im Fettungsschritt hergestellt worden ist, zeichnet sich neben den oben beschriebenen Vorteilen dadurch aus, dass, sofern es sich um chromgegerbtes Leder handelt, nur geringe Mengen an Chromverbindungen aus dem Leder ausgewaschen werden.Leather produced according to the invention, which has been prepared by using methanesulfonic acid in the fatliquoring step, is distinguished, in addition to the advantages described above, by the fact that, if it is chrome-tanned leather, only small amounts of chromium compounds are washed out of the leather.

Ein weiterer Gegenstand der vorliegenden Erfindung ist Leder, das nach dem erfindungsgemäßen Verfahren hergestellt worden ist.Another object of the present invention is leather, which has been produced by the process according to the invention.

BeispieleExamples

Die Erfindung wird durch Arbeitsbeispiele weiter erläutert.The invention will be further explained by working examples.

Verwendete Abkürzungen:

  • Decaltal(R) RN: Sauer reagierendes Gemisch der Ammoniumsalze anorganischer Säuren und
  • organischer Dicarbonsäuren
  • Decaltal(R) Pic S: Mischung schwacher, wasserlöslicher aliphatischer Dicarbonsäuren
  • Decaltal(R) ESN: flüssig Mischung von Carbonsäureestern
Used abbreviations:
  • Decaltal (R) RN: acid reacting mixture of ammonium salts of inorganic acids and
  • organic dicarboxylic acids
  • Decaltal (R) Pic S: Mixture of weak, water-soluble aliphatic dicarboxylic acids
  • Decaltal (R) ESN: liquid mixture of carboxylic acid esters

Beispiele I.1 bis I.6Examples I.1 to I.6

Eine Rohhaut vom Rind wurde enthaart und entfleischt. Die Enthaarung geschah unter Zusatz von gebranntem Kalk und Natriumsulfid. Zur Entkälkung wurden die Leder mit Entkälkungsmittel gemäß Beispiel I.1 bis I.6 behandelt um einen pH von 8 einzustellen. Dabei wurden die Häute zunächst bei Raumtemperatur für 20 Minuten mit einer Mischung A und anschließend für 60 Minuten mit einer Mischung B behandelt. Anschließend wurden die Häute einer Gerbung und Nachgerbung mit identischen Chrom-Gerbstoffrezepturen unterworfen.A rawhide of beef was depilated and fleshed. The depilation took place with the addition of quick lime and sodium sulfide. For deliming, the leathers were treated with decalcifier according to Example I.1 to I.6 to adjust a pH of 8. The skins were first treated at room temperature for 20 minutes with a mixture A and then for 60 minutes with a mixture B. Subsequently, the skins were subjected to tanning and retanning with identical chromium-tanning formulations.

Beispiel 1.1:Example 1.1:

  • Mischung A: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit und 0,5 Gew% Ammoniumsulfat.Mixture A: aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.5% by weight of ammonium sulfate.
  • Mischung B: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit, 0,14 Gew% Methansulfonsäure (70 Gew%ig in Wasser) und 1,5 Gew% einer sauer reagierenden Mischung von Decaltal(R) RN.Mixture B: aqueous solution containing 0.1 wt% sodium bisulfite, 0.14 wt% of methanesulfonic acid (70 wt% in water) and 1.5 wt% of an acid-reacting mixture of Decaltal (R) RN.
Beispiel I.2:Example I.2:

  • Mischung A: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit und 0,5 Gew% Ammoniumsulfat.Mixture A: aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.5% by weight of ammonium sulfate.
  • Mischung B: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit und 0,3 Gew% Decaltal(R) Pic S und 1,5 Gew% Ammoniumsulfat.Mixture B: aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.3% by weight of Decaltal (R) Pic S and 1.5% by weight of ammonium sulfate.
Beispiel I.3:Example I.3:

  • Mischung A: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit und 0,5 Gew Decaltal(R) RN.Mixture A: aqueous solution containing 0.1 wt% sodium hydrogen sulfite and 0.5 weight Decaltal (R) RN.
  • Mischung B: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit, 0,14 Gew% Methansulfonsäure (70 Gew%ig in Wasser) und 1,5 Gew Decaltal(R) RN.Mixture B: aqueous solution containing 0.1 wt% sodium bisulfite, 0.14 wt% of methanesulfonic acid (70 wt% in water) and 1.5 wt Decaltal (R) RN.
Beispiel I.4:Example I.4:

  • Mischung A: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit und 0,5 Gew Decaltal(R) RN.Mixture A: aqueous solution containing 0.1 wt% sodium hydrogen sulfite and 0.5 weight Decaltal (R) RN.
  • Mischung B: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit, 0,3 Gew% Methansulfonsäure (70Gew%ig in Wasser) und 1,5 Gew% Decaltal(R) RN.Mixture B: aqueous solution containing 0.1 wt% sodium hydrogen sulfite, 0.3 wt% methanesulfonic acid (70 wt% in water) and 1.5% by weight Decaltal (R) RN.
Beispiel I.5:Example I.5:

  • Mischung A: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit und 0,14 Gew% Methansulfonsäure (70Gew%ig in Wasser).Mixture A: aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.14% by weight of methanesulfonic acid (70% by weight in water).
  • Mischung B: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit, 0,14 Gew% Methansulfonsäure (70Gew%ig in Wasser) und 1,2 Gew% Decaltal(R) ESN.Mixture B: aqueous solution containing 0.1 wt% sodium bisulfite, 0.14 wt% methanesulfonic acid (70 wt% in water) and 1.2 wt% Decaltal (R) ESN.
Beispiel I.6.Example I.6.

  • Mischung A: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit und 0,25 Gew% Decaltal(R) Pic S.Mixture A: aqueous solution containing 0.1% by weight of sodium hydrogen sulfite and 0.25% by weight of Decaltal (R) Pic S.
  • Mischung B: wässrige Lösung enthaltend 0,1 Gew% Natriumhydrogensulfit, 0,25 Gew% Decaltal(R) Pic S und 1,2 Gew% Decaltal(R) ESN.Mixture B: aqueous solution containing 0.1 wt% sodium bisulfite, 0.25 wt% Decaltal (R) Pic S and 1.2% by weight Decaltal (R) ESN.

Die Verwendung von Methansulfonsäure ermöglichte die Einstellung des pH in kürzerer Zeit und ergab saubere und flache Rohhäute, die nicht so sehr aufgeschwollen waren, wie Häute die ohne Methansulfonsäure der Entkälkung unterworfen wurden.The use of methanesulfonic acid made it possible to adjust the pH in a shorter time and gave clean and flat raw skins which were not so much swollen as skins which were subjected to deliming without methanesulfonic acid.

Die unter Verwendung von Methansulfonsäure im Entkälkungsschritt hergestellten Leder sind weicher als Leder, die gemäß dem Stand der Technik hergestellt worden sind, und sie haben schöne, feine und saubere Narben. Die physikalischen Eigenschaften sind vergleichbar oder besser als die von Leder, die gemäß dem Stand der Technik hergestellt worden sind.The leathers made using methanesulfonic acid in the deleting step are softer than leathers made according to the prior art and have them nice, fine and clean scars. The physical properties are comparable to or better than those of leathers made according to the prior art.

Beispiel 11.1Example 11.1

Vier Stücke einer Rohhaut vom Rind wurden enthaart und entfleischt. Die Enthaarung geschah unter Zusatz von gebranntem Kalk und Natriumsulfid. Zur Entkälkung wurden die Häute zunächst bei Raumtemperatur für 20 Minuten mit Wasser gewaschen und anschließend zunächst mit einer 1,2 Gew%igen Lösung von Ammoniumsulfat und anschließend mit einer 3,5 Gew%igen Lösung von Ammoniumsulfat versetzt und 10 Minuten einwirken gelassen um eine pH von 8,3 bis 8,5 einzustellen.Four pieces of cowhide rawhide were depilated and fleshed. The depilation took place with the addition of quick lime and sodium sulfide. For deliming, the skins were first washed at room temperature for 20 minutes with water and then first treated with a 1.2 wt% solution of ammonium sulfate and then with a 3.5 wt% solution of ammonium sulfate and allowed to act for 10 minutes to a pH from 8.3 to 8.5.

Beispiel II.2Example II.2

Zwei Stücke der Rohhaut aus Beispiel II.1 wurden anschließend mit einer wässrigen Lösung enthaltend 0,6 Gew% Methansulfonsäure versetzt um einen pH von 8,3 einzustellenTwo pieces of the rawhide from Example II.1 were subsequently mixed with an aqueous solution containing 0.6% by weight of methanesulphonic acid to adjust it to a pH of 8.3

Von den wässrigen Lösungen aus Beispiel II.1 und II.2 wurden nach 10, 20, 40, 80 und 140 Minuten der pH und der Gehalt an Calciumionen gemessen. Die Ergebnisse sind in Tabelle 1 wieder gegeben. Tabelle 1: pH und Calciumionenkonzentration in ppm in der Entkälkungslösung zu Beispielen II.1 und II.2, Ca2+-Konzentration bestimmt mittels Atomemissionsspektroskopie t [min] 10 20 40 80 140 pH Beispiel II.1 8.4 8.55 8.55 8.45 8.43 pH Beispiel II.2 9.0 8.13 8.38 8.35 8.3 [Ca2+], Beispiel 11.1 [ppm] 450 475 525 530 550 [Ca2+], Beispiel II.2 [ppm] 415 620 610 700 700 From the aqueous solutions from Examples II.1 and II.2, the pH and the content of calcium ions were measured after 10, 20, 40, 80 and 140 minutes. The results are given in Table 1 again. Table 1: pH and calcium ion concentration in ppm in the deliming solution for examples II.1 and II.2, Ca <sup> 2 + </ sup> concentration determined by means of atomic emission spectroscopy t [min] 10 20 40 80 140 pH Example II.1 8.4 8:55 8:55 8:45 8:43 pH Example II.2 9.0 8.13 8:38 8:35 8.3 [Ca 2+], Example 11.1 [ppm] 450 475 525 530 550 [Ca 2+], Example II.2 [ppm] 415 620 610 700 700

Der pH der Entkälkungslösungen zu Beispielen II.1 und II.2 lag in beiden Fällen zwischen 8,3 und 8,43 und war sehr ähnlich.
Der Gehalt an freien Calciumionen in der Entkälkungslösung zu Beispiel II.1 und II.2 war bei Zusatz von Methansulfonsäure deutlich höher als ohne Zusatz von Methansulfonsäure.The pH of the deliming solutions for Examples II.1 and II.2 was between 8.3 and 8.43 in both cases and was very similar.
The content of free calcium ions in the decalcification solution to Example II.1 and II.2 was significantly higher with the addition of methanesulfonic acid than without the addition of methanesulfonic acid.

Beispiel II.3: Bestimmung des Calcium Gehaltes im LederExample II.3: Determination of calcium content in leather

Das nachfolgende Verfahren wurde an unterschiedlichen Stücken vor Beginn des Entkälkungsprozesses sowie nach Abschluss des Entkälkungsprozesses durchgeführt.
Die Leder aus Beispielen II.1 und II.2 wurden vor Beginn bzw. nach Abschluss der Entkälkung getrocknet. 0,15 g Leder wurden in einen 50 ml Erlenmeyerkolben gegeben und 4 ml einer Mischung von Salpetersäure und Salzsäure (Massenverhältnis 1.3) wurden hinzu gegeben. Sobald die Mischung wieder auf Raumtemperatur abgekühlt war, wurden hierzu 1 ml Wasserstoffperoxid gegeben (32Gew% in Wasser). Die Mischung wurde für 180 min auf 120°C erhitzt. Die Mischung wurde auf Raumtemperatur abgekühlt und auf 50 ml Volumen mit Wasser aufgefüllt. Der Gehalt an Calciumionen im Leder wurde durch Bestimmung der Konzentration an Calciumionen in der Lösung per Atomabsorptionsspektrometrie bestimmt.The following procedure was performed on different pieces before the start of the deliming process and after completion of the deliming process.
The leathers of Examples II.1 and II.2 were dried before or after completion of the deliming. 0.15 g of leather was placed in a 50 ml Erlenmeyer flask and 4 ml of a mixture of nitric acid and hydrochloric acid (mass ratio 1.3) were added. As soon as the mixture was cooled back to room temperature, to this was added 1 ml of hydrogen peroxide (32 wt% in water). The mixture was heated to 120 ° C for 180 min. The mixture was cooled to room temperature and made up to 50 ml volume with water. The content of calcium ions in the leather was determined by determining the concentration of calcium ions in the solution by atomic absorption spectrometry.

Es zeigte sich, dass bei Verwendung von Ammoniumsulfat als Neutralisierungsmittel 29 % des Calciums aus dem Leder entfernt worden war, während bei Verwendung von Ammoniumsulfat und Methansulfonsäure 52 % des Calciums aus dem Leder entfernt worden war.It was found that when ammonium sulfate was used as the neutralizing agent 29% of the calcium had been removed from the leather, while using ammonium sulfate and methanesulfonic acid 52% of the calcium had been removed from the leather.

Beispiel II.4Example II.4

Die Leder aus Beispielen II.1 und II.2 wurden zwei Mal für 10 Minuten mit Wasser gewaschen. Anschließend wurden die Häute einer Gerbung und Nachgerbung mit identischen Chrom-Gerbstoffrezepturen unterworfen.
Die Leder aus Beispiel II.2 (mit Zusatz von Methansulfonsäure) waren weniger geschwollen und weicher als die Leder aus Beispiel II.1 (ohne Methansulfonsäure).The leathers of Examples II.1 and II.2 were washed twice with water for 10 minutes. Subsequently, the skins were subjected to tanning and retanning with identical chromium-tanning formulations.
The leathers of Example II.2 (with the addition of methanesulfonic acid) were less swollen and softer than the leathers of Example II.1 (without methanesulfonic acid).

Beispiel IIIExample III

Chromgegerbtes Wet-Blue Leder (Rind) wurde in 1x1 cm große Stücke geschnitten und jeweils 25 g wurden in einen 250 ml Glaskolben gegeben. Hierzu wurden jeweils 5 g Fettungsmittel gemäß Tabelle 2 gegeben sowie jeweils so viel voll entsalztes (VE) Wasser, dass die Flüssigkeitsmenge im Kolben inklusive Fettungsmittel 75 ml betrug. Die Kolben wurden für drei Stunden auf 40 °C erhitzt.Chromium-tanned wet-blue leather (beef) was cut into 1-by-1 cm pieces and 25 g each was placed in a 250-ml glass flask. For this purpose, in each case 5 g of fatliquoring agent according to Table 2 were given and in each case so much fully desalted (VE) water that the amount of liquid in the flask including fatliquoring agent was 75 ml. The flasks were heated to 40 ° C for three hours.

Zu den so erhaltenen Mischungen wurden gemäß Tabelle 2 mittels Ameisensäure oder Methansulfonsäure verschiedene pH Werte eingestellt. Die so erhaltenen Mischungen wurden für drei Stunden auf 40 °C erhitzt. Von den so erhaltenen Mischungen wurde eine Probe der überstehenden Lösung entnommen und mittels Atomabsorptionsspektrometrie der Gehalt an Chrom Salzen bestimmt.To the mixtures thus obtained, various pH values were adjusted according to Table 2 by means of formic acid or methanesulfonic acid. The resulting mixtures were heated to 40 ° C for three hours. From the mixtures thus obtained, a sample of the supernatant solution was taken and the content of chromium salts was determined by atomic absorption spectrometry.

Die Ergebnisse sind in Tabelle 2 wieder gegeben. Fettungsmittel Ameisensäure/% pH Chromgehalt (mg/L) MSA /% pH Chromgehalt (mg/L) SIM 0.6 4.79 37 0.5 4.9 15.6 0.8 4.21 44.4 0.9 4.08 18.7 1.0 3.77 49.7 1.1 3.79 20.4 SXL/N 0.6 4.64 29.2 0.6 4.73 11.2 0.8 4.31 36.2 0.9 3.94 16 1.0 3.87 48.3 1.1 3.66 19.2 SS 0.7 4.89 20 0.8 4.13 10.3 0.9 4.02 21.2 0.9 3.68 13.9 1.1 3.81 25.3 1.1 3.36 14.5 OSL 0.6 4.91 40.9 0.7 4.36 18.1 0.8 4.03 52.5 0.9 3.96 23.6 1.0 3.59 55 1.1 3.7 24.3 sulfated cas tor oil 0.8 4.8 8.6 0.7 4.67 6 1.0 4.24 10.9 1.0 3.97 6.4 1.2 3.9 15.1 1.2 3.66 7 kein Fet tungsmittel 0.6 4.94 1.42 0.7 3.89 1.65 0.8 4.16 17.79 0.9 3.57 3.33 1.2 3.74 37.03 1.1 3.04 4.94 The results are given in Table 2 again. fatliquors Formic acid /% pH Chromium content (mg / L) MSA /% pH Chromium content (mg / L) SIM 0.6 4.79 37 0.5 4.9 15.6 0.8 4.21 44.4 0.9 4:08 18.7 1.0 3.77 49.7 1.1 3.79 20.4 SXL / N 0.6 4.64 29.2 0.6 4.73 11.2 0.8 4.31 36.2 0.9 3.94 16 1.0 3.87 48.3 1.1 3.66 19.2 SS 0.7 4.89 20 0.8 4.13 10.3 0.9 4:02 21.2 0.9 3.68 13.9 1.1 3.81 25.3 1.1 3:36 14.5 OSL 0.6 4.91 40.9 0.7 4:36 18.1 0.8 4:03 52.5 0.9 3.96 23.6 1.0 3:59 55 1.1 3.7 24.3 sulfated cas tor oil 0.8 4.8 8.6 0.7 4.67 6 1.0 4.24 10.9 1.0 3.97 6.4 1.2 3.9 15.1 1.2 3.66 7 no fat 0.6 4.94 1:42 0.7 3.89 1.65 0.8 4.16 17.79 0.9 3:57 3:33 1.2 3.74 37.03 1.1 3:04 4.94

Tabelle 2: Chromgehalt der Abwasser verschiedener Wet-Blue Leder bei Zusatz von Ameisensäure oder MSA im Fettungsschritt; benutzte Fettungsmittel: SS: sulfoniertes Rapsöl, SIM: Sulfit Fischöl, OSL: Sulfitfischöl, SXL / N: Zusammengesetztes Fettungsmittel, Sulfat-Castoröl; Mengenangaben Säure in Gew% relativ zum eingesetzten Leder.Table 2: Chromium content of the wastewater of various wet-blue leathers with addition of formic acid or MSA in the fatliquoring step; fatliquoring agents used: SS: sulfonated rapeseed oil, SIM: sulfite fish oil, OSL: sulfite fish oil, SXL / N: composite fatliquor, sulfate castor oil; Quantities of acid in% by weight relative to the leather used.

Bei gleichem pH wird aus Leder in Gegenwart von MSA deutlich weniger Chrom ausgewaschen als in Gegenwart von Ameisensäure.At the same pH, significantly less chromium is washed out of leather in the presence of MSA than in the presence of formic acid.

Claims (10)

  1. A method of producing leather comprising a plurality of steps, wherein methanesulfonic acid is used in at least one step selected from deliming and fatliquoring.
  2. The method according to at least one of the preceding claims, wherein methanesulfonic acid is used in the deliming step at least.
  3. The method according to at least one of the preceding claims, wherein methanesulfonic acid is used in the fatliquoring step at least.
  4. The method according to at least one of the preceding claims, wherein methanesulfonic acid is used in the form of a mixture with salts and/or other acids and/or acid derivatives.
  5. The method according to at least one of the preceding claims, wherein methanesulfonic acid is used in the form of a from 0.05 to 0.5 wt% aqueous solution.
  6. The method according to at least one of the preceding claims, wherein the leather is chrometanned leather.
  7. The use of methanesulfonic acid for production of leather, wherein methanesulfonic acid is used in the deliming step or in the fatliquoring step.
  8. The use according to claim 7, wherein methanesulfonic acid is used in the deliming step.
  9. The use according to claim 7 or 8, wherein methanesulfonic acid is used in the fatliquoring step.
  10. The use according to claim 7 or 8 or 9, wherein methanesulfonic acid is used in combination with salts and/or other acids and/or acid derivatives.
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CA2944676A1 (en) 2014-04-11 2015-10-15 Basf Se Process for acidizing using retarded acid formulations
CN104313199B (en) * 2014-10-28 2016-03-09 北京泛博化学股份有限公司 Little liquor ratio prepares the method for lamb skin clothes hair leather
ES2927983T3 (en) * 2016-06-14 2022-11-14 Basf Se A process for producing leather
CN109485562B (en) * 2017-09-13 2022-11-25 斯塔尔国际有限公司 Deliming agent, use thereof and deliming method
EP3670675A1 (en) * 2018-12-21 2020-06-24 LANXESS Deutschland GmbH Leather agents for beamhouse
WO2020126855A1 (en) * 2018-12-21 2020-06-25 Basf Se Mixture comprising methanesulfonic acid and sulfuric acid
PL3923923T3 (en) * 2019-02-13 2024-10-07 DEBx Medical Holding B.V. Compositions for removing necrotic or infected tissues from body surface lesions and from oral cavity
IT202000017719A1 (en) 2020-07-22 2022-01-22 Beken Italia S R L PROCESS WITH REDUCED ENVIRONMENTAL IMPACT FOR LEATHER TANNING
NL2027083B1 (en) 2020-12-09 2022-07-07 Stahl Int B V Process for deliming of hides, skins or pelts

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