EP3924523A1 - Leather auxiliaries for the beamhouse - Google Patents

Leather auxiliaries for the beamhouse

Info

Publication number
EP3924523A1
EP3924523A1 EP19828654.4A EP19828654A EP3924523A1 EP 3924523 A1 EP3924523 A1 EP 3924523A1 EP 19828654 A EP19828654 A EP 19828654A EP 3924523 A1 EP3924523 A1 EP 3924523A1
Authority
EP
European Patent Office
Prior art keywords
salts
alkaline earth
acids
earth metal
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP19828654.4A
Other languages
German (de)
French (fr)
Other versions
EP3924523C0 (en
EP3924523B1 (en
Inventor
Kai BURGER
Thomas Schneider
Christopher Henzel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TFL Ledertechnik GmbH and Co KG
Original Assignee
Lanxess Deutschland GmbH
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Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Publication of EP3924523A1 publication Critical patent/EP3924523A1/en
Application granted granted Critical
Publication of EP3924523C0 publication Critical patent/EP3924523C0/en
Publication of EP3924523B1 publication Critical patent/EP3924523B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/06—Facilitating unhairing, e.g. by painting, by liming

Definitions

  • leather is made from a raw skin in several process steps.
  • the process steps summarized as a water workshop are at the beginning of this process and prepare the raw skin for tanning, i.e. takes place before the actual tanning.
  • the water workshop includes the typical steps in this sequence: switch, liming, descaling, pickling and pimples.
  • the liming takes place in aqueous liquor typically in so-called liming barrels or alternatively in liming reels.
  • liming barrels or alternatively in liming reels.
  • process chemicals and the action of movement By adding process chemicals and the action of movement, the hair and other non-leather components of the skin are removed and an opening up of the skin is achieved by separating the collagen fibers.
  • reducing sulfur-containing products eg Na 2 S, NaHS, mercaptoethanol, thioglycolic acids
  • strong oxidizing agents eg H 2 0 2
  • ethanolamines and partly also sugars are mostly used as swelling regulators, but the latter have to be used in relatively large quantities because of their low efficiency.
  • All products added during the water workshop are not permanently bound in the skin, but remain in the liming liquor, the washing liquors or the liquors of the subsequent processes (e.g. descaling).
  • the addition of all process chemicals ultimately leads to an increase in the pollution load of the wastewater.
  • the object according to the invention is achieved by using pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids in leather production, in particular when these substances are used as swelling regulators in the switch, in the limer or in the limer and in the limer , especially in the liming.
  • Ammonium, sodium, potassium, calcium and / or magnesium salts of the sugar acids are preferably used in the present invention.
  • Sodium and / or potassium salts of the sugar acids are particularly preferably used, very particularly preferably sodium salts of the sugar acids.
  • Sugar acids are understood to be polyhydroxycarboxylic acids that are formed by oxidation from simple sugars (monosaccharides). These include aldonic acids (e.g. D-gluconic acid), uronic acids (e.g. D-glucuronic acid), aldar acids (e.g. D-glucaric acid, D-threaric acid, D-mannosugaric acid) and ketoaldonic acids (e.g. D-2-oxo-gluconic acid).
  • aldonic acids e.g. D-gluconic acid
  • uronic acids e.g. D-glucuronic acid
  • aldar acids e.g. D-glucaric acid, D-threaric acid, D-mannosugaric acid
  • ketoaldonic acids e.g. D-2-oxo-gluconic acid
  • ammonium, sodium, potassium, calcium and / or magnesium salts of aldonic acids are preferably used.
  • ammonium, sodium and / or potassium gluconate, preferably sodium and / or potassium gluconate and particularly preferably sodium gluconate are used.
  • Pseudoalkali metal salts are understood to be salts whose cations are not alkali metals, but largely behave as such.
  • the term is to be understood as ammonium and / or tetraalkylammonium salts.
  • the effect of the salts of the sugar acids according to the invention can be improved by using them together with alkaline earth metal formates, preferably magnesium and / or calcium formate, particularly preferably with calcium formate.
  • the effect of the salts of sugar acids according to the invention can be optimized by combining them with alkaline earth metal salts of CC 3 carboxylic acids, preferably magnesium and / or calcium salts of formic, acetic or propionic acid, particularly preferably magnesium and / or calcium salts of Formic acid and mostly used with calcium formate.
  • alkaline earth metal salts of CC 3 carboxylic acids preferably magnesium and / or calcium salts of formic, acetic or propionic acid, particularly preferably magnesium and / or calcium salts of Formic acid and mostly used with calcium formate.
  • An increase in activity can also be achieved by using the salts of the sugar acids according to the invention together with ethanolamines (i.e. monoethanolamine, diethanolamine and / or triethanolamine) or urea.
  • ethanolamines i.e. monoethanolamine, diethanolamine and / or triethanolamine
  • the effect of the above salts of the sugar acids can be increased by using a combination of alkaline earth metal salts of CC 3 carboxylic acids and ethanolamines or urea.
  • the salts of the sugar acids according to the invention can be used in combination with alkali metal salts of CC 3 carboxylic acids, in particular sodium formate, sodium acetate, sodium propionate, potassium formate, potassium acetate and / or potassium propionate, which can be carried out together with alkaline earth metal salts of CC 3 carboxylic acids, ethanolamines or urea .
  • the present invention also relates to processes for the treatment of animal skins in liming using pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids, these being added to the liquor in which the treatment of the skins takes place.
  • This treatment also includes variants in which the pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids are added to the liquor before the liming in the switch.
  • the above-mentioned compounds are additionally added to the liquor, which support the action of the swelling regulators, such as alkaline earth metal formates, alkaline earth metal acetates, alkaline earth metal propionates, ethanolamines and / or urea.
  • the liquor in which the skins are treated in the liming typically contains further compounds known to the person skilled in the art, such as reducing sulfur-containing products (for example Na 2 S, NaHS, mercaptoethanol, thioglycolic acids), strong oxidizing agents (for example H 2 0 2 ) and / or strongly alkaline substances (e.g. lime).
  • reducing sulfur-containing products for example Na 2 S, NaHS, mercaptoethanol, thioglycolic acids
  • strong oxidizing agents for example H 2 0 2
  • strongly alkaline substances e.g. lime
  • the present invention also relates to processes for the production of leather comprising the treatment of animal hides according to the invention.
  • Said methods may further include steps of leather production familiar to those skilled in the art, such as Softening, fleshing, splitting, decalcification, enzymatic pickling, degreasing, pimples, tanning, dewatering, folding, bleaching, retanning, dyeing, greasing, stretching, drying, moistening, softening and dry dressing.
  • the tanning is preferably carried out with mineral tanning agents such as aluminum salts, in particular alums, trivalent chromium salts, zirconium salts, iron, zinc or titanium salts, with polyphosphates, with aldehydes such as formaldehyde and glutardialdehyde, with synthetic tanning agents based on phenol derivatives (syntans) or with polymer tanning agents (Resin tanning agents) such as acrylates and polyurethanes or vegetable dyes.
  • mineral tanning agents such as aluminum salts, in particular alums, trivalent chromium salts, zirconium salts, iron, zinc or titanium salts, with polyphosphates, with aldehydes such as formaldehyde and glutardialdehyde, with synthetic tanning agents based on phenol derivatives (syntans) or with polymer tanning agents (Resin tanning agents) such as acrylates and polyurethanes or vegetable dyes.
  • the tanning
  • the addition of ethanolamines and urea is dispensed with in the process according to the invention or in the use of salts of the sugar acids according to the invention, since the introduction of nitrogen into the waste water can thereby be reduced.
  • alkali metal salts of gluconic acids are used in the processes according to the invention or in the use according to the invention.
  • the salt weight of the raw skin used based on the salt weight of the raw skin used, from 0.05 to 5.0% by weight, preferably from 0.1 to 2.0% by weight and particularly preferably from 0.2 to 1.0% by weight of pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids are used.
  • the tanner understands by the salt weight the weight that the skin has after the preservation with salt.
  • the preserved skin typically has a moisture content of 35% by weight.
  • the present invention also includes leather auxiliary compositions comprising one or more pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids, preferably ammonium, sodium and / or potassium salts of the sugar acids, particularly preferably sodium salts of the sugar acids.
  • leather auxiliary compositions according to the invention advantageously contain one or more pseudoalkali metal, alkali metal and / or alkaline earth metal salts of gluconic acid, preferably ammonium, sodium and / or potassium gluconate, particularly preferably sodium gluconate.
  • Further advantageous leather auxiliary compositions additionally contain one or more compounds from the group comprising alkaline earth metal salts of CC 3 carboxylic acids, monoethanolamine, diethanolamine, triethanolamine and urea, preferably magnesium and / or calcium salts of formic, acetic or propionic acid, monoethanolamine, diethanolamine, triethanolamine and urethane , particularly preferably magnesium and / or calcium salts of formic or acetic acid and most preferably calcium formate.
  • leather auxiliary compositions contain ammonium, sodium and / or potassium gluconate in combination with magnesium formate, calcium formate magnesium acetate and / or calcium acetate, preferably sodium and / or potassium gluconate in combination with magnesium formate and / or calcium formate.
  • the leather auxiliary composition preferably contains sodium gluconate and one or more compounds from the group comprising calcium formate and magnesium formate, preferably calcium formate.
  • Urea in the leather auxiliary composition is from 10:90 to 90:10, preferably from 20:80 to 80:20 and particularly preferably from 30:70 to 70:30.
  • the ratio is determined as the quotient from the total mass of the compounds of the above salts of the sugar acids to the total mass of the compounds of the above formates, acetates and propionates.
  • the leather auxiliary compositions according to the invention are typically swelling regulators, in particular swelling regulators for the water workshop, preferably swelling regulators for use in the switch or in the liming, mostly preferably swelling regulators for use in the liming.
  • the leather auxiliary compositions according to the invention can be in liquid or in solid form.
  • the leather auxiliary composition according to the invention is at 25 ° C. as a solid, ideally in particulate form, such as, for example, as a powder, granulate or pellet.
  • the screening tests were carried out on raw skin samples DIN A4. These were cut from the core area of a salted raw skin, so that all samples had a similar fiber structure. The samples of a series were taken from the same skin because the fiber structure of the skin differs from animal to animal. The test specimens were weighed individually. All percentages of the process recipe refer to this weight (the raw skin salt weight).
  • test procedure included the process steps "switch” and "liming".
  • the amounts of chemicals and products used in the process as well as the amount of water are in percent by weight based on the raw skin salt weight of the individual samples.
  • the quantities were weighed on a balance with an accuracy of 0.5 g.
  • test tanning drums diameter 300 mm with temperature regulation (manufacturer Dose).
  • the process temperature was kept constant at 28 ° C +/- 1 ° C.
  • test specimen was added individually to the sample barrel and 200% water (based on the salt weight) at a temperature of 28 ° C. and 0.3% Peltec BH softening agent (mixture of surfactant and bactericide from LANXESS Deutschland GmbH) were added.
  • the test barrel was rotated at 10 RPM for 300 minutes.
  • the liquor (process water) was then drained off.
  • the specimen is now dabbed off, weighed and the average thickness is determined at four measuring points.
  • the test specimen was put back into the test barrel and 200% water at a temperature of 28 ° C. was added and 15 min. rotates. The remaining salinity of the fleet was then determined. This should not exceed 3.5 ° Be. If the salt content is too high, the fleet should be changed once.
  • the swelling regulator was added to the fleet and the test keg 60 min. rotates. The weight was then determined and the average thickness was determined.
  • the test specimen was returned to the liquor, 3% lime (Ca (OH) 2 ) and 2.5% Na 2 S were added and the mixture was rotated for 4 hours. Then there were 15 hours. Barrel rotation in interval mode (rotate 10 min. / 50 min. Break). The pH of the liquor was then measured (pH 12- 12.5), the specimen was removed, weighed again and the average thickness measured. The swelling was determined from the increase in thickness.
  • test specimens were then washed and tanned using a standard chrome tanning (as described, for example, in E. Heidemann, Fundamentals of Leather Manufacturing, pp. 295-340, E. Roether Verlag, Darmstadt, 1993) and the firmness of the grain was then checked by bending the leather. If the surface in the crease was smooth, did not rise, and did not curl, a positive firm grain was found.
  • chrome tanning as described, for example, in E. Heidemann, Fundamentals of Leather Manufacturing, pp. 295-340, E. Roether Verlag, Darmstadt, 1993
  • results show that the use of salts of the sugar acids according to the invention makes it possible to dispense with the use of nitrogen-containing compounds such as urea or ethanolamines, as a result of which the introduction of nitrogen into the wastewater can be substantially reduced, but at the same time the pitting can be maintained or improved .
  • the results show that the use of salts of the sugar acids according to the invention together with nitrogen-containing compounds such as urea or ethanolamines, ie with a constant nitrogen input into the waste water, can achieve a substantial improvement in the solid grain.

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

Abstract

On the basis of pseudo-alkali metal, alkali metal and alkaline earth metal salts of saccharic acids, new leather auxiliaries are provided for the beamhouse, which have a balanced properties profile, in terms of the swelling and grain tightness of the leather to be produced and in terms of the nitrogen and COD input into the wastewater.

Description

LEDERHILFSMITTEL FÜR DIE WASSERWERKSTATT LEATHER TOOLS FOR THE WATER WORKSHOP
Beschreibung description
Während des Lederherstellung wird aus einer Rohhaut in mehreren Prozessschritten Leder hergestellt. Die als Wasserwerkstatt zusammengefassten Prozessschritte stehen am Anfang dieses Verfahrens und bereitet die Rohhaut auf die Gerbung vor, d.h. findet vor der eigentlichen Gerbung statt. Die Wasserwerkstatt umfasst die typischerweise in dieser Reihenfolge vorgenommenen Arbeitsschritte Weiche, Äscher, Entkälkung, Beize und Pickel. During the production of leather, leather is made from a raw skin in several process steps. The process steps summarized as a water workshop are at the beginning of this process and prepare the raw skin for tanning, i.e. takes place before the actual tanning. The water workshop includes the typical steps in this sequence: switch, liming, descaling, pickling and pimples.
Der Äscher erfolgt in wässriger Flotte typischerweise in sogenannten Äscherfässern oder alternativ in Äscherhaspeln. Hierbei werden durch Zugabe von Prozesschemikalien und der Bewegungseinwirkung die Haare und andere Nicht-Leder gebende Hautbestandteile entfernt und ein Hautaufschluss („opening up“) durch die Separierung der Kollagenfasern erreicht. Hierbei werden für die Haarentfernung üblicherweise entweder reduzierende schwefelhaltige Produkte (z.B. Na2S, NaHS, Mercaptoethanol, Thioglycolsäuren) oder starke Oxidationsmitteln (z.B. H202) zugegeben. Für den Hautaufschluss werden meist Kalk oder andere alkalische Stoffe hinzugegeben. The liming takes place in aqueous liquor typically in so-called liming barrels or alternatively in liming reels. By adding process chemicals and the action of movement, the hair and other non-leather components of the skin are removed and an opening up of the skin is achieved by separating the collagen fibers. For the hair removal either reducing sulfur-containing products (eg Na 2 S, NaHS, mercaptoethanol, thioglycolic acids) or strong oxidizing agents (eg H 2 0 2 ) are usually added. Lime or other alkaline substances are usually added to the skin.
Durch Zugabe dieser Stoffe steigt der pH in der Flotte und in der Haut auf üblicherweise ca. 11 ,8 - 12,5. Dies führt zu einer deutlichen Alkalischwellung der Haut. Abhängig von Wassermenge, Produktzugabe, Bewegungseinwirkung und Hautstruktur ist diese Schwellung der Haut unterschiedlich stark ausgeprägt. Eine starke Alkalischwellung führt in Verbindung mit der Fass-/Haspelbewegung zu Qualitätseinbußen am fertigen Leder in Form ausgeprägter Mastriefen („growth marks“) oder Narbenzug („lime draw“) in lose strukturierten Hautpartien. Durch die Verwendung von Schwellungsregulatoren wird die Narbenschwellung verringert, so dass ausgeprägte Mastriefen und Narbenzug vermieden werden können. Eine starke Schwellungsreduzierung bringt jedoch meist den Nachteil einer erhöhten Losnarbigkeit in den locker strukturierten Hautpartien mit sich, d.h. die Oberschicht der Haut haftet nicht mehr richtig am Corium. Dies manifestiert sich dann beim Biegen des Leders durch wulstartiges Aufwerfen des Narben, d.h. in schlechterer Festnarbigkeit. By adding these substances, the pH in the liquor and in the skin usually rises to approximately 11.8 - 12.5. This leads to a significant alkaline swelling of the skin. Depending on the amount of water, the addition of product, the effects of movement and the structure of the skin, this swelling of the skin is pronounced differently. A strong alkaline swelling in connection with the barrel / reel movement leads to a loss of quality in the finished leather in the form of pronounced mast marks ("growth marks") or scar traction ("lime draw") in loosely structured skin areas. The use of swelling regulators reduces the scar swelling, so that pronounced mast striations and scar tension can be avoided. However, a strong reduction in swelling usually has the disadvantage of increased loose grain in the loosely structured skin areas, i.e. the upper layer of the skin no longer adheres properly to the corium. This then manifests itself when the leather is bent by bulging the scars, i.e. in poor firmness.
Als Schwellungsregulatoren werden im Stand der Technik zumeist Ethanolamine und zum Teil auch Zucker (z.B. Melasse) verwendet, wobei letztere aber wegen geringer Effizienz in relativ großer Menge eingesetzt werden müssen. Alle während der Wasserwerkstatt zugesetzten Produkte werden nicht permanent in der Haut gebunden, sondern verbleiben in der Äscherflotte, den Waschflotten oder den Flotten der Folgeprozesse (z.B. Entkälkung). Somit führen die Zugaben aller Prozesschemikalien endgültig zur Erhöhung der Schmutzfracht des Abwassers. In the state of the art, ethanolamines and partly also sugars (eg molasses) are mostly used as swelling regulators, but the latter have to be used in relatively large quantities because of their low efficiency. All products added during the water workshop are not permanently bound in the skin, but remain in the liming liquor, the washing liquors or the liquors of the subsequent processes (e.g. descaling). The addition of all process chemicals ultimately leads to an increase in the pollution load of the wastewater.
Die Anforderungen zur Vermeidung von Abwässern und Reduzierung der Schmutzfrachten ist in den vergangenen Jahren stetig gestiegen und werden sich vermutlich weiter verschärfen. Gerade der zusätzliche Eintrag von Stickstoff führt neben hohem COD-Gehalten zu Kapazitätsengpässen der Kläranlagen. Daher ist die Reduzierung des Stickstoff- aber auch des COD-eintrags ein kontinuierlicher Entwicklungsschwerpunkt der Lederhilfsmittelindustrie. Allerdings kann derzeit aus Qualitätsgründen trotz der schlechteren Abwasserwerte auf diese Aminoethanol- bzw. melassehaltigen Produkte nicht verzichtet werden. Sie finden sich somit in fast allen Gerbereien der Welt. The requirements for avoiding waste water and reducing the amount of dirt have risen steadily in recent years and are likely to become even more stringent. In addition to high COD contents, the additional input of nitrogen leads to capacity bottlenecks in the sewage treatment plants. Therefore, the reduction of nitrogen and COD input is a continuous development focus of the leather auxiliary industry. However, for quality reasons, these aminoethanol and molasses-containing products cannot be dispensed with, despite the poorer wastewater values. You can find them in almost all tanneries in the world.
Vor diesem Hintergrund bestand ein Bedarf an alternativen Schwellungsregulatoren, welche die Nachteile des Stands der Technik vermeiden und eine ausbalanciertes Eigenschaftsprofil aufweisen hinsichtlich der Schwellung und Festnarbigkeit des zu erzeugenden Leders einerseits und des Stickstoff- oder COD-Eintrags in das Abwasser andererseits. Against this background, there was a need for alternative swelling regulators which avoid the disadvantages of the prior art and have a balanced property profile with regard to the swelling and graininess of the leather to be produced on the one hand and the nitrogen or COD entry into the waste water on the other hand.
Überraschend wurde nun gefunden, dass die erfindungsgemäße Aufgabe gelöst wird durch Verwendung von Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalzen der Zuckersäuren bei der Lederherstellung, insbesondere bei Verwendung dieser Substanzen als Schwellungsregulator in der Weiche, im Äscher oder in der Weiche und im Äscher, ganz besonders im Äscher. Surprisingly, it has now been found that the object according to the invention is achieved by using pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids in leather production, in particular when these substances are used as swelling regulators in the switch, in the limer or in the limer and in the limer , especially in the liming.
Bevorzugt werden bei der vorliegenden Erfindung Ammonium-, Natrium-, Kalium-, Calcium- und/oder Magnesiumsalze der Zuckersäuren verwendet. Ammonium, sodium, potassium, calcium and / or magnesium salts of the sugar acids are preferably used in the present invention.
Besonders bevorzugt werden Natrium- und/oder Kaliumsalze der Zuckersäuren verwendet, ganz besonders bevorzugt Natriumsalze der Zuckersäuren. Sodium and / or potassium salts of the sugar acids are particularly preferably used, very particularly preferably sodium salts of the sugar acids.
Unter Zuckersäuren versteht man Polyhydroxycarbonsäuren, die durch Oxidation aus einfachen Zuckern (Monosacchariden) entstehen. Hierzu gehören Aldonsäuren (z.B. D-Gluconsäure), Uronsäuren (z.B. D-Glucuronsäure), Aldarsäuren ( z.B. D-Glucarsäure, D-Threarsäure, D-Mannozuckersäure) und Ketoaldonsäuren (z.B. D-2-Oxo-gluconsäure). Sugar acids are understood to be polyhydroxycarboxylic acids that are formed by oxidation from simple sugars (monosaccharides). These include aldonic acids (e.g. D-gluconic acid), uronic acids (e.g. D-glucuronic acid), aldar acids (e.g. D-glucaric acid, D-threaric acid, D-mannosugaric acid) and ketoaldonic acids (e.g. D-2-oxo-gluconic acid).
Bevorzugt werden bei der vorliegenden Erfindung Ammonium-, Natrium-, Kalium-, Calcium- und/oder Magnesiumsalze der Aldonsäuren, besonders bevorzugt der D- Gluconsäure eingesetzt. ln einer bevorzugten Ausführungsform werden Ammonium-, Natrium- und/oder Kaliumgluconat, bevorzugt Natrium- und/oder Kaliumgluconat und besonders bevorzugt Natriumgluconat eingesetzt. In the present invention, ammonium, sodium, potassium, calcium and / or magnesium salts of aldonic acids, particularly preferably D-gluconic acid, are preferably used. In a preferred embodiment, ammonium, sodium and / or potassium gluconate, preferably sodium and / or potassium gluconate and particularly preferably sodium gluconate are used.
Als Pseudoalkalimetallsalze sind Salze zu verstehen, deren Kationen keine Alkalimetalle sind, aber sich weitgehend wie solche verhalten. Der Begriff ist im Sinne der vorliegenden Erfindung verstehen als Ammonium- und/oder Tetraalkylammoniumsalze. Pseudoalkali metal salts are understood to be salts whose cations are not alkali metals, but largely behave as such. For the purposes of the present invention, the term is to be understood as ammonium and / or tetraalkylammonium salts.
Die Wirkung der erfindungsgemäßen Salze der Zuckersäuren kann verbessert werden, in dem man diese zusammen mit Erdalkalimetallformiaten, vorzugsweise Magnesium- und/oder Calciumformiat, besonders bevorzugt mit Calciumformiat verwendet. The effect of the salts of the sugar acids according to the invention can be improved by using them together with alkaline earth metal formates, preferably magnesium and / or calcium formate, particularly preferably with calcium formate.
Weiterhin kann die Wirkung der erfindungsgemäßen Salze der Zuckersäuren optimiert werden, in dem man diese zusammen mit Erdalkalimetallsalzen von C C3 Carbonsäuren, vorzugsweise Magnesium- und/oder Calciumsalzen der Ameisen-, Essig- oder Propion säure, besonders bevorzugt Magnesium- und/oder Calciumsalzen der Ameisensäure und meist bevorzugt mit Calciumformiat verwendet. Furthermore, the effect of the salts of sugar acids according to the invention can be optimized by combining them with alkaline earth metal salts of CC 3 carboxylic acids, preferably magnesium and / or calcium salts of formic, acetic or propionic acid, particularly preferably magnesium and / or calcium salts of Formic acid and mostly used with calcium formate.
Auch durch die Verwendung der erfindungsgemäßen Salze der Zuckersäuren zusammen mit Ethanolaminen (d.h. Monoethanolamin, Diethanolamin und/oder Triethanolamin) oder Harnstoff kann eine Wirkungssteigerung erzielt werden. An increase in activity can also be achieved by using the salts of the sugar acids according to the invention together with ethanolamines (i.e. monoethanolamine, diethanolamine and / or triethanolamine) or urea.
Nicht zuletzt kann die Wirkung der obigen Salze der Zuckersäuren durch die Verwendung einer Kombination von Erdalkalimetallsalzen von C C3 Carbonsäuren und Ethanolaminen oder Harnstoff gesteigert werden. Last but not least, the effect of the above salts of the sugar acids can be increased by using a combination of alkaline earth metal salts of CC 3 carboxylic acids and ethanolamines or urea.
Alternativ ist die Verwendung der erfindungsgemäßen Salze der Zuckersäuren in Kombi nation mit Alkalimetallsalzen der C C3 Carbonsäuren, insbesondere Natriumformiat, Natriumacetat, Natriumpropionat, Kaliumformiat, Kaliumacetat und/oder Kaliumpropionat möglich, welcher durchaus zusammen mit Erdalkalimetallsalzen von C C3 Carbonsäuren, Ethanolaminen oder Harnstoff erfolgen kann. Alternatively, the salts of the sugar acids according to the invention can be used in combination with alkali metal salts of CC 3 carboxylic acids, in particular sodium formate, sodium acetate, sodium propionate, potassium formate, potassium acetate and / or potassium propionate, which can be carried out together with alkaline earth metal salts of CC 3 carboxylic acids, ethanolamines or urea .
Die vorliegende Erfindung betrifft auch Verfahren zur Behandlung von tierischen Häuten im Äscher unter Verwendung von Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkali metallsalzen der Zuckersäuren, wobei diese der Flotte zugegeben werden, in der die Behandlung der Häute erfolgt. Diese Behandlung umfasst auch Varianten, bei denen die Zugabe der Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalzen der Zuckersäuren zur Flotte bereits vor dem Äscher in der Weiche erfolgt. ln einer bevorzugten Ausführungsform werden der Flotte zusätzlich oben aufgeführte Verbindungen zugegeben, die die Wirkung der Schwellungsregler unterstützen, wie Erdalkalimetallformiate, Erdalkalimetallacetate, Erdalkalimetallpropionate, Ethanolamine und/oder Harnstoff. The present invention also relates to processes for the treatment of animal skins in liming using pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids, these being added to the liquor in which the treatment of the skins takes place. This treatment also includes variants in which the pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids are added to the liquor before the liming in the switch. In a preferred embodiment, the above-mentioned compounds are additionally added to the liquor, which support the action of the swelling regulators, such as alkaline earth metal formates, alkaline earth metal acetates, alkaline earth metal propionates, ethanolamines and / or urea.
Die Flotte in der die Behandlung der Häute im Äscher erfolgt enthält typischerweise noch weitere, dem Fachmann bekannte Verbindungen, wie reduzierende schwefelhaltige Produkte (z.B. Na2S, NaHS, Mercaptoethanol, Thioglycolsäuren), starke Oxidationsmittel (z.B. H202) und/oder stark alkalische Stoffe (z.B. Kalk). The liquor in which the skins are treated in the liming typically contains further compounds known to the person skilled in the art, such as reducing sulfur-containing products (for example Na 2 S, NaHS, mercaptoethanol, thioglycolic acids), strong oxidizing agents (for example H 2 0 2 ) and / or strongly alkaline substances (e.g. lime).
Die vorliegende Erfindung betrifft auch Verfahren zur Herstellung von Leder beinhaltend die erfindungsgemäße Behandlung von tierischen Häuten. Besagte Verfahren können weiterhin dem Fachmann vertraute Schritte der Lederherstellung umfassen, wie z.B. Weiche, Entfleischen, Spalten, Entkälkung, Enzymatische Beize, Entfettung, Pickel, Gerbung, Entwässern, Falzen, Bleichen, Nachgerben, Färben, Fetten, Ausrecken, Trocknen, Anfeuchten, Weichmachen und Trockenzurichtung. The present invention also relates to processes for the production of leather comprising the treatment of animal hides according to the invention. Said methods may further include steps of leather production familiar to those skilled in the art, such as Softening, fleshing, splitting, decalcification, enzymatic pickling, degreasing, pimples, tanning, dewatering, folding, bleaching, retanning, dyeing, greasing, stretching, drying, moistening, softening and dry dressing.
Die Gerbung erfolgt bevorzugt mit Mineralgerbstoffen wie Aluminiumsalzen, insbesondere Alaunen, dreiwertigen Chromsalzen, Zirkoniumsalzen, Eisen-, Zink- oder Titansalzen, mit Polyphosphaten, mit Aldehyden wie Formaldehyd und Glutardialdehyd, mit synthetischen Gerbstoffen auf Basis von Phenolderivaten (Syntanen) oder mit Polymer-Gerbstoffen (Harzgerbstoffen) wie Acrylate und Polyurethane oder Vegetabilfarbstoffen. Besonders bevorzugt erfolgt die Gerbung mit dreiwertigen Chromsalzen oder Syntanen. Am meisten bevorzugt erfolgt die Gerbung mit dreiwertigen Chromsalzen. The tanning is preferably carried out with mineral tanning agents such as aluminum salts, in particular alums, trivalent chromium salts, zirconium salts, iron, zinc or titanium salts, with polyphosphates, with aldehydes such as formaldehyde and glutardialdehyde, with synthetic tanning agents based on phenol derivatives (syntans) or with polymer tanning agents (Resin tanning agents) such as acrylates and polyurethanes or vegetable dyes. The tanning is particularly preferably carried out using trivalent chromium salts or syntans. Most preferably tanning is carried out with trivalent chromium salts.
In bevorzugten Ausführungsformen wird bei erfindungsgemäßen Verfahren bzw. bei der erfindungsgemäßen Verwendung von Salzen der Zuckersäuren auf Zugabe von Ethanolaminen und Harnstoff verzichtet, da dadurch der Eintrag von Stickstoff ins Abwasser reduziert werden kann. In preferred embodiments, the addition of ethanolamines and urea is dispensed with in the process according to the invention or in the use of salts of the sugar acids according to the invention, since the introduction of nitrogen into the waste water can thereby be reduced.
In bevorzugten Ausführungsformen werden bei erfindungsgemäßen Verfahren bzw. bei der erfindungsgemäßen Verwendung Alkalimetallsalze der Gluconsäuren, besonders bevorzugt Natriumgluconat eingesetzt. In preferred embodiments, alkali metal salts of gluconic acids, particularly preferably sodium gluconate, are used in the processes according to the invention or in the use according to the invention.
In bevorzugten Ausführungsformen werden bei dem erfindungsgemäßen Verfahren bzw. bei der erfindungsgemäßen Verwendung bezogen auf das Salzgewicht der eingesetzten Rohhaut von 0,05 bis 5,0 Gew.-%, vorzugsweise von 0,1 bis 2,0 Gew.-% und besonders bevorzugt von 0.2 bis 1.0 Gew.-% Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkali metallsalze der Zuckersäuren verwendet. Unter dem Salzgewicht versteht der Gerber das Gewicht, dass die Haut nach der erfolgten Konservierung mit Salz besitzt. Dabei hat die konservierte Haut typischerweise einen Feuchtigkeitsgehalt von 35 Gew.-%. In preferred embodiments, in the process according to the invention or in the use according to the invention, based on the salt weight of the raw skin used, from 0.05 to 5.0% by weight, preferably from 0.1 to 2.0% by weight and particularly preferably from 0.2 to 1.0% by weight of pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids are used. The tanner understands by the salt weight the weight that the skin has after the preservation with salt. The preserved skin typically has a moisture content of 35% by weight.
Weitere bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens bzw. der der erfindungsgemäßen Verwendung betreffen die Kombination von Alkalimetallsalzen der Gluconsäuren mit Erdalkalimetallformiaten allein oder zusammen mit Erdalkali metallacetaten, und/oder Erdalkalimetallpropionaten. Further preferred embodiments of the method according to the invention or the use according to the invention relate to the combination of alkali metal salts of gluconic acids with alkaline earth metal formates alone or together with alkaline earth metal acetates, and / or alkaline earth metal propionates.
Weitere bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens bzw. der der erfindungsgemäßen Verwendung betreffen die Kombination von Natriumgluconat mit Magnesium- und/oder Calciumformiat. Further preferred embodiments of the method according to the invention or of the use according to the invention relate to the combination of sodium gluconate with magnesium and / or calcium formate.
Weitere bevorzugten Ausführungsformen des erfindungsgemäßen Verfahrens bzw. der der erfindungsgemäßen Verwendung betreffen die Kombination von Natriumgluconat mit Magnesium- und/oder Calciumformiat und Alkali- oder Erdalkalimetallacetaten und/oder Erdalkalimetallpropionaten. Further preferred embodiments of the method according to the invention or of the use according to the invention relate to the combination of sodium gluconate with magnesium and / or calcium formate and alkali or alkaline earth metal acetates and / or alkaline earth metal propionates.
Die vorliegende Erfindung umfasst auch Lederhilfsmittelzusammensetzungen enthaltend ein oder mehrere Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalze der Zuckersäuren, vorzugsweise Ammonium-, Natrium- und/oder Kaliumsalze der Zuckersäuren, besonders bevorzugt Natriumsalze der Zuckersäuren. The present invention also includes leather auxiliary compositions comprising one or more pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids, preferably ammonium, sodium and / or potassium salts of the sugar acids, particularly preferably sodium salts of the sugar acids.
Vorteilhafterweise enthalten erfindungsgemäße Lederhilfsmittelzusammensetzungen ein oder mehrere Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalze der Gluconsäure, vorzugsweise Ammonium-, Natrium- und/oder Kaliumgluconat, besonders bevorzugt Natriumgluconat. Leather auxiliary compositions according to the invention advantageously contain one or more pseudoalkali metal, alkali metal and / or alkaline earth metal salts of gluconic acid, preferably ammonium, sodium and / or potassium gluconate, particularly preferably sodium gluconate.
Weitere vorteilhafte Lederhilfsmittelzusammensetzungen enthalten zusätzlich ein oder mehrere Verbindungen aus der Gruppe enthaltend Erdalkalimetallsalze von C C3 Carbonsäuren, Monoethanolamin, Diethanolamin, Triethanolamin und Harnstoff, vorzugsweise Magnesium- und/oder Calciumsalze der Ameisen-, Essig- oder Propionsäure, Monoethanolamin, Diethanolamin, Triethanolamin und Harnstoff, besonders bevorzugt Magnesium- und/oder Calciumsalze der Ameisen- oder Essigsäure und meist bevorzugt Calciumformiat. Further advantageous leather auxiliary compositions additionally contain one or more compounds from the group comprising alkaline earth metal salts of CC 3 carboxylic acids, monoethanolamine, diethanolamine, triethanolamine and urea, preferably magnesium and / or calcium salts of formic, acetic or propionic acid, monoethanolamine, diethanolamine, triethanolamine and urethane , particularly preferably magnesium and / or calcium salts of formic or acetic acid and most preferably calcium formate.
Weitere vorteilhafte Lederhilfsmittelzusammensetzungen enthalten Ammonium-, Natrium- und/oder Kaliumgluconat in Kombination mit Magnesiumformiat, Calciumformiat Magnesiumacetat und/oder Calciumacetat, bevorzugt Natrium- und/oder Kaliumgluconat in Kombination mit Magnesiumformiat und/oder Calciumformiat. Bevorzugt enthält die Lederhilfsmittelzusammensetzung Natriumgluconat und ein oder mehrere Verbindungen aus der Gruppe enthaltend Calciumformiat und Magnesiumformiat, vorzugsweise Calciumformiat. Further advantageous leather auxiliary compositions contain ammonium, sodium and / or potassium gluconate in combination with magnesium formate, calcium formate magnesium acetate and / or calcium acetate, preferably sodium and / or potassium gluconate in combination with magnesium formate and / or calcium formate. The leather auxiliary composition preferably contains sodium gluconate and one or more compounds from the group comprising calcium formate and magnesium formate, preferably calcium formate.
In besonders vorteilhaften Ausführungsformen beträgt das Verhältnis der Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalze der Zuckersäuren zu den Verbindungen aus der Gruppe enthaltend Erdalkalimetallformiate, Erdalkalimetallacetate, Erdalkalimetallpropionate, Monoethanolamin, Diethanolamin, Triethanolamin undIn particularly advantageous embodiments, the ratio of the pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids to the compounds from the group comprising alkaline earth metal formates, alkaline earth metal acetates, alkaline earth metal propionates, monoethanolamine, diethanolamine, triethanolamine and
Harnstoff in der Lederhilfsmittelzusammensetzung von 10:90 bis 90:10, vorzugsweise von 20:80 bis 80:20 und besonders bevorzugt von 30:70 bis 70:30 beträgt. Das Verhältnis bestimmt sich dabei als Quotient aus der Gesamtmasse der eingesetzten Verbindungen der obigen Salze der Zuckersäuren zu der Gesamtmasse der eingesetzten Verbindungen der obigen Formiate, Acetate und Propionate. Urea in the leather auxiliary composition is from 10:90 to 90:10, preferably from 20:80 to 80:20 and particularly preferably from 30:70 to 70:30. The ratio is determined as the quotient from the total mass of the compounds of the above salts of the sugar acids to the total mass of the compounds of the above formates, acetates and propionates.
Typischerweise sind die erfindungsgemäßen Lederhilfsmittelzusammensetzungen Schwellungsregulatoren, insbesondere Schwellungsregulatoren für die Wasserwerkstatt bevorzugt Schwellungsregulatoren zur Anwendung in der Weiche oder im Äscher, meist bevorzugt Schwellungsregulatoren zur Anwendung im Äscher . The leather auxiliary compositions according to the invention are typically swelling regulators, in particular swelling regulators for the water workshop, preferably swelling regulators for use in the switch or in the liming, mostly preferably swelling regulators for use in the liming.
Die erfindungsgemäßen Lederhilfsmittelzusammensetzungen können in flüssiger oder in fester Form vorliegen. In einer bevorzugten Ausführungsform liegt die erfindungsgemäße Lederhilfsmittelzusammensetzung bei 25°C als Feststoff vor, idealerweise in partikulärer Form, wie zum Beispiel als Pulver, Granulat oder Pellets. The leather auxiliary compositions according to the invention can be in liquid or in solid form. In a preferred embodiment, the leather auxiliary composition according to the invention is at 25 ° C. as a solid, ideally in particulate form, such as, for example, as a powder, granulate or pellet.
Beispiele Examples
Probenvorbereitung: Sample preparation:
Die Screening-Versuche wurden auf Rohhautproben DIN A4 ausgeführt. Diese wurden aus dem Kernbereich einer gesalzenen Rohhaut geschnitten, so dass alle Proben eine ähnliche Faserstruktur aufwiesen. Die Proben einer Reihe wurden von der selben Haut entnommen da sich die Faserstruktur der Haut von Tier zu Tier unterscheidet. Die Probenkörper wurden einzeln gewogen. Auf dieses Gewicht (der Rohhaut-Salzgewicht) beziehen sich alle Prozentangaben der Prozess-Rezeptur. The screening tests were carried out on raw skin samples DIN A4. These were cut from the core area of a salted raw skin, so that all samples had a similar fiber structure. The samples of a series were taken from the same skin because the fiber structure of the skin differs from animal to animal. The test specimens were weighed individually. All percentages of the process recipe refer to this weight (the raw skin salt weight).
Das Prüfverfahren umfasste die Prozessschritte„Weiche“ und„Äscher“. Die Mengen der in dem Prozess verwendeten Chemikalien und Produkte sowie die Wassermenge sind in Gewichtsprozent auf das Rohhaut-Salzgewicht der einzelnen Proben bezogen. Die Mengen wurden auf einer Waage mit der Genauigkeit von 0,5g abgewogen. The test procedure included the process steps "switch" and "liming". The amounts of chemicals and products used in the process as well as the amount of water are in percent by weight based on the raw skin salt weight of the individual samples. The quantities were weighed on a balance with an accuracy of 0.5 g.
Die Versuche wurden in kleinen Versuchs-Gerbfässern, Durchmesser 300mm mit Temperaturregulierung (Hersteller Fa. Dose), durchgeführt. Die Prozesstemperatur wurde konstant auf 28°C +/- 1°C gehalten. The tests were carried out in small test tanning drums, diameter 300 mm with temperature regulation (manufacturer Dose). The process temperature was kept constant at 28 ° C +/- 1 ° C.
Weiche: Switch:
Der Probenkörper wurde einzeln in das Musterfass gegeben und 200% Wasser (bezogen auf das Salzgewicht) mit einer Temperatur von 28°C, und 0,3% Weichhilfsmittel Peltec BH (Mischung Tensid und Bakterizid der Fa. LANXESS Deutschland GmbH) zugegeben. Das Versuchsfass wurde 300 Minuten mit 10RPM rotiert. Danach wurde die Flotte (Prozess- Wasser) abgelassen. Der Probenkörper wird nun abgetupft, gewogen und die durchschnittliche Dicke an vier Messpunkten ermittelt. The test specimen was added individually to the sample barrel and 200% water (based on the salt weight) at a temperature of 28 ° C. and 0.3% Peltec BH softening agent (mixture of surfactant and bactericide from LANXESS Deutschland GmbH) were added. The test barrel was rotated at 10 RPM for 300 minutes. The liquor (process water) was then drained off. The specimen is now dabbed off, weighed and the average thickness is determined at four measuring points.
Äscher: Liming:
Der Probenkörper wurde wieder in das Versuchsfass gegeben und 200% Wasser mit einer Temperatur von 28°C hinzugefügt und 15 min. rotiert. Danach wurde der restliche Salzgehalt der Flotte ermitteln. Dieser soll 3,5°Be nicht übersteigen. Bei zu hohem Salzgehalt ist die Flotte einmal zu wechseln. The test specimen was put back into the test barrel and 200% water at a temperature of 28 ° C. was added and 15 min. rotates. The remaining salinity of the fleet was then determined. This should not exceed 3.5 ° Be. If the salt content is too high, the fleet should be changed once.
Der Schwellungsregulator wurde in die Flotte geben und das Versuchsfass 60 min. rotiert. Danach wurde gewogen und durchschnittliche Dicke bestimmt. Der Probenkörper wurde zurück in die Flotte gegeben, 3% Kalk (Ca(OH)2) und 2,5% Na2S zugeben und für 4 Std. rotieren gelassen. Danach erfolgten 15Std. Fassrotation im Intervallbetrieb (10min. rotieren/ 50 min. Pause). Anschließend wurde der pH-Wert der Flotte gemessen (pH 12- 12,5), der Probenkörper entnommen, wieder gewogen und die durchschnittliche Dicke gemessen. Aus der Dickenzunahme wurde die Schwellung bestimmt. The swelling regulator was added to the fleet and the test keg 60 min. rotates. The weight was then determined and the average thickness was determined. The test specimen was returned to the liquor, 3% lime (Ca (OH) 2 ) and 2.5% Na 2 S were added and the mixture was rotated for 4 hours. Then there were 15 hours. Barrel rotation in interval mode (rotate 10 min. / 50 min. Break). The pH of the liquor was then measured (pH 12- 12.5), the specimen was removed, weighed again and the average thickness measured. The swelling was determined from the increase in thickness.
Die Probenkörper wurden anschließend gewaschen und mit einer Standard Chromgerbung (wie beispielsweise beschrieben in E. Heidemann, Fundamentals of Leather Manufacturing, S. 295 - 340, E. Roether Verlag, Darmstadt, 1993) gegerbt und danach die Festnarbigkeit durch Biegen des Leders geprüft. Wenn die Oberfläche in der Biegefalte glatt war, sich nicht aufwarf und nicht wellte, wurde eine positive Festnarbigkeit beschieden. The test specimens were then washed and tanned using a standard chrome tanning (as described, for example, in E. Heidemann, Fundamentals of Leather Manufacturing, pp. 295-340, E. Roether Verlag, Darmstadt, 1993) and the firmness of the grain was then checked by bending the leather. If the surface in the crease was smooth, did not rise, and did not curl, a positive firm grain was found.
Die Ergebnisse der Schwellungsmessung und der Beurteilung der Festnarbigkeit sind in Tabelle 1 aufgeführt. The results of the swelling measurement and the assessment of the solid pitting are shown in Table 1.
Die Ergebnisse belegen, dass die erfindungsgemäße Verwendung von Salzen der Zuckersäuren es erlaubt, auf die Verwendung von stickstoffhaltiger Verbindungen wie Harnstoff oder Ethanolaminen zu verzichten, wodurch der Stickstoff-Eintrag in das Abwasser wesentlich reduziert werden kann, aber gleichzeitig die Festnarbigkeit beibehalten oder verbessert werden kann. Zudem geht aus den Ergebnissen hervor, dass bei der erfindungsgemäßen Verwendung von Salzen der Zuckersäuren zusammen mit stickstoffhaltigen Verbindungen wie Harnstoff oder Ethanolaminen, d.h. bei gleichbleibendem Stickstoff-Eintrag in das Abwasser, eine wesentliche Verbesserung der Festnarbigkeit erzielt werden kann. The results show that the use of salts of the sugar acids according to the invention makes it possible to dispense with the use of nitrogen-containing compounds such as urea or ethanolamines, as a result of which the introduction of nitrogen into the wastewater can be substantially reduced, but at the same time the pitting can be maintained or improved . In addition, the results show that the use of salts of the sugar acids according to the invention together with nitrogen-containing compounds such as urea or ethanolamines, ie with a constant nitrogen input into the waste water, can achieve a substantial improvement in the solid grain.
Tabelle 1 Table 1

Claims

Patentansprüche Claims
1. Verwendung von Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalzen der Zuckersäuren bei der Lederherstellung in der Weiche, im Äscher oder in der Weiche und im Äscher. 1. Use of pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids in leather production in the switch, in the limer or in the switch and in the limer.
2. Verwendung gemäß Anspruch 1 , wobei Verbindungen ausgewählt aus der Gruppe Ammonium-, Natrium-, Kalium-, Calcium- und Magnesiumsalze der Zuckersäuren, bevorzugt Natrium- und Kaliumsalze der Zuckersäuren, besonders bevorzugt Natriumsalze der Zuckersäuren eingesetzt werden. 2. Use according to claim 1, wherein compounds selected from the group consisting of ammonium, sodium, potassium, calcium and magnesium salts of the sugar acids, preferably sodium and potassium salts of the sugar acids, particularly preferably sodium salts of the sugar acids.
3. Verwendung gemäß einem oder mehreren der Ansprüche 1 und 2, wobei Salze der Aldonsäuren, Uronsäuren, Aldarsäuren oder Ketoaldonsäuren, bevorzugt der Aldonsäuren und besonders bevorzugt der Gluconsäure eingesetzt werden. 3. Use according to one or more of claims 1 and 2, wherein salts of aldonic acids, uronic acids, aldar acids or ketoaldonic acids, preferably aldonic acids and particularly preferably gluconic acid, are used.
4. Verwendung gemäß einem oder mehreren der Ansprüche 1 bis 3, wobei Ammonium-, Natrium- und/oder Kaliumgluconat, bevorzugt Natrium- und/oder Kaliumgluconat und besonders bevorzugt Natriumgluconat eingesetzt wird. 4. Use according to one or more of claims 1 to 3, wherein ammonium, sodium and / or potassium gluconate, preferably sodium and / or potassium gluconate and particularly preferably sodium gluconate is used.
5. Verwendung gemäß einem oder mehreren der Ansprüche 1 bis 4 als Schwellungsregulator im Äscher. 5. Use according to one or more of claims 1 to 4 as a swelling regulator in the liming.
6. Verwendung gemäß einem oder mehreren der Ansprüche 1 bis 5, wobei die Verwendung zusammen mit Erdalkalimetallsalzen von C C3 Carbonsäuren, vorzugsweise Magnesium- und/oder Calciumsalzen der Ameisen-, Essig- oder Propionsäure, besonders bevorzugt Magnesium- und/oder Calciumsalzen der Ameisensäure und meist bevorzugt mit Calciumformiat erfolgt. 6. Use according to one or more of claims 1 to 5, wherein the use together with alkaline earth metal salts of CC 3 carboxylic acids, preferably magnesium and / or calcium salts of formic, acetic or propionic acid, particularly preferably magnesium and / or calcium salts of formic acid and most preferably with calcium formate.
7. Verwendung gemäß einem oder mehreren der Ansprüche 1 bis 6, wobei die Verwendung zusammen mit Monoethanolamin, Diethanolamin, Triethanolamin oder Harnstoff erfolgt. 7. Use according to one or more of claims 1 to 6, wherein the use is carried out together with monoethanolamine, diethanolamine, triethanolamine or urea.
8. Verwendung gemäß einem oder mehreren der Ansprüche 1 bis 7, wobei bezogen auf eingesetzte Rohhaut als Salzgewicht von 0,05 bis 5,0 Gew.-%, vorzugsweise von 0,1 bis 2,0 Gew.-% und besonders bevorzugt von 0.2 bis 1.0 Gew.-% Pseudoalkalimetall- , Alkalimetall-, und/oder Erdalkalimetallsalze der Zuckersäuren verwendet werden. 8. Use according to one or more of claims 1 to 7, wherein based on the raw skin used as the salt weight of 0.05 to 5.0 wt .-%, preferably from 0.1 to 2.0 wt .-% and particularly preferably of 0.2 to 1.0 wt .-% pseudoalkali metal, alkali metal, and / or alkaline earth metal salts of the sugar acids are used.
9. Verfahren zur Behandlung von tierischen Häuten im Äscher unter Verwendung von Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalzen der Zuckersäuren gemäß einem oder mehreren der Ansprüche 1 bis 8, wobei die Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalze der Zuckersäuren der Flotte zugegeben werden, in der die Behandlung der Häute erfolgt. 9. A process for the treatment of animal skins in the liming using pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids according to one or more of claims 1 to 8, wherein the pseudoalkali metal, Alkali metal and / or alkaline earth metal salts of the sugar acids are added to the liquor in which the skins are treated.
10. Verfahren zur Herstellung von Leder umfassend die Behandlung gemäß Anspruch 9. 10. A method for producing leather comprising the treatment according to claim 9.
11. Lederhilfsmittelzusammensetzung enthaltend ein oder mehrere Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalze der Zuckersäuren, vorzugsweise Ammonium-, Natrium- und/oder Kaliumsalze der Zuckersäuren, besonders bevorzugt Natriumsalze der Zuckersäuren. 11. Leather auxiliary composition containing one or more pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids, preferably ammonium, sodium and / or potassium salts of the sugar acids, particularly preferably sodium salts of the sugar acids.
12. Lederhilfsmittelzusammensetzung gemäß Anspruch 11 enthaltend ein oder mehrere mehrere Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalze der Gluconsäure, vorzugsweise Ammonium-, Natrium- und/oder Kaliumgluconat, besonders bevorzugt Natriumgluconat. 12. Leather auxiliary composition according to claim 11 containing one or more pseudoalkali metal, alkali metal and / or alkaline earth metal salts of gluconic acid, preferably ammonium, sodium and / or potassium gluconate, particularly preferably sodium gluconate.
13. Lederhilfsmittelzusammensetzung gemäß einem oder mehreren der Ansprüche 11 und 12 enthaltend zusätzlich ein oder mehrere Verbindungen aus der Gruppe enthaltend Erdalkalimetallsalze von C C3 Carbonsäuren, Monoethanolamin, Diethanolamin, Triethanolamin und Harnstoff, vorzugsweise Magnesium- und/oder Calciumsalze der Ameisen-, Essig- oder Propionsäure, Monoethanolamin, Diethanolamin, Triethanolamin und Harnstoff, besonders bevorzugt Magnesium- und/oder Calciumsalze der Ameisen- oder Essigsäure und meist bevorzugt Calciumformiat. 13. Leather auxiliary composition according to one or more of claims 11 and 12 additionally containing one or more compounds from the group comprising alkaline earth metal salts of CC 3 carboxylic acids, monoethanolamine, diethanolamine, triethanolamine and urea, preferably magnesium and / or calcium salts of the ant, vinegar or Propionic acid, monoethanolamine, diethanolamine, triethanolamine and urea, particularly preferably magnesium and / or calcium salts of formic or acetic acid and most preferably calcium formate.
14. Lederhilfsmittelzusammensetzung gemäß einem oder mehreren der Ansprüche 11 bis 13, enthaltend Natriumgluconat und ein oder mehrere Verbindungen aus der Gruppe enthaltend Calciumformiat und Magnesiumformiat, vorzugsweise Calciumformiat. 14. Leather auxiliary composition according to one or more of claims 11 to 13, containing sodium gluconate and one or more compounds from the group containing calcium formate and magnesium formate, preferably calcium formate.
15. Lederhilfsmittelzusammensetzung gemäß einem oder mehreren der Ansprüche 13 bis 15, wobei das Verhältnis der Pseudoalkalimetall-, Alkalimetall-, und/oder Erdalkalimetallsalze der Zuckersäuren zu den Verbindungen aus der Gruppe enthaltend Erdalkalimetallformiate, Erdalkalimetallacetate, Erdalkalimetallpropionate, Monoethanolamin, Diethanolamin, Triethanolamin und Harnstoff von 10:90 bis 90:10, vorzugsweise von 20:80 bis 80:20 und besonders bevorzugt von 30:70 bis 70:30 beträgt. 15. Leather auxiliary composition according to one or more of claims 13 to 15, wherein the ratio of the pseudoalkali metal, alkali metal and / or alkaline earth metal salts of the sugar acids to the compounds from the group comprising alkaline earth metal formates, alkaline earth metal acetates, alkaline earth metal propionates, monoethamine amine, monoethamine amine, monoethamine amine, monoethamine amine, monoethanolamine, 10:90 to 90:10, preferably from 20:80 to 80:20 and particularly preferably from 30:70 to 70:30.
EP19828654.4A 2018-12-21 2019-12-16 Leather agents for beamhouse Active EP3924523B1 (en)

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EP18215380.9A EP3670675A1 (en) 2018-12-21 2018-12-21 Leather agents for beamhouse
PCT/EP2019/085260 WO2020126987A1 (en) 2018-12-21 2019-12-16 Leather auxiliaries for the beamhouse

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NL2027083B1 (en) 2020-12-09 2022-07-07 Stahl Int B V Process for deliming of hides, skins or pelts
NL2031083B1 (en) * 2022-02-25 2023-09-07 Stahl Int B V Process for liming of hides, skins or pelts

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CH647259A5 (en) * 1980-04-29 1985-01-15 Sandoz Ag METHOD FOR TANNING ANIMAL SKIN AND SKIN WITH IRON SALT.
GB8802747D0 (en) * 1988-02-06 1988-03-09 Tioxide Group Plc Tanning agent & process
DE10249077A1 (en) * 2002-10-21 2004-04-29 Basf Ag Process for the production of leather
CN1676614A (en) * 2005-04-07 2005-10-05 张壮斗 New-type adjuvant for leather production
WO2009115487A1 (en) * 2008-03-20 2009-09-24 Basf Se Method for manufacturing leather
EP2607499A3 (en) * 2013-02-14 2013-07-10 Basf Se Method for producing leather
CN107653350A (en) * 2017-09-27 2018-02-02 徐州双辰服饰有限公司 A kind of leather dye agent prescription

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BR112021011977A2 (en) 2021-09-08
BR112021011977A8 (en) 2023-05-09
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WO2020126987A1 (en) 2020-06-25
ES2963618T3 (en) 2024-04-01
AR117464A1 (en) 2021-08-11
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CN113227407A (en) 2021-08-06
EP3924523B1 (en) 2023-08-09

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