EP0569410B1 - Method of self-tanning, pre-tanning and co-tanning skins and hides and for retanning leather and hides - Google Patents

Method of self-tanning, pre-tanning and co-tanning skins and hides and for retanning leather and hides Download PDF

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Publication number
EP0569410B1
EP0569410B1 EP92903337A EP92903337A EP0569410B1 EP 0569410 B1 EP0569410 B1 EP 0569410B1 EP 92903337 A EP92903337 A EP 92903337A EP 92903337 A EP92903337 A EP 92903337A EP 0569410 B1 EP0569410 B1 EP 0569410B1
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Prior art keywords
tanning
groups
leather
hides
weight
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German (de)
French (fr)
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EP0569410A1 (en
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Juergen Weiser
Wolfgang Reuther
Hermann Birkhofer
Karl Stork
Ortwin Schaffer
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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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes

Definitions

  • the present invention relates to an improved method for sole tanning, pretanning and tanning of pelts and pelts and for retanning leather and hide.
  • DE-A-17 69 059 relates to a process for leather production by treating tannable material with zinc salts, water-soluble sulfates and aldehydes or aldehyde-releasing substances and aftertreatment with dulling agents.
  • acetal residues the residues customary for this are usually used, for example C1-C8-alkyl groups, preferably C1-C4-alkyl groups, such as methyl, ethyl, n-propyl, n-butyl or 2-ethylhexyl.
  • the two acetal residues can be different or preferably the same.
  • these two radicals can form a five- or six-membered ring, for example a 1,3-dioxolane, 1,3-dioxane, 5,5-dimethyl-1,3-dioxane or 5-n-butyl-5 -ethyl-1,3-dioxane ring.
  • the compound I and its acetals are known in principle; they are prepared by the relevant methods given in the literature.
  • the tanning process according to the invention is outstandingly suitable for tanning alone and pretanning skins and skins in an aqueous liquor.
  • the procedure here is such that the pickled pelts, for example cowhide pelts with a gap thickness of 1.5 to 4 mm, or pelts, for example sheepskin pelts, at a pH of 2 to 7, in particular 2.5 to 4, and one Temperature of 15 to 50 °, in particular 25 to 45 ° C, are treated with an aqueous solution or dispersion of the carbonyl compound I for a period of 3 to 20 hours.
  • the treatment takes place, for example, by drumming in a barrel.
  • the required amount of carbonyl compound I is normally 2 to 30% by weight, in particular 5 to 20% by weight, based on the pelt weight.
  • the fleet length, i.e. the percentage weight ratio of the treatment liquor to the goods is usually 30 to 200% for the bare and 100 to 2000% for the bare, in each case based on the bare weight.
  • the leather or fur is usually adjusted to a pH of 4 to 8, in particular 5 to 7, for which purpose magnesium oxide, sodium carbonate or sodium hydrogen carbonate is used, optionally treated with further tanning agents and, if desired, dyed after the tanning process has ended and greased.
  • the tanning process according to the invention is also outstandingly suitable for tanning bare and pelted skin together with the tanning agents of the main tanning process, which can be, for example, chrome or aluminum tanning.
  • the working conditions regarding pH, temperature and duration of the treatment are adjusted to the requirements of the main components of the tanning, the same applies to the Treatment equipment and the length of the liquor as well as for post-treatment.
  • the amount of carbonyl compound I required is normally 0.1 to 20% by weight, in particular 0.5 to 15% by weight, based on the pelt weight.
  • the tanning process according to the invention is also outstandingly suitable for retanning leather and fur which has already been tanned, for example chrome leather, in an aqueous liquor. It is usually carried out in such a way that the pickled pelts and skins, for example cowhide pelts with a gap thickness of 1.5 to 4 mm, are used, for example, with a customary chromium-containing tanning agent such as a chromium (III) salt, e.g.
  • a customary chromium-containing tanning agent such as a chromium (III) salt, e.g.
  • Chromium (III) sulfate tanned in a manner known per se, the pretanned skins obtained in this way (in the case of chrome tanning "wet blues") deacidified and at a pH of 2 to 7, in particular 2.5 to 4, and at temperatures of 15 to 50 ° C, in particular 25 to 45 ° C, treated with an aqueous solution or dispersion of the carbonyl compound I for a period of 1 to 12 hours.
  • This treatment takes place, for example, by drumming in a barrel.
  • the amount of carbonyl compound I required, based on the shaved weight of the leather, is normally 2 to 30% by weight, in particular 5 to 20% by weight.
  • the liquor length is usually 30 to 200% for bare and 100 to 2000% for bare, each based on the fold weight of the leather.
  • the leather or fur is usually adjusted to a pH of 3 to 5, for which purpose magnesium oxide or an organic acid such as formic acid or its salts are used, and, if desired, dyed and greased after the treatment.
  • the leather or fur retanned according to the invention may also have been treated with other tanning agents, such as polymer tanning agents or syntans, before retanning with the carbonyl compound I.
  • the carbonyl compound I can also be used simultaneously with such additional tanning agents, for example in main tanning.
  • tanning agents As additional or simultaneously used tanning agents, all usual agents with tanning effects on bare or fur bare are considered. A comprehensive treatment of such tannins can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 3rd edition, 11th volume, pages 585 to 612 (1960). Tannin classes to be mentioned individually are the mineral tannins, for example chromium, aluminum, zinc and zirconium salts, the synthetic tannins such as the polymer tannins and syntans already mentioned above, and the vegetable (vegetable) tannins.
  • mineral tannins for example chromium, aluminum, zinc and zirconium salts
  • synthetic tannins such as the polymer tannins and syntans already mentioned above
  • vegetable (vegetable) tannins the vegetable (vegetable) tannins.
  • leather and furs are produced which, in comparison to the products obtained with previously known aldehyde tannins such as glutardialdehyde, have not only a full and very soft feel and, in addition to high shrinking temperatures, but also a significantly improved tear and tensile strength.
  • the leather and skins tanned according to the invention no longer have a disturbing yellow color.
  • Another advantage of the tanning process according to the invention is the low volatility of the carbonyl compound I used, which has an effect, for example, on the amount of these tanning agents used, which need only be relatively low. Furthermore, the carbonyl compound I is, in a sense, a universal tanning agent since it can be combined with all other customary tanning agents and can be used both for the sole, the pre, the co-tanning and for the retanning.
  • a white leather with a shrinking temperature of approx. 85 ° C. was obtained, which was very soft and easy to grip.
  • a soft and non-slip leather with a shrinking temperature of approx. 90 ° C. was obtained.
  • Usual sheepskin pelt was mixed with 60% by weight of table salt, 12% by weight of common fatliquor and 18% by weight of 3-oxaglutardialdehyde, based in each case on the dry weight of the pelts, at a liquor length of 1500% and 4 hours at 35 ° C. and a pH of 3.2 in the barrel. Then a pH of 5.5 was set with sodium carbonate.

Abstract

Disclosed is a method of self-tanning, pre-tanning and co-tanning skins and hides and for retanning leather and hides, using carbonyl compounds of formula (I), in which R1 is hydrogen, C¿1?-C8 alkyl groups, phenylalkyl groups with a total of up to 12 C-atoms or phenyl groups, wherein phenyl residues may also be substituted with one or two C1-C4 alkyl groups, C1-C4 alkoxy groups, hydroxyl groups, amino groups, carboxyl groups, sulfo groups or halogen atoms; n is 1, 2, 3, or 4; and x is an OH, SH, NH2 or PH2 residue when n = 1, a bridging O, S, SO, SO2, NH, NR?2¿, PH or PR2 group, where R2 is C1-C4 alkyl, when n = 2, a tertiary N- or P-atom or the trivalent group P =O when n = 3, and a quaternary N-atom when n = 4. The corresponding acetals or ketals of the carbonyl compounds of formula (I) may also be used.

Description

Die vorliegende Erfindung betrifft ein verbessertes Verfahren zum Alleingerben, Vorgerben und Mitgerben von Blößen und Fellblößen und zum Nachgerben von Leder und Fell.The present invention relates to an improved method for sole tanning, pretanning and tanning of pelts and pelts and for retanning leather and hide.

Aldehyde und insbesondere Dialdehyde wie Glutardialdehyd werden als Ledergerbstoffe oft in der Literatur beschrieben und häufig in der Praxis eingesetzt. So betrifft beispielsweise die DE-A-17 69 059 ein Verfahren zur Lederherstellung durch Behandeln von gerbbarem Material mit Zinksalzen, wasserlöslichen Sulfaten und Aldehyden oder Aldehyde abspaltenden Stoffen und Nachbehandeln mit Abstumpfungsmitteln.Aldehydes and especially dialdehydes such as glutardialdehyde are often described in the literature as leather tanning agents and are frequently used in practice. For example, DE-A-17 69 059 relates to a process for leather production by treating tannable material with zinc salts, water-soluble sulfates and aldehydes or aldehyde-releasing substances and aftertreatment with dulling agents.

Aus der US-A-2 516 283 ist ein Verfahren zum Gerben von Leder mit einer wäßrigen Losung aus Thiodiglykolaldehyd der Formel OHCCH₂SCH₂CHO bekannt.From US-A-2 516 283 a method for tanning leather with an aqueous solution of thiodiglycolaldehyde of the formula OHCCH₂SCH₂CHO is known.

Diese Verfahren und die durch diese Verfahren erhaltenen Leder und Felle weisen aber häufig eine Reihe von Nachteilen auf. Bei der Gerbung insbesondere mit Glutardialdehyd werden häufig vergilbte Leder erhalten; besonders starke Störungen können bei der Anwendung von Glutardialdehyd als Gerbstoff auf Pelzwerk auftreten, da ein derartig gegerbtes Pelzmaterial nicht nur auf der Fleisch- sondern auch auf der Haarseite stark vergilbt sein kann. Weiterhin gestalten zu hohe Flüchtigkeiten und oft zu hohe Toxizitäten oder Gesundheitsgefährdungspotentiale der verwendeten Aldehyde die Gerbeverfahren problematisch, weil hierdurch Schutzmaßnahmen getroffen werden müssen und außerdem eine relativ hohe Einsatzmenge an Gerbstoff notwendig ist.However, these processes and the leather and skins obtained by these processes often have a number of disadvantages. When tanning, especially with glutardialdehyde, yellowed leather is often obtained; Particularly strong disturbances can occur when glutardialdehyde is used as a tanning agent on fur, since such a tanned fur material can be strongly yellowed not only on the meat but also on the hair side. Furthermore, too high volatilities and often too high toxicities or health hazards of the aldehydes used make the tanning processes problematic because protective measures have to be taken and a relatively high amount of tanning agent is necessary.

Aufgabe der vorliegenden Erfindung war es daher, neue Gerbstoffe für die Allein-, Vor-, Mit- und Nachgerbung bereitzustellen, die die Nachteile der Mittel des Standes der Technik nicht mehr aufweisen.It was therefore an object of the present invention to provide new tanning agents for single, pre-tanning and retanning, which no longer have the disadvantages of the agents of the prior art.

Demgemäß wurde ein verbessertes Verfahren zum Alleingerben, Vorgerben und Mitgerben von Blößen und Fellblößen und zum Nachgerben von Leder und Fell gefunden, welches dadurch gekennzeichnet ist, daß man hierzu die Verbindung der Formel I

Figure imgb0001

sowie deren Acetale verwendet.Accordingly, an improved process for solo tanning, pre-tanning and co-tanning of pelts and pelts and for retanning leather and fur has been found, which is characterized in that for this purpose the compound of the formula I
Figure imgb0001
as well as their acetals used.

Neben 3-Oxaglutardialdehyd I selber können auch die entsprechenden Acetale zur Anwendung kommen. Als Acetalreste werden üblicherweise die hierfür gebräuchlichen Reste verwendet, beispielsweise C₁-C₈-Alkylgruppen, vorzugsweise C₁-C₄-Alkylgruppen, wie Methyl, Ethyl, n-Propyl, n-Butyl oder 2-Ethylhexyl. Die beiden Acetalreste können verschieden oder vorzugsweise gleich sein. Weiterhin können diese beiden Reste unter Ausbildung eines fünf- oder sechsgliedrigen Ringes, z.B. eines 1,3-Dioxolan-, 1,3-Dioxan-, 5,5-Dimethyl-1,3-dioxan- oder 5-n-Butyl-5-ethyl-1,3-dioxan-Ringes, miteinander verbunden sein.In addition to 3-oxaglutardialdehyde I itself, the corresponding acetals can also be used. As acetal residues, the residues customary for this are usually used, for example C₁-C₈-alkyl groups, preferably C₁-C₄-alkyl groups, such as methyl, ethyl, n-propyl, n-butyl or 2-ethylhexyl. The two acetal residues can be different or preferably the same. Furthermore, these two radicals can form a five- or six-membered ring, for example a 1,3-dioxolane, 1,3-dioxane, 5,5-dimethyl-1,3-dioxane or 5-n-butyl-5 -ethyl-1,3-dioxane ring.

Die Verbindung I und ihre Acetale sind im Prinzip bekannt, ihre Herstellung erfolgt nach einschlägigen in der Literatur angegebenen Methoden.The compound I and its acetals are known in principle; they are prepared by the relevant methods given in the literature.

Das erfindungsgemäße Gerbeverfahren eignet sich in hervorragender Weise zum Alleingerben und Vorgerben von Blößen und Fellblößen in wäßriger Flotte. Hierbei geht man zweckmäßigerweise so vor, daß die gepickelten Blößen, beispielsweise Rindsblößen mit einer Spaltstärke von 1,5 bis 4 mm, oder Fellblößen, beispielsweise Schaffellblößen, bei einem pH-Wert von 2 bis 7, insbesondere 2,5 bis 4, und einer Temperatur von 15 bis 50°, insbesondere 25 bis 45°C, während eines Zeitraumes von 3 bis 20 Stunden mit einer wäßrigen Lösung oder Dispersion der Carbonylverbindung I behandelt werden. Die Behandlung erfolgt beispielsweise durch Walken in einem Faß. Die benötigte Menge an Carbonylverbindung I beträgt normalerweise, bezogen auf das Blößengewicht, 2 bis 30 Gew.-%, insbesondere 5 bis 20 Gew.-%. Die Flottenlänge, d.h. das prozentuale Gewichtsverhältnis der Behandlungsflotte zur Ware, beträgt üblicherweise 30 bis 200 % bei Blößen und 100 bis 2000 % bei Fellblößen, jeweils bezogen auf das Blößengewicht.The tanning process according to the invention is outstandingly suitable for tanning alone and pretanning skins and skins in an aqueous liquor. Appropriately, the procedure here is such that the pickled pelts, for example cowhide pelts with a gap thickness of 1.5 to 4 mm, or pelts, for example sheepskin pelts, at a pH of 2 to 7, in particular 2.5 to 4, and one Temperature of 15 to 50 °, in particular 25 to 45 ° C, are treated with an aqueous solution or dispersion of the carbonyl compound I for a period of 3 to 20 hours. The treatment takes place, for example, by drumming in a barrel. The required amount of carbonyl compound I is normally 2 to 30% by weight, in particular 5 to 20% by weight, based on the pelt weight. The fleet length, i.e. the percentage weight ratio of the treatment liquor to the goods is usually 30 to 200% for the bare and 100 to 2000% for the bare, in each case based on the bare weight.

Nach erfolgter Behandlung wird das Leder bzw. Fell üblicherweise auf einen pH-Wert von 4 bis 8, insbesondere 5 bis 7, eingestellt, wozu man beispielsweise Magnesiumoxid, Natriumcarbonat oder Natriumhydrogencarbonat verwendet, gegebenenfalls mit weiteren Gerbstoffen behandelt und nach Abschluß des Gerbeprozesses gewünschtenfalls gefärbt und gefettet.After the treatment, the leather or fur is usually adjusted to a pH of 4 to 8, in particular 5 to 7, for which purpose magnesium oxide, sodium carbonate or sodium hydrogen carbonate is used, optionally treated with further tanning agents and, if desired, dyed after the tanning process has ended and greased.

Das erfindungsgemäße Gerbeverfahren eignet sich ebenfalls in hervorragender Weise zum Mitgerben von Blößen und Fellblößen zusammen mit den Gerbstoffen der Hauptgerbung, welche beispielsweise eine Chrom- oder eine Aluminiumgerbung sein kann. In diesem Fall werden die Arbeitsbedingungen bezüglich pH-Wert, Temperatur und Dauer der Behandlung auf die Anforderungen der Hauptkomponenten der Gerbung eingestellt, das gleiche gilt für die Behandlungsapparatur und die Flottenlänge sowie für die Nachbehandlung. Die benötigte Menge an Carbonylverbindung I beträgt hierbei normalerweise, bezogen auf das Blößengewicht, 0,1 bis 20 Gew.-%, insbesondere 0,5 bis 15 Gew.-%.The tanning process according to the invention is also outstandingly suitable for tanning bare and pelted skin together with the tanning agents of the main tanning process, which can be, for example, chrome or aluminum tanning. In this case, the working conditions regarding pH, temperature and duration of the treatment are adjusted to the requirements of the main components of the tanning, the same applies to the Treatment equipment and the length of the liquor as well as for post-treatment. The amount of carbonyl compound I required is normally 0.1 to 20% by weight, in particular 0.5 to 15% by weight, based on the pelt weight.

Das erfindungsgemäße Gerbeverfahren eignet sich ebenfalls in hervorragender Weise zum Nachgerben von bereits gegerbtem Leder und Fell, beispielsweise Chromleder, in wäßriger Flotte. Es wird in der Regel so durchgeführt, daß man die gepickelten Blößen und Felle, beispielsweise Rindsblößen mit Spaltstärken von 1,5 bis 4 mm, mit beispielsweise einem üblichen chromhaltigen Gerbstoff wie einem Chrom(III)-Salz, z.B. Chrom(III)-Sulfat, in an sich bekannter Weise gerbt, die so erhaltenen vorgegerbten Häute (bei Chromgerbung "Wetblues") entsäuert und bei einem pH-Wert von 2 bis 7, insbesondere 2,5 bis 4, und bei Temperaturen von 15 bis 50°C, insbesondere 25 bis 45°C, während eines Zeitraumes von 1 bis 12 Stunden mit einer wäßrigen Lösung oder Dispersion der Carbonylverbindung I behandelt. Diese Behandlung erfolgt beispielsweise durch Walken in einem Faß. Die benötigte Menge an Carbonylverbindung I beträgt normalerweise, bezogen auf das Falzgewicht des Leders, 2 bis 30 Gew.-%, insbesondere 5 bis 20 Gew.-%. Die Flottenlänge beträgt üblicherweise 30 bis 200 % bei Blößen und 100 bis 2000 % bei Fellblößen, jeweils bezogen auf das Falzgewicht des Leders.The tanning process according to the invention is also outstandingly suitable for retanning leather and fur which has already been tanned, for example chrome leather, in an aqueous liquor. It is usually carried out in such a way that the pickled pelts and skins, for example cowhide pelts with a gap thickness of 1.5 to 4 mm, are used, for example, with a customary chromium-containing tanning agent such as a chromium (III) salt, e.g. Chromium (III) sulfate, tanned in a manner known per se, the pretanned skins obtained in this way (in the case of chrome tanning "wet blues") deacidified and at a pH of 2 to 7, in particular 2.5 to 4, and at temperatures of 15 to 50 ° C, in particular 25 to 45 ° C, treated with an aqueous solution or dispersion of the carbonyl compound I for a period of 1 to 12 hours. This treatment takes place, for example, by drumming in a barrel. The amount of carbonyl compound I required, based on the shaved weight of the leather, is normally 2 to 30% by weight, in particular 5 to 20% by weight. The liquor length is usually 30 to 200% for bare and 100 to 2000% for bare, each based on the fold weight of the leather.

Nach und erforderlichenfalls auch vor der Behandlung wird das Leder bzw. Fell üblicherweise auf einen pH-Wert von 3 bis 5 eingestellt, wozu man beispielsweise Magnesiumoxid oder eine organische Säure wie Ameisensäure oder deren Salze verwendet, und nach der Behandlung gewünschtenfalls gefärbt und gefettet.After and, if necessary, also before the treatment, the leather or fur is usually adjusted to a pH of 3 to 5, for which purpose magnesium oxide or an organic acid such as formic acid or its salts are used, and, if desired, dyed and greased after the treatment.

Das erfindungsgemäß nachgegerbte Leder oder Fell kann vor der Nachgerbung mit der Carbonylverbindung I zusätzlich mit anderen Gerbstoffen wie Polymergerbstoffen oder Syntanen behandelt worden sein. Auch kann die Carbonylverbindung I gleichzeitig mit derartigen zusätzlichen Gerbemitteln, beispielsweise in der Hauptgerbung, eingesetzt werden.The leather or fur retanned according to the invention may also have been treated with other tanning agents, such as polymer tanning agents or syntans, before retanning with the carbonyl compound I. The carbonyl compound I can also be used simultaneously with such additional tanning agents, for example in main tanning.

Als zusätzliche oder gleichzeitig eingesetzte Gerbstoffe kommen alle üblichen Mittel mit Gerbwirkung auf Blößen oder Fellblößen in Betracht. Eine umfassende Abhandlung derartiger Gerbstoffe findet sich beispielsweise in Ullmanns Encyklopädie der technischen Chemie, 3. Auflage, 11. Band, Seiten 585 bis 612 (1960). Einzeln zu erwähnende Gerbstoffklassen sind die mineralischen Gerbstoffe, z.B. Chrom-, Aluminium-, Zink- und Zirkoniumsalze, die synthetischen Gerbstoffe wie die bereits oben genannten Polymergerbstoffe und Syntane, und die vegetabilischen (pflanzlichen) Gerbstoffe.As additional or simultaneously used tanning agents, all usual agents with tanning effects on bare or fur bare are considered. A comprehensive treatment of such tannins can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 3rd edition, 11th volume, pages 585 to 612 (1960). Tannin classes to be mentioned individually are the mineral tannins, for example chromium, aluminum, zinc and zirconium salts, the synthetic tannins such as the polymer tannins and syntans already mentioned above, and the vegetable (vegetable) tannins.

Beim erfindungsgemäßen Gerbeverfahren entstehen Leder und Pelze, die im Vergleich zu den mit bisher bekannten Aldehydgerbstoffen wie Glutardialdehyd erhaltenen Erzeugnissen neben einem vollen und sehr weichen Griff und neben hohen Schrumpfungstemperaturen eine deutlich verbesserte Reiß- und Zugfestigkeit aufweisen. Zudem weisen die erfindungsgemäß gegerbten Leder und Felle keine störende gelbe Farbe mehr auf.In the tanning process according to the invention, leather and furs are produced which, in comparison to the products obtained with previously known aldehyde tannins such as glutardialdehyde, have not only a full and very soft feel and, in addition to high shrinking temperatures, but also a significantly improved tear and tensile strength. In addition, the leather and skins tanned according to the invention no longer have a disturbing yellow color.

Ein weiterer Vorteil des erfindungsgemäßen Gerbeverfahrens ist die geringe Flüchtigkeit der eingesetzten Carbonylverbindung I, was sich beispielsweise auf die Einsatzmenge dieser Gerbstoffe auswirkt, welche nur verhältnismäßig gering zu sein braucht. Weiterhin stellt die Carbonylverbindung I in gewissem Sinne einen Universalgerbstoff dar, da sie mit allen anderen üblichen Gerbstoffen kombiniert werden kann und sowohl für die Allein-, die Vor-, die Mit- als auch für die Nachgerbung einsetzbar ist.Another advantage of the tanning process according to the invention is the low volatility of the carbonyl compound I used, which has an effect, for example, on the amount of these tanning agents used, which need only be relatively low. Furthermore, the carbonyl compound I is, in a sense, a universal tanning agent since it can be combined with all other customary tanning agents and can be used both for the sole, the pre, the co-tanning and for the retanning.

BeispieleExamples Beispiel 1example 1 Alleingerbung von Rindsblößen mit 3-OxaglutardialdehydSolitary tantring with 3-oxaglutardialdehyde

Gut entkälkte und gepickelte Rindsblöße mit einer Spaltstärke von 2 mm wurde bei einer Flottenlänge von 140 % mit 5 Gew.-% 3-Oxaglutardialdehyd, bezogen auf das Spaltgewicht der Blöße, versetzt und 3 Stunden bei 40°C und einem pH-Wert von ca. 2,8 im Faß gewalkt. Danach wurde mit Magnesiumoxid ein pH-Wert von 5,8 bis 6,0 eingestellt. Nach kurzem Spülen wurde das Leder wie üblich fertiggestellt.Well descaled and pickled bark with a gap thickness of 2 mm was mixed with 5% by weight of 3-oxaglutardialdehyde, based on the gap weight of the pelt, at a liquor length of 140% and 3 hours at 40 ° C and a pH value of approx 2.8 Tumbled in barrel. A pH of 5.8 to 6.0 was then set using magnesium oxide. After a short rinse, the leather was finished as usual.

Man erhielt ein weißes Leder mit einer Schrumpfungstemperatur von ca. 85°C, welches sehr weich und griffig war.A white leather with a shrinking temperature of approx. 85 ° C. was obtained, which was very soft and easy to grip.

Beispiel 2Example 2 Nachgerbung von Chromrindleder mit 3-OxaglutardialdehydRetanning of chrome cowhide with 3-oxaglutardialdehyde

Ein in üblicher Weise hergestelltes Rindwetblue der Falzstärke 1,5 mm wurde bei einer Flottenlänge von 100 % mit 2,5 Gew.-% 3-Oxaglutardialdehyd, bezogen auf das Falzgewicht des Leders, versetzt und 1,5 Stunden bei 40°C und einem pH-Wert von ca. 3,4 im Faß gewalkt. Danach wurde mit einer Mischung aus 1 Gew.-% Natriumformiat und 0,5 Gew.-% Natriumhydrogencarbonat, jeweils bezogen auf das Falzgewicht des Leders, auf einen pH-Wert von 4,6 eingestellt.A 1.5 mm thick 3-oxaglutardialdehyde, based on the folding weight of the leather, was added to a beef wetting blue of the folding thickness 1.5 mm with a liquor length of 100%, and 1.5 hours at 40 ° C. and one pH of about 3.4 tumbled in the barrel. The pH was then adjusted to 4.6 using a mixture of 1% by weight sodium formate and 0.5% by weight sodium hydrogen carbonate, based in each case on the shaved weight of the leather.

Nach anschließender Färbung mit einem üblichen Lederfarbstoff, Fettung mit einem üblichen Licker und üblicher Fertigstellung resultierte ein weiches, volles und griffiges Leder.After subsequent dyeing with a customary leather dye, greasing with a customary licker, and customary completion, the result was a soft, full and non-slip leather.

Beispiel 3Example 3 Mitgerbung (Vorgerbung) mit 3-Oxaglutardialdehyd bei der Aluminiumgerbung von RindsblößenCo-tanning (pre-tanning) with 3-oxaglutardialdehyde in the aluminum tanning of bare bare skin

Gut entkälkte und gepickelte Rindsblöße mit einer Spaltstärke von 2 mm wurde bei einer Flottenlänge von 140 % mit 5 Gew.-% 3-Oxaglutardialdehyd, bezogen auf das Spaltgewicht der Blöße, in drei Portionen in jeweils einstündigem Abstand versetzt und insgesamt 3 Stunden bei 40°C bei einem pH-Wert von 3,2 im Faß gewalkt. Danach wurden 8 Gew.-% Aluminiumsulfat (kristallwasserfrei), bezogen auf das Spaltgewicht der Blöße, hinzugegeben und die Behandlung wurde weitere 4 Stunden bei derselben Temperatur fortgesetzt. Anschließend wurde mit Natriumacetat wieder ein pH-Wert von ca. 3,2 eingestellt. Nach einer weiteren Stunde Walken bei 40°C wurde mit Magnesiumoxid der pH-Wert auf 4,5 bis 5,0 erhöht und das Leder wie üblich fertiggestellt.Well decalcified and pickled bovine pelts with a gap thickness of 2 mm were mixed with 3% oxaglutardialdehyde, based on the gap weight of the pelts, in three portions at an hourly interval and a total of 3 hours at 40 ° with a liquor length of 140% C drummed at a pH of 3.2 in the barrel. Then 8% by weight of aluminum sulfate (free of water of crystallization), based on the gap weight of the bare, was added and the treatment was continued for a further 4 hours at the same temperature. A pH of about 3.2 was then adjusted again with sodium acetate. After a further hour of walking at 40 ° C, the pH was raised to 4.5 to 5.0 with magnesium oxide and the leather was finished as usual.

Man erhielt ein weiches und griffiges Leder mit einer Schrumpfungstemperatur von ca. 90°C.A soft and non-slip leather with a shrinking temperature of approx. 90 ° C. was obtained.

Beispiel 4Example 4 Alleingerbung von Schaffellblöße mit 3-OxaglutardialdehydSolo tanning of sheepskin bare with 3-oxaglutardialdehyde

Übliche Schaffellblöße wurde bei einer Flottenlänge von 1500 % mit 60 Gew.-% Kochsalz, 12 Gew.-% üblicher Fettungsmittel und 18 Gew.-% 3-Oxaglutardialdehyd, jeweils bezogen auf das Trockengewicht der Fellblöße, versetzt und 4 Stunden bei 35°C und einem pH-Wert von 3,2 im Faß gewalkt. Danach wurde mit Natriumcarbonat ein pH-Wert von 5,5 eingestellt.Usual sheepskin pelt was mixed with 60% by weight of table salt, 12% by weight of common fatliquor and 18% by weight of 3-oxaglutardialdehyde, based in each case on the dry weight of the pelts, at a liquor length of 1500% and 4 hours at 35 ° C. and a pH of 3.2 in the barrel. Then a pH of 5.5 was set with sodium carbonate.

Nach abschließendem Trocknen, Spänen, Stollen, Rauhen und Scheren wurde ein Fell mit einer Schrumpfungstemperatur von 70°C erhalten.After drying, shavings, tunnels, roughing and shearing, a fur with a shrinking temperature of 70 ° C. was obtained.

Claims (1)

  1. A process for self-tanning, pretanning and assist tanning leather pelts and skin pelts and for retanning leather and skin, which comprises using for this purpose the compound of the formula I
    Figure imgb0003
     or an acetal thereof.
EP92903337A 1991-01-29 1992-01-21 Method of self-tanning, pre-tanning and co-tanning skins and hides and for retanning leather and hides Expired - Lifetime EP0569410B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4102545 1991-01-29
DE4102545A DE4102545A1 (en) 1991-01-29 1991-01-29 METHOD FOR GELING, PRELIMINATING AND GIVING BARE AND FUR BLOSSES AND FOR LEAVING LEATHER AND FUR
PCT/EP1992/000116 WO1992013105A1 (en) 1991-01-29 1992-01-21 Method of self-tanning, pre-tanning and co-tanning skins and hides and for retanning leather and hides

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EP0569410B1 true EP0569410B1 (en) 1995-03-29

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DE59303163D1 (en) * 1992-01-28 1996-08-14 Ciba Geigy Ag Process for pimples and tanning skin bones
DE19906190A1 (en) * 1999-02-15 2000-08-17 Boehme Chem Fab Kg Tanning process
BR9901948B1 (en) * 1999-04-30 2008-11-18 leather tanning process with carbonic compounds.
EP2055481B1 (en) * 2007-10-18 2017-08-16 Bobst Italia S.P.A. Doctor blade assembly and a method for allowing different inks to be used
ITUB20152180A1 (en) * 2015-07-14 2017-01-14 Db Patents Ltd IMPROVED METHOD TO SKIN ANIMAL SKIN.
DE102016004192A1 (en) * 2016-04-06 2017-10-12 Tfl Ledertechnik Gmbh Tanning composition and method based on an acetal of an aldehyde tanning agent
DE102016004191A1 (en) * 2016-04-06 2017-10-12 Tfl Ledertechnik Gmbh Tanning composition and method based on an acetal of an aldehyde tanning agent
EP3529382B1 (en) * 2016-10-18 2020-06-10 Stahl International B.V. Processes for making leather

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US2351338A (en) * 1943-08-02 1944-06-13 American Cyanamid Co Tanning with d'-methoxy-d-hydroxymethyl diglycollic aldehyde
US2516283A (en) * 1947-03-20 1950-07-25 Adolph H Winheim Resin impregnation of a dialdehyde tanned hide
BE593301A (en) * 1959-07-24
DE1769059A1 (en) * 1968-03-28 1971-08-19 Basf Ag Process for the production of leather
DE2137603A1 (en) * 1971-07-27 1973-02-08 Diamalt Ag PRODUCTS FOR TANNING SKIN AND FUR
DE2549527C3 (en) * 1975-11-05 1980-03-20 Basf Ag, 6700 Ludwigshafen Process for the production of leather
BR8605597A (en) * 1985-11-13 1987-08-18 Cassella Farbwerke Mainkur Ag TANINE AND PROCESS FOR OBTAINING AND USING IT

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US5372609A (en) 1994-12-13
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ES2070632T3 (en) 1995-06-01
WO1992013105A1 (en) 1992-08-06
JPH06504800A (en) 1994-06-02

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