EP0408097B1 - Gerbungsverfahren von Pelzen - Google Patents

Gerbungsverfahren von Pelzen Download PDF

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Publication number
EP0408097B1
EP0408097B1 EP90201637A EP90201637A EP0408097B1 EP 0408097 B1 EP0408097 B1 EP 0408097B1 EP 90201637 A EP90201637 A EP 90201637A EP 90201637 A EP90201637 A EP 90201637A EP 0408097 B1 EP0408097 B1 EP 0408097B1
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Prior art keywords
bath
hides
tanning
process according
water
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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.)
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EP90201637A
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English (en)
French (fr)
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EP0408097A1 (de
Inventor
Francoise Silvestre
Christine Godawa
Michel Delmas
Antoine Gaset
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.)
CHAMBRE SYNDICALE DE L'INDUSTRIE DU CUIR DE MAZAMET
CHAMBRE SYNDICALE DES PATRONS MEGISSIERS (Syndicat Professionnel)
GACHES CHIMIE SA
Institut National Polytechnique de Toulouse INPT
Original Assignee
CHAMBRE SYNDICALE DE L'INDUSTRIE DU CUIR DE MAZAMET
CHAMBRE SYNDICALE DES PATRONS MEGISSIERS (Syndicat Professionnel)
GACHES CHIMIE SA
Institut National Polytechnique de Toulouse INPT
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Priority to AT90201637T priority Critical patent/ATE93898T1/de
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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
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • C14C9/04—Fixing tanning agents in the leather
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning

Definitions

  • the invention relates to a tanning process for acidified raw hides or waste acidified raw hides; it aims to provide leather of improved qualities, benefiting in particular from better fixation of the tanning agents. It applies in particular to the skins of sheep, cattle, pigs, mestizos, goats (preferentially striped skins but also, if necessary, woolen skins).
  • the process of the invention therefore proposes to carry out a tanning of acidified raw hides (or waste of acidified raw hides) by completely exhausting the tanning baths and obtaining a fixing of the tanning agent capable of preventing any subsequent release.
  • the method of the invention provides a radical solution to the problem of pollution by the discharge of metallic tanning agents such as chromium.
  • metallic tanning agents such as chromium.
  • the hydration rate of the skins is sufficient to swell the fibers evenly over the entire surface, but reduced enough to avoid passage of water through the organic bath.
  • the mineral tanning agent alone in suspension in the organic water-free bath, is attracted to wet skin because of its affinity for water, dissolves in the water of hydration retained by each skin and diffuses to the heart of it evenly. Thus, the dissolution of this tanning agent takes place only inside the skin.
  • the slow basification develops, in a homogeneous manner, the metal agent / protein bonds, so as to obtain a good quality binding, uniform and non-reversible; slow olification of the complexes of metal agents (increase in size) occurs and results in slow crosslinking with the proteins of the skin, which explains the complete absence of salting out.
  • the maximum skin hydration threshold (corresponding to the total water retention limit) depends on the species; for sheep or goat skins, this threshold is 310%.
  • the process of the invention can be carried out with a chromium salt or complex, in particular chromium sulphate.
  • the base is then introduced into the bath so as to increase the pH to a final value between a minimum threshold of 3.9 and a maximum threshold of 4.4 corresponding to the appearance of the phenomenon of tense skin. .
  • the base is introduced gradually so as to obtain a rate of basification ⁇ pH ⁇ t less than 0.6 pH unit per hour.
  • the amount of salt or chromium complex or suspended in the bath is advantageously such that the chromium / acidified skin weight ratio is between 0.7% and 1.5%.
  • the process of the invention can also be implemented with other metallic tanning agents, in particular with an aluminum salt or complex, in particular aluminum sulphate.
  • the base is then introduced into the bath so as to increase the pH to a final value between a minimum threshold of 3.5 and a maximum threshold of 3.9 corresponding to the precipitation pH of the aluminum.
  • the base is introduced gradually so as to obtain a rate of basification ⁇ pH ⁇ t less than 0.3 pH unit per hour.
  • the amount of aluminum salt or complex suspended in the bath is advantageously such that the aluminum / acidified skin weight ratio is between 0.3% and 0.8%.
  • the organic bath can be prepared from a compound of the following families (anhydrous or substantially anhydrous): halogenated hydrocarbons in particular 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1-trichloroethane , tetrachlorethylene, dichloromethane; aliphatic hydrocarbons from C6 to C16.
  • families anhydrous or substantially anhydrous: halogenated hydrocarbons in particular 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,1-trichloroethane , tetrachlorethylene, dichloromethane; aliphatic hydrocarbons from C6 to C16.
  • the base is introduced into the bath in the form of a crystallized powder of the following group: sodium bicarbonate, sodium formate, sodium acetate, sodium phthalate, sodium citrate.
  • the final quality of the leathers obtained was improved (flexibility, feel %) by first performing a degreasing of acidified wet skins by putting in the presence of a liquid bath based on trichloro- 1,1,2, trifluoro-1,2,2 ethane, free of surfactant.
  • This degreasing allows a satisfactory reduction in the quantities of fat contained in the skin, the fatty residue remaining uniformly distributed in the skins.
  • such a degreasing takes place in the absence of surfactants, which avoids polluting discharges of these compounds.
  • the hydration rate of the skins is adjusted to 250% (based on the dry weight of the skin) by rewetting using a brine bath at 8 ° Baumé for about 1 hour at room temperature.
  • the final pH of the water retained in the skins is 4.15.
  • the skins are removed from the solvent bath and left to stand for 48 hours (extended skins stacked on top of each other).
  • the organic bath is then analyzed by direct observation, atomic absorption and elementary chemical analysis. It is found that it is rigorously free of water, tanning agents and basification products. This bath is recovered and recycled.
  • the tanned skins obtained are subject to a visual analysis and a chromium analysis after the rest period: the chromium is uniformly distributed and fixed, the skins having a shrinkage temperature greater than 100 ° C., which characterizes good tanning quality. These skins then undergo a traditional procedure in an aqueous medium of food, dyeing and drying, during which no release of Cr is observed (assay by atomic absorption of the element in successive baths).
  • the organic bath is free of water, tanning agents and basification products.
  • the final pH of the water retained in the skins is 5.
  • the skins are removed from the solvent bath and left to stand for 48 hours.
  • the organic bath is free of water, tanning and basification products.
  • the finished leather obtained is of poor quality. Its appearance and flexibility are not correct due to a phenomenon of tightness (tightening of the skin fibers).
  • the final pH of the water retained in the skins is 3.6.
  • the skins are removed from the solvent bath and left to stand for 48 hours.
  • the organic bath contains a small amount of water in which a small fraction of tanning products is dissolved, resulting in a non-total exhaustion of the tanning bath (exhaustion rate of the order of 80%).
  • the skins are placed in the presence of 1,1,2-trichloro-1,1,2-trifluoroethane in which 6% chromium salt is in suspension. After one hour of stirring, basification is carried out by simultaneously and gradually introducing 1% of sodium formate and 2% of sodium hydrogencarbonate for 1 hour 30 minutes.
  • the final pH of the water retained in the skins is 4.01.
  • the skins are removed from the solvent bath and left to stand for 48 hours.
  • the organic bath is free of water, agents for tanning basification products.
  • the leather obtained is not of very good quality. Its appearance and flexibility are not correct due to a slight phenomenon of tension.
  • the skins are placed in the presence of 20 liters of trichloro-1,1,2 trifluoro-1,2,2 ethane in which 6% chromium salt is in suspension. After one hour of stirring, the basification is carried out by introducing 1% sodium formate at one time. Stirring is continued for 1 hour and then 2% sodium hydrogen carbonate is added all at once (basification rate equal to 2 pH units per hour). The mixture is left to stir for 4 hours. The final pH of the water retained in the skins is 4.12. The skins are removed from the solvent bath and left to stand for 48 hours.
  • the organic bath is free of water, tanning agents and basifying agents.
  • the skins then undergo a traditional procedure in an aqueous medium of food, dyeing and drying, during which no release of Cr is observed.
  • the skins are put in the presence of 1,12,2 trichloro-1,2,2 trifluoroethane in which 6% chromium salt is in suspension. After one hour of stirring, the basification is carried out by gradually introducing 1% of sodium formate over a period of 1 hour. 0.25% of sodium hydrogen carbonate is then added every half hour for 4 hours. The bases are introduced in the form of powder.
  • the final pH of the water retained in the skins is 4.11.
  • the skins are removed from the bath and they are immediately subjected to an aqueous food, dyeing and drying procedure. During these subsequent steps, there is a significant release of chromium from the skin (10-20%).
  • the finished leather obtained is of poor quality. Hollow skins are obtained, the feel of which is not correct.
  • the final pH of the water retained in the skins is 4.13.
  • the skins are removed from the solvent bath and left to stand for 48 hours.
  • the organic bath is free of water, tanning agents and basifying agents.
  • the final leather is of quality at least equivalent to that obtained by a traditional tanning process.
  • Example 2 The experimental procedure followed is identical to that of Example 1, but the starting point is from wet, acidified and defatted goat skins with a skin hydration rate adjusted to 250% by rewetting with a brine bath. .
  • the final pH of the water retained in the skins is 4.17.
  • the skins are left to stand for 48 hours.
  • the hydration rate of the skins is adjusted to 280% relative to the dry weight by rewetting using a brine bath at 8 ° B for about 1 hour at room temperature. During this operation, the pH is brought from 2.0 to 2.9 by the addition of 1% sodium formate.
  • the skins are placed in the presence of 10 liters of 1,1,1-trichloroethane in which 10% of aluminum salt (sulfate at 8.6% by mass of aluminum element) is in suspension; this corresponds to a weight of 0.86% Al relative to the weights of initial skins.
  • the skins are removed from the solvent bath and left to stand for 48 hours.
  • the organic bath is free of water, tanning agents and basifying agents.
  • Aluminum salting out is not observed during the subsequent operations in an aqueous bath: vegetable retanning, food, dyeing.
  • the finished leather is of quality at least equivalent to that obtained by a traditional tanning process.
  • Example 12 The experimental procedure followed is identical to that of Example 12, but an amount of 0.35% of sodium bicarbonate is added every half hour for 4 hours.
  • the final pH of the water retained in the skins is 4.5 (rate of basification: 0.25 pH unit per hour).
  • the organic bath is free of water, but the presence of a precipitate of aluminum hydroxide in suspension is noted, and the aluminum is not completely fixed on the skin.

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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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Supplying Of Containers To The Packaging Station (AREA)
  • Separation By Low-Temperature Treatments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (12)

  1. Verfahren zum Gerben von angesäuerten Rohhäuten (oder von Abfällen von angesäuerten Rohhäuten), dadurch gekennzeichnet, daß es darin besteht, daß:
    (a) ein flüssiges organisches Bad bereitet wird, das wasserunlöslich und gegenüber der Haut und den mineralischen Gerbstoffen chemisch inert ist,
    (b) im besagten organischen Bad ein mineralischer Gerbstoff auf der Grundlage einer Metallverbindung aufgeschlämmt wird,
    (c) der Hydratisierungsgrad der Häute in einem Bereich eingestellt wird zwischen:
    . einer Untergrenze von 200 % (Wassergewicht bezogen auf das Trockengewicht der Haut), über der alle Fasern der Haut mit 'Wasser imprägniert sind, mit Schaffung einer homogenen Porosität im Kern und an der Oberfläche durch Solvation und Quellen der Fasern,
    . und einer Obergrenze, die der Gesamtspeichergrenze von Wasser in der Struktur der Haut durch hydrophile Affinität der Fasern entspricht,
    (d) die auf diese Weise hydratisierten Häute mit dem organischen, Gerbstoffe enthaltenden Bad in einem Zeitraum, der mindestens 4 Stunden beträgt, in Kontakt gebracht werden, und während dieses Kontaktes langsam eine Base in das Bad hineingegeben wird, die eine basische Stärke kPa zwischen 3,5 und 7 hat, und zwar unter Bedingungen, die geeignet sind, daß ein Hydratisierungsgrad der Häute zwischen den weiter oben genannten Unter- und Obergrenzen beibehalten wird, wob-ei die besagte Base so hineingegeben wird, daß der pH-Wert des in der Haut gespeicherten Wassers bis zu einem Endwert schrittweise gesteigert wird, wobei dieser Endwert liegt zwischen:
    . einer Untergrenze, die der Gesamatvernetzungsgrenze der Metallverbindung entspricht,
    . und einer Obergrenze, die dem Auftreten von Kräuselerscheinungen der Häute oder dem Fällungs-pH-Wert der Metallverbindung in Wasser entspricht,
    (e) die Häute aus dem Bad genommen und sie mindestens 24 Stunden ruhengelassen werden.
  2. Verfahren zum Gerben nach Anspruch 1, dadurch gekennzeichnet, daß
    (b) im organischen Bad ein Chromsalz oder ein Chromkomplex, insbesondere Chromsulfat, aufgeschlämmt wird,
    (d) die Base dem Bad auf eine solche Weise zugegeben wird, daß der pH-Wert bis zu einem Endwert zwischen einer Untergrenze von 3,9 und einer Obergrenze von 4,4, die dem Auftreten der Kräuselerscheinungen der Häute entspricht, angehoben wird.
  3. Verfahren zum Gerben nach Anspruch 2, dadurch gekennzeichnet, daß (b) im organischen Bad eine Menge an Chromsalz oder Chromkomplex aufgeschlämmt wird, die so groß ist, daß das Gewichtsverhältnis zwischen Chrom und angesäuerter Haut zwischen 0,7 % und 1,5 % liegt.
  4. Verfahren nach Anspruch 2 und 3, dadurch gekennzeichnet, daß (d) die Base nach und nach auf eine solche Weise zugegeben wird, daß eine Geschwindigkeit des Basischstellens ΔpH Δt
    Figure imgb0005
     erreicht wird, die kleiner als 0,6 pH-Einheiten pro Stunde ist.
  5. Verfahren zum Gerben nach Anspruch 1, dadurch gekennzeichnet, daß
    (b) im organischen Bad ein Aluminiumsalz oder ein Aluminiumkomplex, insbesondere Aluminiumsulfat, aufgeschlämmt wird,
    (d) die Base dem Bad auf eine solche Weise zugegeben wird, daß der pH-Wert bis zu einem Endwert zwischen einer Untergrenze von 3,5 und einer Obergrenze von 3,9, die dem Fällungs-pH-Wert von Aluminium entspricht, angehoben wird.
  6. Verfahren zum Gerben nach Anspruch 5, dadurch gekennzeichnet, daß im organischen Bad eine Menge an Aluminiumsalz oder Aluminiumkomplex aufgeschlämmt wird, die so groß ist, daß das Gewichtsverhältnis zwischen Aluminium und angesäuerter Haut zwischen 0,3 % und 0,8 % liegt.
  7. Verfahren nach Anspruch 5 und 6, dadurch gekennzeichnet, daß (d) die Base nach und nach auf eine solche Weise zugegeben wird, daß eine Geschwindigkeit des Basischstellens ΔpH Δt
    Figure imgb0006
     erreicht wird, die kleiner als 0,3 pH-Einheiten pro Stunde ist.
  8. Verfahren zum Gerben nach Anspruch 1 bis 7, dadurch gekennzeichnet, daß (a) das organische Bad aus einer wasserfreien Verbindung der folgenden Familien hergestellt wird: Halogenkohlenwasserstoffe, insbesondere Trichlor-1,1,2-trifluor-1,2,2-ethan, Trichlor-1,1,1-ethan, Tetrachlorethylen, Dichlormethan; aliphatische Kohlenwasserstoffe von C₆ bis C₁₆.
  9. Verfahren zum Gerben von Schaf- oder Ziegenhäuten nach Anspruch 1 bis 8, dadurch gekennzeichnet, daß (c) der Hydratisierungsgrad der Häute in einem Bereich eingestellt wird, der zwischen einer Untergrenze von 200 % und einer Obergrenze von 310 % liegt, die der Gesamtspeichergrenze von Wasser in Schaf- oder Ziegenhäuten entspricht.
  10. Verfahren nach Anspruch 1 bis 9, dadurch gekennzeichnet, daß (d) in das Bad eine Base in Form eines kristallisierten Pulvers der folgenden Gruppe eingeführt wird: Natriumbicarbonat, Natriumformiat, Natriumacetat, Natriumphtalat, Natriumcitrat.
  11. Verfahren nach Anspruch 1 bis 10, dadurch gekennzeichnet,daß:
    (d) die Häute mit dem Bad in einem Zeitraum zwischen 6 und 10 Stunden in Kontakt gebracht werden,
    (e) nach dem Herausnehmen die Häute in einem Zeitraum zwischen 24 und 96 Stunden ruhengelassen werden.
  12. Verfahren nach Anspruch 1 bis 11, dadurch gekennzeichnet, daß die feuchten angesäuerten Häute zuvor entfettet wurden, indem sie in ein Flüssigkeitsbad auf der Grundlage von Trichlor-1,1,2-trifluor-1,2,2-ethan, das keine grenzflächenaktiven Stoffe enthält, gegeben wurden.
EP90201637A 1989-07-10 1990-06-22 Gerbungsverfahren von Pelzen Expired - Lifetime EP0408097B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT90201637T ATE93898T1 (de) 1989-07-10 1990-06-22 Gerbungsverfahren von pelzen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8909655A FR2649413B1 (fr) 1989-07-10 1989-07-10 Procede de tannage de peaux
FR8909655 1989-07-10

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EP0408097A1 EP0408097A1 (de) 1991-01-16
EP0408097B1 true EP0408097B1 (de) 1993-09-01

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EP (1) EP0408097B1 (de)
JP (1) JPH03129000A (de)
KR (1) KR910003119A (de)
CN (1) CN1049526A (de)
AT (1) ATE93898T1 (de)
BR (1) BR9003194A (de)
CA (1) CA2020548A1 (de)
CS (1) CS276444B6 (de)
DD (1) DD296506A5 (de)
DE (1) DE69003040D1 (de)
ES (1) ES2045762T3 (de)
FR (1) FR2649413B1 (de)
MA (1) MA21899A1 (de)
PT (1) PT94631B (de)
TR (1) TR25083A (de)
YU (1) YU131890A (de)

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IN2014DE00085A (de) * 2014-01-13 2015-07-17 Council Scient Ind Res
CN105525047B (zh) * 2016-02-19 2017-12-26 北京泛博化学股份有限公司 一种麝鼠皮的铝油鞣制方法
CN106435053B (zh) * 2016-12-12 2018-10-19 温州大学 一种用于皮革无铬鞣鞣制工序的络合剂及其制备方法和应用

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AR212025A1 (es) * 1975-07-19 1978-04-28 Boehme Chem Fab Kg Procedimiento de preparacion de cueros y pieles
SU821489A1 (ru) * 1978-11-28 1981-04-15 Восточно-Сибирский Технологическийинститут Способ дублени шкур

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PT94631B (pt) 1996-01-31
ES2045762T3 (es) 1994-01-16
CS276444B6 (en) 1992-05-13
YU131890A (sh) 1992-07-20
EP0408097A1 (de) 1991-01-16
DE69003040D1 (de) 1993-10-07
ATE93898T1 (de) 1993-09-15
FR2649413A1 (fr) 1991-01-11
MA21899A1 (fr) 1991-04-01
DD296506A5 (de) 1991-12-05
BR9003194A (pt) 1991-08-27
CN1049526A (zh) 1991-02-27
CA2020548A1 (fr) 1991-01-11
FR2649413B1 (fr) 1993-05-28
PT94631A (pt) 1991-03-20
TR25083A (tr) 1992-11-01
JPH03129000A (ja) 1991-05-31
KR910003119A (ko) 1991-02-26

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