EP0349892A2 - Tanning method presenting a high chrome exhaustion of the tanning bath - Google Patents

Tanning method presenting a high chrome exhaustion of the tanning bath Download PDF

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Publication number
EP0349892A2
EP0349892A2 EP89111743A EP89111743A EP0349892A2 EP 0349892 A2 EP0349892 A2 EP 0349892A2 EP 89111743 A EP89111743 A EP 89111743A EP 89111743 A EP89111743 A EP 89111743A EP 0349892 A2 EP0349892 A2 EP 0349892A2
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Prior art keywords
tanning
weight
chromium
blunted
aldehyde
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German (de)
French (fr)
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EP0349892A3 (en
EP0349892B1 (en
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Hans-Herbert Dr. Friese
Emil Ruscheinsky
Rudolf Dr. Zauns
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds

Definitions

  • the invention relates to a chrome tanning process with which complete tanning is achieved and with which the chrome broths are practically completely exhausted.
  • the object of the invention was therefore to develop a chrome tanning process with which an even higher consumption of the tanning liquors is achieved in comparison with the known processes.
  • the invention is based on the surprising finding that the degree of exhaustion of tanning liquors is substantially improved if the tanning liquor is pre-blunted with basic agents in the presence of aldehyde and / or keto acids.
  • the invention accordingly relates to a process for chrome tanning with high chromium exhaustion of the tanning liquors, which is characterized in that tanned pelts pickled with formic acid and / or sulfuric acid are tanned with 0.5 to 12 percent by weight chromium III salts, based on the pelt weight
  • Pre-blunting is preferably carried out in the presence of glyoxylic acid.
  • the process according to the invention is distinguished by a very high degree of exhaustion of the chrome tanning agents, with the result that the concentration of the chromium III salts in the tanning liquor can be significantly reduced in comparison with known processes.
  • the residual chromium content of the exhausted tanning liquors is reduced to values less than 0.2 g Cr2O3 per liter of tanning liquor.
  • the quality of the wetblue which are subjected to the tanning process according to the invention is significantly improved.
  • the scar is finer and the wet blue color is lighter than in conventional tanning processes, in which the blunting is carried out in the presence of dicarboxylic acids.
  • the tanning of pelts piqued with formic acid and / or sulfuric acid is masked in a manner known per se with chromium III salts, for example with chromium III sulfates, basic chromium III sulfates and / or with organic acids such as formic acid, acetic acid Chromium III salts carried out in a pimple bath or in a new fleet.
  • chromium III salts for example with chromium III sulfates, basic chromium III sulfates and / or with organic acids such as formic acid, acetic acid Chromium III salts carried out in a pimple bath or in a new fleet.
  • chromium III salts for example with chromium III sulfates, basic chromium III sulfates and / or with organic acids such as formic acid, acetic acid Chromium III salts carried out in a pimple bath or in a new fleet.
  • the tanning liquor 0.5 to 3.0% by weight, based on pelt weight, of electrolyte-resistant fatliquors, for example sulfited fish oil, or 0.5 to 3.0% by weight, based on pelvic weight, mixtures of electrolyte-resistant fatliquoring agents and surfactants, such as alkyl sulfates containing 12-18 carbon atoms.
  • electrolyte-resistant fatliquors for example sulfited fish oil
  • surfactants such as alkyl sulfates containing 12-18 carbon atoms.
  • the tanning liquors preferably 0.3 to 0.7% by weight, based on the pelt weight, of basifying agents in the presence of preferably 0.3 to 4.0% by weight, particularly preferably 0.5 to 2.0% by weight .-%, based in each case on pelt weight, aldehyde and / or keto acids, such as pyruvic acid and / or glyoxylic acid.
  • Suitable base agents are, for example, magnesium oxide, dolomite, alkali carbonates, alkali bi carbonates and / or alkaline earth carbonates. However, magnesium oxide is preferably used.
  • the tanning liquor is dulled to pH values between 4.2 and 5.5, preferably to pH values between 4.5 and 5.0, with 0.5 to 3.0% by weight, preferably with 1.0 to 2.0 wt .-%, each based on pelt weight, carried out alkali aluminum silicates.
  • the alkali aluminum silicates preferably sodium aluminum silicates, are added to the tanning liquors either in solid form or in the form of aqueous dispersions.
  • the alkali aluminum silicates are accessible by known processes, for example by the processes written in DE-OS 27 32 217.
  • the temperature of the tanning liquor after the addition of the alkali aluminum silicates is between 30 and 50 ° C., preferably between 35 and 45 ° C.
  • all skin types for example of beef, pork, goat or sheep, can be tanned.
  • Example 2 (comparison: DE-OS 35 16 842)
  • Chromium oxide content of the remaining liquors is a Chromium oxide content of the remaining liquors:

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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

Chromgerbung mit hoher Chromauszehrung der Gerbflotten wird dadurch erreicht daß man mit Ameisensäure und/oder Schwefelsäure gepickelte Blößen mit Chrom III-Salzen gerbt, die Gerbflotte mit Basifizierungsmitteln in Gegenwart von Aldehyd- und/oder Ketosäuren auf einen pH-Wert zwischen 3,6 und 4,3 vorabstumpft und anschließend mit Alkali-Aluminiumsilikaten auf einen pH-Wert zwischen 4,2 und 5,5 abstumpft.Chromium tanning with high chromium exhaustion of the tanning liquors is achieved by tanning pelts pickled with formic acid and / or sulfuric acid with chromium III salts, the tanning liquor with base agents in the presence of aldehyde and / or keto acids to a pH between 3.6 and 4 , 3 blunted and then blunted with alkali aluminum silicates to a pH between 4.2 and 5.5.

Description

Die Erfindung betrifft ein Chromgerbverfahren, mit dem man eine vollständige Durchgerbung erreicht und mit dem die Chrombrühen praktisch restlos ausgezehrt werden.The invention relates to a chrome tanning process with which complete tanning is achieved and with which the chrome broths are practically completely exhausted.

Bei der Herstellung chromgegerbter Leder nach herkömmlichen Ver­fahren werden je nach Arbeitsweise etwa 70 bis 80 % der angebote­nen Chrommenge in der Haut fixiert. Die restlichen 20 bis 30 % verbleiben in der sogenannten Restflotte, die nur mit großem Auf­wand gereinigt werden kann.In the production of chrome-tanned leather using conventional methods, around 70 to 80% of the amount of chromium offered is fixed in the skin, depending on the working method. The remaining 20 to 30% remain in the so-called residual liquor, which can only be cleaned with great effort.

Sowohl aus ökologischen als auch aus ökonomischen Gründen hat es in der Vergangenheit nicht an Versuchen gefehlt, die Chrom­aufnahme der Haut zu verbessern und die für eine kochgare Ger­bung notwendige Chrommenge zu reduzieren.In the past, for ecological as well as economic reasons, there has been no lack of attempts to improve the chromium absorption of the skin and to reduce the amount of chromium required for cookable tanning.

Zur Verbesserung der Chromauszehrung wurden beispielsweise in "Das Leder" 26, 21 bis 31 (1975) Recyclingverfahren vorge­schlagen, bei denen die Restflotten nach Zusatz von frischen Chromsalzen erneut zur Gerbung oder nach Ausfällung und Auf­arbeitung zu Chromgerbstoffen wieder verwendet werden. Der Nachteil dieser Verfahren besteht jedoch darin, daß sich Lederfasern und unerwünschte Salze in den Gerbflotten an­reichern und somit keine optimalen Gerbresultate mehr zulassen. Darüber hinaus sind diese Verfahren sehr umständlich in der Durchführung.To improve chromium exhaustion, recycling processes have been proposed, for example, in "Das Leder" 26 , 21 to 31 (1975), in which the remaining liquors are used again for tanning after the addition of fresh chromium salts or after precipitation and processing to give chrome tannins. The disadvantage of this process, however, is that leather fibers and unwanted salts accumulate in the tanning liquors and therefore no longer permit optimal tanning results. In addition, these procedures are very cumbersome to implement.

In "Das Leder" 34, 89 bis 93 (1983) wird beschrieben, daß durch Verwendung von Magnesiumoxyd und Dicarbonsäuren zur Vorab­stumpfung und von Natrium-Aluminiumsilikaten zur Endab­stumpfung eine gute Auszehrung der Chromgerbflotte erzielt wird. Weiterhin ist aus DE-OS 35 16 842 bekannt, daß die Verwendung von Glyoxylsäure im Pickel zu einer Verbesserung der Chromauszehrung in Gerbflotten führt. Mit beiden Verfahren läßt sich jedoch kein zufriedenstellend hoher Auszehrungsgrad der Chromgerbflotten erreichen.In "Das Leder" 34 , 89 to 93 (1983) it is described that the use of magnesium oxide and dicarboxylic acids for pre-dulling and sodium aluminum silicates for final dulling results in a good exhaustion of the chrome tanning liquor. It is also known from DE-OS 35 16 842 that the use of glyoxylic acid in the pimple leads to an improvement in the chromium exhaustion in tanning liquors. However, with both processes it is not possible to achieve a satisfactorily high level of chromium tanning liquor consumption.

Die Aufgabe der Erfindung bestand daher in der Entwicklung eines Chromgerbverfahrens, mit dem im Vergleich zu den bekannten Ver­fahren eine noch höhere Auszehrung der Gerbflotten erreicht wird.The object of the invention was therefore to develop a chrome tanning process with which an even higher consumption of the tanning liquors is achieved in comparison with the known processes.

Die Erfindung geht von der überraschenden Feststellung aus, daß der Auszehrungsgrad von Gerbflotten wesentlich verbessert wird, wenn die Vorabstumpfung der Gerbflotte mit Basifizierungsmitteln in Gegenwart von Aldehyd- und/oder Ketosäuren durchgeführt wird.The invention is based on the surprising finding that the degree of exhaustion of tanning liquors is substantially improved if the tanning liquor is pre-blunted with basic agents in the presence of aldehyde and / or keto acids.

Gegenstand der Erfindung ist demzufolge ein Verfahren zur Chromgerbung mit hoher Chromauszehrung der Gerbflotten, welches dadurch gekennzeichnet ist, daß man mit Ameisensäure und/oder Schwefelsäure gepickelte Blößen mit 0,5 bis 12 Ge­wichtsprozent Chrom-III-Salzen, bezogen auf Blößengewicht, gerbt, die Gerbflotte mit Basifizierungsmitteln in Gegenwart von Aldehyd- und/oder Ketosäuren auf einen pH-Wert zwischen 3,6 und 4,3 vorabstumpft und anschließend mit Alkali-Aluminiumsili­katen auf einen pH-Wert von 4,2 bis 5,5 abstumpft. Vorzugsweise wird die Vorabstumpfung in Gegenwart von Glyoxylsäure durchgeführt.The invention accordingly relates to a process for chrome tanning with high chromium exhaustion of the tanning liquors, which is characterized in that tanned pelts pickled with formic acid and / or sulfuric acid are tanned with 0.5 to 12 percent by weight chromium III salts, based on the pelt weight Pre-dull tanning liquor with base agents in the presence of aldehyde and / or keto acids to a pH between 3.6 and 4.3 and then blunted to a pH of 4.2 to 5.5 with alkali aluminum silicates. Pre-blunting is preferably carried out in the presence of glyoxylic acid.

Das erfindungsgemäße Verfahren zeichnet sich durch einen sehr hohen Auszehrungsgrad der Chromgerbstoffe aus, mit der Folge, daß die Konzentration der Chrom-III-Salze in der Gerbflotte im Vergleich zu bekannten Verfahren deutlich verringert werden kann. Der Restchromgehalt der ausgezehrten Gerbflotten wird auf Werte kleiner 0,2 g Cr₂O₃ pro Liter Gerbflotte reduziert. Die Qualität der wetblue, die dem erfindungsgemäßen Gerbprozeß un­terworfen werden, ist deutlich verbessert. Das Narbenbild ist feiner und die wetblue-Farbe heller als bei herkömmlichen Gerb­verfahren, bei denen die Verabstumpfung in Gegenwart von Dicar­bonsäuren durchgeführt wird.The process according to the invention is distinguished by a very high degree of exhaustion of the chrome tanning agents, with the result that the concentration of the chromium III salts in the tanning liquor can be significantly reduced in comparison with known processes. The residual chromium content of the exhausted tanning liquors is reduced to values less than 0.2 g Cr₂O₃ per liter of tanning liquor. The quality of the wetblue which are subjected to the tanning process according to the invention is significantly improved. The scar is finer and the wet blue color is lighter than in conventional tanning processes, in which the blunting is carried out in the presence of dicarboxylic acids.

Die Gerbung von mit Ameisensäure und/oder Schwefelsäure gepik­kelten Blößen wird in an sich bekannter Weise mit Chrom-III-­Salzen, beispielsweise mit Chrom-III-Sulfaten, basischen Chrom-­III-Sulfaten und/oder mit organischen Säuren wie Ameisensäure, Essigsäure, maskierten Chrom-III-Salzen im Pickelbad oder in neu­er Flotte durchgeführt. Es werden 0,5 bis 12 Gew.-%, vorzugswei­se 3 bis 6 Gew.-%, jeweils bezogen auf Blößengewicht, Chrom-III-­Salze eingesetzt. In der Gerbflotte können 0,5 bis 3,0 Gew.-%, bezogen auf Blößengewicht, elektrolytbeständige Fettungsmittel, beispielsweise sulfitiertes Fischöl oder 0,5 bis 3,0 Gew.-%, be­zogen auf Blößengewicht, Mischungen aus elektolytbeständigen Fet­tungsmitteln und Tensiden, wie Alkylsulfate mit 12-18 C-Atomen enthalten sein.The tanning of pelts piqued with formic acid and / or sulfuric acid is masked in a manner known per se with chromium III salts, for example with chromium III sulfates, basic chromium III sulfates and / or with organic acids such as formic acid, acetic acid Chromium III salts carried out in a pimple bath or in a new fleet. 0.5 to 12% by weight, preferably 3 to 6% by weight, based in each case on the pelt weight, of chromium III salts are used. In the tanning liquor, 0.5 to 3.0% by weight, based on pelt weight, of electrolyte-resistant fatliquors, for example sulfited fish oil, or 0.5 to 3.0% by weight, based on pelvic weight, mixtures of electrolyte-resistant fatliquoring agents and surfactants, such as alkyl sulfates containing 12-18 carbon atoms.

Zur Vorabstumpfung der Gerbflotten werden vorzugsweise 0,3 bis 0,7 Gew.-%, bezogen auf Blößengewicht, Basifizierungsmittel in Gegenwart von vorzugsweise 0,3 bis 4,0 Gew.-%, besonders be­vorzugt von 0,5 bis 2,0 Gew.-%, jeweils bezogen auf Blößenge­wicht, Aldehyd- und/oder Ketosäuren, wie Brenztraubensäure und/­oder Glyoxylsäure eingesetzt. Als Basifizierungsmittel eignen sich beispielsweise Magnesiumoxid, Dolomit, Alkalicarbonate, Alkalibi­ carbonate und/oder Erdalkalicarbonate. Vorzugsweise wird jedoch Magnesiumoxid eingesetzt.To pre-dull the tanning liquors, preferably 0.3 to 0.7% by weight, based on the pelt weight, of basifying agents in the presence of preferably 0.3 to 4.0% by weight, particularly preferably 0.5 to 2.0% by weight .-%, based in each case on pelt weight, aldehyde and / or keto acids, such as pyruvic acid and / or glyoxylic acid. Suitable base agents are, for example, magnesium oxide, dolomite, alkali carbonates, alkali bi carbonates and / or alkaline earth carbonates. However, magnesium oxide is preferably used.

Die Abstumpfung der Gerbflotte auf pH-Werte zwischen 4,2 und 5,5, vorzugsweise auf pH-Werte zwischen 4,5 und 5,0 wird mit 0,5 bis 3,0 Gew.-%, vorzugsweise mit 1,0 bis 2,0 Gew.-%, jeweils bezogen auf Blößengewicht, Alkali-Aluminiumsilikaten durchge­führt. Die Alkali-Aluminiumsilikate, vorzugsweise Natrium-­Aluminiumsilikate, werden den Gerbflotten entweder in fester Form oder in Form wäßriger Dispersionen zugesetzt. Die Alkali-­Aluminiumsilikate sind nach bekannten Verfahren, beispielsweise nach den in DE-OS 27 32 217 geschriebenen Verfahren zugäng­lich. Die Temperatur der Gerbflotte nach Zugabe der Alkali-­Aluminiumsilikate liegt zwischen 30 und 50 °C, vorzugsweise zwischen 35 und 45 °C.The tanning liquor is dulled to pH values between 4.2 and 5.5, preferably to pH values between 4.5 and 5.0, with 0.5 to 3.0% by weight, preferably with 1.0 to 2.0 wt .-%, each based on pelt weight, carried out alkali aluminum silicates. The alkali aluminum silicates, preferably sodium aluminum silicates, are added to the tanning liquors either in solid form or in the form of aqueous dispersions. The alkali aluminum silicates are accessible by known processes, for example by the processes written in DE-OS 27 32 217. The temperature of the tanning liquor after the addition of the alkali aluminum silicates is between 30 and 50 ° C., preferably between 35 and 45 ° C.

Mit dem erfindungsgemäßen Verfahren lassen sich alle Hauttypen, beispielsweise von Rind, Schwein, Ziege oder Schaf, gerben.With the method according to the invention, all skin types, for example of beef, pork, goat or sheep, can be tanned.

BeispieleExamples

Die Angabe Gewichtsprozent bezieht sich, sofern nicht anders angegeben, auf Blößengewicht.
konz. = konzentriert
min = MinutenUnless otherwise stated, the percent by weight relates to the weight of the nakedness.
conc. = concentrated
min = minutes

Beispiel 1 (Vergleich: "Das Leder" 34, 89 - 93 (1983)) Example 1 (comparison: "Das Leder" 34 , 89-93 (1983))

Ausgangsmaterial - Entkälkte und gebeizte Rindblößen, Dicke 4 mm

Figure imgb0001
wetblue auf Bock und betriebsüblich weiterarbeitenStarting material - decalcified and pickled beef, thickness 4 mm
Figure imgb0001
 Wetblue on the goat and continue working as usual

Beispiel 2 (Vergleich: DE-OS 35 16 842) Example 2 (comparison: DE-OS 35 16 842)

Ausgangsmaterial - Entkälkte und gebeizte Rindblößen, Dicke 4 mm

Figure imgb0002
wetblue auf Bock und betriebsüblich weiterarbeitenStarting material - decalcified and pickled beef, thickness 4 mm
Figure imgb0002
 Wetblue on the goat and continue working as usual

Beispiel 3 (erfindungsgemäß) Example 3

Ausgangsmaterial - Entkälkte und gebeizte Rindblößen, Dicke 4 mm

Figure imgb0003
wetblue auf Bock und betriebsüblich weiterarbeitenStarting material - decalcified and pickled beef, thickness 4 mm
Figure imgb0003
 Wetblue on the goat and continue working as usual

Chromoxid-Gehalte der Restflotten:Chromium oxide content of the remaining liquors:

Beispiel 1example 1 0,4 g CR₂O₃/l0.4 g CR₂O₃ / l Beispiel 2Example 2 0,8 g CR₂O₃/l0.8 g CR₂O₃ / l Beispiel 3 (erfindungsgemäß)Example 3 0,07 g CR₂O₃/l0.07 g CR₂O₃ / l

Claims (5)

1. Verfahren zur Chromgerbung mit hoher Chromauszehrung der Gerbflotten, dadurch gekennzeichnet, daß man mit Ameisensäure und/oder Schwefelsäure gepickelte Blößen mit 0,5 bis 12 Gew.-% Chrom-III-Salzen, bezogen auf Blößengewicht, gerbt, die Gerbflotte mit Basi­fizierungsmitteln in Gegenwart von Aldehyd- und/oder Keto­säuren auf einen pH-Wert zwischen 3,6 und 4,3 vorabstumpft und anschließend mit Alkali-Aluminiumsilikaten auf einen pH-Wert zwischen 4,2 und 5,5 abstumpft.1. A process for chrome tanning with high chromium exhaustion of the tanning liquors, characterized in that pelts pickled with formic acid and / or sulfuric acid are tanned with 0.5 to 12% by weight of chromium III salts, based on pelvis weight, the tanning liquor with base agents in the presence of aldehyde and / or keto acids, blunted to a pH between 3.6 and 4.3 and then blunted with alkali aluminum silicates to a pH between 4.2 and 5.5. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Gerbflotte mit 0,3 bis 0,7 Gew.-%, bezogen auf Blößengewicht, Basifizierungsmitteln in Gegenwart von 0,3 bis 4,0 Gew.-%, vorzugsweise von 0,5 bis 2,0 Gew.-%, jeweils bezogen auf Blößengewicht, Aldehyd- und/oder Keto­säuren vorabstumpft.2. The method according to claim 1, characterized in that the tanning liquor with 0.3 to 0.7 wt .-%, based on pelt weight, basifying agents in the presence of 0.3 to 4.0 wt .-%, preferably from 0 , 5 to 2.0 wt .-%, in each case based on pelt weight, blunted aldehyde and / or keto acids. 3. Verfahren nach einem oder beiden der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß als Basifizierungsmittel Mag­nesiumoxid, Dolomit, Alkalicarbonate, Alkalibicarbonate, Erdalkalicarbonate oder Mischungen dieser Substanzen, vorzugsweise Magnesiumoxid eingesetzt werden.3. The method according to one or both of claims 1 to 2, characterized in that magnesium oxide, dolomite, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal carbonates or mixtures of these substances, preferably magnesium oxide, are used as the base agents. 4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als Aldehyd- und/oder Ketosäuren Glyoxylsäure eingesetzt wird.4. The method according to one or more of claims 1 to 3, characterized in that glyoxylic acid is used as the aldehyde and / or keto acids. 5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man die Gerbflotte mit Natrium-Aluminiumsilikaten auf einen pH-Wert zwischen 4,5 und 5,0 abstumpft.5. The method according to one or more of claims 1 to 4, characterized in that the tanning liquor is dulled to a pH between 4.5 and 5.0 with sodium aluminum silicates.
EP89111743A 1988-07-06 1989-06-28 Tanning method presenting a high chrome exhaustion of the tanning bath Expired - Lifetime EP0349892B1 (en)

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DE3822823 1988-07-06
DE3822823A DE3822823A1 (en) 1988-07-06 1988-07-06 GERB PROCESSES OF HIGH CHROME PERFORMANCE OF GERBFLOTTEN

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EP0349892A2 true EP0349892A2 (en) 1990-01-10
EP0349892A3 EP0349892A3 (en) 1992-01-15
EP0349892B1 EP0349892B1 (en) 1994-09-21

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0583697A2 (en) * 1992-08-14 1994-02-23 Hoechst Aktiengesellschaft Tanning process saving chrome and improved fixing of chrome
CN104109723A (en) * 2014-07-18 2014-10-22 四川德华皮革制造有限公司 Preparation method of dual-purpose hide for hair and leather by formaldehyde-free chrome-free tanning

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4323123A1 (en) * 1993-07-10 1995-01-12 Hoechst Ag Process for dyeing fur skins with oxidation dyes
EP2853604A1 (en) * 2013-09-30 2015-04-01 Rhodia Poliamida E Especialidades Ltda Tanning process
EP2853605A1 (en) * 2013-09-30 2015-04-01 Rhodia Poliamida E Especialidades Ltda Tanning process for obtaining leather

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201054A1 (en) * 1985-05-10 1986-11-12 Hoechst Aktiengesellschaft Tanning process saving chrome

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4272242A (en) * 1977-07-16 1981-06-09 Henkel Kommanditgesellschaft Auf Aktien Use of water-insoluble aluminosilicates in tanning process for the production of leather
DE2732217A1 (en) * 1977-07-16 1979-02-01 Henkel Kgaa USE OF FINE-PIECE WATER-INSOLUBLE ALKALIAL ALUMINUM SILICATES IN THE MANUFACTURING OF LEATHER

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201054A1 (en) * 1985-05-10 1986-11-12 Hoechst Aktiengesellschaft Tanning process saving chrome
DE3516842A1 (en) * 1985-05-10 1986-11-13 Hoechst Ag, 6230 Frankfurt METHOD FOR CHROME SAVING

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LEDER. Bd. 34, Juni 1983, DARMSTADT DE Seiten 89 - 93; H.H. FRIESE: 'VERWENDUNG VON NATRIUM-ALUMINIUMSILIKATEN BEI DER LEDERHERSTELLUNG' *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0583697A2 (en) * 1992-08-14 1994-02-23 Hoechst Aktiengesellschaft Tanning process saving chrome and improved fixing of chrome
EP0583697A3 (en) * 1992-08-14 1994-04-27 Hoechst Ag
US5501709A (en) * 1992-08-14 1996-03-26 Hoechst Ag Economy and plumping chrome tanning
CN104109723A (en) * 2014-07-18 2014-10-22 四川德华皮革制造有限公司 Preparation method of dual-purpose hide for hair and leather by formaldehyde-free chrome-free tanning

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Publication number Publication date
DE58908384D1 (en) 1994-10-27
JPH0270800A (en) 1990-03-09
EP0349892A3 (en) 1992-01-15
FI94149C (en) 1995-07-25
EP0349892B1 (en) 1994-09-21
FI893276A (en) 1990-01-07
ES2058406T3 (en) 1994-11-01
KR0126916B1 (en) 1997-12-26
FI893276A0 (en) 1989-07-05
AR245505A1 (en) 1994-01-31
KR900001862A (en) 1990-02-27
TR26613A (en) 1994-04-05
ATE111963T1 (en) 1994-10-15
BR8903305A (en) 1990-02-13
FI94149B (en) 1995-04-13
US4938779A (en) 1990-07-03
DE3822823A1 (en) 1990-01-11
MX170321B (en) 1993-08-16

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