EP0349892B1 - 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

Info

Publication number
EP0349892B1
EP0349892B1 EP89111743A EP89111743A EP0349892B1 EP 0349892 B1 EP0349892 B1 EP 0349892B1 EP 89111743 A EP89111743 A EP 89111743A EP 89111743 A EP89111743 A EP 89111743A EP 0349892 B1 EP0349892 B1 EP 0349892B1
Authority
EP
European Patent Office
Prior art keywords
tanning
weight
chromium
aldehyde
acid
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.)
Expired - Lifetime
Application number
EP89111743A
Other languages
German (de)
French (fr)
Other versions
EP0349892A3 (en
EP0349892A2 (en
Inventor
Hans-Herbert Dr. Friese
Emil Ruscheinsky
Rudolf Dr. Zauns
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6358054&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0349892(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0349892A2 publication Critical patent/EP0349892A2/en
Publication of EP0349892A3 publication Critical patent/EP0349892A3/en
Application granted granted Critical
Publication of EP0349892B1 publication Critical patent/EP0349892B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • 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 exhaustion 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-dulled with basic agents in the presence of aldehyde and / or keto acids.
  • the invention accordingly relates to a process for chrome tanning with a high chromium exhaustion of the tanning liquors, which is characterized in that pelts pickled with formic acid and / or sulfuric acid are tanned with 0.5 to 12 percent by weight of chromium III salts, based on pelvis weight, which 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.
  • 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 wetblue color 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 0.5 to 12% by weight, preferably 3 to 6% by weight, based in each case on the pelvic weight, of chromium III salts are used.
  • chromium III salts 0.5 to 3.0 wt. such as alkyl sulfars containing 12-18 carbon atoms.
  • the tanning liquors preferably 0.3 to 0.7% by weight, based on the pelt weight, of base 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.
  • base agents 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.
  • aldehyde and / or keto acids such as pyruvic acid and / or glyoxylic acid.
  • keto acids such as pyruvic acid and / or glyoxylic acid.
  • Magnesium oxide, dolomite, alkali metal carbonates, alkali metal bicarbonates are suitable as base agents and
  • 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% by weight, based in each case on the pelt weight, of 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)

Landscapes

  • 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)

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 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 hicht an Versuchen gefehlt, die Chromaufnahme der Haut zu verbessern und die für eine kochgare Gerbung notwendige Chrommenge zu reduzieren.In the past, there has been a lack of attempts to improve the chromium absorption of the skin and to reduce the amount of chromium required for cookable tanning, both for ecological and economic reasons.

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 working up to chromium 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 "The Leather" 34 , 89 to 93 (1983) it is described that the use of magnesium oxide and dicarboxylic acids for preliminary bluntings and sodium aluminum silicates for final bluntings 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 methods 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 exhaustion 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-dulled 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 a high chromium exhaustion of the tanning liquors, which is characterized in that pelts pickled with formic acid and / or sulfuric acid are tanned with 0.5 to 12 percent by weight of chromium III salts, based on pelvis weight, which 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 wetblue color 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 Alkylsulfare 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 pelvic weight, of chromium III salts are used. In the tanning liquor, 0.5 to 3.0 wt. such as alkyl sulfars 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, Alkalibicarbonate 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 base 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. Magnesium oxide, dolomite, alkali metal carbonates, alkali metal bicarbonates are suitable as base agents 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% by weight, based in each case on the pelt weight, of 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 weiterarbeiten Chromoxid-Gehalte der Restflotten: Beispiel 1 0,4 g Cr₂O₃/l Beispiel 2 0,8 g Cr₂O₃/l Beispiel 3 (erfindungsgemäß) 0,07 g Cr₂O₃/l Starting material - decalcified and pickled beef, thickness 4 mm
Figure imgb0003
Wetblue on the goat and continue working as usual Chromium oxide content of the remaining liquors: example 1 0.4 g Cr₂O₃ / l Example 2 0.8 g Cr₂O₃ / l Example 3 0.07 g Cr₂O₃ / l

Claims (5)

  1. A chrome tanning process with high chrome extraction 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 chromium(III) salts, based on pelt rate, the tanning liquor is prebasified to pH 3.6 to 4.3 with basifying agents in the presence of aldehyde and/or keto acids and is then basified to pH 4.2 to 5.5 with alkali metal aluminium silicates.
  2. A process as claimed in claim 1, characterized in that the tanning liquor is prebasified with 0.3 to 0.7% by weight, based on pelt weight, basifying agents in the presence of 0.3 to 4.0% by weight and preferably 0.5 to 2.0% by weight, based on pelt weight, of aldehyde and/or keto acids.
  3. A process as claimed in 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 thereof, preferably magnesium oxide, are used as basifying agents.
  4. A process as claimed in one or more of claims 1 to 3, characterized in that glyoxylic acid is used as the aldehyde and/or keto acid.
  5. A process as claimed in one or more of claims 1 to 4, characterized in that the tanning liquor is basified to pH 4.5 to 5.0 with sodium aluminium silicates.
EP89111743A 1988-07-06 1989-06-28 Tanning method presenting a high chrome exhaustion of the tanning bath Expired - Lifetime EP0349892B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3822823 1988-07-06
DE3822823A DE3822823A1 (en) 1988-07-06 1988-07-06 GERB PROCESSES OF HIGH CHROME PERFORMANCE OF GERBFLOTTEN

Publications (3)

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

Family

ID=6358054

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89111743A Expired - Lifetime EP0349892B1 (en) 1988-07-06 1989-06-28 Tanning method presenting a high chrome exhaustion of the tanning bath

Country Status (12)

Country Link
US (1) US4938779A (en)
EP (1) EP0349892B1 (en)
JP (1) JPH0270800A (en)
KR (1) KR0126916B1 (en)
AR (1) AR245505A1 (en)
AT (1) ATE111963T1 (en)
BR (1) BR8903305A (en)
DE (2) DE3822823A1 (en)
ES (1) ES2058406T3 (en)
FI (1) FI94149C (en)
MX (1) MX170321B (en)
TR (1) TR26613A (en)

Families Citing this family (5)

* 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
DE4323123A1 (en) * 1993-07-10 1995-01-12 Hoechst Ag Process for dyeing fur skins with oxidation dyes
EP2853605A1 (en) * 2013-09-30 2015-04-01 Rhodia Poliamida E Especialidades Ltda Tanning process for obtaining leather
EP2853604A1 (en) * 2013-09-30 2015-04-01 Rhodia Poliamida E Especialidades Ltda Tanning process
CN104109723B (en) * 2014-07-18 2016-02-03 四川德华皮革制造有限公司 A kind of preparation method of both fur and leather skin of formaldehydeless chrome-free tanning

Citations (1)

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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2732217A1 (en) * 1977-07-16 1979-02-01 Henkel Kgaa USE OF FINE-PIECE WATER-INSOLUBLE ALKALIAL ALUMINUM SILICATES IN THE MANUFACTURING OF LEATHER
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

Patent Citations (1)

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

Also Published As

Publication number Publication date
ATE111963T1 (en) 1994-10-15
US4938779A (en) 1990-07-03
FI94149B (en) 1995-04-13
TR26613A (en) 1994-04-05
MX170321B (en) 1993-08-16
EP0349892A3 (en) 1992-01-15
FI94149C (en) 1995-07-25
DE3822823A1 (en) 1990-01-11
BR8903305A (en) 1990-02-13
KR0126916B1 (en) 1997-12-26
JPH0270800A (en) 1990-03-09
FI893276A (en) 1990-01-07
ES2058406T3 (en) 1994-11-01
DE58908384D1 (en) 1994-10-27
EP0349892A2 (en) 1990-01-10
AR245505A1 (en) 1994-01-31
KR900001862A (en) 1990-02-27
FI893276A0 (en) 1989-07-05

Similar Documents

Publication Publication Date Title
DE2626430C2 (en) Process for tanning leather and tanning mix
CH615224A5 (en)
EP0349892B1 (en) Tanning method presenting a high chrome exhaustion of the tanning bath
EP0201054B1 (en) Tanning process saving chrome
EP0339437A1 (en) Tanning process saving chromium
DE740472C (en) Process for pickling ashed skin
DE2626429A1 (en) METHOD OF TANNING SKIN
DE888741C (en) Process for pickling dehaired skins and pelts using proteolytic enzymes
DE4430290A1 (en) Leather mfr. with reduced chemical consumption and amt. of waste liquor
EP3740595B1 (en) Chromium tanning agents
EP0583697A2 (en) Tanning process saving chrome and improved fixing of chrome
EP0554217B1 (en) Aqueous composition for pretanning hides
DE2424301C3 (en) Process for chrome tanning and tanning mix therefor
DE2549527C3 (en) Process for the production of leather
DE2424300A1 (en) Chrome tanning of leather - by adding a powdered mixt. of chromium salt, acid binding agent and a di-or tricarboxylic acid to the acid treated hides
DE2739844B2 (en) Process for chrome tanning
DE1257352B (en) Soluble chelate complexes for mineral tanning
EP0270767A1 (en) Tanning process saving chrome
EP0210481B1 (en) Method of deliming hides and use of sulphurous acid cyclic esters as deliming agents
DE587724C (en) Process for the production of chrome tanning agents
DE679298C (en) Process for the treatment of vegetable-tanned leather
DE1769983C (en) Process for improving the properties of hides or hides tanned with basic metal salts
DE894430C (en) Process for the production of chrome leather
DE334004C (en) Process for tanning using salt solutions of trivalent iron
DE2131015C3 (en) Rapid tanning process for the production of vegetable tanned leather

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19920604

17Q First examination report despatched

Effective date: 19931124

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 111963

Country of ref document: AT

Date of ref document: 19941015

Kind code of ref document: T

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19940926

REF Corresponds to:

Ref document number: 58908384

Country of ref document: DE

Date of ref document: 19941027

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2058406

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3013409

ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

EAL Se: european patent in force in sweden

Ref document number: 89111743.4

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: HOECHST AG

Effective date: 19950619

NLR1 Nl: opposition has been filed with the epo

Opponent name: HOECHST AG

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19960524

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960611

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19960619

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19960624

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960626

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19960701

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960812

Year of fee payment: 8

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19970628

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970630

Ref country code: BE

Effective date: 19970630

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19970630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19980101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980227

EUG Se: european patent has lapsed

Ref document number: 89111743.4

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19980101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980619

Year of fee payment: 10

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

PLBN Opposition rejected

Free format text: ORIGINAL CODE: 0009273

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: OPPOSITION REJECTED

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990628

27O Opposition rejected

Effective date: 19990513

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990628

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20000628

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20080625

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080703

Year of fee payment: 20

Ref country code: ES

Payment date: 20080717

Year of fee payment: 20

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20090629