EP0554218B1 - Process for pickling hides - Google Patents
Process for pickling hides Download PDFInfo
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- EP0554218B1 EP0554218B1 EP93810032A EP93810032A EP0554218B1 EP 0554218 B1 EP0554218 B1 EP 0554218B1 EP 93810032 A EP93810032 A EP 93810032A EP 93810032 A EP93810032 A EP 93810032A EP 0554218 B1 EP0554218 B1 EP 0554218B1
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- Prior art keywords
- phenol
- weight
- reaction product
- process according
- acid
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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
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
Definitions
- the present invention relates to a method for pickling skin bumps, a means for producing pickled skin bumps and the material picked by the method according to the invention.
- a decalcified pale must be acidified in a pimple treatment, from a pH value of approx. 8 to 3-4, since chrome and other mineral tannins become ineffective in a neutral to weakly alkaline environment.
- Vegetable tanning agents only have a full tanning effect in the acidic pH range.
- Sulfuric, hydrochloric or formic acid is usually used to acidify the skin.
- these acids cause a harmful acidic swelling of the collagen ("acid swelling"), which is avoided by reducing the water absorption capacity of the skin by adding a neutral salt such as e.g. Sodium chloride or sodium sulfate decreased.
- acid-salt solutions which are also referred to as pimples, represent an essential load factor due to their neutral salt-containing wastewater. There has therefore been no lack of attempts to develop salt-free or low-salt pimple systems. These systems essentially consist of so-called non-swelling acids, e.g. Phthalic acid.
- Document DE-A-85 933 relates to a process for containing, pickling and swelling all types of hides and hides.
- a pimple process has now been found which, on the one hand, can be carried out without the addition of neutral salts and, on the other hand, surprisingly increases the shrinking temperature of the pale and reduces the tanning time of a subsequent vegetable tanning.
- the present invention accordingly relates to a method for pimples of skin bumps, which is characterized in that a decalcified skin pellet is treated with an aqueous liquor which contains a reaction product of phenol and a sulfonating agent, the molar ratio (phenol) :( SO 3 ) (1) :( 1.1-2.2) and which is free of neutral salts.
- the preferred sulfonating agent used to prepare the reaction product according to the invention is SO 3 or, above all, oleum.
- Oleum is a solution of SO 3 in concentrated sulfuric acid.
- reaction products of phenol and oleum are particularly suitable, the molar ratio (phenol) :( SO 3 ) being above all (1) :( 1.4-1.8).
- reaction products of phenol and oleum used according to the invention are known per se.
- GB-A-0,683,084 the production of reaction products from phenol and oleum, which, however, subsequently contains e.g. Formaldehyde and urea or thiourea are further implemented and used as tanning agents.
- the reaction products used according to the invention are mixtures, the main constituent of which are sulfonated dihydroxydiphenyl sulfones.
- the reaction products used according to the invention are normally in the form of the free sulfonic acids. However, the reaction products can also be completely or partially neutralized in aqueous solution or slurry by adding alkalis. Suitable alkalis are e.g. Sodium hydroxide solution, potassium hydroxide solution, ammonia, organic amines, such as e.g. Ethylamine, trimethylamine, triethylamine or morpholine, or alkanolamines such as e.g. Ethanolamine, diethanolamine or triethanolamine.
- the pH of the aqueous solutions of the reaction products thus obtained is 0 to 10, preferably 0 to 4.5.
- the decalcified skin is washed with water at room temperature, preferably at a temperature of 20 to 30 ° C. for 10 to 20 minutes and then treated in an aqueous pickle liquor which contains the reaction product in an amount contains from 1 to 10, preferably 3 to 5% by weight, based on the weight of the goods.
- the pH of the pimple liquor is between 3 and 4.
- the pimple treatment is carried out at room temperature, preferably between 20 and 30, and very particularly between 20 and 25 ° C. The treatment takes place e.g. in a rotating barrel or in a reel.
- a C 1 -C 3 carboxylic acid or a mineral acid is used as an optional component for the process according to the invention, which is present in the pickling liquor in an amount of 0 to 1% by weight.
- these carboxylic acids are formic acid, acetic acid or propionic acid and examples of suitable mineral acids are hydrochloric acid or sulfuric acid.
- suitable mineral acids are hydrochloric acid or sulfuric acid.
- the pickle liquor additionally contains a C 1 -C 3 carboxylic acid or mineral acid, the procedure is such that the pellets are treated within 15 minutes in an aqueous liquor which contains half the concentration of the reaction product stated above.
- the second half of the reaction product is added to the pickling liquor and 0.1 to 1% by weight of the C 1 -C 3 carboxylic acid or mineral acid and treated for a further 90 to 180 minutes.
- the pH is between 3.0 and 3.5.
- the skin size picked by the present method is suitable for further processing, i.e. for pre-tanning or tanning.
- the present method can be combined with all common tanning methods, such as mineral tanning, synthetic or vegetable tanning, whereby the tanning times can be shortened with the latter method.
- Formic acid is preferably used as component (b).
- the agent according to the invention further contains 0 to 5, preferably 0 to 2,% by weight of sulfuric acid resulting from the preparation of component (a).
- Phenolsulfonic acid is also a by-product educated.
- Example 2 A decalcified pale is washed with 200% water at 25 ° C for 15 minutes.
- the pH is approximately 3.0.
- a pH of 3.3 to 3.5 is established. It is treated at the same temperature for 150 minutes.
- the result is a pimpled skin that is suitable for further processing.
- the shrinkage temperature is increased by approx.
- a decalcified pale is washed with 200% water at 25 ° C for 15 minutes.
- the result is a pimpled skin that is suitable for further processing.
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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)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Pickeln von Hautblössen, ein Mittel zur Herstellung von gepickelten Hautblössen sowie das nach dem erfindungsgemässen Verfahren gepickelte Material.The present invention relates to a method for pickling skin bumps, a means for producing pickled skin bumps and the material picked by the method according to the invention.
Zur Vorbereitung für die Gerbung muss eine entkälkte Blösse in einer Pickelbehandlung sauer eingestellt werden, von einem pH-Wert von ca. 8 auf 3-4, da im neutralen bis schwach alkalischen Milieu Chrom- und andere Mineralgerbstoffe unwirksam werden. Vegetabile Gerbstoffe besitzen nur im sauren pH-Bereich volle Gerbwirkung.To prepare for tanning, a decalcified pale must be acidified in a pimple treatment, from a pH value of approx. 8 to 3-4, since chrome and other mineral tannins become ineffective in a neutral to weakly alkaline environment. Vegetable tanning agents only have a full tanning effect in the acidic pH range.
Zur Sauerstellung der Hautblösse werden gewöhnlich Schwefel-, Salz- oder Ameisensäure verwendet. Allerdings verursachen diese Säuren eine schädigende saure Quellung des Kollagens ("Säureschwellung"), die dadurch vermieden wird, dass man das Wasseraufnahme-Vermögen der Hautblösse durch Zusetzen eines Neutralsalzes wie z.B. Natriumchlorid oder Natriumsulfat vermindert. Solche Säure-Salzlösungen, die auch als Pickel bezeichnet werden, stellen jedoch auf Grund ihrer neutralsalzhaltigen Abwässer einen wesentlichen Lastfaktor dar. Es hat daher nicht an Versuchen gefehlt, salzfreie oder salzarme Pickelsysteme zu entwickeln. Diese Systeme bestehen im wesentlichen aus sogenannten nichtschwellenden Säuren, wie z.B. Phthalsäure.Sulfuric, hydrochloric or formic acid is usually used to acidify the skin. However, these acids cause a harmful acidic swelling of the collagen ("acid swelling"), which is avoided by reducing the water absorption capacity of the skin by adding a neutral salt such as e.g. Sodium chloride or sodium sulfate decreased. Such acid-salt solutions, which are also referred to as pimples, represent an essential load factor due to their neutral salt-containing wastewater. There has therefore been no lack of attempts to develop salt-free or low-salt pimple systems. These systems essentially consist of so-called non-swelling acids, e.g. Phthalic acid.
Dokument DE-A-85 933 betrifft ein Verfahen zum Enthalten, Beizen und Schwellen aller Art von Fellen und Hänten.Document DE-A-85 933 relates to a process for containing, pickling and swelling all types of hides and hides.
Es wurde nun ein Pickel-Verfahren gefunden, das einerseits ohne den Zusatz von Neutralsalzen durchgeführt werden kann und andrerseits überraschenderweise die Schrumpfungstemperatur der Blösse erhöht und die Gerbzeit einer anschliessenden vegetabilen Gerbung erniedrigt.A pimple process has now been found which, on the one hand, can be carried out without the addition of neutral salts and, on the other hand, surprisingly increases the shrinking temperature of the pale and reduces the tanning time of a subsequent vegetable tanning.
Gegenstand der vorliegenden Erfindung ist demnach ein Verfahren zum Pickeln von Hautblössen, das dadurch gekennzeichnet ist, dass man eine entkälkte Hautblösse mit einer wässrigen Flotte behandelt, die ein Umsetzungsprodukt aus Phenol und einem Sulfonierungsmittel enthält, wobei das Molverhältnis (Phenol):(SO3) (1):(1,1-2,2) beträgt und die frei von Neutralsalzen ist.The present invention accordingly relates to a method for pimples of skin bumps, which is characterized in that a decalcified skin pellet is treated with an aqueous liquor which contains a reaction product of phenol and a sulfonating agent, the molar ratio (phenol) :( SO 3 ) (1) :( 1.1-2.2) and which is free of neutral salts.
Bevorzugt wird als Sulfonierungsmittel zur Darstellung des erfindungsgemässen Umsetzungsproduktes SO3 oder vor allem Oleum verwendet. Oleum ist eine Lösung von SO3 in konzentrierter Schwefelsäure. Somit kommen insbesondere Umsetzungsprodukte aus Phenol und Oleum in Frage, wobei das Molverhältnis (Phenol):(SO3) vor allem (1):(1,4-1,8) beträgt.The preferred sulfonating agent used to prepare the reaction product according to the invention is SO 3 or, above all, oleum. Oleum is a solution of SO 3 in concentrated sulfuric acid. Thus, reaction products of phenol and oleum are particularly suitable, the molar ratio (phenol) :( SO 3 ) being above all (1) :( 1.4-1.8).
Die erfindungsgemäss verwendeten Umsetzungsprodukte aus Phenol und Oleum sind an sich bekannt. So beschreibt z.B. die GB-A-0,683,084 die Herstellung von Umsetzungsprodukten aus Phenol und Oleum, die jedoch anschliessend mit z.B. Formaldehyd und Harnstoff oder Thioharnstoff weiter umgesetzt werden und als Gerbstoffe Verwendung finden. Die erfindungsgemäss verwendeten Umsetzungsprodukte stellen Gemische dar, deren Hauptbestandteil sulfonierte Dihydroxydiphenylsulfone sind.The reaction products of phenol and oleum used according to the invention are known per se. For example, GB-A-0,683,084 the production of reaction products from phenol and oleum, which, however, subsequently contains e.g. Formaldehyde and urea or thiourea are further implemented and used as tanning agents. The reaction products used according to the invention are mixtures, the main constituent of which are sulfonated dihydroxydiphenyl sulfones.
Die erfindungsgemäss verwendeten Umsetzungsprodukte liegen normalerweise in Form der freien Sulfonsäuren vor. Man kann aber auch die Umsetzungsprodukte in wässriger Lösung oder Anschlämmung durch Zugabe von Alkalien vollständig oder teilweise neutralisieren. Geeignete Alkalien sind z.B. Natronlauge, Kalilauge, Ammoniak, organische Amine, wie z.B. Ethylamin, Trimethylamin, Triethylamin oder Morpholin, oder Alkanolamine, wie z.B. Ethanolamin, Diethanolamin oder Triethanolamin. Der pH-Wert der so erhaltenen wässrigen Lösungen der Umsetzungsprodukte beträgt 0 bis 10, vorzugsweise 0 bis 4,5.The reaction products used according to the invention are normally in the form of the free sulfonic acids. However, the reaction products can also be completely or partially neutralized in aqueous solution or slurry by adding alkalis. Suitable alkalis are e.g. Sodium hydroxide solution, potassium hydroxide solution, ammonia, organic amines, such as e.g. Ethylamine, trimethylamine, triethylamine or morpholine, or alkanolamines such as e.g. Ethanolamine, diethanolamine or triethanolamine. The pH of the aqueous solutions of the reaction products thus obtained is 0 to 10, preferably 0 to 4.5.
Bei dem vorliegenden Verfahren geht man beispielsweise so vor, dass man die entkälkte Hautblösse mit Wasser bei Raumtemperatur, vorzugsweise bei einer Temperatur von 20 bis 30°C 10 bis 20 Minuten wäscht und diese anschliessend in einer wässrigen Pickelflotte behandelt, die das Umsetzungsprodukt in einer Menge von 1 bis 10, vorzugsweise 3 bis 5 Gew.%, bezogen auf das Warengewicht, enthält. Der pH-Wert der Pickelflotte liegt zwischen 3 und 4. Die Pickel-Behandlung wird bei Raumtemperatur, vorzugsweise zwischen 20 und 30, und ganz besonders zwischen 20 und 25°C durchgeführt. Die Behandlung erfolgt z.B. im rotierenden Fass oder im Haspel.In the present process, for example, the decalcified skin is washed with water at room temperature, preferably at a temperature of 20 to 30 ° C. for 10 to 20 minutes and then treated in an aqueous pickle liquor which contains the reaction product in an amount contains from 1 to 10, preferably 3 to 5% by weight, based on the weight of the goods. The pH of the pimple liquor is between 3 and 4. The pimple treatment is carried out at room temperature, preferably between 20 and 30, and very particularly between 20 and 25 ° C. The treatment takes place e.g. in a rotating barrel or in a reel.
Neben dem Umsetzungsprodukt wird für das erfindungsgemässe Verfahren als fakultative Komponente eine C1-C3Carbonsäure oder eine Mineralsäure verwendet, die in einer Menge von 0 bis 1 Gew.% in der Pickelflotte vorhanden ist. Als Beispiele für diese Carbonsäuren seien Ameisensäure, Essigsäure oder Propionsäure genannt und Beispiele für geeignete Mineralsäuren sind Salzsäure oder Schwefelsäure. Vorzugsweise wird für das erfindungsgemässe Verfahren Ameisensäure oder Schwefelsäure verwendet. Enthält in dieser bevorzugten Ausführungsform die Pickelflotte zusätzlich eine C1-C3Carbonsäure oder Mineralsäure, geht man so vor, dass man die Blösse innerhalb von 15 Minuten in einer wässrigen Flotte behandelt, die die Hälfte der oben angegebenen Konzentration des Umsetzungsproduktes enthält. Im Anschluss daran gibt man die zweite Hälfte des Umsetzungsproduktes zur Pickelflotte sowie 0,1 bis 1 Gew.% der C1-C3Carbonsäure oder Mineralsäure und behandelt für weitere 90 bis 180 Minuten. Der pH-Wert liegt zwischen 3,0 und 3,5.In addition to the reaction product, a C 1 -C 3 carboxylic acid or a mineral acid is used as an optional component for the process according to the invention, which is present in the pickling liquor in an amount of 0 to 1% by weight. Examples of these carboxylic acids are formic acid, acetic acid or propionic acid and examples of suitable mineral acids are hydrochloric acid or sulfuric acid. Preferably for the method according to the invention uses formic acid or sulfuric acid. If, in this preferred embodiment, the pickle liquor additionally contains a C 1 -C 3 carboxylic acid or mineral acid, the procedure is such that the pellets are treated within 15 minutes in an aqueous liquor which contains half the concentration of the reaction product stated above. Subsequently, the second half of the reaction product is added to the pickling liquor and 0.1 to 1% by weight of the C 1 -C 3 carboxylic acid or mineral acid and treated for a further 90 to 180 minutes. The pH is between 3.0 and 3.5.
Weitere Zusätze sind für die Pickelflotte nicht erforderlich.No other additives are required for the pickle fleet.
Die nach dem vorliegenden Verfahren gepickelte Hautblösse ist geeignet zur Weiterverarbeitung, d.h. zum Vorgerben bzw. Gerben. Das vorliegende Verfahren ist dabei mit allen gängigen Gerbmethoden kombinierbar, wie z.B mit der Mineralgerbung, synthetischen oder vegetabilen Gerbung, wobei sich bei der letztgenannten Methode die Gerbzeiten verkürzen lassen.The skin size picked by the present method is suitable for further processing, i.e. for pre-tanning or tanning. The present method can be combined with all common tanning methods, such as mineral tanning, synthetic or vegetable tanning, whereby the tanning times can be shortened with the latter method.
Als Hautblössen kommen alle tierischen Häute in Betracht, die sich zu Leder weiterverarbeiten lassen.All animal hides that can be further processed into leather come into consideration as skin bones.
Einen weiteren Erfindungsgegenstand der vorliegenden Anmeldung bildet ein Mittel zur Herstellung von gepickelten Hautblössen. Dieses Mittel ist dadurch gekennzeichnet, dass es
- (a) 1 bis 10, vorzugsweise 2 bis 5 Gew.% eines Umsetzungsproduktes erhalten aus Phenol und einem Sulfonierungsmittel, wobei das Molverhältnis (Phenol):(SO3) (1):(1,1-2,2) beträgt,
- (b) 0 bis 1, vorzugsweise 0 bis 0,5 Gew,% einer C1-C3Carbonsäure oder Mineralsäure und
- (c) 89 bis 99 Gew.% Wasser
- (a) 1 to 10, preferably 2 to 5% by weight of a reaction product obtained from phenol and a sulfonating agent, the molar ratio (phenol) :( SO 3 ) (1) :( being 1.1-2.2),
- (b) 0 to 1, preferably 0 to 0.5% by weight of a C 1 -C 3 carboxylic acid or mineral acid and
- (c) 89 to 99% by weight water
Vorzugsweise wird ein Mittel eingesetzt, das als Komponente
- (a) ein Umsetzungsprodukt aus Phenol und einem Sulfonierungsmittel enthält, wobei das Molverhältnis des Umsetzungsproduktes (Phenol):(SO3) (1):(1,4-1,8) beträgt.
- (a) contains a reaction product of phenol and a sulfonating agent, the molar ratio of the reaction product (phenol) :( SO 3 ) (1) :( being 1.4-1.8).
Weitere bevorzugte Mittel enthalten
- (a) 1 bis 10, vorzugsweise 2 bis 5 Gew.% eines Umsetzungsproduktes aus Phenol und einem Sulfonierungsmittel, wobei das Molverhältnis (Phenol):(SO3) (1):(1,1-2,2) beträgt,
- (b) 0,1 bis 1, vorzugsweise 0,1 bis 0,5 Gew,% einer C1-C3Carbonsäure oder Mineralsäure und
- (c) 89 bis 98,9 Gew.% Wasser.
- (a) 1 to 10, preferably 2 to 5% by weight of a reaction product of phenol and a sulfonating agent, the molar ratio (phenol) :( SO 3 ) (1) :( being 1.1-2.2),
- (b) 0.1 to 1, preferably 0.1 to 0.5% by weight of a C 1 -C 3 carboxylic acid or mineral acid and
- (c) 89 to 98.9 wt% water.
Als Komponente (b) wird vorzugsweise Ameisensäure verwendet.Formic acid is preferably used as component (b).
Das erfindungsgemässe Mittel enthält weiterhin 0 bis 5, vorzugsweise 0 bis 2 Gew.% Schwefelsäure, die von der Herstellung der Komponente (a) herrührt.The agent according to the invention further contains 0 to 5, preferably 0 to 2,% by weight of sulfuric acid resulting from the preparation of component (a).
Die in der nachfolgenden Herstellungsvorschrift und in dem nachfolgenden Applikationsbeispiel angegebenen Prozente und Teile beziehen sich auf das Gewicht. Die Prozentangaben beziehen sich, sofern nicht anders vermerkt, auf das Gewicht der Hautblösse.The percentages and parts stated in the following manufacturing instructions and in the following application example relate to the weight. Unless otherwise stated, the percentages relate to the weight of the skin.
136,5 Teile Phenol (1,45 Mol) werden bei 45°C geschmolzen. Zu dieser Schmelze werden 193,4 Teile Oleum 20% (2,08 Mol SO3) langsam so zugegeben, dass die Temperatur des Reaktionsgemisches nicht über 160°C ansteigt. Nun wird das Reaktionsgemisch unter vermindertem Druck bei 2666,44 Pa (20 Torr) und 160°C während 6 Stunden unter Rühren gehalten, wobei das durch die Reaktion gebildete Wasser zusammen mit geringen Anteilen Phenol aus dem Reaktionsgemisch azeotrop entfernt wird. Anschliessend wird das Reaktionsgemisch unter Normaldruck auf 40°C abgekühlt. Man erhält 253 Teile eines geschmolzenen Gemisches, das die Sulfonsäure der Formel
als Hauptbestandteil enthält. Als Nebenprodukt wird auch noch Phenolsulfonsäure gebildet.as the main ingredient. Phenolsulfonic acid is also a by-product educated.
Diese Blösse gibt man in eine Pickelflotte, die
- 50%
- Wasser und
- 2%
- des gemäss Beispiel 1 hergestellten Umsetzungsproduktes
- 50%
- water and
- 2%
- of the reaction product prepared according to Example 1
Man behandelt 30 Minuten bei 25°C. Der pH-Wert beträgt ca. 3,0.Treated at 25 ° C for 30 minutes. The pH is approximately 3.0.
Zu dieser Flotte gibt man dann
- 2%
- des gemäss Beispiel 1 hergestellten Umsetzungsproduktes sowie
- 0,4%
- Ameisensäure 85%ig.
- 2%
- of the reaction product prepared according to Example 1 and
- 0.4%
- Formic acid 85%.
Es stellt sich ein pH-Wert von 3,3 bis 3,5 ein. Man behandelt bei gleicher Temperatur 150 Minuten.A pH of 3.3 to 3.5 is established. It is treated at the same temperature for 150 minutes.
Man erhält eine gepickelte Hautblösse, die für die Weiterverarbeitung geeignet ist.The result is a pimpled skin that is suitable for further processing.
Im Vergleich zu einer mit einem "traditionellen" Pickel hergestellten Hautblösse wird die Schrumpfungstemperatur um ca. 10°C erhöht.The shrinkage temperature is increased by approx.
Eine entkälkte Blösse wird mit 200% Wasser bei 25°C 15 Minuten gewaschen.A decalcified pale is washed with 200% water at 25 ° C for 15 minutes.
Diese Blösse gibt man in eine Pickelflotte, die
- 30%
- Wasser und
- 3%
- des gemäss Beispiel 1 hergestellten Umsetzungsproduktes, das jedoch durch Zugabe von Natronlauge auf einen pH-Wert von 3,5 eingestellt wurde,
- 30%
- water and
- 3%
- of the reaction product prepared according to Example 1, but which was adjusted to a pH of 3.5 by adding sodium hydroxide solution,
Man behandelt 30 Minuten bei 25°C. Der pH-Wert beträgt ca. 6,3.Treated at 25 ° C for 30 minutes. The pH is approximately 6.3.
Zu dieser Flotte gibt man dann
- 0,7%
- Schwefelsäure conc. zu.
- 0.7%
- Sulfuric acid conc. to.
Man behandelt bei gleicher Temperatur 150 Minuten. Es stellt sich ein pH-Wert von 3,4 bis 3,6 ein.It is treated at the same temperature for 150 minutes. A pH of 3.4 to 3.6 is established.
Man erhält eine gepickelte Hautblösse, die für die Weiterverarbeitung geeignet ist.The result is a pimpled skin that is suitable for further processing.
Claims (15)
- A process for pickling raw hides, which comprises treating a delimed raw hide with an aqueous liquor that comprises a reaction product of phenol and a sulfonating agent, the molar ratio of (phenol):(SO3) being (1):(1.1-2.2), and which is free from neutral salts, the reaction product being a mixture which substantially contains a sulfonated dihydroxydiphenyl sulfone as main component.
- A process according to claim 1, wherein the molar ratio of (phenol):(SO3) in the reaction product is (1):(1.4-1.8).
- A process according to claim 1, wherein the reaction product is a mixture which substantially contains a sulfonated dihydroxydiphenyl sulfone as main component and which has been adjusted to a pH of 0 to 10, preferably 0 to 4.5, by addition of alkali.
- A process according to any one of claims 1 to 3, wherein the aqueous liquor contains the reaction product in a concentration of 1 to 10 % by weight, based on the weight of the hide.
- A process according to any one of claims 1 to 4, wherein the pickling treatment is carried out at a pH between 3 and 4.
- A process according to any one of claims 1 to 5, wherein the pickling treatment is carried out at room temperature.
- A process according to claim 6, wherein the pickling treatment is carried out at a temperature between 20 and 30°C.
- A process as claimed in any one of claims 1 to 7, wherein the treatment is between 90 and 180 minutes.
- A process according to any one of claims 1 to 8, wherein the pickling liquor comprises a C1-C3carboxylic acid or a mineral acid as optional component.
- A process according to claim 9, wherein the pickling liquor contains the C1-C3carboxylic acid or the mineral acid in a concentration of 0 to 1 % by weight.
- A process according to either of claim 9 or claim 10, wherein the C1-C3carboxylic acid used is formic acid.
- A composition for the preparation of pickled raw hides, which comprises(a) 1 to 10 % by weight of a reaction product of phenol and a sulfonating agent, the molar ratio of (phenol):(SO3) being (1):(1.1-2.2),(b) 0 to 1 % by weight of a C1-C3carboxylic acid or a mineral acid, and(c) 89 to 99 % by weight of water.
- A composition according to claim 12, which comprises(a) 1 to 10 % by weight of a reaction product obtained from phenol and a sulfonating agent, the molar ratio of (phenol):(SO3) being (1):(1.1-2.2), and(b) 0.1 to 1 % by weight of a C1-C3carboxylic acid or a mineral acid, and(c) 89 to 98.9 % by weight of water.
- A composition according to either of claim 12 or claim 13, wherein the molar ratio of (phenol):(SO3) in the reaction product is (1):(1.4-1.8).
- A composition according to any one of claims 12 to 14, wherein formic acid is used as component (b).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH241/92 | 1992-01-28 | ||
| CH24192 | 1992-01-28 | ||
| CH2675/92 | 1992-08-28 | ||
| CH267592 | 1992-08-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0554218A1 EP0554218A1 (en) | 1993-08-04 |
| EP0554218B1 true EP0554218B1 (en) | 1996-07-24 |
Family
ID=25683999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93810032A Expired - Lifetime EP0554218B1 (en) | 1992-01-28 | 1993-01-19 | Process for pickling hides |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5427594A (en) |
| EP (1) | EP0554218B1 (en) |
| JP (1) | JPH05247499A (en) |
| DE (1) | DE59303282D1 (en) |
| ES (1) | ES2090932T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200641140A (en) * | 2004-12-17 | 2006-12-01 | Tfl Ledertechnik Gmbh | Composition for the treatment of leather |
| EP2607499A3 (en) * | 2013-02-14 | 2013-07-10 | Basf Se | Method for producing leather |
| CN106755627B (en) * | 2017-01-09 | 2018-06-26 | 南雄西顿化工有限公司 | A kind of few salt auxiliary pickling agent and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE85933C (en) * | ||||
| FR18041E (en) * | 1912-05-11 | 1914-01-15 | Basf Ag | New tanning process, new tanning products and process for their production |
| GB148898A (en) * | 1916-07-20 | 1922-01-10 | Chemische Fabriken Worms Ag | Manufacture of tanning agents and the application thereof |
| FR879525A (en) * | 1941-02-20 | 1943-02-25 | Ig Farbenindustrie Ag | Tanning agents and process for preparing such bodies |
| GB683084A (en) * | 1949-06-20 | 1952-11-19 | Geigy Ag J R | Manufacture of new condensation products, being more especially improved tanning agents and their application |
| US4830632A (en) * | 1986-05-05 | 1989-05-16 | Ciba-Geigy Corporation | Aqueous composition from a sulfonated phenol, an amine and a tanning salt, process for the production thereof and use thereof as a tanning agent |
-
1993
- 1993-01-19 ES ES93810032T patent/ES2090932T3/en not_active Expired - Lifetime
- 1993-01-19 DE DE59303282T patent/DE59303282D1/en not_active Expired - Lifetime
- 1993-01-19 EP EP93810032A patent/EP0554218B1/en not_active Expired - Lifetime
- 1993-01-22 US US08/007,424 patent/US5427594A/en not_active Expired - Lifetime
- 1993-01-28 JP JP5012088A patent/JPH05247499A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05247499A (en) | 1993-09-24 |
| ES2090932T3 (en) | 1996-10-16 |
| EP0554218A1 (en) | 1993-08-04 |
| DE59303282D1 (en) | 1996-08-29 |
| US5427594A (en) | 1995-06-27 |
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