EP0554216B1 - Process for pickling and pretanning of hides - Google Patents

Process for pickling and pretanning of hides Download PDF

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Publication number
EP0554216B1
EP0554216B1 EP93810030A EP93810030A EP0554216B1 EP 0554216 B1 EP0554216 B1 EP 0554216B1 EP 93810030 A EP93810030 A EP 93810030A EP 93810030 A EP93810030 A EP 93810030A EP 0554216 B1 EP0554216 B1 EP 0554216B1
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EP
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Prior art keywords
process according
weight
component
phenol
pickling
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German (de)
French (fr)
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EP0554216A1 (en
Inventor
Alain Dr. Lauton
Markus Hess
Günter Streicher
Alois Dr. Püntener
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BASF Schweiz AG
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Ciba Geigy AG
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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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents

Definitions

  • the present invention relates to a method for pickling and pre-tanning skin bumps and the leather material produced by the present method.
  • a decalcified and pickled pale must first be subjected to a pimple treatment.
  • This treatment is used to adjust the bare skin to a pH of approx. 3-4, at which the common tanning agents show their best effect.
  • Sulfuric, hydrochloric or formic acid is generally used for the picking process, with the addition of a neutral salt such as e.g. Sodium chloride or sodium sulfate is required.
  • neutral salts prevent damaging acidic swelling of the collagen ("acid swelling") caused by the acids.
  • the pre-tanning that follows the pimple process is usually carried out in liquors containing heavy metals, e.g. highly basic aluminum or zirconium, and preferably chrome salt baths.
  • heavy metals e.g. highly basic aluminum or zirconium, and preferably chrome salt baths.
  • DE-A-3 811 267 discloses a process for the production of semi-finished leather products by pretanning, in which a mixture of a dialdehyde and a specific hydroxy compound is used as the tanning agent formulation.
  • DE-A-190 702 describes a process for decalcifying skins, in which the skins are soaked in a bath of sulfur and a carbohydrate which is in alcoholic fermentation.
  • DE-A-85 933 relates to a method for decalcifying (pickling) and swelling everyone Types of skins and skins by treating them with sulfonic acids of phenol and cresols in aqueous solution.
  • a combined pimple-pretanning process has now been found, which surprisingly makes it possible to carry out the pimple and tanning process in a one-bath process, in which mineral and neutral salts can be dispensed with and with which good pimple and tanning results are achieved.
  • the preferred sulfonating agent used to prepare component (a) 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)
  • the reaction product of phenol and oleum is known per se.
  • GB-A-0,683,084 the production of reaction products from phenol and oleum, which however, e.g. Formaldehyde and urea or thiourea are further implemented and used as tanning agents.
  • the reaction product according to the invention is a mixture, the main constituent of which is sulfonated dihydroxydiphenyl sulfones.
  • Component (a) is contained in the pickle liquor A in an amount of 1 to 10, preferably 3 to 5% by weight, based on the weight of the pomace.
  • a C 1 -C 3 carboxylic acid is added to the pickle liquor A as an optional component (a1), which is present in the pickle liquor in an amount of 0 to 1, preferably 0.1 to 1% by weight.
  • carboxylic acids are formic acid, acetic acid or propionic acid.
  • Formic acid is preferably used for the picking process
  • aldoses or ketoses with a dextrose equivalent of 10 to 100 come into consideration as component (b). They are primarily mono- and disaccharides, but also oligo- and polysaccharides.
  • the dextrose equivalent is the amount of saccharide calculated in grams, which corresponds to 100 grams of dextrose in terms of reducing power.
  • Mono- or disaccharides are preferably used in the process according to the invention.
  • Suitable monosaccharides are, for example, glucose, fructose, mannose, arabinose and ribose.
  • Sucrose, maltose or lactose may be mentioned as representatives of the disaccharides.
  • Monosaccharides are preferred for the process according to the invention.
  • the aldoses are to be mentioned here, the glucose being of very special interest because of its easy accessibility and availability in technical quantities. preferably 40 to 80.
  • dialdehydes or mixtures thereof which have 2 to 8 carbons and structurally saturated aliphatic C-C linkages can generally be used as dialdehydes corresponding to component (c).
  • dialdehydes corresponding to component (c) examples include glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, adipindialdehyde, pimeline dialdehyde and dialdehyde derived from suberic acid.
  • Preferred representatives are succindialdehyde, glutardialdehyde, adipindialdehyde and glyoxal, of which glutardialdehyde is of primary interest.
  • the dialdehydes are usually available as commercially available dialdehydes containing 25 to 50% by weight of water.
  • the aqueous composition B is expediently prepared by dissolving component (a) at a temperature between 20 and 60 ° C. and then adding component (b) to the clear solution obtained.
  • the aqueous composition thus obtained is liquid and has good storage stability.
  • Component (b) is preferably a monosaccharide with a dextrose equivalent of 100 or a disaccharide with a dextrose equivalent of 20-60.
  • aqueous compositions B which contain 0.05 to 0.19 mol of component (b) per mole of component (c).
  • 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 washed in an aqueous pimple liquor which contains the component ( a) contains, treated for 90 to 180 minutes.
  • 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. If, in a preferred embodiment, the pimple liquor additionally contains the optional component (a1), the procedure is such that the pellets are treated within 15 minutes in the aqueous liquor A which contains half the concentration of component (a) given above.
  • component (a) is added to the pickling liquor and component (a1) and further treated as usual. Then you give for the Pre-tanning the pickle liquor with the aqueous composition B.
  • the pH is adjusted to a value between 3.5 and 4.5. Treatment is continued for 8 to 14 hours at a temperature between 20 and 30 ° C.
  • the entire treatment takes place in the reel or preferably in a rotating barrel.
  • the leather treated in this way can be drained very well and therefore also makes it easier to fold to the desired thickness.
  • This pre-tanned leather is ideally suited for further processing with all common mineral, vegetable and synthetic tanning agents.
  • the pre-tanned leather is particularly suitable for the production of wet white leather. It is characterized by a soft, voluminous handle.
  • the present process can also be used to produce finished tanned leather.
  • Phenolsulfonic acid is also formed as a by-product.
  • a clear, light solution is obtained which has a pH of 3.9-4.2.
  • the dry content is 50%.
  • 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.
  • Example 2 1.5% of the composition according to Example 2 are added to the pickling liquor.
  • the pH is adjusted to 4.0 using powdered sodium hydrogen carbonate or sodium hydrogen sulfate. Treatment is continued for 8 to 16 hours at a temperature of 25 ° C.
  • the wet white leather produced in this way is dewatered and folded to the desired thickness.
  • This pre-tanned leather is ideally suited for further processing with mineral, vegetable or synthetic tanning agents to produce leather free of heavy metals.
  • Example 3 If one works as described in Example 3, but instead of using 1.5% of the composition according to Example 2, 1% glutardialdehyde and 0.6% of a 50% glucose syrup with a dextrose equivalent of 60, a wet white is obtained. Leather with a shrinking temperature of approx. 75 ° C.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Cosmetics (AREA)

Abstract

The invention relates to a process for pickling and pretanning hides, which is characterised in that (I) the hides are pickled in an aqueous liquor A which is free from salts, and (a) contains a product of the reaction of phenol and a sulphonating agent, where the phenol:SO3 molar ratio is from 1:1.1 to 2.2, and (II) the pickled hides are pretanned in the same bath by addition of an aqueous composition B containing (b) a reductive saccharide having a dextrose equivalent of from 10 to 100, and (c) an aliphatic dialdehyde containing 2 to 8 carbon atoms. The present combined one-bath pickling/pretanning process allows the production, in treatment baths which are free from neutral salts and heavy metals, of readily shavable wet-white leathers which are suitable for further processing by all customary tanning methods.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Pickeln und Vorgerben von Hautblössen sowie das nach dem vorliegenden Verfahren hergestellte Ledermaterial.The present invention relates to a method for pickling and pre-tanning skin bumps and the leather material produced by the present method.

Zur Vorbereitung für die Gerbung muss eine entkälkte und gebeizte Blösse zunächst einer Pickelbehandlung unterzogen werden. Diese Behandlung dient zur Einstellung der Hautblössen auf einen pH-Wert von ca. 3-4, bei welchem die gängigen Gerbmittel ihre beste Wirkung zeigen. Für den Pickelvorgang verwendet man im allgemeinen Schwefel-, Salz- oder Ameisensäure, wobei gleichzeitig der Zusatz eines Neutralsalzes wie z.B. Natriumchlorid oder Natriumsulfat erforderlich ist. Durch diese Neutralsalze wird eine durch die Säuren verursachte schädigende saure Quellung des Kollagens ("Säureschwellung") verhindert.To prepare for tanning, a decalcified and pickled pale must first be subjected to a pimple treatment. This treatment is used to adjust the bare skin to a pH of approx. 3-4, at which the common tanning agents show their best effect. Sulfuric, hydrochloric or formic acid is generally used for the picking process, with the addition of a neutral salt such as e.g. Sodium chloride or sodium sulfate is required. These neutral salts prevent damaging acidic swelling of the collagen ("acid swelling") caused by the acids.

Die sich an den Pickelprozess anschliessende Vorgerbung wird gewöhnlich in schwermetallhaltigen Flotten durchgeführt, wie z.B. hochbasischen Aluminium- oder Zirkonium-, und vozugsweise Chromsalzbädern.The pre-tanning that follows the pimple process is usually carried out in liquors containing heavy metals, e.g. highly basic aluminum or zirconium, and preferably chrome salt baths.

Die Abwässer dieser neutralsalz- und schwermetallhaltigen Behandlungsbäder sind aus ökologischer Sicht sehr bedenklich, da sie einen wesentlichen Lastfaktor darstellen. Man ist daher bestrebt, Behandlungsbäder zu finden, die frei von diesen Verbindungen sind oder diese zumindest nur in geringen Mengen enthalten.The wastewater from these treatment baths containing neutral salt and heavy metals is very dangerous from an ecological point of view, since they represent a significant load factor. Efforts are therefore made to find treatment baths which are free from these compounds or at least only contain them in small amounts.

Aus der DE-A-3 811 267 ist ein Verfahren zur Herstellung von Lederhalbfabrikaten durch Vorgerben bekannt, in dem als Gerbstoff-Formulierung eine Mischung aus einem Dialdehyd und einer spezifischen Hydroxyverbindung verwendet wird.DE-A-3 811 267 discloses a process for the production of semi-finished leather products by pretanning, in which a mixture of a dialdehyde and a specific hydroxy compound is used as the tanning agent formulation.

In der DE-A-190 702 ist ein Verfahren zur Entkalkung von Häuten beschrieben, in dem die Häute in einem Bad aus Schwefel und einem in alkoholischer Gärung befindlichen Kohlehydrat geweicht werden.DE-A-190 702 describes a process for decalcifying skins, in which the skins are soaked in a bath of sulfur and a carbohydrate which is in alcoholic fermentation.

Die DE-A-85 933 betrifft ein Verfahren zum Entkalken (Beizen) und Schwellen aller Arten von Fellen und Häuten, in dem diese mit Sulfosäuren des Phenols und der Kresole in wässeriger Lösunug behandelt werden.DE-A-85 933 relates to a method for decalcifying (pickling) and swelling everyone Types of skins and skins by treating them with sulfonic acids of phenol and cresols in aqueous solution.

Es wurde nun ein kombiniertes Pickel-Vorgerbeverfahren gefunden, das es überraschenderweise ermöglicht, den Pickel- und Gerbvorgang in einem Einbad-Prozess durchzuführen, bei dem auf Mineral- und Neutralsalze verzichtet werden kann und mit dem gute Pickel-und Gerbresultate erzielt werden.A combined pimple-pretanning process has now been found, which surprisingly makes it possible to carry out the pimple and tanning process in a one-bath process, in which mineral and neutral salts can be dispensed with and with which good pimple and tanning results are achieved.

Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zum Pickeln und Vorgerben von Hautblössen, das dadurch gekennzeichnet ist, dass man

  • (I) die Hautblösse in einer wässrigen Flotte A pickelt, die frei von Salzen ist und
    • (a) ein Umsetzungsprodukt aus Phenol und einem Sulfonierungsmittel enthält,wobei das Molverhältnis (Phenol):(SO3) (1):(1,1-2,2) beträgt, und
  • (II) die gepickelte Hautblösse im selben Bad durch Zugabe einer wässrigen Zusammensetzung B, enthaltend
    • (b) ein reduktives Saccharid mit einem Dextrose-Äquivalent von 10 bis 100 und
    • (c) einen aliphatischen, 2 bis 8 Kohlenstoffatome enthaltenden Dialdehyd, vorgerbt
The present invention therefore relates to a method for pimples and tanning skin bumps, which is characterized in that
  • (I) pimples the skin in an aqueous liquor A which is free of salts and
    • (a) contains a reaction product of phenol and a sulfonating agent, the molar ratio being (phenol) :( SO 3 ) (1) :( 1.1-2.2), and
  • (II) containing the pickled skin in the same bath by adding an aqueous composition B.
    • (b) a reductive saccharide with a dextrose equivalent of 10 to 100 and
    • (c) pre-tanned an aliphatic dialdehyde containing 2 to 8 carbon atoms

Bevorzugt wird als Sulfonierungsmittel zur Darstellung der Komponente (a) 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) beträgtThe preferred sulfonating agent used to prepare component (a) 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)

Das Umsetzungsprodukt aus Phenol und Oleum ist an sich bekannt. So beschreibt z.B. die GB-A-0,683,084 die Herstellung von Umsetzungsprodukten aus Phenol und Oleum, die jedoch mit z.B. Formaldehyd und Harnstoff oder Thioharnstoff weiter umgesetzt werden und als Gerbstoffe Verwendung finden. Das erfindungsgemässe Umsetzungsprodukt stellt ein Gemisch dar, dessen Hauptbestandteil sulfonierte Dihydroxydiphenylsulfone sind.The reaction product of phenol and oleum is known per se. For example, GB-A-0,683,084 the production of reaction products from phenol and oleum, which however, e.g. Formaldehyde and urea or thiourea are further implemented and used as tanning agents. The reaction product according to the invention is a mixture, the main constituent of which is sulfonated dihydroxydiphenyl sulfones.

Die Komponente (a) ist in der Pickelflotte A in einer Menge von 1 bis 10, vorzugsweise 3 bis 5 Gew.%, bezogen auf das Gewicht der Blösse, enthalten.Component (a) is contained in the pickle liquor A in an amount of 1 to 10, preferably 3 to 5% by weight, based on the weight of the pomace.

Neben der Komponente (a) wird der Pickelflotte A als fakultative Komponente (a1) eine C1-C3Carbonsäure zugegeben, die in einer Menge von 0 bis 1, vorzugsweise 0,1 bis 1 Gew.% in der Pickelflotte vorhanden ist. Als Beispiele für diese Carbonsäuren seien Ameisensäure, Essigsäure oder Propionsäure genannt. Vorzugsweise wird für den Pickelvorgang Ameisensäure verwendetIn addition to component (a), a C 1 -C 3 carboxylic acid is added to the pickle liquor A as an optional component (a1), which is present in the pickle liquor in an amount of 0 to 1, preferably 0.1 to 1% by weight. Examples of these carboxylic acids are formic acid, acetic acid or propionic acid. Formic acid is preferably used for the picking process

Als Komponente (b) kommen die üblichen Aldosen bzw. Ketosen mit einem Dextrose-Äquivalent von 10 bis 100 in Betracht. Es handelt sich vor allem um Mono- und Disaccharide, aber auch um Oligo- und Polysaccharide.The usual aldoses or ketoses with a dextrose equivalent of 10 to 100 come into consideration as component (b). They are primarily mono- and disaccharides, but also oligo- and polysaccharides.

Als Dextrose-Äquivalent bezeichnet man die in Gramm berechnete Menge an Saccharid, welche bezüglich des Reduktionsvermögens 100 Gramm Dextrose entsprechen.The dextrose equivalent is the amount of saccharide calculated in grams, which corresponds to 100 grams of dextrose in terms of reducing power.

Bevorzugt verwendet man im erfindungsgemässen Verfahren Mono- oder Disaccharide. Geeignete Monosaccharide sind z.B. Glucose, Fructose, Mannose, Arabinose und Ribose.Mono- or disaccharides are preferably used in the process according to the invention. Suitable monosaccharides are, for example, glucose, fructose, mannose, arabinose and ribose.

Als Vertreter der Disaccharide seien Saccharose, Maltose oder Lactose genannt. Für das erfindungsgemässe Verfahren werden Monosaccharide bevorzugt Hier seien insbesondere die Aldosen genannt, wobei die Glucose wegen ihrer leichten Zugänglichkeit und Verfügbarkeit in technischen Mengen von ganz besonderem Interesse ist Besonders geeignet wegen des günstigen Preises sind sogenannte Glucosesirupe mit einem Dextrose-Äquivalent von 20 bis 90, vorzugsweise 40 bis 80.Sucrose, maltose or lactose may be mentioned as representatives of the disaccharides. Monosaccharides are preferred for the process according to the invention. In particular, the aldoses are to be mentioned here, the glucose being of very special interest because of its easy accessibility and availability in technical quantities. preferably 40 to 80.

Als Dialdehyde entsprechend der Komponente (c) sind generell alle Dialdehyde oder deren Gemische verwendbar, die 2 bis 8 Kohlenstoffe und strukturell gesättigte aliphatische C-C-Verknüpfungen aufweisen. Als Beispiele seien Glyoxal, Malondialdehyd, Succindialdehyd, Glutardialdehyd, Adipindialdehyd, Pimelindialdehyd sowie der von der Korksäure sich ableitende Dialdehyd genannt. Bevorzugte Vertreter sind Succindialdehyd, Glutardialdehyd, Adipindialdehyd und Glyoxal, von denen Glutardialdehyd im Vordergrund des Interesses steht. Die Dialdehyde stehen gewöhnlich als handelsübliche 25 bis 50 Gew.% Wasser enthaltende Dialdehyde zur Verfügung.All dialdehydes or mixtures thereof which have 2 to 8 carbons and structurally saturated aliphatic C-C linkages can generally be used as dialdehydes corresponding to component (c). Examples include glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, adipindialdehyde, pimeline dialdehyde and dialdehyde derived from suberic acid. Preferred representatives are succindialdehyde, glutardialdehyde, adipindialdehyde and glyoxal, of which glutardialdehyde is of primary interest. The dialdehydes are usually available as commercially available dialdehydes containing 25 to 50% by weight of water.

Die Herstellung der wässrigen Zusammensetzung B erfolgt zweckmässig so, dass man die Komponente (a) bei einer Temperatur zwischen 20 und 60°C löst und anschliessend die erhaltene klare Lösung mit der Komponente (b) versetzt.The aqueous composition B is expediently prepared by dissolving component (a) at a temperature between 20 and 60 ° C. and then adding component (b) to the clear solution obtained.

Die so erhaltene wässrige Zusammensetzung ist flüssig und weist eine gute Lagerstabilität auf.The aqueous composition thus obtained is liquid and has good storage stability.

Bevorzugt ist die Komponente (b) ein Monosaccharid mit einem Dextrose-Äquivalent von 100 oder ein Disaccharid mit einem Dextrose-Äquivalent von 20-60.Component (b) is preferably a monosaccharide with a dextrose equivalent of 100 or a disaccharide with a dextrose equivalent of 20-60.

Bevorzugt enthält die Zusammensetzung B

  • (b) ein reduktives Saccharid mit einem Dextrose-Äquivalent von 10 bis 100 und
  • (c) Glutardialdehyd.
Composition B preferably contains
  • (b) a reductive saccharide with a dextrose equivalent of 10 to 100 and
  • (c) Glutardialdehyde.

In einer besonders bevorzugten Ausführungsform enthält die Zusammensetzung B

  • (b) ein Monosaccharid mit einem Dextrose-Äquivalent von 100 und
  • (c) Glutardialdehyd.
In a particularly preferred embodiment, the composition contains B
  • (b) a monosaccharide with a dextrose equivalent of 100 and
  • (c) Glutardialdehyde.

In einer weiteren bevorzugten Ausführungsform enthält die Zusammensetzung B

  • (b) ein Disaccharid mit einem Dextrose-Äquivalent von 20 bis 60 und
  • (c) Glutardialdehyd.
In a further preferred embodiment, the composition contains B
  • (b) a disaccharide with a dextrose equivalent of 20 to 60 and
  • (c) Glutardialdehyde.

Im Vordergrund des Interesses stehen Zusammensetzungen B, die

  • 2 bis 60, vorzugsweise 10 bis 40 Gew.% der Komponente (b),
  • 2 bis 75, vorzugsweise 30 bis 55 Gew.% der Komponente (c) und
  • Wasser zum Auffüllen auf 100 % enthalten.
In the foreground of interest are compositions B that
  • 2 to 60, preferably 10 to 40% by weight of component (b),
  • 2 to 75, preferably 30 to 55% by weight of component (c) and
  • Contain water to make up to 100%.

Ausserdem sind solche wässrigen Zusammensetzungen B bevorzugt, welch pro Mol der Komponente (c) 0,05 bis 0,19 Mol der Komponente (b) enthalten.In addition, those aqueous compositions B are preferred which contain 0.05 to 0.19 mol of component (b) per mole of component (c).

In einer bevorzugten Ausführungsform des erfindungsgemässen Verfahrens enthält die Flotte A

  • 1 bis 10 Gew.% der Komponente (a) und
  • 0 bis 5 Gew.% der Komponente (a1) und anschliessend an das Pickeln wird die gepickelte Hautblösse durch Zugabe einer wässrigen Zusammensetzung B, enthaltend
  • 2 bis 60 Gew.% der Komponente (b) und
  • 2 bis 75 Gew.% der Komponente (c), vorgegerbt.
In a preferred embodiment of the process according to the invention, the liquor contains A
  • 1 to 10% by weight of component (a) and
  • 0 to 5% by weight of component (a1) and subsequent to the pimples, the pickled skin is exposed by adding an aqueous composition B.
  • 2 to 60% by weight of component (b) and
  • 2 to 75% by weight of component (c), pre-tanned.

In einer ganz besonders bevorzugten Ausführungsform enthält die Flotte A

  • (a) 1 bis 10 Gew.% des Umsetzungsproduktes aus Phenol und einem Sulfonierungsmittel, wobei das Molverhältnis (Phenol):(SO3) (1):(1,4-1,8) beträgt, und
  • (a1) 0 bis 5 Gew. % Ameisensäure und die Zusammensetzung B
  • (b) 2 bis 60 Gew.% eines Monsaccharids mit einem Dextrose-Äquivalent von 100 und
  • (c) 2 bis 75 Gew.% Glutardialdehyd.
In a very particularly preferred embodiment, the liquor contains A
  • (a) 1 to 10% by weight of the reaction product of phenol and a sulfonating agent, the molar ratio (phenol) :( SO 3 ) (1) :( being 1.4-1.8), and
  • (a1) 0 to 5% by weight of formic acid and the composition B
  • (b) 2 to 60% by weight of a monsaccharide with a dextrose equivalent of 100 and
  • (c) 2 to 75% by weight of glutaraldehyde.

Bei dem erfindungsgemässen kombinierten Pickel-Vorgerbeverfahren 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, die die Komponente (a) enthält, 90 bis 180 Minuten behandelt. 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. Enthält in einer bevorzugten Ausführungsform die Pickelflotte zusätzlich die fakultative Komponente (a1), geht man so vor, dass man die Blösse innerhalb von 15 Minuten in der wässrigen Flotte A behandelt, die die Hälfte der oben angegebenen Konzentration der Komponente (a) enthält. Im Anschluss daran gibt man die zweite Hälfte der Komponente (a) zur Pickelflotte sowie die Komponente (a1) und behandelt wie üblich weiter. Im Anschluss gibt man für die Vorgerbung der Pickelflotte die wässrige Zusammensetzung B hinzu. Der pH-Wert wird auf einen Wert zwischen 3,5 und 4,5 eingestellt. Man behandelt während 8 bis 14 Stunden bei einer Temperatur zwischen 20 und 30°C weiter.In the combined pimple pre-tanning process according to the invention, 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 washed in an aqueous pimple liquor which contains the component ( a) contains, treated for 90 to 180 minutes. 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. If, in a preferred embodiment, the pimple liquor additionally contains the optional component (a1), the procedure is such that the pellets are treated within 15 minutes in the aqueous liquor A which contains half the concentration of component (a) given above. Then the second half of component (a) is added to the pickling liquor and component (a1) and further treated as usual. Then you give for the Pre-tanning the pickle liquor with the aqueous composition B. The pH is adjusted to a value between 3.5 and 4.5. Treatment is continued for 8 to 14 hours at a temperature between 20 and 30 ° C.

Weitere Zusätze für das Behandlungsbad sind zur Durchführung des erfindungsgemässen Verfahrens nicht erforderlich.No further additives for the treatment bath are required to carry out the method according to the invention.

Die gesamte Behandlung erfolgt im Haspel oder vorzugsweise im rotierenden Fass.The entire treatment takes place in the reel or preferably in a rotating barrel.

Das so behandelte Leder lässt sich sehr gut entwässern und erleichtert daher auch die Falzbarkeit auf die gewünschte Dicke. Dieses vorgegerbte Leder ist hervorragend geeignet für eine Weiterverarbeitung mit allen gängigen mineralischen, vegetabilen und synthetischen Gerbstoffen. Ganz besonders ist das vorgegerbte Leder geeignet zur Herstellung von Wet-White-Ledern. Es zeichnet sich durch einen weichen, fülligen Griff aus.The leather treated in this way can be drained very well and therefore also makes it easier to fold to the desired thickness. This pre-tanned leather is ideally suited for further processing with all common mineral, vegetable and synthetic tanning agents. The pre-tanned leather is particularly suitable for the production of wet white leather. It is characterized by a soft, voluminous handle.

Bei entsprechender Prozessführung lassen sich mit dem vorliegenden Verfahren auch fertig gegerbte Leder herstellen.With appropriate process control, the present process can also be used to produce finished tanned leather.

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.

Die in den nachfolgenden Herstellungsvorschriften und Applikationsbeispielen angegebenen Prozente und Teile beziehen sich auf das Gewicht.The percentages and parts given in the following manufacturing instructions and application examples refer to the weight.

Beispiel 1: Herstellung der Komponente (a)Example 1: Preparation of component (a)

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 bei 160°C während 6 Stunden unter Rühren gehalten, wobei das durch die Reaktion gebildete Wasser zusammen mit geringen Anteilen geschmolzenen Phenols aus dem Reaktionsgemisch azeotrop entfernt werden. Anschliessend wird das Reaktionsgemisch unter Normaldruck auf 40°C abgekühlt. Man erhält 253 Teile eines geschmolzenen Gemisches, das als Hauptbestandteil Sulfonsäuren der Formel

Figure imgb0001
(n= 1 oder 2)
enthält.136.5 parts of phenol (1.45 moles) are melted at 45 ° C. 193.4 parts of 20% oleum (2.08 mol of SO 3 ) are slowly added to this melt such that the temperature of the reaction mixture does not rise above 160.degree. The reaction mixture is then kept under reduced pressure at 2666.44 Pa (20 torr) and at 160 ° C. for 6 hours with stirring, the water formed by the reaction together with small amounts of molten phenol being removed from the reaction mixture azeotropically. The reaction mixture is then cooled to 40 ° C. under normal pressure. 253 parts of a molten mixture are obtained, the main constituent being sulfonic acids of the formula
Figure imgb0001
 (n = 1 or 2)
contains.

Als Nebenprodukt wird auch noch Phenolsulfonsäure gebildet.Phenolsulfonic acid is also formed as a by-product.

Beispiel 2: Herstellung der Zusammensetzung BExample 2: Preparation of composition B.

In einem Sulfierkolben werden

  • 167 ml Wasser vorgelegt und auf 60°C erhitzt. Unter gutem Rühren werden
  • 167 g Glucosemonohydrat (Dextrose-Äquivalent 100) innerhalb von 20 Minuten zugegeben.
Be in a sulfonation flask
  • Submitted 167 ml of water and heated to 60 ° C. With good stirring
  • 167 g of glucose monohydrate (dextrose equivalent 100) were added within 20 minutes.

Wenn alles gelöst ist, lässt man bei 20°CWhen everything is solved, leave at 20 ° C

666 g Glutardialdehyd 50%ig zufliessen.Add 666 g of 50% glutardialdehyde.

Man ehhält eine klare, helle Lösung, die einen pH-Wert von 3,9-4,2 aufweist. Der Trockengehalt beträgt 50%.A clear, light solution is obtained which has a pH of 3.9-4.2. The dry content is 50%.

Applikationsbeispiele:Application examples: Beispiel 3: Example 3 :

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, bezogen auf das der Gewicht der Blösse,

  • 50% Wasser und
  • 2% des gemäss Beispiel 1 hergestellten Umsetzungsproduktes enthält.
This nakedness is placed in a pickle fleet which, based on the weight of the naked woman,
  • 50% water and
  • Contains 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.
You then add to this fleet
  • 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.

Anschliessend gibt man zur Pickelflotte 1,5 % der Zusammensetzung gemäss Beispiel 2. Mit pulverisierterm Natriumhydrogencarbonat oder Natriumhydrogensulfat wird der pH-Wert auf 4,0 eingestellt Man behandelt während 8 bis 16 Stunden bei einer Temperatur von 25°C weiter.Then 1.5% of the composition according to Example 2 are added to the pickling liquor. The pH is adjusted to 4.0 using powdered sodium hydrogen carbonate or sodium hydrogen sulfate. Treatment is continued for 8 to 16 hours at a temperature of 25 ° C.

Das so hergestellte Wet-White-Leder wird entwässert und auf die gewünschte Dicke gefalzt. Dieses vorgegerbte Leder ist hervorragend geeignet für eine Weiterverarbeitung mit mineralischen, vegetabilen oder synthetischen Gerbstoffen zur Herstellung von schwermetallfreien Ledern.The wet white leather produced in this way is dewatered and folded to the desired thickness. This pre-tanned leather is ideally suited for further processing with mineral, vegetable or synthetic tanning agents to produce leather free of heavy metals.

Beispiel 4:Example 4:

Arbeitet man wie im Beispiel 3 beschrieben, verwendet jedoch anstelle von 1,5 % der Zusammensetzung gemäss Beispiel 2 1% Glutardialdehyd und 0,6 % eines 50 %igen Glucosesirups mit einem Dextrose-Äquivalent von 60, so erhält man ein Wet-White-Leder mit einer Schrumpfungstemperatur von ca. 75° C.If one works as described in Example 3, but instead of using 1.5% of the composition according to Example 2, 1% glutardialdehyde and 0.6% of a 50% glucose syrup with a dextrose equivalent of 60, a wet white is obtained. Leather with a shrinking temperature of approx. 75 ° C.

Claims (20)

  1. A process for pickling and pretanning raw hides, which comprises
    (I) pickling the raw hide in an aqueous liquor A which is devoid of salts and comprises
    (a) a reaction product of phenol and a sulfonating agent, the molar ratio of (phenol):(SO3) being (1):(1.1-2.2) and
    (II) pretanning the pickled raw hide in the same bath by addition of an aqueous formulation B comprising
    (b) a reductive saccharide having a dextrose equivalent of 10 to 100, and
    (c) an aliphatic dialdehyde containing 2 to 8 carbon atoms.
  2. A process according to claim 1, wherein the molar ratio of (phenol):(SO3) in the reaction product (a) is (1):(1.4-1.8).
  3. A process according to claim 1 or 2, wherein the reaction product (a) is a mixture that contains sulfonated dihydroxydiphenylsulfones as main component.
  4. A process according to any one of claims 1 to 3, wherein the aqueous pickling liquor A contains the reaction product (a) in an amount of 1 to 10% by weight, based on the weight of the hide.
  5. A process according to any one of claims 1 to 4, wherein the aqueous pickling liquor comprises a C1-C3-carboxylic acid as optional component (a1).
  6. A process according to claim 5, wherein the optional component (a1) is formic acid.
  7. A process according to claim 6, wherein the liquor A contains component (a1) in a concentration of 0 to 1 % by weight.
  8. A process according to claim 1, wherein component (b) is a monosaccharide having a dextrose equivalent of 100 or a disaccharide having a dextrose equivalent of 20 to 60.
  9. A process according to claim 8, wherein the monosaccharide is glucose.
  10. A process according to any one of claims 1, 8 or 9, wherein component (c) is glutaraldehyde.
  11. A process according to any one of claims 1 or 8 to 10, wherein a formulation B is used comprising
    (b) a monosaccharide having a dextrose equivalent of 100, and
    (c) glutaraldehyde.
  12. A process according to claim 10, wherein an aqueous liquor comprising
    (b) a disaccharide having a dextrose equivalent of 20 to 60, and
    (c) glutaraldehyde,
    is used for pretanning.
  13. A process according to claim 1, wherein a formulation B is used comprising 2 to 60 % by weight, preferably 10 to 40 % by weight, of component (b), 2 to 75 % by weight, preferably 30 to 55 % by weight, of component (c), and water to make up to 100 %.
  14. A process according to any one of claims 1 to 13, which comprises the use of a formulation B which contains, per mole of component (c), 0.05 to 0.19 mole of component (b).
  15. A process according to claim 1. wherein a liquor A is used comprising 1 to 10 % by weight of component (a),
    0 to 5 % by weight of component (a1), and
    a formulation B comprising
    2 to 60 % by weight of component (b), and
    2 to 75 % by weight of component (c).
  16. A process according to claim 15, wherein a liquor A is used comprising
    (a) 1 to 10 % by weight of the reaction product of phenol and a sulfonating agent, the molar ratio of (phenol):(SO3) being(1):(1.4-1.8), and
    (a1) 0 to 5 % by weight of formic acid, and a formulation B comprising
    (b) 2 to 60 % by weight of a monosaccharide having a dextrose equivalent of 100, and
    (c) 2 to 75 % by weight of glutaraldehyde.
  17. A process according to any one of claims 1 to 16, wherein the pickling treatment time is between 90 to 180 minutes.
  18. A process according to any one of claims 1 to 17, wherein the pickling treatment is carried out at a pH between 3 and 4.
  19. A process according to any one of claims 1 to 18, wherein the pickling treatment is carried out at room temperature.
  20. A process according to any one of claims 1 to 19, wherein the pickling treatment is carried out at a temperature between from 20 and 30°C.
EP93810030A 1992-01-28 1993-01-19 Process for pickling and pretanning of hides Revoked EP0554216B1 (en)

Applications Claiming Priority (2)

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CH239/92 1992-01-28
CH23992 1992-01-28

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JP (1) JPH089720B2 (en)
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DE (1) DE59303163D1 (en)
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Publication number Priority date Publication date Assignee Title
AU703154B2 (en) * 1994-09-01 1999-03-18 Australian Association Of Leather Industries Pickling of hides and skins
AUPM780494A0 (en) * 1994-09-01 1994-09-22 Commonwealth Scientific And Industrial Research Organisation Pickling of hides and skins
EP0717114A3 (en) * 1994-12-15 1996-08-21 Ciba Geigy Ag Aqueous composition for pretanning hides or retanning of leather
DE19930735A1 (en) * 1999-07-02 2000-01-05 Jozef Sagala Production of stabilized wet-white leather products free of aldehyde, syntan and metal
CN105238888A (en) * 2015-10-27 2016-01-13 兴业皮革科技股份有限公司 Production technology for preparing wet white leather on basis of Zr-Al-Ti complex
CN114277202A (en) * 2021-11-12 2022-04-05 宁夏西部皮草有限公司 Production and processing technology of high-density shorn sheepskin

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Publication number Priority date Publication date Assignee Title
DE85933C (en) *
US20502A (en) * 1858-06-08 Improvement in methods of tanning
US30393A (en) * 1860-10-16 Improvement in the treatment of tanned leather
DE190702C (en) *
FR18041E (en) * 1912-05-11 1914-01-15 Basf Ag New tanning process, new tanning products and process for their production
GB148126A (en) * 1916-07-20 1921-12-09 Chemische Fabriken Worms Ag Manufacture of tanning agents and the application thereof
GB148898A (en) * 1916-07-20 1922-01-10 Chemische Fabriken Worms Ag Manufacture of tanning agents and the application thereof
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
US2941859A (en) * 1959-04-08 1960-06-21 Martin L Fein Tanning with glutaraldehyde
AR196921A1 (en) * 1972-04-01 1974-02-28 Basf Ag PROCEDURE FOR OBTAINING CURTIENT FORMULATIONS
DE3001301A1 (en) * 1980-01-16 1981-07-23 Basf Ag, 6700 Ludwigshafen Mfg. anionically tanned leather for anionic dyeing - by treating with ammonium salt and aldehyde
DE3308087A1 (en) * 1983-03-08 1984-09-27 Röhm GmbH, 6100 Darmstadt Process for the chrome-tanning of pelts
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
FR2610643B1 (en) * 1987-02-11 1989-05-12 Centre Tech Cuir Chaussure BIOLOGICALLY STABILIZED AND NON-TANNED SKINS AND PROCESS FOR OBTAINING THE SAME
DE3731810A1 (en) * 1987-09-22 1989-03-30 Basf Ag CONDENSATION PRODUCTS OF BIS (4-HYDROXYPHENYL) SULPHONE AS A TANE AUXILIARY AGENT, THEIR PRODUCTION AND USE AND A METHOD FOR TANNING LEATHER
DE3811267C1 (en) * 1988-04-02 1989-05-18 Schill & Seilacher Gmbh & Co, 7030 Boeblingen, De
DE4102545A1 (en) * 1991-01-29 1992-07-30 Basf Ag METHOD FOR GELING, PRELIMINATING AND GIVING BARE AND FUR BLOSSES AND FOR LEAVING LEATHER AND FUR

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US5360453A (en) 1994-11-01
JPH089720B2 (en) 1996-01-31
KR930016547A (en) 1993-08-26
DE59303163D1 (en) 1996-08-14
ES2089770T3 (en) 1996-10-01
MX9300458A (en) 1993-07-01
ATE140268T1 (en) 1996-07-15
BR9300294A (en) 1993-08-03
KR960001664B1 (en) 1996-02-03
ZA93579B (en) 1993-07-28
AU3207093A (en) 1993-07-29
AU664225B2 (en) 1995-11-09
JPH05247498A (en) 1993-09-24
EP0554216A1 (en) 1993-08-04
DK0554216T3 (en) 1996-08-19

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