EP0554218B1 - Procédé pour piquage de peaux - Google Patents

Procédé pour piquage de peaux Download PDF

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Publication number
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
Authority
EP
European Patent Office
Prior art keywords
phenol
weight
reaction product
process according
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
EP93810032A
Other languages
German (de)
English (en)
Other versions
EP0554218A1 (fr
Inventor
Alain Dr. Lauton
Markus Hess
Günter Streicher
Alois Dr. Püntener
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.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
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
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0554218A1 publication Critical patent/EP0554218A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
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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
    • 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.

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)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (15)

  1. Procédé de picklage de peaux, caractérisé en ce que l'on traite une peau déchaulée dans un bain aqueux contenant un produit résultant de la réaction de phénol avec un agent de sulfonation, le rapport molaire phénol/SO3 étant compris entre 1/1,1 et 1/2,2, et qui est exempt de sels neutres, le produit réactionnel étant un mélange contenant, comme composant principal, essentiellement une dihydroxydiphénylsulfone sulfonée.
  2. Procédé conforme à la revendication 1, caractérisé en ce que le rapport molaire phénol/SO3 du produit réactionnel est compris entre 1/1,4 et 1/1,8.
  3. Procédé conforme à la revendication 1, caractérisé en ce que le produit réactionnel est un mélange contenant, comme composant principal, une dihydroxydiphénylsulfone sulfonée, dont le pH a été ajusté à une valeur comprise entre 0 et 10, de préférence entre 0 et 4,5, par addition d'un produit alcalin.
  4. Procédé conforme à une des revendications 1 à 3, caractérisé en ce que le bain de picklage aqueux contient le produit réactionnel à raison de 1 à 10 % en poids, par rapport au poids de la peaux.
  5. Procédé conforme à une des revendications 1 à 4, caractérisé en ce que le traitement de picklage est réalisé à un pH compris entre 3 et 4.
  6. Procédé conforme à une des revendications 1 à 5, caractérisé en ce que le traitement de picklage est effectué à température ambiante.
  7. Procédé conforme à la revendication 6, caractérisé en ce que le picklage est effectué à une température comprise entre 20 et 30 °C.
  8. Procédé conforme à une des revendications 1 à 7, caractérisé en ce que la durée de traitement est comprise entre 90 et 180 minutes.
  9. Procédé conforme à une des revendications 1 à 8, caractérisé en ce que le bain de picklage contient, comme composant facultatif, un acide carboxylique en C1-3 ou un acide minéral.
  10. Procédé conforme à la revendication 9, caractérisé en ce que l'acide carboxylique en C1-3 ou l'acide minéral est présent dans le bain de picklage à raison de 0 à 1 % en poids.
  11. Procédé conforme à la revendication 9 ou 10, caractérisé en ce que l'on utilise, comme acide carboxylique en C1-3, de l'acide formique.
  12. Agent pour la préparation de peaux picklées, caractérisé en ce qu'il contient
    (a) de 1 à 10 % en poids d'un produit réactionnel obtenu par réaction de phénol et d'un agent de sulfonation, le rapport molaire phénol/SO3 étant compris entre 1/1,1 et 1/2,2,
    (b) de 0 à 1 % en poids d'un acide carboxylique en C1-3 ou d'un acide minéral, et
    (c) de 89 à 99 % en poids d'eau.
  13. Agent conforme à la revendication 12, caractérisé en ce qu'il contient
    (a) de 1 à 10 % en poids d'un produit réactionnel obtenu par réaction de phénol et d'un agent de sulfonation, le rapport molaire phénol/SO3 étant compris entre 1/1,1 et 1/2,2,
    (b) de 0,1 à 1 % en poids d'un acide carboxylique en C1-3 ou d'un acide minéral, et
    (c) de 89 à 98,9 % en poids d'eau.
  14. Agent conforme à une des revendications 12 ou 13, caractérisé en ce que le rapport molaire phénol/SO3 du produit réactionnel est compris entre 1/1,4 et 1/1,8.
  15. Agent conforme à une des revendications 12 à 14, caractérisé en ce que l'on utilise, comme composant (b), de l'acide formique.
EP93810032A 1992-01-28 1993-01-19 Procédé pour piquage de peaux Expired - Lifetime EP0554218B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH24192 1992-01-28
CH241/92 1992-01-28
CH267592 1992-08-28
CH2675/92 1992-08-28

Publications (2)

Publication Number Publication Date
EP0554218A1 EP0554218A1 (fr) 1993-08-04
EP0554218B1 true EP0554218B1 (fr) 1996-07-24

Family

ID=25683999

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93810032A Expired - Lifetime EP0554218B1 (fr) 1992-01-28 1993-01-19 Procédé pour piquage de peaux

Country Status (5)

Country Link
US (1) US5427594A (fr)
EP (1) EP0554218B1 (fr)
JP (1) JPH05247499A (fr)
DE (1) DE59303282D1 (fr)
ES (1) ES2090932T3 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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 (fr) * 2013-02-14 2013-07-10 Basf Se Procédé destiné à la fabrication de cuir
CN106755627B (zh) * 2017-01-09 2018-06-26 南雄西顿化工有限公司 一种少盐浸酸助剂及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE85933C (fr) *
FR18041E (fr) * 1912-05-11 1914-01-15 Basf Ag Nouveau procédé de tannage, nouveaux produits tannants et procédé pour leur production
GB148898A (en) * 1916-07-20 1922-01-10 Chemische Fabriken Worms Ag Manufacture of tanning agents and the application thereof
FR879525A (fr) * 1941-02-20 1943-02-25 Ig Farbenindustrie Ag Agents de tannage et procédé de préparation de ces corps
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

Also Published As

Publication number Publication date
DE59303282D1 (de) 1996-08-29
JPH05247499A (ja) 1993-09-24
US5427594A (en) 1995-06-27
EP0554218A1 (fr) 1993-08-04
ES2090932T3 (es) 1996-10-16

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