EP0554216B1 - Verfahren zum Pickeln und Vorgerben von Hautblössen - Google Patents

Verfahren zum Pickeln und Vorgerben von Hautblössen 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
Authority
EP
European Patent Office
Prior art keywords
process according
weight
component
phenol
pickling
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.)
Revoked
Application number
EP93810030A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0554216A1 (de
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
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Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0554216A1 publication Critical patent/EP0554216A1/de
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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.

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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP93810030A 1992-01-28 1993-01-19 Verfahren zum Pickeln und Vorgerben von Hautblössen Revoked EP0554216B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH23992 1992-01-28
CH239/92 1992-01-28

Publications (2)

Publication Number Publication Date
EP0554216A1 EP0554216A1 (de) 1993-08-04
EP0554216B1 true EP0554216B1 (de) 1996-07-10

Family

ID=4182461

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93810030A Revoked EP0554216B1 (de) 1992-01-28 1993-01-19 Verfahren zum Pickeln und Vorgerben von Hautblössen

Country Status (13)

Country Link
US (1) US5360453A (es)
EP (1) EP0554216B1 (es)
JP (1) JPH089720B2 (es)
KR (1) KR960001664B1 (es)
AT (1) ATE140268T1 (es)
AU (1) AU664225B2 (es)
BR (1) BR9300294A (es)
DE (1) DE59303163D1 (es)
DK (1) DK0554216T3 (es)
ES (1) ES2089770T3 (es)
GR (1) GR3020511T3 (es)
MX (1) MX9300458A (es)
ZA (1) ZA93579B (es)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPM780494A0 (en) * 1994-09-01 1994-09-22 Commonwealth Scientific And Industrial Research Organisation Pickling of hides and skins
AU703154B2 (en) * 1994-09-01 1999-03-18 Australian Association Of Leather Industries Pickling of hides and skins
EP0717114A3 (de) * 1994-12-15 1996-08-21 Ciba Geigy Ag Wässrige Zusammensetzung zum Vorgerben von Hautblössen oder Nachgerben von Leder
DE19930735A1 (de) * 1999-07-02 2000-01-05 Jozef Sagala Mittel und Verfahren zur Herstellung von Lederhalbfabrikaten
CN105238888A (zh) * 2015-10-27 2016-01-13 兴业皮革科技股份有限公司 一种基于锆铝钛配合物制备白湿革的生产工艺
CN114277202A (zh) * 2021-11-12 2022-04-05 宁夏西部皮草有限公司 一种高密度羊剪绒生产加工工艺

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE85933C (es) *
US20502A (en) * 1858-06-08 Improvement in methods of tanning
DE190702C (es) *
US30393A (en) * 1860-10-16 Improvement in the treatment of tanned leather
FR18041E (fr) * 1912-05-11 1914-01-15 Basf Ag Nouveau procédé de tannage, nouveaux produits tannants et procédé pour leur 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 (es) * 1972-04-01 1974-02-28 Basf Ag Procedimiento para la obtencion de formulaciones curtientes
DE3001301A1 (de) * 1980-01-16 1981-07-23 Basf Ag, 6700 Ludwigshafen Verfahren zum vorbereiten von anionisch gegerbtem oder nachgegerbtem leder
DE3308087A1 (de) * 1983-03-08 1984-09-27 Röhm GmbH, 6100 Darmstadt Verfahren zur chromgerbung von bloessen
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 (fr) * 1987-02-11 1989-05-12 Centre Tech Cuir Chaussure Peaux biologiquement stabilisees et non tannees et procede d'obtention de ces peaux
DE3731810A1 (de) * 1987-09-22 1989-03-30 Basf Ag Kondensationsprodukte des bis-(4-hydroxyphenyl)-sulfons als gerbereihilfsmittel, deren herstellung und verwendung sowie ein verfahren zum gerben von leder
DE3811267C1 (es) * 1988-04-02 1989-05-18 Schill & Seilacher Gmbh & Co, 7030 Boeblingen, De
DE4102545A1 (de) * 1991-01-29 1992-07-30 Basf Ag Verfahren zum alleingerben, vorgerben und mitgerben von bloessen und fellbloessen und zum nachgerben von leder und fell

Also Published As

Publication number Publication date
US5360453A (en) 1994-11-01
DE59303163D1 (de) 1996-08-14
GR3020511T3 (en) 1996-10-31
ES2089770T3 (es) 1996-10-01
ZA93579B (en) 1993-07-28
AU3207093A (en) 1993-07-29
ATE140268T1 (de) 1996-07-15
JPH05247498A (ja) 1993-09-24
KR930016547A (ko) 1993-08-26
DK0554216T3 (da) 1996-08-19
MX9300458A (es) 1993-07-01
JPH089720B2 (ja) 1996-01-31
KR960001664B1 (ko) 1996-02-03
AU664225B2 (en) 1995-11-09
BR9300294A (pt) 1993-08-03
EP0554216A1 (de) 1993-08-04

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