EP0210481A2 - Procédé de déchaulage des peaux et utilisation d'esters cycliques de l'acide sulfureux comme agents de déchaulage - Google Patents

Procédé de déchaulage des peaux et utilisation d'esters cycliques de l'acide sulfureux comme agents de déchaulage Download PDF

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Publication number
EP0210481A2
EP0210481A2 EP86109313A EP86109313A EP0210481A2 EP 0210481 A2 EP0210481 A2 EP 0210481A2 EP 86109313 A EP86109313 A EP 86109313A EP 86109313 A EP86109313 A EP 86109313A EP 0210481 A2 EP0210481 A2 EP 0210481A2
Authority
EP
European Patent Office
Prior art keywords
deliming
liquor
agents
skins
descaling
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.)
Granted
Application number
EP86109313A
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German (de)
English (en)
Other versions
EP0210481B1 (fr
EP0210481A3 (en
Inventor
Kurt Dr. Schneider
Dietrich Dr. Lach
Rolf Streicher
Ortwin Dr. Schaffer
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 SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0210481A2 publication Critical patent/EP0210481A2/fr
Publication of EP0210481A3 publication Critical patent/EP0210481A3/de
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Publication of EP0210481B1 publication Critical patent/EP0210481B1/fr
Expired legal-status Critical Current

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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

Definitions

  • the invention relates in particular to a time-saving and efficient method for deliming skins with cyclic esters of sulfurous acid with an aliphatic 1,2-diol and the use of these esters as deliming agents.
  • the usual conditions are liquor lengths of 0 to 300, preferably 0 to 200%, based on the weight of the pelts. Temperatures from 5 to 38, preferably 25 to 35 ° C, pH values in the liquor at the end of the decalcification from 6 to 8.7 and decalcification times from 1 to 6, preferably 1 to 3 hours.
  • a disadvantage of this process is that the cyclic carbonates hydrolyze relatively slowly in the deliming process, so that in the case of thicknesses of around 4.5 mm, times of at least 2 hours are required for complete deliming. These times are sometimes too long for practice.
  • the invention relates to the use of compounds of the formula I. in which R1 is a hydrogen atom or a saturated alkyl radical having 1 to 4 carbon atoms, which is optionally substituted by a chlorine atom, and R2 is a hydrogen atom or a methyl radical, for deliming hides and a process for deliming hides under conventional deliming conditions with regard to liquor length, temperature and pH of the liquor, in which a compound of the formula (I) is used as the active agent.
  • R1 is a hydrogen atom or a saturated alkyl radical having 1 to 4 carbon atoms, which is optionally substituted by a chlorine atom
  • R2 is a hydrogen atom or a methyl radical
  • the decalcification according to the invention takes place completely within 30 minutes to 4 hours, ie, surprisingly, the decalcification times can frequently be halved by the invention compared to the cyclic carbonates described.
  • descaling is completed within 60 to 90 minutes in the case of split beef bare bones with a split thickness of 4 to 4.5 mm.
  • no higher concentration of gaseous hydrogen sulfide was found is, although this would have been expected at a somewhat lower pH range.
  • Alkyl radicals having 1 to 4 carbon atoms are to be understood as meaning saturated, straight-chain or branched aliphatic radicals which are optionally substituted by a chlorine atom. Of these, methyl and ethyl are particularly preferred.
  • R1 and R2 are hydrogen and methyl.
  • the compounds of formula (I) are cyclic esters of sulfurous acid with an aliphatic 1,2-diol.
  • the compounds of the formula I are known or can be prepared in a manner known per se, for example by reacting sulfur dioxide with a corresponding epoxide.
  • Examples of compounds of the formula I which may be mentioned are: ethylene glycol sulfite, propylene glycol sulfite, 1,2-butylene glycol sulfite, isobutylene glycol sulfite and the cyclic ester of epichlorohydrin and sulfur dioxide.
  • Ethylene glycol sulfite and propylene glycol sulfite are mentioned as preferred.
  • Ashes are used in the usual way, for example cattle flanks and skins of small animals such as sheep and goats.
  • Small animal skins, such as those of sheep and goats thicknesses of 1 to 3 mm.
  • liquor lengths are from 0 to 300%, based on the weight of the nakedness. Temperatures of 5 to 38 ° C and pH values within a range of 6 to 8.7 are appropriate.
  • the preferred areas are:
  • the compounds of the formula I to be used according to the invention are expediently used in an amount of 0.5 to 3, preferably 1 to 2%, based on the pelt weight.
  • the compounds of formula I are liquid and are advantageously added directly or in the form of an aqueous solution. Emulsification or dispersion of insufficiently water-soluble compounds of the formula I can be carried out in a conventional manner with cationic, anionic or nonionic emulsifiers. It is in no way problematic.
  • decalcifying agents according to the invention can also be used in mixtures with other customary deliming agents, for example the cyclic carbonates mentioned above, in particular ethylene and propylene carbonate, esters of formic acid, boric acid, ammonium salts or ammonium sulfate.
  • other customary deliming agents for example the cyclic carbonates mentioned above, in particular ethylene and propylene carbonate, esters of formic acid, boric acid, ammonium salts or ammonium sulfate.
  • mixtures of different decalcifying agents are used, decalcifications together with ethylene, propylene carbonate or ethylene glycol formate are preferred.
  • Mixtures of a cyclic sulfite of the formula I and one of the cyclic carbonates mentioned above are advantageously used, in which 10 to 50% by weight of the cyclic sulfite of the formula I have been replaced by a cyclic carbonate.
  • These mixtures are also expediently used in an amount of 0.5 to 3, preferably 1 to 2%, based on the weight of the nakedness.
  • 110 parts of ashed beef flanks with a gap thickness of 4 to 4.5 mm are first washed with 330 parts of water at 35 ° C. for 15 minutes by being drummed in a tanning drum. The wash liquor is then discarded. 110 parts of water at 35 ° C. and then 2.2 parts of propylene glycol sulfite are added to the washed pelts in the same barrel. After 5 minutes of flexing, a pH of 6.9 is measured in the liquor. 30 minutes after adding the descaling agent, the liquor has a pH of 7.2, the degree of descaling is 60%. 30 minutes later, the pH was 7.1 and the pelts were 75% decalcified. The descaling is complete after a further 30 minutes, the final pH is 7.
  • Example 2 In parallel to Example 1, 2.2 parts of propylene carbonate are used as descaling agents under the same conditions. After 5 minutes, the liquor shows a pH of 8.1 with a degree of descaling of 10%. Decalcification is complete after 3 hours and the final pH is 8.4.
  • Example 2 Analogously to Example 1, 1100 parts of ashed beef flanks with a gap thickness of 5 to 5.5 mm are cooled to 1100 parts of aqueous liquor by adding 22 parts of ethylene glycol sulfite. The pH of the liquor is initially 6.6 after 3 hours 6.1. A hydrogen sulfide concentration of 400 ppm is measured above the liquor in the gas space of the tanning drum.
  • Example 3 In parallel to Example 3, the deliming is carried out with 1100 parts of beef flanks of the same gap strength in 1100 parts of aqueous liquor by adding 22 parts of the ethylene glycol formate mentioned in Example 1 in DE-C-28 25 081.
  • the initial pH is 6.7, after 3 hours, well over 2000 ppm of hydrogen sulfide are measured in the gas space above the liquor at pH 6.4.
  • Example 3 In parallel to Example 3 and Comparative Example 3A, descaling is carried out with 22 parts of ethylene carbonate.
  • the initial pH is 7.6. Decalcification is complete after 3 hours.
  • the final pH is 7.5; 800 ppm of hydrogen sulfide are measured above the fleet.
  • the sulfide content is determined in the residual liming liquor obtained according to Example 3 and Comparative Examples 3A and 3B.
  • the decalcified pelts obtained according to Example 3 and Comparative Examples 3A and 3B are washed for 2 minutes in 5000 parts of water at 25 ° C. and then in tanning vats with 1000 parts of pickling liquor (mixture of formic acid, sulfuric acid and sodium chloride) of pH 0.5 25 Pissed for minutes.
  • the pickle liquor shows a pH of 2.7 at the end.
  • the concentration of hydrogen sulfide is then determined in the gas space above the pickling liquor.

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Paper (AREA)
EP86109313A 1985-07-27 1986-07-08 Procédé de déchaulage des peaux et utilisation d'esters cycliques de l'acide sulfureux comme agents de déchaulage Expired EP0210481B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3527013 1985-07-27
DE19853527013 DE3527013A1 (de) 1985-07-27 1985-07-27 Verfahren zum entkaelken von haeuten und verwendung von cyclischen estern der schwefligen saeure als entkaelkungsmittel

Publications (3)

Publication Number Publication Date
EP0210481A2 true EP0210481A2 (fr) 1987-02-04
EP0210481A3 EP0210481A3 (en) 1987-08-12
EP0210481B1 EP0210481B1 (fr) 1988-11-02

Family

ID=6276998

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86109313A Expired EP0210481B1 (fr) 1985-07-27 1986-07-08 Procédé de déchaulage des peaux et utilisation d'esters cycliques de l'acide sulfureux comme agents de déchaulage

Country Status (6)

Country Link
US (1) US4729768A (fr)
EP (1) EP0210481B1 (fr)
JP (1) JPS6330600A (fr)
CA (1) CA1257755A (fr)
DE (2) DE3527013A1 (fr)
ES (1) ES2000764A6 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2825081B1 (de) * 1978-06-08 1979-10-04 Basf Ag Verfahren zum Entkaelken von Haeuten
EP0059909A1 (fr) * 1981-03-06 1982-09-15 BASF Aktiengesellschaft Procédé de déchaulage de peaux

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4078888A (en) * 1976-09-20 1978-03-14 Abbott Laboratories Fungal protection for leather

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2825081B1 (de) * 1978-06-08 1979-10-04 Basf Ag Verfahren zum Entkaelken von Haeuten
EP0059909A1 (fr) * 1981-03-06 1982-09-15 BASF Aktiengesellschaft Procédé de déchaulage de peaux

Also Published As

Publication number Publication date
JPS6330600A (ja) 1988-02-09
DE3527013A1 (de) 1987-02-05
US4729768A (en) 1988-03-08
EP0210481B1 (fr) 1988-11-02
ES2000764A6 (es) 1988-03-16
CA1257755A (fr) 1989-07-25
DE3661082D1 (en) 1988-12-08
EP0210481A3 (en) 1987-08-12

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