EP1511865B1 - Method for removing horn substance from skins, pelts, or furs - Google Patents
Method for removing horn substance from skins, pelts, or furs Download PDFInfo
- Publication number
- EP1511865B1 EP1511865B1 EP03752667A EP03752667A EP1511865B1 EP 1511865 B1 EP1511865 B1 EP 1511865B1 EP 03752667 A EP03752667 A EP 03752667A EP 03752667 A EP03752667 A EP 03752667A EP 1511865 B1 EP1511865 B1 EP 1511865B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- skins
- weight
- pelts
- alkyl
- butyl
- 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
Links
- 238000000034 method Methods 0.000 title claims description 32
- 239000000126 substance Substances 0.000 title claims description 15
- 210000003491 skin Anatomy 0.000 claims description 45
- -1 alkaline earth metal salts Chemical class 0.000 claims description 23
- 239000010985 leather Substances 0.000 claims description 23
- 241001465754 Metazoa Species 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 14
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 12
- 210000002615 epidermis Anatomy 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 10
- 239000004571 lime Substances 0.000 claims description 10
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 5
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 5
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 5
- 150000004714 phosphonium salts Chemical class 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- 239000006227 byproduct Substances 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 239000011734 sodium Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 12
- 239000000920 calcium hydroxide Substances 0.000 description 12
- 235000011116 calcium hydroxide Nutrition 0.000 description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 12
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 6
- 231100000241 scar Toxicity 0.000 description 6
- 241000283690 Bos taurus Species 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 230000035617 depilation Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- WARHEJSPEGFSHO-UHFFFAOYSA-N 1,4-bis(sulfanyl)butane-1,1-diol Chemical compound OC(O)(S)CCCS WARHEJSPEGFSHO-UHFFFAOYSA-N 0.000 description 4
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- NRTLIYOWLVMQBO-UHFFFAOYSA-N 5-chloro-1,3-dimethyl-N-(1,1,3-trimethyl-1,3-dihydro-2-benzofuran-4-yl)pyrazole-4-carboxamide Chemical compound C=12C(C)OC(C)(C)C2=CC=CC=1NC(=O)C=1C(C)=NN(C)C=1Cl NRTLIYOWLVMQBO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- GYXHHICIFZSKKZ-UHFFFAOYSA-N 2-sulfanylacetamide Chemical compound NC(=O)CS GYXHHICIFZSKKZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011297 Brassica napobrassica Nutrition 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 241000700198 Cavia Species 0.000 description 2
- 241000282994 Cervidae Species 0.000 description 2
- 208000032544 Cicatrix Diseases 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 206010020649 Hyperkeratosis Diseases 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 206010000496 acne Diseases 0.000 description 2
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 2
- 244000309466 calf Species 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000002951 depilatory effect Effects 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000037387 scars Effects 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- WQCJLTVZOMTCJF-UHFFFAOYSA-N 1,2-bis(sulfanyl)butane-1,1-diol Chemical compound CCC(S)C(O)(O)S WQCJLTVZOMTCJF-UHFFFAOYSA-N 0.000 description 1
- ZQXIMYREBUZLPM-UHFFFAOYSA-N 1-aminoethanethiol Chemical compound CC(N)S ZQXIMYREBUZLPM-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- PBVAJRFEEOIAGW-UHFFFAOYSA-N 3-[bis(2-carboxyethyl)phosphanyl]propanoic acid;hydrochloride Chemical compound Cl.OC(=O)CCP(CCC(O)=O)CCC(O)=O PBVAJRFEEOIAGW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 241000270322 Lepidosauria Species 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000283903 Ovis aries Species 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 241000270295 Serpentes Species 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 241000271567 Struthioniformes Species 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- VXIVSQZSERGHQP-UHFFFAOYSA-N chloroacetamide Chemical compound NC(=O)CCl VXIVSQZSERGHQP-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000004087 cornea Anatomy 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000011132 hemopoiesis Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000991 leather dye Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 210000000282 nail Anatomy 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000037368 penetrate the skin Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 208000037244 polycythemia vera Diseases 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical class [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000012460 protein solution Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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
- C14C1/06—Facilitating unhairing, e.g. by painting, by liming
Definitions
- 1,4-Dimercaptobutandiol-containing formulations for the removal of horny substances, in particular hair, from living tissue is known, for example in unwanted beard growth.
- DE 21 31 630 shows DE 21 31 630 in that it is possible to apply agents consisting of at least 0.25% by weight of dimercaptobutanediol and about 0.01 to 40% by weight of a water-soluble guanidine compound and a pH of less than 12 to guinea pigs to depilate them, or human cornea to eliminate calluses, without causing skin irritation in guinea pigs or even erythremia (malignant growths of the red blood cell formation system).
- the epidermis remains at the in DE 21 31 630 received treatment described.
- EP-A 0 095 916 For example, the use of formulations containing aminoethanethiol and 1,4-dimercaptobutanediol and an aminoguanidine or diguanide compound is known to eliminate unwanted human body and facial hair. On page 2, line 1 it is taught that small thiol molecules are preferred to induce rapid depilation because they penetrate the skin more quickly. The epidermis remains at the in EP-A 0 095 916 received treatment described.
- EP-A 0 096 521 For example, the use of formulations containing, for example, 1,4-dimercaptobutanediol and an aminoguanidine or diguanide compound is known to eliminate unwanted human body and facial hair. The epidermis remains at the EP-A 0 096 521 received treatment described.
- horny substances are calluses, feathers, nails and claw parts, and in particular hair of animals.
- the skins, epidermis may still contain remnants of meat of the relevant dead animals.
- Essential to the invention is that they contain horny substances.
- the amount of horny substance, based on the total weight of the skin or the fur or the fur coat, is not critical.
- the inventive method is suitable both for the removal of large amounts of horny substance as well as for the removal of small hair residues.
- dead animals are understood not only to be slaughtered, hunted or otherwise deliberately killed by humans, but also to animals that have been due to accidents, for example traffic accidents, or fights with other animals or natural causes as age or disease have died.
- the hides, furs or furskins of the animals are usually skins, furs or fur skins of cattle, calves, pigs, goats, sheep, lambs, elks, game such as deer or deer, and birds such as ostriches, fish or reptiles such as snakes.
- the procedure is advantageously as follows.
- R 1 contains at least one sulfur atom
- at least one radical X 1 to X 4 denotes an SH group
- at least two radicals X 1 to X 4 Group in the event that R 1 contains no sulfur atom, at least two radicals X 1 to X 4 Group.
- At least one, more preferably at least two X 1 to X 4 hydroxyl groups are preferred.
- alkali and alkaline earth metal salts are in particular the mono- and disodium salts, mono- and dipotassium salts and potassium sodium salts of the compounds of general formula I, furthermore the corresponding calcium and magnesium salts.
- ammonium salts or primary, secondary, tertiary and in particular quaternary mono- and diammonium salts and phosphonium salts are also used.
- mixtures of compounds of general formula I and their corresponding alkali or alkaline earth metal salts or ammonium or phosphonium salts can be used.
- Preferred mono- and di-ammonium salts have as cations those of the formula N (R 3 ) (R 4 ) (R 5 ) (R 6 ) + , wherein R 3 to R 6 are each the same or different and selected from hydrogen, C 1 -C 12 -alkyl, phenyl or CH 2 -CH 2 -OH.
- R 3 to R 6 are each the same or different and selected from hydrogen, C 1 -C 12 -alkyl, phenyl or CH 2 -CH 2 -OH.
- Preferred mono- and diphosphonium salts have as cations those of the formula P (R 3 ) (R 4 ) (R 5 ) (R 6 ) + , where R 3 to R 6 are as defined above.
- I a, I a 'and I b one or their corresponding alkali or alkaline earth metal salts.
- I b is also called dithioerythrol.
- racemic dithiothreitol is virtually odorless, easy to dose and readily soluble in water compounds.
- the compounds I a or I a 'and I b are known and commercially available, for example, from Aldrich or AGROS Chemicals.
- the synthesis of further compounds of general formula I succeeds as in US 4,472,569 or J. Chem. Soc. 1949, 248 described or by analogous reactions.
- the treatment according to the invention of the hides, furs or fur skins with one or more compounds of the general formula I is carried out in liming or in the swede, both under hair-destroying and hair-preserving conditions. It succeeds in the liming or the swath instead of the usual concentration of about 4 wt .-% Na 2 S or NaHS or even slightly more, with a concentration of less than 1 wt .-% Na 2 S or NaHS at have the same effect on the removal of horny substances.
- one or more compounds of general formula I are used in the liming together with thiols known from tanning, for example mercaptoethanol or thioglycolic acid. Preference is given to using less than 0.5% by weight of mercaptoethanol or thioglycolic acid.
- the skins are treated according to the invention in an aqueous liquor.
- the process according to the invention is carried out at pH values from 7 to 14, preferably from 8 to 13 and particularly preferably from 9 to 12.5.
- lime also hydrated lime
- the use of lime is dispensed with.
- one or more inorganic alkali metal compounds are added, for example one or more hydroxides or carbonates of alkali metals, preferably sodium or potassium, and most preferably sodium.
- suitable basic inorganic alkali metal compounds are alkali metal silicates.
- basic amines for example ammonia, methylamine, dimethylamine, ethylamine or triethylamine, or combinations of alkali metal compound and one or more basic amines.
- organic solvents may be in the liquor, for example up to 20% by volume of ethanol or isopropanol.
- the process can be carried out in tannery-standard vessels, which are usually limed.
- the process according to the invention is carried out in rotatable drums with internals.
- the speed is usually 0.5 to 100 / min, preferably 1.5 to 10 / min and more preferably to 4.5 / min.
- the pressure and temperature conditions for carrying out the process according to the invention are generally not critical. As suitable, the implementation has proven at atmospheric pressure; a pressure increased up to 10 bar is also conceivable. Suitable temperatures are 10 to 45 ° C, preferably 15 to 35 ° C and particularly preferably 25 to 30 ° C.
- the compound or compounds of the general formula I it is possible to dose the compound or compounds of the general formula I at the beginning of the liming process, but initially it is also possible first to soak the skins under basic conditions and to meter one or more compounds of the general formula I after some time.
- the dosage can be done in one step, ie the total amount of the compound or compounds I used is metered in one step; but I can also dose I in portions or continuously.
- the process of the invention can be carried out in a period of 10 minutes to 48 hours, preferably 1 to 36 hours and more preferably 3 to 15 hours.
- phosphines such as. B. triphenylphosphine or tris (2-carboxyethyl) phosphine hydrochloride, furthermore hydroxylamine, urea, guanidine or guanidinium hydrochloride, hydrazine, biocides, enzymes, surfactants and emulsifiers.
- the method according to the invention can be produced preferably depilated pelts. Surprisingly, it is found that even the epidermis is completely or at least largely detached after a short treatment period.
- the present invention therefore pats, prepared by the process according to the invention.
- the pelts according to the invention are very well suited for the production of leather.
- the pelts according to the invention can be further processed into leather with an improved surface yield and lower swelling damage, compared to leather, the is prepared from pelts, which were depilated with the aid of, for example, Na 2 S, NaHS, thioglycolic acid or aminoethanol.
- Another object of the present invention are leather, made of the pelts according to the invention. They are characterized by overall advantageous performance properties.
- wastewaters produced in the process according to the invention in particular effluents from ashes processes, in which no Na 2 S, NaSH or mercaptans such as aminoethanol or thioglycolic acid are used, can be worked up particularly well.
- the resulting pelts are separated from the liquor, for example by simply removing the pelts or by draining the liquor.
- the liquor contains inter alia unused (reacted) compound of general formula I, from a few ppm up to 4 wt .-%, besides basic alkali metal compound or basic amines or lime and in particular residues of horns separated from the pelts and the epidermis.
- the separated liquor containing unused (reacted) compound of the general formula I, furthermore base and residues of the horn materials separated from the pelts and the epidermis is also referred to below as the remainder liquor.
- Another object of the present invention are therefore residual liquors containing neither Na 2 S nor NaHS and containing as organic sulfur compounds only those of the general formula I, as well as their reaction and secondary products from the removal of horny substances from hides, furs or fur skins of dead animals, and organic sulfur compounds derived from the skins, furs or furskins of the dead animals.
- residual liquors which contain neither Na 2 S nor NaSH are to be understood as meaning those residual liquors which contain up to 100 ppm, preferably up to 75 ppm, of sulphide.
- the sulfide determination is carried out as hydrogen sulfide after acidification with concentrated hydrochloric acid, heating to 90 ° C and stripping.
- the residual liquors according to the invention are obtainable by the process according to the invention. They are almost odorless and particularly easy to work up compared to the known from the prior art residual liquors of tanneries.
- reaction and secondary products of compounds of general formula I which result from the removal of horny substances from the hides, furs and fur skins of dead animals, are mainly hydrolysis and oxidation products of compounds of general formula I call.
- Another object of the present invention is therefore a process for the processing of residual liquors.
- the method according to the invention comprises several steps.
- the pelts according to the invention are separated from the lime.
- this step is only necessary if lime has been used in the treatment of animal skins, otherwise it is not necessary.
- the separation is carried out by settling, flotation, decantation, filtration or centrifugation, wherein for large amounts of residual liquors according to the invention, the separation of the lime by decantation, settling or filtration is preferred.
- the first step described above makes lime-free residual liquors accessible.
- the lime-free residual liquors are then neutralized with an acid until a pH of 2 to 8, preferably 3 to 7, particularly preferably 4 to 5 is reached.
- hydrochloric acid, phosphoric acid, formic acid, sulfuric acid, acetic acid, citric acid, carbonic acid (CO 2 ), adipic acid and dicarboxylic acid mixtures of adipic acid, glutaric acid and succinic acid may be mentioned by way of example.
- acidification it is possible to work without special measures with respect to evolving hydrogen sulfide.
- the proteins removed from the nakedness in the liming or swelling precipitate or float, so that they are separated mechanically in a further step, for example by filtration or flotation.
- the skin of a Southern German cattle was first pre-soaked at 28 ° C with 200 wt .-% water and 0.2 wt .-% of Eusapon® W 120 minutes in a barrel at 1-3 rpm. The liquor was drained and then soaked with 100 wt .-% water, 0.2 wt .-% Eusapon® W and 0.5 wt .-% soda in automatic mode (5 '/ h) 19 hours. Then the fleet was drained.
- the soaked skins of South German cattle were fleshed green (thickness about 4 mm) and the croupons of the skins cut into pieces of skin weighing 2.5 kg each.
- dithiothreitol 60 1.0 Aqueous sodium hydroxide solution (50% by weight) 30 1.0 Aqueous sodium hydroxide solution (50% by weight) 30 50 water 0.4 Aqueous sodium hydroxide solution (50% by weight) 60 50 water 30 1.5 1.0 Basyzyme L10 0.5 Rac. dithiothreitol 60 1.0 Aqueous sodium hydroxide solution (50% by weight) 30 1.0 Aqueous sodium hydroxide solution (50% by weight) 30 Aqueous sodium hydroxide solution (50% by weight) 60 0.4 50 water 1.6 1.0 Rac. dithiothreitol 60 1.0 Aqueous sodium hydroxide solution. (50% by weight) 30 1.0 Aqueous sodium hydroxide solution. (50% by weight) 30 50 water 0.4 Aqueous sodium hydroxide solution. (50% by weight) 60 50 water 30
- the cask was operated for another 45 minutes at 5 revolutions / minute. Subsequently, a further 40 wt .-% of water were metered. After 10 hours at 23 to 27 ° C with periodic operation at 3 revolutions / minute for 5 minutes each hour, the experiments were terminated by draining the liquor and washing the sheets twice for 15 minutes each with 150 wt% water ,
- the pelts treated according to the examples according to the invention were only slightly superior to the skins treated according to Comparative Example C1 with respect to the swelling, but were characterized by a smoother and flatter scar, in particular the pelts of Examples 1.4 to 1.6 according to the invention.
- the epidermis and hair with hair roots in the pelts 1.1 to 1.3 were largely destroyed in the pelts 1.4 to 1.6.
- the deliming or neutralization was carried out in each case with a mixture consisting of two parts by weight of formic acid and three parts by weight of adipic acid.
- the liquor was brought to pH 7.5-8.5 in two dosing steps. Penetration of the acid mixture across the skin cross section was compared with phenolphthalein as In checked. The time required for this was noted.
- the leathers thus obtained were washed with water and dried and stretched and folded by conventional methods.
- The. Folding thickness of the leather was 2.0-2.2 mm.
- the data in% by weight refers to the dried leather, unless stated otherwise.
- the "wet white” cowhides thus obtained were placed in 100% by weight of water and adjusted to a pH of ⁇ 3.0 by addition of sodium formate and sodium bicarbonate.
- the leather was tumbled at 30 ° C for 60 minutes and then washed with 200% by weight of water.
- Relugan® GTP 4% by weight was added and tumbled for 60 minutes.
- 2 wt .-% Tamol® NA commercially available from BASF Aktiengesellschaft
- Lipoderm â licker A1 commercially available from BASF Aktiengesellschaft
- wt .-% wt .-%
- 1 wt .-% Lipoderm® Likker LA
- Crust leather 2.1 was obtained. to 2.6. with very good coloring and good grain tightness at the same time very good body and excellent softness with elegant grip.
- the crust leather 2.4 to 2.6 had a smoother and finer scars than V2. Further performance properties are shown in Table 2.
- Table 2 crust leather Out of nakedness hair decomposition Scar Resistance Wet white leather Puncture pull-out force according to DIN 53331 [N] V2 V1 2 2 140 2.1 1.1 2 2 176 2.2 1.2 1.5 2 173 2.3 1.3 1 2 178 2.4 1.4 1 1 185 2.5 1.5 1 1 1 190 2.6 1.6 1.5 1 188
- the hair decomposition and the scar resistance were assessed visually and haptically by 2 propands (1: very good, 6: insufficient).
- the skin of a Southern German bovine was first pre-soaked at 28 ° C with 150 wt .-% water and 0.2 wt .-% Eusapon® W 120 minutes in a barrel at 1-3 rpm. The liquor was drained and then with 150 wt .-% water, 0.2 wt .-% Eusapon® W and 0.5 wt .-% Soda soaked with occasional stirring for 19 hours. Then the fleet would be drained.
- the soaked skins of South German cattle were fleshed green (thickness about 4 mm) and the croupons of the skins cut into pieces of skin of 2.5 kg each.
- the keg was operated for another 45 minutes at 15 revolutions / minute. Subsequently, an additional 40 parts by weight of water were metered. After 10 hours at 23 to 27 ° C with periodic operation at 3 revolutions / minute for 5 minutes each hour, the experiments were terminated by draining the liquor and washing the sheets twice for 15 minutes each with 150 wt% water ,
- the pelts treated according to the examples according to the invention were only slightly superior to the skins treated according to Comparative Example C3 with regard to swelling, but were characterized by a smoother and flatter scar, in particular the pelts of Examples 3.2 and 3.3 according to the invention.
- the epidermis and the hair with hair root in pelage 3.1 was largely destroyed in the pelts 3.2 to 3.3.
- Crust leather 4.1 was obtained. to 4.2. with very good coloring and good grain tightness at the same time very good body and excellent softness with elegant grip.
- the crust leathers 4.2 to 4.3 had smoother and finer scars than V4. Further performance properties are shown in Table 4. crust leather Out of nakedness hair removal grain tightness Puncture pull-out force according to DIN 53331 [N] V4 V3 2 2 140 4.1 3.1 2 2 176 4.2 3.2 1.5 1 185
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)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Entfernung von Hornsubstanzen aus Häuten, Pelzen oder Pelzfellen toter Tiere, dadurch gekennzeichnet, dass man die Häute, Pelze oder Pelzfelle in wässriger Flotte mit einer oder mehreren Verbindungen der allgemeinen Formel I
- R1
- gewählt wird aus Wasserstoff oder C1-C12-Alkyl, unsubstituiert oder substituiert mit einer oder mehreren S-H oder O-H-Gruppen;
- X1
- bis X4 gleich oder verschieden und ausgewählt aus Wasserstoff, C1-C4-Alkyl, O-H, S-H oder N-HR2,
- R2
- Wasserstoff oder C1-C12-Alkyl oder eine C1-C4-Alkyl-C=O-Gruppe bedeutet,
wobei für den Fall, dass R1 mindestens ein Schwefelatom enthält, mindestens ein Rest X1 bis X4 S-H bedeutet,
und für den Fall, dass R1 kein Schwefelatom enthält, mindestens zwei Reste X1 bis X4 S-H bedeuten.
- R 1
- is selected from hydrogen or C 1 -C 12 alkyl, unsubstituted or substituted with one or more SH or OH groups;
- X 1
- to X 4 are identical or different and selected from hydrogen, C 1 -C 4 -alkyl, OH, SH or N-HR 2 ,
- R 2
- Is hydrogen or C 1 -C 12 -alkyl or a C 1 -C 4 -alkyl-C = O-group,
in the case where R 1 contains at least one sulfur atom, at least one radical X 1 to X 4 SH,
and in the event that R 1 contains no sulfur atom, at least two radicals X 1 to X 4 SH.
Tierische Häute werden seit mehreren tausend Jahren zu Leder verarbeitet. Bevor man mit der eigentlichen Lederherstellung, dem Gerben, beginnen kann, muss man die Häute vorbereiten. Diese Vorbereitungsschritte finden im Allgemeinen in der sogenannten Wasserwerkstatt (englisch: beam house) statt und umfassen zahlreiche Arbeitsgänge. Die meisten dieser Arbeitsgänge dienen der Abtrennung von solchen Bestandteilen der Häute, die bei der späteren Lederherstellung bzw. im späteren Leder unerwünscht sind. Zu den unerwünschten Bestandteilen gehören in der Regel auch die Haare zusammen mit den Haarwurzeln und die Epidermis. Die Enthaarung der Häute wird üblicherweise durch Chemikalien gefördert. Man unterscheidet dabei oxidative, reduktive und enzymatische Enthaarungsmethoden. Ein Überblick über Methoden findet sich in
Meistens erfolgt die Enthaarung der Häute weitgehend oder vollständig im sogenannten Äscher bzw. der Schwöde. Gängige und in der Herstellung günstige Enthaarungsreagenzien sind Na2S und NaSH, letzteres oft auch als Natriumsulfhydrat bezeichnet. Beide Salze können üblicherweise in stark verunreinigter Form eingesetzt werden, "technisches Na2S" hat oft einen 65 Gew.-% nicht übersteigenden Gehalt an Na2S, und "technisches NaHS" üblicherweise einen Gehalt an 70-72 Gew.-% NaHS. Beide, Na2S und NaHS, haben aber in der praktischen Anwendung Nachteile. Na2S und NaHS lassen sich aus Sicherheitsgründen nur in stark alkalischem Milieu anwenden, weil sie beim Ansäuern giftigen und übel riechenden Schwefelwasserstoff entwickeln. Die Beseitigung des nicht verbrauchten Sulfids, insbesondere der sulfidhaltigen Abwässer, ist aus ökologischen und verfahrenstechnischen Gründen ein bedenklicher Schritt. Fällt man überschüssiges Sulfid aus, beispielsweise mit Fe2+ oder Fe3+, so erhält man aufwändig abzutrennende Eisensulfidschlämme. Man kann auch versuchen, durch Oxidation mit beispielsweise H2O2 Sulfide in ökologisch unbedenkliche Salze zu überführen, so muss man Korrosionsprobleme in Kauf nehmen.Mostly, the depilation of the skins is largely or completely in the so-called limewever or the swede. Common depilatory reagents which are cheap in the preparation are Na 2 S and NaSH, the latter often also referred to as sodium sulphohydrate. Both salts can usually be used in strongly contaminated form, "technical Na 2 S" often has a content of Na 2 S which does not exceed 65% by weight, and "technical NaHS" usually contains 70-72% by weight NaHS , Both, Na 2 S and NaHS, however, have disadvantages in practical use. For safety reasons, Na 2 S and NaHS can only be used in highly alkaline environments because they produce toxic and foul-smelling hydrogen sulfide on acidification. The elimination of the unused sulphide, in particular the sulphide-containing wastewater, is a questionable step for environmental and procedural reasons. If one precipitates excess sulfide, for example with Fe 2+ or Fe 3+ , the result is a costly separation of iron sulfide sludges. One can also try to convert by oxidation with, for example H 2 O 2 sulfides in ecologically harmless salts, so you have to accept corrosion problems.
Es hat daher nicht an Versuchen gefehlt, für die Behandlung der Häute von toten Tieren andere Reagenzien als Na2S oder NaHS zu verwenden. Die meisten Versuche gehen aus von SH-Gruppen haltigen organischen Reagenzien.There has therefore been no lack of attempts to use reagents other than Na 2 S or NaHS for treating the skins of dead animals. Most experiments are based on SH-containing organic reagents.
In
In
Versuche, Na2S bzw. NaHS durch Mercaptoessigsäure oder Mercaptoethanol bzw. deren Alkali- oder Erdalkalimetallsalze zu substituieren, führten jedoch nicht zum Erfolg, weil beide Reagenzien und auch ihre Alkali- oder Erdalkalimetallsalze leicht Schwefelwasserstoff abspalten und äußerst unangenehm riechen. Auch Abwässer der Wasserwerkstatt, enthaltend Mercaptoessigsäure oder Mercaptoethanol bzw. Zersetzungs- und Folgeprodukte, sind schlecht zu klären und strömen unangenehme Gerüche aus.Attempts to substitute Na 2 S or NaHS by mercaptoacetic acid or mercaptoethanol or their alkali metal or alkaline earth metal salts, however, did not lead to success because both reagents and also their alkali or alkaline earth metal salts easily split off hydrogen sulfide and smell extremely unpleasant. Wastewater of the water workshop, containing mercaptoacetic acid or mercaptoethanol or decomposition and secondary products, are difficult to clarify and emit unpleasant odors.
Aus der kosmetischen Industrie ist die Verwendung von 1,4-Dimercaptobutandiol-haltigen Formulierungen zur Entfernung von Hornsubstanzen, insbesondere Haaren, aus lebendem Gewebe bekannt, beispielsweise bei unerwünschtem Bartwuchs. So zeigt
Aus
Aus
Schließlich ist bekannt, dass man Collagen modifizieren kann, indem man S-S-Brücken im Collagen durch Umsetzung mit Dithioerythrol und anschließende Chlorierung mit Chloracetamid oder Chloressigsäure öffnen kann, s. beispielsweise
Es wurde nun überraschend gefunden, dass sich das eingangs definierte Verfahren vorzüglich eignet, um Hornsubstanzen aus Häuten, Pelzen und Pelzfellen toter Tiere zu entfernen.It has now surprisingly been found that the method defined at the beginning is excellently suitable for removing horny substances from hides, furs and fur skins of dead animals.
Unter Hornsubstanzen werden im Sinne der vorliegenden Erfindung Schwielen, Federn, Nägel- und Krallenteile und insbesondere Haare von Tieren verstanden.For the purposes of the present invention, horny substances are calluses, feathers, nails and claw parts, and in particular hair of animals.
Die Häute, Epidermis können noch Reste von Fleisch der betreffenden toten Tiere enthalten. Erfindungswesentlich ist jedoch, dass sie Hornsubstanzen enthalten. Dabei ist die Menge an Hornsubstanz, bezogen auf das Gesamtgewicht der Haut bzw. des Pelzes oder des Pelzfells, unkritisch. Das erfindungsgemäße Verfahren eignet sich sowohl zur Entfernung von großen Mengen an Hornsubstanz als auch zur Entfernung kleiner Haarreste.The skins, epidermis may still contain remnants of meat of the relevant dead animals. Essential to the invention, however, is that they contain horny substances. The amount of horny substance, based on the total weight of the skin or the fur or the fur coat, is not critical. The inventive method is suitable both for the removal of large amounts of horny substance as well as for the removal of small hair residues.
Unter toten Tieren werden im Sinne der vorliegenden Erfindung nicht nur geschlachtete, waidmännisch erlegte oder auf andere Art durch Menschen bewusst getötete Tiere verstanden, sondern auch solche Tiere, die aufgrund von Unfällen, beispielsweise Verkehrsunfällen, oder Kämpfen mit Artgenossen oder anderen Tieren oder durch natürliche Ursachen wie Alter oder Krankheit verendet sind.For the purposes of the present invention, dead animals are understood not only to be slaughtered, hunted or otherwise deliberately killed by humans, but also to animals that have been due to accidents, for example traffic accidents, or fights with other animals or natural causes as age or disease have died.
Bei den Häuten, Pelzen bzw. Pelzfellen der Tiere handelt es sich üblicherweise um Häute, Pelze bzw. Pelzfelle von Rindern, Kälbern, Schweinen, Ziegen, Schafen, Lämmern, Elchen, Wild wie beispielsweise Hirschen oder Rehen, weiterhin Vögeln wie beispielsweise Straußen, Fischen oder Reptilien wie beispielsweise Schlangen.The hides, furs or furskins of the animals are usually skins, furs or fur skins of cattle, calves, pigs, goats, sheep, lambs, elks, game such as deer or deer, and birds such as ostriches, fish or reptiles such as snakes.
Zur Ausführung des erfindungsgemäßen Verfahrens geht man vorteilhaft wie folgt vor.To carry out the method according to the invention, the procedure is advantageously as follows.
Man behandelt die Häute mit einer oder mehreren Verbindungen der allgemeinen Formel I
- R1
- ausgewählt aus
C1-C12-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl oder n-Decyl, besonders bevorzugt C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
C1-C12-Alkyl, substituiert mit einer oder mehreren Hydroxy- oder Thiolgruppen wie Hydroxymethyl, 2-Hydroxyethyl, 1,2-Di-hydroxyethyl, 3-Hydroxy-n-Propyl, 2-Hydroxy-iso-Propyl, ω-Hydroxy-n-Butyl, ω-Hydroxy-n-Decyl, HS-CH2-; HS-(CH2)2- oder HS-(CH2)3-,
und ganz besonders bevorzugt Wasserstoff, - X1
- bis X4 gleich oder verschieden und ausgewählt aus Wasserstoff,
C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl
O-H, S-H oder N-HR1, insbesondere O-H oder S-H, - R2
- Wasserstoff oder
C1-C12-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl oder n-Decyl, besonders bevorzugt C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
- R 1
- selected from
C 1 -C 12 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl or n-decyl, particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
C 1 -C 12 -alkyl substituted with one or more hydroxy or thiol groups such as hydroxymethyl, 2-hydroxyethyl, 1,2-di-hydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxy-isopropyl, ω- Hydroxy-n-butyl, ω-hydroxy-n-decyl, HS-CH 2 -; HS- (CH 2 ) 2 - or HS- (CH 2 ) 3 -,
and most preferably hydrogen, - X 1
- to X 4 are identical or different and selected from hydrogen,
C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl
OH, SH or N-HR 1 , in particular OH or SH, - R 2
- Hydrogen or
C 1 -C 12 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl or n-decyl, particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
Dabei bedeutet für den Fall, dass R1 mindestens ein Schwefelatom enthält, mindestens ein Rest X1 bis X4 eine S-H-Gruppe, und für den Fall, dass R1 kein Schwefelatom enthält, mindestens zwei Reste X1 bis X4 eine S-H-Gruppe.In this case, in the event that R 1 contains at least one sulfur atom, at least one radical X 1 to X 4 denotes an SH group, and in the event that R 1 contains no sulfur atom, at least two radicals X 1 to X 4 Group.
Bevorzugt ist mindestens eine, besonders bevorzugt sind mindestens zwei Reste X1 bis X4 Hydroxylgruppen.At least one, more preferably at least two X 1 to X 4 hydroxyl groups are preferred.
Unter den korrespondierenden Alkali- und Erdalkalimetallsalzen sind insbesondere die Mono- und Dinatriumsalze, Mono- und Dikaliumsalze sowie Kaliumnatriumsalze der Verbindungen der allgemeinen Formel I zu nennen, weiterhin die entsprechenden Calcium- und Magnesiumsalze. Auch sind die Ammoniumsalze bzw. primären, sekundären, tertiären und insbesondere quartären Mono- und Diammoniumsalze und Phosphoniumsalze zu nennen. Natürlich sind auch Gemische aus Verbindungen der allgemeinen Formel I und deren korrespondierenden Alkali- oder Erdalkalimetallsalzen oder Ammonium- oder Phosphoniumsalzen einsetzbar.Among the corresponding alkali and alkaline earth metal salts are in particular the mono- and disodium salts, mono- and dipotassium salts and potassium sodium salts of the compounds of general formula I, furthermore the corresponding calcium and magnesium salts. Also to be mentioned are the ammonium salts or primary, secondary, tertiary and in particular quaternary mono- and diammonium salts and phosphonium salts. Of course, mixtures of compounds of general formula I and their corresponding alkali or alkaline earth metal salts or ammonium or phosphonium salts can be used.
Bevorzugte Mono- und Diammoniumsalze haben als Kationen solche der Formel N(R3) (R4) (R5) (R6)+, wobei R3 bis R6 jeweils gleich oder verschieden sind und ausgewählt aus Wasserstoff, C1-C12-Alkyl, Phenyl oder CH2-CH2-OH. Beispielhaft seien Tetramethylammonium, Tetraethylammonium, Methyldiethanolammonium und n-Butyldiethanolammonium genannt. Bevorzugte Mono- und Diphosphoniumsalze haben als Kationen solche der Formel P(R3)(R4)(R5)(R6)+, wobei R3 bis R6 wie oben definiert sind.Preferred mono- and di-ammonium salts have as cations those of the formula N (R 3 ) (R 4 ) (R 5 ) (R 6 ) + , wherein R 3 to R 6 are each the same or different and selected from hydrogen, C 1 -C 12 -alkyl, phenyl or CH 2 -CH 2 -OH. By way of example, mention may be made of tetramethylammonium, tetraethylammonium, methyldiethanolammonium and n-butyldiethanolammonium. Preferred mono- and diphosphonium salts have as cations those of the formula P (R 3 ) (R 4 ) (R 5 ) (R 6 ) + , where R 3 to R 6 are as defined above.
Ganz besonders bevorzugt setzt man ein oder mehrere 1,4-Dimercaptobutandiole, gewählt aus I a, I a' und I b,
Die Verbindungen I a bzw. I a' und I b sind bekannt und beispielsweise bei Aldrich oder AGROS Chemicals kommerziell erhältlich. Die Synthese weiterer Verbindungen der allgemeinen Formel I gelingt wie in
Im Allgemeinen genügt eine Menge von 0,1 bis 5 Gew.-% Verbindung I, bezogen auf das Haut- bzw. Salzgewicht der Häute, Pelze oder Pelzfelle. Bevorzugt sind 0,1 bis 2,5 Gew.-%, besonders bevorzugt sind 0,1 bis 1,5 Gew.-%.In general, an amount of from 0.1 to 5% by weight of compound I, based on the skin or salt weight of the skins, furs or fur skins, is sufficient. Preference is given to 0.1 to 2.5 wt .-%, particularly preferably 0.1 to 1.5 wt .-%.
Bevorzugt erfolgt die erfindungsgemäße Behandlung der Häute, Pelze bzw. Pelzfelle mit einer oder mehreren Verbindungen der allgemeinen Formel I im Äscher bzw. der Schwöde, und zwar sowohl unter haarzerstörenden als auch unter haarerhaltenden Bedingungen. Dabei gelingt es, im Äscher bzw. der Schwöde statt der üblichen Konzentration von etwa 4 Gew.-% Na2S bzw. NaHS oder sogar geringfügig mehr, mit einer Konzentration von weniger als 1 Gew.-% Na2S bzw. NaHS bei gleich großer Wirkung bezüglich der Entfernung von Hornsubstanzen auszukommen.Preferably, the treatment according to the invention of the hides, furs or fur skins with one or more compounds of the general formula I is carried out in liming or in the swede, both under hair-destroying and hair-preserving conditions. It succeeds in the liming or the swath instead of the usual concentration of about 4 wt .-% Na 2 S or NaHS or even slightly more, with a concentration of less than 1 wt .-% Na 2 S or NaHS at have the same effect on the removal of horny substances.
In einer Variante des erfindungsgemäßen Verfahrens setzt man im Äscher eine oder mehrere Verbindungen der allgemeinen Formel I zusammen mit aus der Gerberei bekannten Thiolen wie beispielsweise Mercaptoethanol oder Thioglykolsäure. Bevorzugt setzt man weniger als 0,5 Gew.-% Mercaptoethanol oder Thioglykolsäure ein.In one variant of the process according to the invention, one or more compounds of general formula I are used in the liming together with thiols known from tanning, for example mercaptoethanol or thioglycolic acid. Preference is given to using less than 0.5% by weight of mercaptoethanol or thioglycolic acid.
In einer ganz besonders bevorzugten Variante des erfindungsgemäßen Verfahrens gelingt es jedoch, auf den Einsatz von Na2S bzw. NaHS oder anderer übel riechender schwefelhaltiger Reagenzien zu verzichten.In a very particularly preferred variant of the method according to the invention, however, it is possible to dispense with the use of Na 2 S or NaHS or other foul-smelling sulfur-containing reagents.
Man behandelt die Häute erfindungsgemäß in einer wässrigen Flotte. Dabei beträgt das Flottenverhältnis von 1:10 bis 10:1, bevorzugt 1:2 bis 4:1, besonders bevorzugt bis 3:1 bezogen auf das Hautgewicht bzw. Salzgewicht der Häute.The skins are treated according to the invention in an aqueous liquor. In this case, the liquor ratio of 1:10 to 10: 1, preferably 1: 2 to 4: 1, more preferably up to 3: 1 based on the skin weight or salt weight of the skins.
Das erfindungsgemäße Verfahren wird bei pH-Werten von 7 bis 14, bevorzugt von 8 bis 13 und besonders bevorzugt von 9 bis 12,5 durchgeführt.The process according to the invention is carried out at pH values from 7 to 14, preferably from 8 to 13 and particularly preferably from 9 to 12.5.
Zur Einstellung des pH-Werts kann man so vorgehen, dass man bis zu 3 Gew.-% Kalk (auch Kalkhydrat), bezogen auf die Flotte, zugibt. Man kann aber auch die Kalkmenge deutlich reduzieren. In einer bevorzugten Variante des erfindungsgemäßen Verfahrens verzichtet man auf den Einsatz von Kalk. In der bevorzugten Ausführungsform setzt man eine oder mehrere anorganischebasische Alkalimetallverbindungen zu, beispielsweise ein oder mehrere Hydroxide oder Carbonate von Alkalimetallen, bevorzugt von Natrium oder Kalium und ganz besonders bevorzugt von Natrium. Andere geeignete anorganische basische Alkalimetallverbindungen sind Alkalimetallsilikate. Man kann auch basische Amine, beispielsweise Ammoniak, Methylamin, Dimethylamin, Ethylamin oder Triethylamin zusetzen oder Kombinationen aus Alkalimetallverbindung und einem oder mehreren basischen Aminen.To adjust the pH, it is possible to add up to 3% by weight of lime (also hydrated lime), based on the liquor. But you can also significantly reduce the amount of lime. In a preferred variant of the method according to the invention, the use of lime is dispensed with. In the preferred embodiment, one or more inorganic alkali metal compounds are added, for example one or more hydroxides or carbonates of alkali metals, preferably sodium or potassium, and most preferably sodium. Other suitable basic inorganic alkali metal compounds are alkali metal silicates. It is also possible to add basic amines, for example ammonia, methylamine, dimethylamine, ethylamine or triethylamine, or combinations of alkali metal compound and one or more basic amines.
Neben Wasser können noch weitere organische Lösemittel in der Flotte sein, beispielsweise bis zu 20 Vol.-% Ethanol oder Isopropanol.In addition to water, other organic solvents may be in the liquor, for example up to 20% by volume of ethanol or isopropanol.
Das Verfahren lässt sich in den gerbereiüblichen Gefäßen durchführen, in denen üblicherweise geäschert wird. Vorzugsweise führt man das erfindungsgemäße Verfahren in drehbaren Fässern mit Einbauten durch. Die Drehzahl beträgt üblicherweise 0,5 bis 100/min, bevorzugt 1,5 bis 10/min und besonders bevorzugt bis 4,5/min.The process can be carried out in tannery-standard vessels, which are usually limed. Preferably, the process according to the invention is carried out in rotatable drums with internals. The speed is usually 0.5 to 100 / min, preferably 1.5 to 10 / min and more preferably to 4.5 / min.
Die Druck- und Temperaturbedingungen zur Durchführung des erfindungsgemäßen Verfahrens sind im Allgemeinen unkritisch. Als geeignet hat sich die Durchführung bei Atmosphärendruck erwiesen; ein auf bis zu 10 bar erhöhter Druck ist ebenfalls denkbar. Geeignete Temperaturen sind 10 bis 45°C, bevorzugt 15 bis 35°C und besonders bevorzugt 25 bis 30°C.The pressure and temperature conditions for carrying out the process according to the invention are generally not critical. As suitable, the implementation has proven at atmospheric pressure; a pressure increased up to 10 bar is also conceivable. Suitable temperatures are 10 to 45 ° C, preferably 15 to 35 ° C and particularly preferably 25 to 30 ° C.
Man kann die Verbindung bzw. Verbindungen der allgemeinen Formel I am Beginn des Äscherprozesses dosieren, man kann aber zunächst auch die Häute zunächst unter basischen Bedingungen einweichen und erst nach einiger Zeit eine oder mehrere Verbindungen der allgemeinen Formel I dosieren. Die Dosierung kann in einem Schritt erfolgen, d.h. die Gesamtmenge der eingesetzten Verbindung bzw. Verbindungen I wird in einem Schritt dosiert; man kann aber I auch portionsweise oder kontinuierlich dosieren.It is possible to dose the compound or compounds of the general formula I at the beginning of the liming process, but initially it is also possible first to soak the skins under basic conditions and to meter one or more compounds of the general formula I after some time. The dosage can be done in one step, ie the total amount of the compound or compounds I used is metered in one step; but I can also dose I in portions or continuously.
Das erfindungsgemäße Verfahren lässt sich in einem Zeitraum von 10 Minuten bis 48 Stunden, bevorzugt 1 bis 36 Stunden und besonders bevorzugt 3 bis 15 Stunden durchführen.The process of the invention can be carried out in a period of 10 minutes to 48 hours, preferably 1 to 36 hours and more preferably 3 to 15 hours.
Selbstverständlich kann man zur Ausübung des erfindungsgemäßen Verfahrens noch gerbereiübliche Hilfsstoffe zusetzen, beispielsweise Phosphine, wie z. B. Triphenylphosphin oder Tris(2-Carboxyethyl)-phosphinhydrochlorid, weiterhin Hydroxylamin, Harnstoff, Guanidin bzw. Guanidinium-Hydrochlorid, Hydrazin, Biozide, Enzyme, Tenside und Emulgatoren.Of course, you can add to the exercise of the method according to the invention still tanning customary auxiliaries, such as phosphines, such as. B. triphenylphosphine or tris (2-carboxyethyl) phosphine hydrochloride, furthermore hydroxylamine, urea, guanidine or guanidinium hydrochloride, hydrazine, biocides, enzymes, surfactants and emulsifiers.
Durch das erfindungsgemäße Verfahren lassen sich vorzüglich enthaarte Blößen herstellen. Überraschend findet man, dass auch die Epidermis bereits nach kurzer Behandlungsdauer vollständig oder doch zumindest weitgehend abgelöst wird. Gegenstand der vorliegenden Erfindung sind daher Blößen, hergestellt nach dem erfindungsgemäßen Verfahren.By the method according to the invention can be produced preferably depilated pelts. Surprisingly, it is found that even the epidermis is completely or at least largely detached after a short treatment period. The present invention therefore pats, prepared by the process according to the invention.
Weiterhin wurde überraschend gefunden, dass sich die erfindungsgemäß hergestellten Blößen ganz vorzüglich zur Herstellung von Leder eignen. Nach gerbereiüblicher Weiterverarbeitung der erfindungsgemäßen Blößen, d.h. Beizen, ggf. Entkälken, Pickeln, chromfreies Gerben oder Chromgerbung, Nachgerben und Zurichten beobachtet man, dass man die erfindungsgemäß hergestellten Blößen zu Leder mit einer verbesserten Flächenausbeute und geringeren Schwellungsschäden weiterverarbeiten kann, verglichen mit Leder, das aus Blößen hergestellt wird, die mit Hilfe von beispielsweise Na2S, NaHS, Thioglykolsäure oder Aminethanol enthaart wurden.Furthermore, it was surprisingly found that the pelts according to the invention are very well suited for the production of leather. After tanning customary further processing of the pelts according to the invention, ie pickling, possibly deliming, pimples, chrome-free tanning or chrome tanning, retanning and trimming, it is observed that the pelts according to the invention can be further processed into leather with an improved surface yield and lower swelling damage, compared to leather, the is prepared from pelts, which were depilated with the aid of, for example, Na 2 S, NaHS, thioglycolic acid or aminoethanol.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Leder, hergestellt aus den erfindungsgemäßen Blößen. Sie zeichnen sich durch insgesamt vorteilhafte anwendungstechnische Eigenschaften aus.Another object of the present invention are leather, made of the pelts according to the invention. They are characterized by overall advantageous performance properties.
Weiterhin wurde gefunden, dass sich die bei dem erfindungsgemäßen Verfahren entstehenden Abwässer, insbesondere Abwässer von Äscherverfahren, in denen ohne Na2S, NaSH oder Mercaptane wie Aminoethanol oder Thioglykolsäure gearbeitet wird, besonders gut aufarbeiten lassen. Nach Beendigung der Einwirkung von einer oder mehreren Verbindungen der allgemeinen Formel I auf die Häute, Pelze bzw. Pelzfelle toter Tiere trennt man die erhaltenen Blößen von der Flotte, beispielsweise durch einfaches Herausnehmen der Blößen oder durch Ablassen der Flotte. Die Flotte enthält unter anderem nicht verbrauchte (abreagierte) Verbindung der allgemeinen Formel I, und zwar von wenigen ppm bis zu 4 Gew.-%, daneben basische Alkalimetallverbindung oder basische Amine oder Kalk und insbesondere Reste der von den Blößen abgetrennten Hornmaterialien und der Epidermis. Die abgetrennte Flotte, die nicht verbrauchte (abreagierte) Verbindung der allgemeinen Formel I, weiterhin Base und Reste der von den Blößen abgetrennten Hornmaterialien und der Epidermis enthält, wird im Folgenden auch als Restflotte bezeichnet. Ein weiterer Gegenstand der vorliegenden Erfindung sind daher Restflotten, die weder Na2S noch NaHS enthalten und als organische Schwefelverbindungen nur solche der allgemeinen Formel I enthalten, sowie deren Umsetzungs- und Folgeprodukte aus der Entfernung von Hornsubstanzen aus Häuten, Pelzen oder Pelzfellen toter Tiere, sowie organische Schwefelverbindungen, die aus den Häuten, Pelzen oder Pelzfellen der toten Tiere stammen. Unter Restflotten, die weder Na2S noch NaSH enthalten, sind im Sinne der vorliegenden Erfindung solche Restflotten zu verstehen, die bis zu 100 ppm, bevorzugt bis zu 75 ppm Sulfid enthalten. Die Sulfidbestimmung erfolgt dabei als Schwefelwasserstoff nach Ansäuern mit konzentrierter Salzsäure, Erhitzen auf 90°C und Ausstrippen. Die erfindungsgemäßen Restflotten sind erhältlich nach dem erfindungsgemäßen Verfahren. Sie sind im Vergleich zu den aus dem Stand der Technik bekannten Restflotten der Gerbereien fast geruchlos und besonders einfach aufzuarbeiten.It has furthermore been found that the wastewaters produced in the process according to the invention, in particular effluents from ashes processes, in which no Na 2 S, NaSH or mercaptans such as aminoethanol or thioglycolic acid are used, can be worked up particularly well. After completion of the action of one or more compounds of the general formula I on the skins, furs or fur skins of dead animals, the resulting pelts are separated from the liquor, for example by simply removing the pelts or by draining the liquor. The liquor contains inter alia unused (reacted) compound of general formula I, from a few ppm up to 4 wt .-%, besides basic alkali metal compound or basic amines or lime and in particular residues of horns separated from the pelts and the epidermis. The separated liquor containing unused (reacted) compound of the general formula I, furthermore base and residues of the horn materials separated from the pelts and the epidermis is also referred to below as the remainder liquor. Another object of the present invention are therefore residual liquors containing neither Na 2 S nor NaHS and containing as organic sulfur compounds only those of the general formula I, as well as their reaction and secondary products from the removal of horny substances from hides, furs or fur skins of dead animals, and organic sulfur compounds derived from the skins, furs or furskins of the dead animals. For the purposes of the present invention, residual liquors which contain neither Na 2 S nor NaSH are to be understood as meaning those residual liquors which contain up to 100 ppm, preferably up to 75 ppm, of sulphide. The sulfide determination is carried out as hydrogen sulfide after acidification with concentrated hydrochloric acid, heating to 90 ° C and stripping. The residual liquors according to the invention are obtainable by the process according to the invention. They are almost odorless and particularly easy to work up compared to the known from the prior art residual liquors of tanneries.
Als Umsetzungs- und Folgeprodukte von Verbindungen der allgemeinen Formel I, die aus der Entfernung von Hornsubstanzen aus den Häuten, Pelzen und Pelzfellen toter Tiere resultieren, sind hauptsächlich Hydrolyse- und Oxidationsprodukte von Verbindungen der allgemeinen Formel I zu nennen.As reaction and secondary products of compounds of general formula I, which result from the removal of horny substances from the hides, furs and fur skins of dead animals, are mainly hydrolysis and oxidation products of compounds of general formula I call.
Es wurde nun gefunden, dass sich die erfindungsgemäßen Restflotten besonders leicht aufarbeiten lassen.It has now been found that the residual liquors of the invention can be worked up particularly easily.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Aufarbeitung von Restflotten. Das erfindungsgemäße Verfahren umfasst mehrere Schritte.Another object of the present invention is therefore a process for the processing of residual liquors. The method according to the invention comprises several steps.
In einem ersten, optionalen Schritt trennt man die erfindungsgemäßen Blößen vom Kalk ab. Dieser Schritt ist naturgemäß nur dann erforderlich, wenn man Kalk bei der Behandlung der Tierhäute eingesetzt hat, andernfalls ist er nicht erforderlich. Die Abtrennung erfolgt durch Absetzen, Flotation, Dekantieren, Filtrieren oder Zentrifugieren, wobei bei großen Mengen an erfindungsgemäßen Restflotten die Abtrennung des Kalks durch Dekantieren, Absetzen oder Filtrieren bevorzugt ist. Durch den vorstehend beschriebenen ersten Schritt werden Kalk-freie Restflotten zugänglich.In a first, optional step, the pelts according to the invention are separated from the lime. Naturally, this step is only necessary if lime has been used in the treatment of animal skins, otherwise it is not necessary. The separation is carried out by settling, flotation, decantation, filtration or centrifugation, wherein for large amounts of residual liquors according to the invention, the separation of the lime by decantation, settling or filtration is preferred. The first step described above makes lime-free residual liquors accessible.
Anschließend neutralisiert man die Kalk-freien Restflotten dann mit einer Säure, bis ein pH-Wert von 2 bis 8, bevorzugt 3 bis 7, besonders bevorzugt 4 bis 5 erreicht ist.Subsequently, the lime-free residual liquors are then neutralized with an acid until a pH of 2 to 8, preferably 3 to 7, particularly preferably 4 to 5 is reached.
Als Säuren sind toxikologisch unbedenkliche organische oder anorganische Säuren geeignet. Beispielhaft seien Salzsäure, Phosphorsäure, Ameisensäure, Schwefelsäure, Essigsäure, Zitronensäure, Kohlensäure (CO2), Adipinsäure sowie Dicarbonsäuregemische aus Adipinsäure, Glutarsäure und Bernsteinsäure genannt. Bei Ansäuern kann ohne besondere Maßnahmen bezüglich sich entwickelnden Schwefelwasserstoffs gearbeitet werden.As acids toxicologically harmless organic or inorganic acids are suitable. Hydrochloric acid, phosphoric acid, formic acid, sulfuric acid, acetic acid, citric acid, carbonic acid (CO 2 ), adipic acid and dicarboxylic acid mixtures of adipic acid, glutaric acid and succinic acid may be mentioned by way of example. For acidification, it is possible to work without special measures with respect to evolving hydrogen sulfide.
Die im Äscher bzw. der-Schwöde von der Blöße entfernten Proteine fallen aus oder schwimmen auf, so dass man sie in einem weiteren Schritt mechanisch abtrennt, beispielsweise durch Filtration oder Flotation.The proteins removed from the nakedness in the liming or swelling precipitate or float, so that they are separated mechanically in a further step, for example by filtration or flotation.
Die Erfindung wird durch Arbeitsbeispiele erläutert.The invention will be explained by working examples.
Allgemeine ArbeitsvorschriftenGeneral working instructions
Die Werte in Gew.-% beziehen sich jeweils auf das Salzgewicht, wenn nicht anderes angegeben ist.The values in% by weight are in each case based on the salt weight, unless stated otherwise.
Die Haut eines Süddeutschen Rindes wurde zunächst bei 28°C mit 200 Gew.-% Wasser und 0,2 Gew.-% eines Eusapon® W 120 Minuten in einem Fass bei 1-3 UPM vorgeweicht. Die Flotte wurde abgelassen und danach mit 100 Gew.-% Wasser, 0,2 Gew.-% Eusapon® W und 0,5 Gew.-% Soda im Automatikbetrieb (5'/h) 19 Stunden eingeweicht. Anschließend wurde die Flotte abgelassen.The skin of a Southern German cattle was first pre-soaked at 28 ° C with 200 wt .-% water and 0.2 wt .-% of Eusapon® W 120 minutes in a barrel at 1-3 rpm. The liquor was drained and then soaked with 100 wt .-% water, 0.2 wt .-% Eusapon® W and 0.5 wt .-% soda in automatic mode (5 '/ h) 19 hours. Then the fleet was drained.
Die geweichten Häute süddeutscher Rinder wurden grün entfleischt (Stärke etwa 4 mm) und die Croupons der Häute in Hautstücke zu je 2,5 kg Grüngewicht geschnitten.The soaked skins of South German cattle were fleshed green (thickness about 4 mm) and the croupons of the skins cut into pieces of skin weighing 2.5 kg each.
Im Folgenden beziehen sich die Werte in Gew.-% jeweils auf das Grüngewicht, wenn nicht anderes vermerkt.In the following, the values in% by weight each refer to the green weight, unless otherwise noted.
Für das Vergleichsbeispiel V1 wurden 100 Gewichtsteile Grüngewicht in einem drehbaren 10-1-Fass mit strömungsbrechenden Inneneinbauten nacheinander mit 60 Gewichtsteilen Wasser, 0,8 Gew.-% NaSH und 3 Gew.-% Kalkhydrat beaufschlagt. Es folgten im Abstand von 30 Minuten je 0,75 Gew.-% Natriumsulfid. Das Fass wurde weitere 45 Minuten bei 15 Umdrehungen/Minute betrieben. Anschließend wurden weitere 40 Gewichtsteile Wasser dosiert. Nach 10 Stunden bei 23 bis 27°C und 5 Umdrehungen/Minute wurden die Versuche beendet, indem die Flotte abgelassen wurde und die Haute zweimal 15 Minuten mit 150 Gewichtsteilen Wasser gewaschen wurden.For Comparative Example C1, 100 parts by weight of green weight in a rotatable 10-liter drum with flow-breaking internals were successively charged with 60 parts by weight of water, 0.8% by weight. NaSH and 3 wt .-% hydrated lime applied. It followed at an interval of 30 minutes ever 0.75 wt .-% sodium sulfide. The keg was operated for another 45 minutes at 15 revolutions / minute. Subsequently, an additional 40 parts by weight of water were metered. After 10 hours at 23 to 27 ° C and 5 revolutions / minute, the experiments were terminated by draining the liquor and washing the skin twice for 15 minutes with 150 parts by weight of water.
In den erfindungsgemäßen Beispielen 1 bis 6 wurden 100 Gewichtsteile Grüngewicht in einem drehbaren 10-1-Fass mit strömungsbrechenden Inneneinbauten zunächst mit 60 Gew.-% Wasser versetzt und anschließend wie aus Tabelle 1 ersichtlich mit Produkten beaufschlagt.
Das Fass wurde weitere 45 Minuten bei 5 Umdrehungen/Minute betrieben. Anschließend wurden weitere 40 Gew.-% Wasser dosiert. Nach 10 Stunden bei 23 bis 27°C bei periodischem Betreiben mit 3 Umdrehungen/Minute über jeweils 5 Minuten pro Stunde wurden die Versuche beendet, indem die Flotte abgelassen wurde und die Blößen zweimal für je 15 Minuten mit 150 Gew.-% Wasser gewaschen wurden.The cask was operated for another 45 minutes at 5 revolutions / minute. Subsequently, a further 40 wt .-% of water were metered. After 10 hours at 23 to 27 ° C with periodic operation at 3 revolutions / minute for 5 minutes each hour, the experiments were terminated by draining the liquor and washing the sheets twice for 15 minutes each with 150 wt% water ,
Die gemäß der erfindungsgemäßen Beispiele behandelten Blößen waren den nach Vergleichsbeispiel V1 behandelten Häuten hinsichtlich der Schwellung nur wenig überlegen, zeichneten sich aber durch einen glatteren und flacheren Narben aus, insbesondere die Blößen der erfindungsgemäßen Beispiele 1.4 bis 1.6. Die Epidermis und die Haare mit Haarwurzel in den Blößen 1.1 bis 1.3 waren weitgehend und in den Blößen 1.4 bis 1.6 vollständig zerstört.The pelts treated according to the examples according to the invention were only slightly superior to the skins treated according to Comparative Example C1 with respect to the swelling, but were characterized by a smoother and flatter scar, in particular the pelts of Examples 1.4 to 1.6 according to the invention. The epidermis and hair with hair roots in the pelts 1.1 to 1.3 were largely destroyed in the pelts 1.4 to 1.6.
Die Restflotten der erfindungsgemäßen Beispiele 1.1 bis 1.6 wurden mit Ameisensäure auf pH 4,5 angesäuert, ohne dass eine Entwicklung von Schwefelwasserstoff beobachtet wurde. Anschließend wurden die ausgefällten Proteine problemlos durch Filtration abgetrennt. Die Restflotten der Bespiele 1.4 bis 1.6 waren fast klar.The residual liquors of Examples 1.1 to 1.6 according to the invention were acidified to pH 4.5 with formic acid without any evolution of hydrogen sulfide being observed. Subsequently, the precipitated proteins were easily separated by filtration. The remaining fleets of examples 1.4 to 1.6 were almost clear.
Die Entkälkung bzw. Neutralisation erfolgte jeweils mit einem Gemisch, bestehend aus zwei Gewichtsteilen Ameisensäure und drei Gewichtsteilen Adipinsäure. Die Flotte wurde dazu in zwei Dosierschritten auf pH 7,5-8,5 gebracht. Die Penetration der Säure-Mischung über den Hautquerschnitt wurde mit Phenolphthalein als In dikator überprüft. Der hierzu notwendige Zeitbedarf wurde notiert.The deliming or neutralization was carried out in each case with a mixture consisting of two parts by weight of formic acid and three parts by weight of adipic acid. The liquor was brought to pH 7.5-8.5 in two dosing steps. Penetration of the acid mixture across the skin cross section was compared with phenolphthalein as In checked. The time required for this was noted.
Anschließend wurde mit wurden die oben erhaltenen Zwischenstufen in einem konventionellen Pickelbad bei 25°C über einen Zeitraum von 30 Minuten mit 7 Gew.-% Kochsalz gepickelt. Es wurden danach 1 Gew.-% Lipoderm Licker® A1 zugegeben und nach weiteren 20 Minuten 4 Gew.-% Ameisensäure zugegeben. Nach einer weiteren halben Stunde wurde mit konzentrierter Schwefelsäure ein pH-Wert von 3 eingestellt.Subsequently, with the above obtained intermediates were pickled in a conventional Pickelbad at 25 ° C over a period of 30 minutes with 7 wt .-% sodium chloride. Thereafter, 1% by weight of Lipoderm Licker® A1 was added and, after a further 20 minutes, 4% by weight of formic acid were added. After another half hour, a pH of 3 was adjusted with concentrated sulfuric acid.
Zu den oben beschriebenen Pickelbädern wurden jeweils 2,5 Gew.-% ein Glutardialdehydformulierung, kommerziell erhältlich als Relugan® GT 24 der BASF Aktiengesellschaft, gegeben. Nach 90 Minuten wurden 3 Gew.-% eines synthetischen Gerbstoffes, kommerziell erhältlich als Basyntan® SW fl. der BASF Aktiengesellschaft, zugegeben. Nach 30 Minuten wurde 1 Gew.-% eines Gerbstoffs auf Basis von Naphthalinsulfonsäure, kommerziell erhältlich als Tamol ® M der BASF Aktiengesellschaft, zugegeben und über Nacht stehen gelassen. Anschließend wurde mit Natriumformiat und Natriumbicarbonat neutralisiert und die Flotte abgelassen.In each case, 2.5% by weight of a glutardialdehyde formulation, commercially available as Relugan® GT 24 from BASF Aktiengesellschaft, was added to the pimples described above. After 90 minutes, 3% by weight of a synthetic tanning agent, commercially available as Basyntan® SW fl. From BASF Aktiengesellschaft, was added. After 30 minutes, 1% by weight of a tanning agent based on naphthalenesulfonic acid, commercially available as Tamol® M from BASF Aktiengesellschaft, was added and allowed to stand overnight. It was then neutralized with sodium formate and sodium bicarbonate and drained the liquor.
Die so erhaltenen Leder wurden mit Wasser gewaschen und nach konventionellen Verfahren getrocknet und ausgereckt und gefalzt. Die. Falzstärke der Leder betrug 2,0-2,2 mm. Im Folgenden beziehen sich die Angaben in Gew.-% jeweils auf das getrocknete Leder, wenn nicht anders angegeben.The leathers thus obtained were washed with water and dried and stretched and folded by conventional methods. The. Folding thickness of the leather was 2.0-2.2 mm. In the following, the data in% by weight refers to the dried leather, unless stated otherwise.
Die so erhaltenen "wet white"-Rindleder wurden in 100 Gew.-% Wasser eingelegt und durch Zusatz von Natriumformiat und Natriumhydrogencarbonat auf einen pH-Wert von <3,0 eingestellt. Das Leder wurde bei 30°C für 60 Minuten im Fass gewalkt und dann mit 200 Gew.-% Wasser gewaschen.The "wet white" cowhides thus obtained were placed in 100% by weight of water and adjusted to a pH of <3.0 by addition of sodium formate and sodium bicarbonate. The leather was tumbled at 30 ° C for 60 minutes and then washed with 200% by weight of water.
Danach wurden 4 Gew.-% Relugan® GTP zugegeben und 60 Minuten gewalkt. Nach Zugabe von 2 Gew.-% Tamol® NA, kommerziell erhältlich bei BASF Aktiengesellschaft, und 30 minütigem Walken wurden 3 Gew.-% des Fettungsmittels Lipodermâ Licker A1, kommerziell erhältlich bei BASF Aktiengesellschaft, und 1 Gew.-%. Lipoderm® Likker LA, kommerziell erhältlich bei BASF Aktiengesellschaft, zugegeben und 60 Minuten gewalkt. Nach Ablassen der Flotte gab man 100 Gew.-% Wasser von 40°C und 2 Gew.-% handelsüblicher Polymergerbstoff (Relugan® SE), kommerziell erhältlich bei BASF Aktiengesellschaft, hinzu.Thereafter, 4% by weight of Relugan® GTP was added and tumbled for 60 minutes. After addition of 2 wt .-% Tamol® NA, commercially available from BASF Aktiengesellschaft, and 30 minutes walking 3 of the fatliquoring agent Lipoderm â licker A1, commercially available from BASF Aktiengesellschaft, wt .-%, and 1 wt .-%. Lipoderm® Likker LA, commercially available from BASF Aktiengesellschaft, added and drummed for 60 minutes. After draining the liquor, 100% by weight of water at 40 ° C. and 2% by weight of commercially available polymer tanning agent (Relugan® SE), commercially available from BASF Aktiengesellschaft, were added.
Nach partieller Neutralisation der Flotte mit Natriumhydrogencarbonat auf pH 5 und Färbung des Leders in der gleichen Flotte mit 0,5 Gew.-% des Lederfarbstoffs Luganil® Light Brown NGB, kommerziell erhältlich bei BASF Aktiengesellschaft, wurde mit 30 Gew.-% handelsüblichen Sulfongerbstoffes (Basyntan® SW flüssig) und 4 Gew.-% handelsüblichem Tara (Granofin® TA, Fa. Clariant Deutschland GmbH) 2 Stunden ausgegerbt.After partial neutralization of the liquor with sodium bicarbonate to pH 5 and dyeing of the leather in the same liquor with 0.5% by weight of the leather dye Luganil® Light Brown NGB, commercially available from BASF Aktiengesellschaft, with 30% by weight of commercially available sulfone tanning agent ( Basyntan® SW liquid) and 4% by weight of commercially available tare (Granofin® TA, Clariant Deutschland GmbH), aged for 2 hours.
Anschließend wurde mit einem Gemisch aus 8 Gew.-% Fettungsmittel (Lipoderm® Licker A1) und 4 Gew.-% Lipoderm® Licker LA 1 gefettet. Danach wurde die Flotte mit Ameisensäure auf einen pH-Wert von 3,5 bis 3,8 eingestellt, das Leder kurz kalt gespült und wie allgemein üblich weiter bearbeitet.Subsequently, it was greased with a mixture of 8% by weight of fatliquoring agent (Lipoderm® Licker A1) and 4% by weight of Lipoderm® Licker LA 1. Thereafter, the liquor was adjusted to a pH of 3.5 to 3.8 with formic acid, the leather briefly rinsed cold and further processed as usual.
Anschließend wurden die physikalischen und anwendungstechnischen Eigenschaften geprüft.Subsequently, the physical and application properties were tested.
Man erhielt Crustleder 2.1. bis 2.6. mit sehr guter Färbung und guter Festnarbigkeit bei gleichzeitig sehr guter Fülle und exzellenter Weichheit mit elegantem Griff. Die Crustleder 2.4 bis 2.6 wiesen einen glatteren und feineren Narben auf als V2. Weitere anwendungstechnische Eigenschaften sind Tabelle 2 zu entnehmen.
Die Haarzersetzung und die Narbenfestigkeit wurden optisch und haptisch durch 2 Propanden beurteilt (1: sehr gut, 6: ungenügend).The hair decomposition and the scar resistance were assessed visually and haptically by 2 propands (1: very good, 6: insufficient).
Die Haut eines Süddeutschen Rindes wurde zunächst bei 28°C mit 150 Gew.-% Wasser und 0,2 Gew.-% Eusapon® W 120 Minuten in einem Fass bei 1-3 UPM vorgeweicht. Die Flotte wurde abgelassen und danach mit 150 Gew.-% Wasser, 0,2 Gew.-% Eusapon® W und 0,5 Gew.-% Soda bei gelegentlichem Rühren 19 Stunden eingeweicht. Anschließend würde die Flotte abgelassen.The skin of a Southern German bovine was first pre-soaked at 28 ° C with 150 wt .-% water and 0.2 wt .-% Eusapon® W 120 minutes in a barrel at 1-3 rpm. The liquor was drained and then with 150 wt .-% water, 0.2 wt .-% Eusapon® W and 0.5 wt .-% Soda soaked with occasional stirring for 19 hours. Then the fleet would be drained.
Die geweichten Häute süddeutscher Rinder wurden grün entfleischt (Stärke etwa 4 mm) und die Croupons der Häute in Hautstücke zu je 2,5 kg geschnitten.The soaked skins of South German cattle were fleshed green (thickness about 4 mm) and the croupons of the skins cut into pieces of skin of 2.5 kg each.
Im Folgenden beziehen sich die Werte in Gew.-% jeweils auf das Grüngewicht, wenn nicht anderes vermerkt.In the following, the values in% by weight each refer to the green weight, unless otherwise noted.
Für das Vergleichsbeispiel V3 wurden 100 Gewichtsteile Grüngewicht in einem drehbaren 10-l-Fass mit strömungsbrechenden Inneneinbauten nacheinander mit 60 Gew.-% Wasser und jeweils nach 60 Minuten 1,2 Gew.-% Mollescal MF®, kommerziell erhältlich bei BASF Aktiengesellschaft, 0,8 Gew.-% Kalkhydrat und 1 Gew.-% Natriumsulfid (60%) beaufschlagt. Anschließend wurde über einen Zeitraum von 120 Minuten filtriert. Es folgten im Abstand von 60 Minuten weitere 1,6 Gew.-% Kalkhydrat und 40 Gew.-% Wasser. Nach 10 Stunden bei 23 bis 27°C bei periodischem Betreiben mit 3 Umdrehungen/Minute über jeweils 5 Minuten pro Stunde wurden die Versuche beendet, indem die Flotte abgelassen wurde und die Blößen zweimal für je 15 Minuten mit 150 Gew.-% Wasser gewaschen wurden.For Comparative Example C3, 100 parts by weight of green weight in a rotatable 10 l drum with flow-breaking internals were successively mixed with 60% by weight of water and in each case after 60 minutes 1.2% by weight of Mollescal MF®, commercially available from BASF Aktiengesellschaft, 0 , 8 wt .-% hydrated lime and 1 wt .-% sodium sulfide (60%) applied. It was then filtered over a period of 120 minutes. This was followed at intervals of 60 minutes, another 1.6 wt .-% hydrated lime and 40 wt .-% water. After 10 hours at 23 to 27 ° C with periodic operation at 3 revolutions / minute for 5 minutes each hour, the experiments were terminated by draining the liquor and washing the sheets twice for 15 minutes each with 150 wt% water ,
100 Gewichtsteile Grüngewicht wurden in einem drehbaren 10-1-Fass mit strömungsbrechenden Inneneinbauten zunächst mit 60 Gew.-% Wasser versetzt und anschließend wie aus Tabelle 3 ersichtlich mit Produkten beaufschlagt.
Das Fass wurde weitere 45 Minuten bei 15 Umdrehungen/Minute betrieben. Anschließend wurden weitere 40 Gewichtsteile Wasser dosiert. Nach 10 Stunden bei 23 bis 27°C bei periodischem Betreiben mit 3 Umdrehungen/Minute über jeweils 5 Minuten pro Stunde wurden die Versuche beendet, indem die Flotte abgelassen wurde und die Blößen zweimal für je 15 Minuten mit 150 Gew.-% Wasser gewaschen wurden.The keg was operated for another 45 minutes at 15 revolutions / minute. Subsequently, an additional 40 parts by weight of water were metered. After 10 hours at 23 to 27 ° C with periodic operation at 3 revolutions / minute for 5 minutes each hour, the experiments were terminated by draining the liquor and washing the sheets twice for 15 minutes each with 150 wt% water ,
Die gemäß der erfindungsgemäßen Beispiele behandelten Blößen waren den nach Vergleichsbeispiel V3 behandelten Häuten hinsichtlich der Schwellung nur wenig überlegen, zeichneten sich aber durch einen glatteren und flacheren Narben aus, insbesondere die Blößen der erfindungsgemäßen Beispiele 3.2 und 3.3. Die Epidermis und die Haare mit Haarwurzel in Blöße 3.1 war weitgehend und in den Blößen 3.2 bis 3.3 vollständig zerstört.The pelts treated according to the examples according to the invention were only slightly superior to the skins treated according to Comparative Example C3 with regard to swelling, but were characterized by a smoother and flatter scar, in particular the pelts of Examples 3.2 and 3.3 according to the invention. The epidermis and the hair with hair root in pelage 3.1 was largely destroyed in the pelts 3.2 to 3.3.
Anschließend wurden die Blößen aus V3 sowie 3.1 bis 3.3 wie unter 2. beschrieben weiterverarbeitet.Subsequently, the pelts of V3 and 3.1 to 3.3 were further processed as described under 2.
Anschließend wurden die physikalischen und anwendungstechnischen Eigenschaften geprüft.Subsequently, the physical and application properties were tested.
Man erhielt Crustleder 4.1. bis 4.2. mit sehr guter Färbung und guter Festnarbigkeit bei gleichzeitig sehr guter Fülle und exzellenter Weichheit mit elegantem Griff. Die Crustleder 4.2 bis 4.3 wiesen einen glatteren-und feineren Narben auf als V4. Weitere anwendungstechnische Eigenschaften sind Tabelle 4 zu entnehmen.
Die Restflotten der erfindungsgemäßen Beispiele 3.1 und 3.2 wurden mit Ameisensäure auf pH 4,5 angesäuert, ohne dass eine Entwicklung von Schwefelwasserstoff beobachtet wurde. Anschließend wurden die ausgefällten Proteine problemlos durch Filtration abgetrennt. Die Restflotten der Bespiele 3.2 bis 3.3 waren fast klar.The residual liquors of Examples 3.1 and 3.2 according to the invention were acidified to pH 4.5 with formic acid, without a development of hydrogen sulfide was observed. Subsequently, the precipitated proteins were easily separated by filtration. The remaining fleets of examples 3.2 to 3.3 were almost clear.
Claims (8)
- A process for removing horny substances from and at least substantial stripping of the epidermis from hides, pelts or skins of dead animals, wherein the hides, pelts or skins are treated in aqueous liquor containing one or more compounds of the formula I
R1 is selected from hydrogen and C1-C12-alkyl, unsubstituted or substituted by one or more S-H or O-H groups;X1 to X4 are identical or different and are selected from hydrogen, C1-C4-alkyl, O-H, S-H and N-HR2,R2 is hydrogen or C1-C12-alkyl or a C1-C14-alkyl-C=O group,
at least one X1 to X4 being S-H when R1 contains at least one sulfur atom
and at least two X1 to X4 being S-H when R1 contains no sulfur atom. - The process according to claim 1, wherein one or more basic alkali metal compounds are added and the use of lime is dispensed with.
- The process according to either of claims 1 and 2, wherein X1 to X4 are each O-H or S-H.
- The process according to any of claims 1 to 3, wherein R1 is hydrogen.
- An animal pelt obtained by process according to any of claims 1 to 4.
- A leather produced by tanning a pelt according to claim 5.
- A residual liquor which contains neither Na2S nor NaHS and containing, as organic sulfur compounds, only those of the formula I and their reaction products and byproducts which result from the removal of horny substances from hides, pelts or skins of dead animals, and organic sulfur compounds which originate from the hides, pelts or skins of dead animals, obtained by a process according to any of claims 1 to 4.
- A process for working up a residual liquor according to claim 7, wherein, in an optional step, said liquor is separated from the lime and neutralized with an acid, after which the proteins are separated off.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10223012 | 2002-05-22 | ||
| DE10223012 | 2002-05-22 | ||
| PCT/EP2003/005231 WO2003097880A1 (en) | 2002-05-22 | 2003-05-19 | Method for removing horn substance from skins, pelts, or furs |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1511865A1 EP1511865A1 (en) | 2005-03-09 |
| EP1511865B1 true EP1511865B1 (en) | 2009-08-05 |
Family
ID=29432259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03752667A Expired - Lifetime EP1511865B1 (en) | 2002-05-22 | 2003-05-19 | Method for removing horn substance from skins, pelts, or furs |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US7404826B2 (en) |
| EP (1) | EP1511865B1 (en) |
| JP (1) | JP2005531650A (en) |
| KR (1) | KR20050010825A (en) |
| CN (1) | CN100381581C (en) |
| AR (1) | AR039980A1 (en) |
| AT (1) | ATE438742T1 (en) |
| AU (1) | AU2003232797A1 (en) |
| BR (1) | BR0311165A (en) |
| DE (1) | DE50311784D1 (en) |
| ES (1) | ES2329463T3 (en) |
| PT (1) | PT1511865E (en) |
| WO (1) | WO2003097880A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR039980A1 (en) | 2002-05-22 | 2005-03-09 | Basf Ag | PROCEDURE TO ELIMINATE CORNEAL SKIN OR SKIN SUBSTANCES |
| WO2004038046A1 (en) * | 2002-10-21 | 2004-05-06 | Basf Aktiengesellschaft | Method for removing horn substances from animal skin |
| DE10353746A1 (en) * | 2003-11-17 | 2005-06-09 | Basf Ag | Method for removing horny substances from hides of dead animals |
| CN102559948B (en) * | 2010-12-14 | 2015-05-20 | 张壮斗 | Sheepskin leather making process with infinite cycling of waste liquid for liming (or restoring ash alkalinity) |
| KR20220092672A (en) | 2020-12-24 | 2022-07-04 | 한국신발피혁연구원 | Deliming agent for leather deliming process without ammonia generation and Leather deliming method using the same |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1973130A (en) | 1933-07-21 | 1934-09-11 | Rohm & Haas | Process of unhairing hides or skins |
| AT187223B (en) | 1954-06-24 | 1956-10-25 | Chemie Linz Ag | Process for preparing animal hides for tanning |
| US3097912A (en) * | 1959-03-30 | 1963-07-16 | Booth Henry | Hair and wool depilation method and composition |
| DE2131630A1 (en) * | 1970-06-29 | 1972-01-05 | Avon Prod Inc | Removing keratinous substances - with aq soln contg dithiobutanediol and guanidine cpds |
| US3865546A (en) * | 1970-10-22 | 1975-02-11 | Collaborative Res Inc | Depilatory composition and method of use |
| YU36755B (en) * | 1971-11-17 | 1984-08-31 | Basf Ag | Process for the elimination of hairs from hides and furs |
| DE2917376C2 (en) * | 1979-04-28 | 1987-03-26 | Röhm GmbH, 6100 Darmstadt | Enzymatic process for hair extraction and simultaneous skin disintegration |
| EP0095916A3 (en) | 1982-06-01 | 1984-08-08 | THE PROCTER & GAMBLE COMPANY | Depilatory compositions |
| EP0096521A3 (en) | 1982-06-01 | 1985-01-23 | THE PROCTER & GAMBLE COMPANY | Depilatory compositions |
| US4618344A (en) * | 1982-06-01 | 1986-10-21 | The Procter & Gamble Company | Depilatory compositions |
| DE3224881A1 (en) | 1982-07-03 | 1984-03-01 | Röhm GmbH, 6100 Darmstadt | METHOD FOR THE PRODUCTION OF HAIRY, STORAGE SKIN MATERIAL |
| US4472569A (en) | 1983-06-13 | 1984-09-18 | Phillips Petroleum Company | Mercaptohydroxy alkanes |
| DE19933968A1 (en) * | 1999-07-20 | 2001-01-25 | Trumpler Gmbh & Co Chem Fab | Aid for skin disintegration and hair loosening of animal skins |
| AR039980A1 (en) | 2002-05-22 | 2005-03-09 | Basf Ag | PROCEDURE TO ELIMINATE CORNEAL SKIN OR SKIN SUBSTANCES |
| DE10249077A1 (en) | 2002-10-21 | 2004-04-29 | Basf Ag | Process for the production of leather |
| WO2004038046A1 (en) | 2002-10-21 | 2004-05-06 | Basf Aktiengesellschaft | Method for removing horn substances from animal skin |
| DE10309221A1 (en) | 2003-02-28 | 2004-09-09 | Basf Ag | Leveling agent for dyeing fibers |
-
2003
- 2003-05-08 AR ARP030101611A patent/AR039980A1/en not_active Application Discontinuation
- 2003-05-19 WO PCT/EP2003/005231 patent/WO2003097880A1/en active Application Filing
- 2003-05-19 JP JP2004505393A patent/JP2005531650A/en not_active Withdrawn
- 2003-05-19 AT AT03752667T patent/ATE438742T1/en not_active IP Right Cessation
- 2003-05-19 AU AU2003232797A patent/AU2003232797A1/en not_active Abandoned
- 2003-05-19 ES ES03752667T patent/ES2329463T3/en not_active Expired - Lifetime
- 2003-05-19 EP EP03752667A patent/EP1511865B1/en not_active Expired - Lifetime
- 2003-05-19 KR KR10-2004-7018716A patent/KR20050010825A/en not_active Application Discontinuation
- 2003-05-19 BR BR0311165-2A patent/BR0311165A/en not_active IP Right Cessation
- 2003-05-19 PT PT03752667T patent/PT1511865E/en unknown
- 2003-05-19 CN CNB038113422A patent/CN100381581C/en not_active Expired - Fee Related
- 2003-05-19 US US10/513,800 patent/US7404826B2/en not_active Expired - Fee Related
- 2003-05-19 DE DE50311784T patent/DE50311784D1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| AR039980A1 (en) | 2005-03-09 |
| EP1511865A1 (en) | 2005-03-09 |
| CN1653195A (en) | 2005-08-10 |
| ATE438742T1 (en) | 2009-08-15 |
| CN100381581C (en) | 2008-04-16 |
| JP2005531650A (en) | 2005-10-20 |
| WO2003097880A1 (en) | 2003-11-27 |
| KR20050010825A (en) | 2005-01-28 |
| DE50311784D1 (en) | 2009-09-17 |
| AU2003232797A1 (en) | 2003-12-02 |
| BR0311165A (en) | 2005-03-15 |
| PT1511865E (en) | 2009-08-21 |
| US20050229326A1 (en) | 2005-10-20 |
| US7404826B2 (en) | 2008-07-29 |
| ES2329463T3 (en) | 2009-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1801099B1 (en) | Dithiol mixtures in order to remove horny substances of skins | |
| EP1511865B1 (en) | Method for removing horn substance from skins, pelts, or furs | |
| DE10249077A1 (en) | Process for the production of leather | |
| DE1297274B (en) | Process for the production of chrome-tanned leather | |
| WO2004038046A1 (en) | Method for removing horn substances from animal skin | |
| EP0569410B1 (en) | Method of self-tanning, pre-tanning and co-tanning skins and hides and for retanning leather and hides | |
| EP3561081A1 (en) | Composition and method for tanning based on an acetal of an aldehydic tanning agent | |
| EP1687454A1 (en) | Method for the extraction of keratin from dead animal skins | |
| DE10319240A1 (en) | Removal of keratin, i.e. callous, feather, nail, claw and hair or residual hair, from animal skin for leather manufacture, uses di- and poly-mercapto-alkane compound and peptide bond hydrolysis catalyst, e.g. enzyme | |
| WO2019141603A1 (en) | Chromium tanning agents | |
| EP0574800B1 (en) | Process for tanning leather and furs | |
| DE1230517B (en) | Process for depilation and loosening of skins and fur | |
| DE1203416B (en) | Process for the production of bare animals | |
| DE579634C (en) | Process for the production of tanned bare bones from animal hides and skins | |
| DE2307603C3 (en) | ||
| DE1288728B (en) | Process for the production of tanned bare | |
| DE2726576A1 (en) | Rapid hair removal from fresh hides - by treating with sodium di:sulphide removing hair, then treating with sodium chlorite | |
| AT132392B (en) | Process for the production of ready-to-tan pelts from animal hides and skins. | |
| DE2301591C3 (en) | Process for the production of ready-to-tan pelts from animal hides and skins | |
| DE1769160C3 (en) | Enzymatic depilation process for hides and skins | |
| AT73691B (en) | Procedure for preparing pelts and raw hides for shedding the grain. | |
| DE3306374A1 (en) | METHOD FOR TANNING SKIN WITH A HIGH BASIC CHROME TANNER | |
| DE2157034A1 (en) | METHOD FOR DEHAIRING OF SKIN AND FUR | |
| DE1282838B (en) | Process for softening, dehairing or pickling fur or skins with proteolytic enzymes | |
| DE3339104A1 (en) | Compositions and methods for hair treatment and for depilation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 20041222 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
| AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: TAEGER, TILMAN, LUEDECKE Inventor name: LAMALLE, PHILIPPE Inventor name: HUEFFER, STEPHAN Inventor name: PABST, GUNTHER Inventor name: SCHROEDER, STEFAN |
|
| DAX | Request for extension of the european patent (deleted) | ||
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: BASF SE |
|
| 17Q | First examination report despatched |
Effective date: 20080221 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20090813 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REF | Corresponds to: |
Ref document number: 50311784 Country of ref document: DE Date of ref document: 20090917 Kind code of ref document: P |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2329463 Country of ref document: ES Kind code of ref document: T3 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 |
|
| NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091105 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20100330 Year of fee payment: 8 |
|
| 26N | No opposition filed |
Effective date: 20100507 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20100611 Year of fee payment: 8 Ref country code: FR Payment date: 20100611 Year of fee payment: 8 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20100528 Year of fee payment: 8 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091106 |
|
| BERE | Be: lapsed |
Owner name: BASF SE Effective date: 20100531 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20100730 Year of fee payment: 8 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100531 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100531 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100531 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20110428 Year of fee payment: 9 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100519 |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20110519 |
|
| REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20120131 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110519 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 50311784 Country of ref document: DE Effective date: 20111201 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110531 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110519 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100206 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100519 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090805 |
|
| REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20121119 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121119 |
|
| REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20130604 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20111201 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110520 |