EP1511865B1 - Verfahren zur entfernung von hornsubstanzen aus häuten, pelzen oder pelzfellen - Google Patents
Verfahren zur entfernung von hornsubstanzen aus häuten, pelzen oder pelzfellen 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
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- 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)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10223012 | 2002-05-22 | ||
DE10223012 | 2002-05-22 | ||
PCT/EP2003/005231 WO2003097880A1 (de) | 2002-05-22 | 2003-05-19 | Verfahren zur entfernung von hornsubstanzen aus häuten, pelzen oder pelzfellen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1511865A1 EP1511865A1 (de) | 2005-03-09 |
EP1511865B1 true EP1511865B1 (de) | 2009-08-05 |
Family
ID=29432259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03752667A Expired - Lifetime EP1511865B1 (de) | 2002-05-22 | 2003-05-19 | Verfahren zur entfernung von hornsubstanzen aus häuten, pelzen oder pelzfellen |
Country Status (13)
Country | Link |
---|---|
US (1) | US7404826B2 (pt) |
EP (1) | EP1511865B1 (pt) |
JP (1) | JP2005531650A (pt) |
KR (1) | KR20050010825A (pt) |
CN (1) | CN100381581C (pt) |
AR (1) | AR039980A1 (pt) |
AT (1) | ATE438742T1 (pt) |
AU (1) | AU2003232797A1 (pt) |
BR (1) | BR0311165A (pt) |
DE (1) | DE50311784D1 (pt) |
ES (1) | ES2329463T3 (pt) |
PT (1) | PT1511865E (pt) |
WO (1) | WO2003097880A1 (pt) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR039980A1 (es) | 2002-05-22 | 2005-03-09 | Basf Ag | Procedimiento para eliminar sustancias corneas de pieles o pellejos |
WO2004038046A1 (de) * | 2002-10-21 | 2004-05-06 | Basf Aktiengesellschaft | Verfahren zur entfernung von hornsubstanzen aus tierhäuten |
DE10353746A1 (de) * | 2003-11-17 | 2005-06-09 | Basf Ag | Verfahren zum Entfernen von Hornsubstanzen aus Häuten toter Tiere |
CN102559948B (zh) * | 2010-12-14 | 2015-05-20 | 张壮斗 | 一种循环废液进行浸灰碱或复灰碱的羊皮制革工艺 |
KR20220092672A (ko) | 2020-12-24 | 2022-07-04 | 한국신발피혁연구원 | 피혁 탈회 처리용 암모니아 무발생 탈회제 및 이를 이용한 피혁의 탈회 처리법 |
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 (de) | 1954-06-24 | 1956-10-25 | Chemie Linz Ag | Verfahren zum Vorbereiten von tierischen Häuten für die Gerbung |
US3097912A (en) * | 1959-03-30 | 1963-07-16 | Booth Henry | Hair and wool depilation method and composition |
DE2131630A1 (de) * | 1970-06-29 | 1972-01-05 | Avon Prod Inc | Mittel zur Entfernung von Hornsubstanzen,insbesondere Haaren |
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 (de) * | 1979-04-28 | 1987-03-26 | Röhm GmbH, 6100 Darmstadt | Enzymatisches Verfahren zur Haargewinnung und zum gleichzeitigen Hautaufschluß |
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 (de) | 1982-07-03 | 1984-03-01 | Röhm GmbH, 6100 Darmstadt | Verfahren zur herstellung von enthaartem, lagerfaehigem hautmaterial |
US4472569A (en) | 1983-06-13 | 1984-09-18 | Phillips Petroleum Company | Mercaptohydroxy alkanes |
DE19933968A1 (de) * | 1999-07-20 | 2001-01-25 | Trumpler Gmbh & Co Chem Fab | Hilfsmittel für den Hautaufschluß und die Haarlockerung von Tierhäuten |
AR039980A1 (es) | 2002-05-22 | 2005-03-09 | Basf Ag | Procedimiento para eliminar sustancias corneas de pieles o pellejos |
DE10249077A1 (de) | 2002-10-21 | 2004-04-29 | Basf Ag | Verfahren zur Herstellung von Leder |
WO2004038046A1 (de) | 2002-10-21 | 2004-05-06 | Basf Aktiengesellschaft | Verfahren zur entfernung von hornsubstanzen aus tierhäuten |
DE10309221A1 (de) | 2003-02-28 | 2004-09-09 | Basf Ag | Egalisierhilfsmittel für das Färben von Fasern |
-
2003
- 2003-05-08 AR ARP030101611A patent/AR039980A1/es not_active Application Discontinuation
- 2003-05-19 WO PCT/EP2003/005231 patent/WO2003097880A1/de active Application Filing
- 2003-05-19 JP JP2004505393A patent/JP2005531650A/ja not_active Withdrawn
- 2003-05-19 AT AT03752667T patent/ATE438742T1/de not_active IP Right Cessation
- 2003-05-19 AU AU2003232797A patent/AU2003232797A1/en not_active Abandoned
- 2003-05-19 ES ES03752667T patent/ES2329463T3/es not_active Expired - Lifetime
- 2003-05-19 EP EP03752667A patent/EP1511865B1/de not_active Expired - Lifetime
- 2003-05-19 KR KR10-2004-7018716A patent/KR20050010825A/ko not_active Application Discontinuation
- 2003-05-19 BR BR0311165-2A patent/BR0311165A/pt not_active IP Right Cessation
- 2003-05-19 PT PT03752667T patent/PT1511865E/pt unknown
- 2003-05-19 CN CNB038113422A patent/CN100381581C/zh 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/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
AR039980A1 (es) | 2005-03-09 |
EP1511865A1 (de) | 2005-03-09 |
CN1653195A (zh) | 2005-08-10 |
ATE438742T1 (de) | 2009-08-15 |
CN100381581C (zh) | 2008-04-16 |
JP2005531650A (ja) | 2005-10-20 |
WO2003097880A1 (de) | 2003-11-27 |
KR20050010825A (ko) | 2005-01-28 |
DE50311784D1 (de) | 2009-09-17 |
AU2003232797A1 (en) | 2003-12-02 |
BR0311165A (pt) | 2005-03-15 |
PT1511865E (pt) | 2009-08-21 |
US20050229326A1 (en) | 2005-10-20 |
US7404826B2 (en) | 2008-07-29 |
ES2329463T3 (es) | 2009-11-26 |
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