EP0607554B1 - Gerbmittel und Gerbverfahren - Google Patents
Gerbmittel und Gerbverfahren Download PDFInfo
- Publication number
- EP0607554B1 EP0607554B1 EP93119884A EP93119884A EP0607554B1 EP 0607554 B1 EP0607554 B1 EP 0607554B1 EP 93119884 A EP93119884 A EP 93119884A EP 93119884 A EP93119884 A EP 93119884A EP 0607554 B1 EP0607554 B1 EP 0607554B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tanning
- minutes
- move
- formula
- tanning agents
- 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 abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 40
- 239000010985 leather Substances 0.000 claims abstract description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000005554 pickling Methods 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 48
- 239000000178 monomer Substances 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 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 17
- 235000019253 formic acid Nutrition 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 235000013311 vegetables Nutrition 0.000 description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 11
- 150000001299 aldehydes Chemical class 0.000 description 10
- 239000007859 condensation product Substances 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- -1 polyethylene propylene glycols Polymers 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 206010000496 acne Diseases 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001844 chromium Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- 235000011468 Albizia julibrissin Nutrition 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 241001070944 Mimosa Species 0.000 description 3
- 239000004280 Sodium formate Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 2
- 241000283707 Capra Species 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000013011 aqueous formulation Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- IJLJDZOLZATUFK-UHFFFAOYSA-N 2,2-dimethylpropyl prop-2-enoate Chemical compound CC(C)(C)COC(=O)C=C IJLJDZOLZATUFK-UHFFFAOYSA-N 0.000 description 1
- OWPUOLBODXJOKH-UHFFFAOYSA-N 2,3-dihydroxypropyl prop-2-enoate Chemical compound OCC(O)COC(=O)C=C OWPUOLBODXJOKH-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 125000004042 4-aminobutyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])N([H])[H] 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002610 basifying agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 235000019846 buffering salt Nutrition 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004065 wastewater treatment 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
Definitions
- the invention relates to tanning agents which contain an ⁇ , ⁇ '-dialdehyde in combination with a polymer P containing hydroxyl groups as well as a tanning process in which the tanning agents are used in combination.
- chrome tanning which supplies excellent leather (chrome leather) but is ecologically unsafe (cf.Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd.Ed.Vol. 14 , pg. 200 - 231 , pg. 226ff, J. Wiley 1981; Ullmanns Encyclopedia of Industrial Chemistry, 5th Ed. Vol. A15, pg. 259-282, VCH 1990).
- chrome tanning process previously used in practice, chromium salts are used in an amount of 1.5-2.5% chromium-III-oxide, based on the weight of the nakedness, to achieve a cookable leather.
- Chromium-free or low-chromium tanning can also be carried out, for example, with aldehydes as the tanning agent (so-called aldehyde tanning, see Kirk-Othmer, loc.cit; F. Stather, tanning chemistry and tanning technology, Akademie-Verlag, Berlin 1967).
- aliphatic dialdehydes in particular glutardialdehyde and succinic dialdehyde, have prevailed, but these are predominantly used in pretanning, ie followed by other tanning processes such as chrome tanning and retanning.
- the amounts of pure glutaraldehyde required for pretanning - about 0.5 to 1% by weight, based on the weight of the nakedness - are comparatively small.
- the crosslinking caused by glutaraldehyde is extremely stable to hydrolysis.
- glutaraldehyde in pre-tanning, one often encounters difficulties because of the uneven penetration of the pimples pecked in cross-section; the peripheral zones were thus more networked than the middle class. In practice, therefore, lower shrinkage temperatures are observed in the middle layers than in the peripheral areas.
- DE-C 38 11 267 proposes a process for the production of semi-finished leather products in which a reversibly inactivated C 2 -C 8 - ⁇ - ⁇ '-dialdehyde is used as the tanning agent with high penetration properties.
- the inactivation is done by adding 0.2 to 4.0 mol of a hydroxy compound of the formula R - O - [- (C 2 H 4 O) x - (C 3 H 6 O) y - (C 4 H 8 O) z -] n H wherein n is from zero to 10, x + y + z is an integer from 1 to 20, R is hydrogen (if n ⁇ O) or C 1 -C 12 alkyl optionally substituted with one or more hydroxyl groups.
- EP-A-0 118 213 describes a tanning process in which copolymers of at least 60 mole percent methacrylic acid units and at least 5 mole percent C 1 -C 4 -alkyl acrylate units with a molecular weight in the range 3000 to 9000 are used as tanning agents. If necessary, tanning agents from different provenances can be simultaneously applied to the skins.
- the proportion of the monomers of the formulas III and IV which contain hydroxyl groups or can release them hydrolytically in a polymer-analogous reaction is in the range from 100 to 5% by weight, based on the polymers P.
- the ratio between the tanning agent ⁇ , ⁇ '-dialdehyde of the formula I and the polymer P is usually in the range from 1: 4 to 4: 1 parts by weight.
- the partial inactivation of the aldehydes of the formula I occurs on the one hand through the hydroxyl functions of the polymers P themselves, but it can advantageously be enhanced by adding one or more alcohols, preferably water-soluble alcohols.
- Alcohols preferably water-soluble alcohols.
- Polyhydric alcohols from the group consisting of glycol, glycerol, pentaerythritol, butyl glycol, 1,4-butanediol, polyethylene glycols, polyethylene propylene glycols and sugars and sugar alcohols such as glucose, fructose, sorbitol are particularly suitable for this purpose.
- Hydroxycarboxylic acids such as glycolic acid are also suitable.
- these alcohols are used in a molar ratio of 0 to 3.5, in particular 1 to 2 mol, based on the aldehydes of the formula I.
- Glutardialdehyde is particularly preferred as the aldehyde of the formula I, as well as succinic dialdehyde.
- the monomeric compounds of the formula II which may be mentioned are in particular (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, if appropriate also in a mixture, and also as the compound of the formula II-A Maleic anhydride and the itaconic anhydride called.
- the hydroxy group-containing monomers of the formula III are the hydroxyethyl acrylate and the methacrylate, the 3-hydroxypropyl acrylate, the hydroxypropyl acrylate and the methacrylate, the and the methacrylate, and also monoacrylates or methacrylates of polyols, such as, for example, the glycerol monoacrylate and the methacrylate, the neopentyl acrylate and the methacrylate.
- Particularly suitable compounds of the formula IV are vinyl acetate and vinyl propionate.
- Monomers of the formula V which may be mentioned in particular are methyl methacrylate and methyl acrylate, ethyl acrylate, furthermore ethylhexyl acrylate and ethylhexyl methacrylate.
- the polymers P to be used according to the invention preferably have a molar mass in the range from 1,000 to 50,000, in particular less than 5,000 g / mol. Molecular weight is determined using size exclusion chromatography (SEC) (cf. HF Mark et al. Encyclopedia of Polymer Science & Engineering, 2nd. Ed. Vol. 10 , pg. 1 - 18, J. Wiley 1987; Ullmann's Encyclopedia of Industrial Chemistry 5th Ed. Vol. 20A, pg. 563-568, VCI (1992)).
- SEC size exclusion chromatography
- the tanning agents GM usually have a polymer content P (dry weight) of 10-60% by weight, preferably 20-40% by weight.
- the tanning agents GM according to the invention have, as aqueous formulations, a pH in the range from 0.5 to 5, preferably from 2 to 4.
- the polymers P can be prepared in a manner known per se by radical polymerization of the monomers of the formulas II-V in accordance with the desired proportions (cf. H. Rauch Puntigam, Th. Völker, Acryl- und Methacrylitatien, Springer Verlag 1968).
- the polymers P in hydrophilic monomers it is advisable to carry out the polymerization in the form of solution polymerization. This is carried out in an aqueous phase with the addition of water-soluble accelerators, the concentration of the monomers generally being kept below 25% by weight, since the reaction is exothermic.
- water-soluble accelerators the concentration of the monomers generally being kept below 25% by weight, since the reaction is exothermic.
- molecular weight regulators in particular sulfur regulators, especially water-soluble regulators such as mercaptoethanol or thioglycolic acid or, if necessary.
- the initiator content is generally in the range from 0.01 to 1% by weight, based on the monomers.
- Redox systems known per se are particularly preferred as initiators, for example those which contain heavy metal ions, for example iron ions, in combination with water-soluble per compounds such as hydrogen peroxide or persulfate.
- the polymerization can advantageously be carried out as a two-stage redox batch polymerization in a suitable reaction vessel. For example, half of the monomers are placed in the aqueous phase if necessary. together with the reducing component of the initiator at room temperature before, as a guide, about 3 to 3.5 times the amount of water can be used.
- the polymerization is then started by adding the per compound, for example 30% aqueous perhydrol solution. The temperature then rises, for example to approximately 80 degrees C.
- the mixture is cooled, for example to about 35 ° C., and the complete batch of the second stage, usually consisting of the second half of the monomers and the regulator or the reducing agent, is added and the is added by adding about the same amount of per compound Reaction started, the temperature rising again, for example to 85 degrees C.
- the mixture is advantageously stirred for another hour and then cooled.
- the process products can advantageously be used in the liquid phase, ie without isolating the polymers P.
- the chrome retanning of the chrome-free pre-tanned leather can be carried out, for example, in such a way that the goods, for example folded wet-whites in a chrome tanning liquor - usually 150 to 250% based on the folding weight - treated, for example overnight.
- the goods can be briefly agitated, for example, in a liquor brought to a pH of approx. 3.5 with formic acid, then with the addition of the chrome tanning agent (as a guide: approx. 25% by weight Cr 2 O 3 , 33% by weight basicity) again for approx. 1/2 hour.
- fatliquor for example alkyl sulfonates
- fatliquor for example alkyl sulfonates
- chromium syntan for example, butyl sulfonates
- further fatliquor for example natural sulfinated oils
- a system for example from the group of the phenol condensation products, can first be added and then moved for about 1/2 hour, followed by the addition of a fatliquor, for example of the straight-chain hydrocarbon type, with about 20 minutes of agitation.
- the vegetable tanning agent for example Mimosa tanning agent
- the vegetable tanning agent is then expediently added in amounts of - as a reference - 8% by weight, based on the shaved weight, and again extensive movement, for example over 3 hours.
- agitation is again carried out for about 1/2 hour and, appropriately after the addition of formic acid, agitation is first carried out continuously for about 1/2 hour, then discontinuously overnight (agitation for about 1 minute, rest for 10 minutes).
- the wash water is drained off and neutralizing tanning agent, for example, is released in about 150% of water (based on the fold weight) the group of salts of organic acids.
- the mixture is agitated for about another 3/4 hour, the liquor usually assuming a pH in the range from 5.0 to 5.5, and the liquor is then drained off.
- greasing which can be carried out, for example, with greasing agents from the group of the sulfited oils and the sulfosuccinic acid esters in approx. 150% water (based on the shaved weight).
- the tanning step is also carried out in a similar way, in that a suitable syntan, for example from the group of the phenol condensation products - approximately 4% based on the fold weight - is added and agitated for about 30 minutes, followed by the addition of a fatliquor and shorter, about 20 minutes of movement. Then three further portions of the syntan are added, preferably at 1/2 hour intervals while moving, so that the total syntan content as a guideline is about 22% by weight, based on the shaved weight. Subsequently, it is moved continuously for about 3 hours and furthermore - overnight - discontinuously (approximately in time: move 1 minute, Rest for 20 minutes).
- a suitable syntan for example from the group of the phenol condensation products - approximately 4% based on the fold weight - is added and agitated for about 30 minutes, followed by the addition of a fatliquor and shorter, about 20 minutes of movement.
- three further portions of the syntan are added, preferably at
- the advantage of the process according to the invention is, inter alia, that the di-aldehydes of the formula I, in particular the glutardialdehyde, are inactivated to the desired extent by the organically bound hydroxyl groups present, and thus the self-condensation is prevented. It is of particular importance that the polymer penetrates deeper in the skin cross-section due to the modification that occurs with the dialdehyde and this results in a better filling effect. Furthermore, with a subsequent low-chrome retanning, a more even chrome distribution is obtained. When using the polymer P there is also a better leveling of the coloring and better foldability.
- Polymer P-1 polymer based on acrylic acid and 2-hydroxyethyl acrylate in a weight ratio of 9/1.
- Polymer P-2 polymer based on acrylic acid and 2-hydroxyethyl acrylate in a weight ratio of 8/2
- the polymer P-1 with a molecular weight of approx. 1200 is produced in a 2-stage redox batch.
- the entire 1st stage (7.49 kg water, 2.097 kg acrylic acid, 0.233 kg 2-hydroxyethyl acrylate, 466 g mercaptoethanol and 23 g FeSO 4 solution 1%) is placed in the reaction vessel and at room temperature by adding 585 g perhydrol ( 30% H 2 O 2 ) started. The temperature rises to 80 degrees C. After the maximum temperature has been exceeded, the mixture is cooled to 35 ° C. and the complete second stage (2.097 kg of acrylic acid and 0.233 kg of 2-hydroxyethyl acrylate and 466 g of mercaptoethanol) is used and started again by adding 585 g of perhydrol. The temperature rises to 85 degrees C. After the maximum temperature has been reached, stirring is continued for 1 hour and then cooling. The polymer P is obtained in an aqueous phase which can be used as such.
- Polymer P-2 is prepared analogously. TABLE 1: Properties of the polymers P polymer Dryness (%) viscosity pH P-1 40 ⁇ 50 mPas 4.0 P-2 40 ⁇ 50 mPas 3.8
- the tanning agents GM according to the invention are obtained by mixing the components, the polymer (s) P, the aldehyde of the formula I and if necessary. alcohol at room temperature or by briefly heating to 50 degrees C (pH 3-4).
- the polymers P are preferably used, as are directly obtained in the polymerization.
- a list of tested GM tanning agents is given in Table 2 below: TABLE 2: Tanning agent GM No. Glutardialdehyde + polymer P + alcohol Molar ratio glutar.
- the percentages relate to the weight of the nakedness.
- Example C-1a Chromium-free pre-tanning
- the percentages relate to the weight of the nakedness
- Example C-2 Chrome Tanning
- Example C-2a Chrome retanning of the chrome-free pretanned leather from Example C-1
- Example C-3a Vegetable retanning of the chrome-free pretanned leather from Example C-1
- Example C-4a Synthetic retanning of the chrome-free pretanned leather from Example C-1
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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE4242076 | 1992-12-14 | ||
DE4242076A DE4242076A1 (de) | 1992-12-14 | 1992-12-14 | Gerbmittel und Gerbverfahren |
Publications (2)
Publication Number | Publication Date |
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EP0607554A1 EP0607554A1 (de) | 1994-07-27 |
EP0607554B1 true EP0607554B1 (de) | 1997-03-05 |
Family
ID=6475182
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Application Number | Title | Priority Date | Filing Date |
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EP93119884A Expired - Lifetime EP0607554B1 (de) | 1992-12-14 | 1993-12-09 | Gerbmittel und Gerbverfahren |
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US (2) | US5505864A (pt) |
EP (1) | EP0607554B1 (pt) |
JP (1) | JPH06212200A (pt) |
KR (1) | KR940014813A (pt) |
AT (1) | ATE149573T1 (pt) |
BR (1) | BR9305035A (pt) |
DE (2) | DE4242076A1 (pt) |
ES (1) | ES2099357T3 (pt) |
TW (1) | TW229232B (pt) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20200291493A1 (en) * | 2017-08-23 | 2020-09-17 | DB Patents Ltd. | Method for tanning an animal skin with dialdehydes |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4440846A1 (de) * | 1994-11-15 | 1996-05-23 | Basf Ag | Verfahren zur Herstellung von Leder und Pelzfellen unter Verwendung von Polymergerbstoffen |
EP0717114A3 (de) * | 1994-12-15 | 1996-08-21 | Ciba Geigy Ag | Wässrige Zusammensetzung zum Vorgerben von Hautblössen oder Nachgerben von Leder |
DE19546254A1 (de) * | 1995-12-12 | 1997-06-19 | Basf Ag | Verwendung von wäßrigen Lösungen oder Dispersionen von Copolymerisaten aus carboxylgruppenhaltigen Monomeren, ethylenisch ungesättigten Acetalen, Ketalen oder Orthocarbonsäureestern und gegebenenfalls weiteren copolymerisierbaren Monomeren als Ledergerbstoffe |
DE19906190A1 (de) * | 1999-02-15 | 2000-08-17 | Boehme Chem Fab Kg | Gerbverfahren |
DE102005032585A1 (de) * | 2005-07-11 | 2007-01-25 | Basf Ag | Verfahren zur Herstellung von Leder |
JP5172228B2 (ja) * | 2007-06-28 | 2013-03-27 | ミドリホクヨー株式会社 | 革 |
ITUB20152180A1 (it) | 2015-07-14 | 2017-01-14 | Db Patents Ltd | Metodo migliorato per conciare una pelle animale. |
CN111747593A (zh) * | 2020-07-01 | 2020-10-09 | 河北东明皮革有限公司 | 制革准备与鞣制工段废液分段循环系统及其使用方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2205883A (en) * | 1938-06-16 | 1940-06-25 | Du Pont | Tanning |
US2941859A (en) * | 1959-04-08 | 1960-06-21 | Martin L Fein | Tanning with glutaraldehyde |
GB952557A (en) * | 1961-08-29 | 1964-03-18 | Degussa | Process for the treatment of leather |
US3945792A (en) * | 1969-07-09 | 1976-03-23 | Ciba-Geigy Corporation | Process for the filling of leather and compositions therefor |
ES421535A1 (es) * | 1973-01-13 | 1976-06-16 | Roehm Gmbh | Procedimiento para la preparacion de pellejos dispuestos para curtir a partir de cuero y pieles de origen animal. |
DE2404789C3 (de) * | 1974-02-01 | 1979-02-15 | Roehm Gmbh, 6100 Darmstadt | Verfahren zur Herstellung gerbfertiger Blößen aus tierischen Häuten und Fellen |
DE2423118C3 (de) * | 1974-05-13 | 1979-04-26 | Schill & Seilacher Gmbh & Co, 7030 Boeblingen | Verfahren zur Herstellung von Leder |
DE2930342A1 (de) * | 1979-07-26 | 1981-02-19 | Roehm Gmbh | Verbessertes verfahren zur herstellung von leder |
US4439201A (en) * | 1981-03-06 | 1984-03-27 | Ciba-Geigy Corporation | Process for retanning leather with acrylic-based oligomers |
US4526581A (en) * | 1983-02-07 | 1985-07-02 | Rohm And Haas Company | Process for producing leather |
SU1520068A1 (ru) * | 1987-11-12 | 1989-11-07 | Ереванский государственный университет | Тройной сополимер N, N-диметиламиноэтилметакрилата, винилацетата и винилового спирта в качестве стабилизатора дубител дл обработки голь |
DE3811267C1 (pt) * | 1988-04-02 | 1989-05-18 | Schill & Seilacher Gmbh & Co, 7030 Boeblingen, De | |
DE3926168A1 (de) * | 1989-08-08 | 1991-02-14 | Basf Ag | Verwendung von copolymerisaten auf basis von langkettigen alkylvinylethern und ethylenisch ungesaettigten dicarbonsaeureanhydriden zum hydrophobieren von leder und pelzfellen |
-
1992
- 1992-12-14 DE DE4242076A patent/DE4242076A1/de not_active Withdrawn
-
1993
- 1993-12-09 AT AT93119884T patent/ATE149573T1/de not_active IP Right Cessation
- 1993-12-09 DE DE59305626T patent/DE59305626D1/de not_active Expired - Lifetime
- 1993-12-09 ES ES93119884T patent/ES2099357T3/es not_active Expired - Lifetime
- 1993-12-09 EP EP93119884A patent/EP0607554B1/de not_active Expired - Lifetime
- 1993-12-13 BR BR9305035A patent/BR9305035A/pt not_active IP Right Cessation
- 1993-12-13 JP JP5311940A patent/JPH06212200A/ja active Pending
- 1993-12-14 US US08/167,561 patent/US5505864A/en not_active Expired - Lifetime
- 1993-12-14 KR KR1019930027562A patent/KR940014813A/ko not_active Application Discontinuation
-
1994
- 1994-01-17 TW TW083100333A patent/TW229232B/zh active
-
1995
- 1995-06-05 US US08/459,462 patent/US5492539A/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20200291493A1 (en) * | 2017-08-23 | 2020-09-17 | DB Patents Ltd. | Method for tanning an animal skin with dialdehydes |
Also Published As
Publication number | Publication date |
---|---|
US5505864A (en) | 1996-04-09 |
ES2099357T3 (es) | 1997-05-16 |
DE59305626D1 (de) | 1997-04-10 |
EP0607554A1 (de) | 1994-07-27 |
US5492539A (en) | 1996-02-20 |
ATE149573T1 (de) | 1997-03-15 |
BR9305035A (pt) | 1994-06-21 |
DE4242076A1 (de) | 1994-06-16 |
TW229232B (pt) | 1994-09-01 |
KR940014813A (ko) | 1994-07-19 |
JPH06212200A (ja) | 1994-08-02 |
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