EP0690135A1 - Polyisocyanates bloqués avec bisulfites pour des agents de tannage - Google Patents
Polyisocyanates bloqués avec bisulfites pour des agents de tannage Download PDFInfo
- Publication number
- EP0690135A1 EP0690135A1 EP95109198A EP95109198A EP0690135A1 EP 0690135 A1 EP0690135 A1 EP 0690135A1 EP 95109198 A EP95109198 A EP 95109198A EP 95109198 A EP95109198 A EP 95109198A EP 0690135 A1 EP0690135 A1 EP 0690135A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyether
- white
- hdi
- transparent
- ethylene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 36
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 title abstract description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title description 6
- 229940079826 hydrogen sulfite Drugs 0.000 title 1
- 229920000570 polyether Polymers 0.000 claims abstract description 60
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 58
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- BEXMOORQHNTVJZ-UHFFFAOYSA-N amino(oxo)methanesulfonic acid Chemical compound NC(=O)S(O)(=O)=O BEXMOORQHNTVJZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 25
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical class OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 claims description 4
- 229920001864 tannin Polymers 0.000 claims description 4
- 239000001648 tannin Substances 0.000 claims description 4
- 235000018553 tannin Nutrition 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 43
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 22
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 239000010985 leather Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- -1 Aliphatic aldehydes Chemical class 0.000 description 8
- 150000001298 alcohols Chemical class 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 7
- 125000005442 diisocyanate group Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 5
- 102000008186 Collagen Human genes 0.000 description 5
- 108010035532 Collagen Proteins 0.000 description 5
- 229920001436 collagen Polymers 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 235000013311 vegetables Nutrition 0.000 description 5
- 235000011468 Albizia julibrissin Nutrition 0.000 description 4
- 241001070944 Mimosa Species 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000005829 trimerization reaction Methods 0.000 description 4
- 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 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 206010000496 acne Diseases 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 2
- RLAUGOOVNMKKCB-UHFFFAOYSA-N 1-isocyanato-4-(isocyanatomethyl)-1-methylcyclohexane Chemical compound O=C=NC1(C)CCC(CN=C=O)CC1 RLAUGOOVNMKKCB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 235000015278 beef Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical compound CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920005613 synthetic organic polymer Polymers 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- QKOWXXDOHMJOMQ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)biuret Chemical compound O=C=NCCCCCCNC(=O)N(CCCCCCN=C=O)C(=O)NCCCCCCN=C=O QKOWXXDOHMJOMQ-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- LUWZGNOSOQUFAE-UHFFFAOYSA-N 1,4-diisocyanatohexane Chemical compound O=C=NC(CC)CCCN=C=O LUWZGNOSOQUFAE-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- OUJCKESIGPLCRN-UHFFFAOYSA-N 1,5-diisocyanato-2,2-dimethylpentane Chemical compound O=C=NCC(C)(C)CCCN=C=O OUJCKESIGPLCRN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- ISNRCPCOXSJZRZ-UHFFFAOYSA-N 1-benzhydryl-2,3,4-triisocyanatobenzene Chemical class N(=C=O)C1=C(C(=C(C=C1)C(C1=CC=CC=C1)C1=CC=CC=C1)N=C=O)N=C=O ISNRCPCOXSJZRZ-UHFFFAOYSA-N 0.000 description 1
- AFVMPODRAIDZQC-UHFFFAOYSA-N 1-isocyanato-2-(isocyanatomethyl)cyclopentane Chemical compound O=C=NCC1CCCC1N=C=O AFVMPODRAIDZQC-UHFFFAOYSA-N 0.000 description 1
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- PLKYFCNQLSKVBV-UHFFFAOYSA-N 2-isocyanatohexanoyl chloride Chemical compound CCCCC(C(Cl)=O)N=C=O PLKYFCNQLSKVBV-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical group N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 1
- DNBQKIFNYIZSRX-UHFFFAOYSA-N 3-isocyanatohexane Chemical compound CCCC(CC)N=C=O DNBQKIFNYIZSRX-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000014036 Castanea Nutrition 0.000 description 1
- 241001070941 Castanea Species 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- JUVFXOACQHHNBE-UHFFFAOYSA-N N(=C=O)C1(C(CCCC1)(CC1CCCCC1)N=C=O)N=C=O Chemical compound N(=C=O)C1(C(CCCC1)(CC1CCCCC1)N=C=O)N=C=O JUVFXOACQHHNBE-UHFFFAOYSA-N 0.000 description 1
- 229910004879 Na2S2O5 Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000017343 Quebracho blanco Nutrition 0.000 description 1
- 241000065615 Schinopsis balansae Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- BSLPBBRZOUQCST-UHFFFAOYSA-L [Li+].[Li+].[O-]S(=O)OS([O-])=O Chemical compound [Li+].[Li+].[O-]S(=O)OS([O-])=O BSLPBBRZOUQCST-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001414 amino alcohols Chemical class 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
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical class N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- HAHLURFXZPKIQK-UHFFFAOYSA-N diazanium;sulfinato sulfite Chemical compound [NH4+].[NH4+].[O-]S(=O)OS([O-])=O HAHLURFXZPKIQK-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- SLWVNFIPVAOWSN-UHFFFAOYSA-M hydrogen sulfite;tetraethylazanium Chemical compound OS([O-])=O.CC[N+](CC)(CC)CC SLWVNFIPVAOWSN-UHFFFAOYSA-M 0.000 description 1
- BSPCDVNIYGDPPA-UHFFFAOYSA-M hydrogen sulfite;tetramethylazanium Chemical compound OS([O-])=O.C[N+](C)(C)C BSPCDVNIYGDPPA-UHFFFAOYSA-M 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- SUPUVLWGKPVHBQ-UHFFFAOYSA-M lithium sulfite Chemical compound [Li+].OS([O-])=O SUPUVLWGKPVHBQ-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 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
- 229940042880 natural phospholipid Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 1
- 229940099427 potassium bisulfite Drugs 0.000 description 1
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 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
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
Definitions
- the invention relates to the use of bisulfite-blocked polyisocyanates containing ether groups as tanning agents.
- the tanning transforms animal skins into leather by cross-linking the collagen.
- One of the most important characteristics of leather is the increased shrinking temperature compared to untanned hides, i.e. the improved hot water resistance, and the white appearance (non-transparent, non-pigment-like) after drying.
- the still dominant type of tanning is chrome tanning, in which covalent bonds with the carboxyl groups of the collagen are formed using chromium (III) compounds under the influence of OH ions.
- the hydrogen bonds to the amide groups of collagen that can be obtained with polyfunctional vegetable tannins are much weaker, which also results in a moderately increased shrinking temperature.
- Aliphatic aldehydes e.g. Glutaraldehyde, which leads to crosslinking via the primary amino groups of collagen, has been recommended as a tanning agent (US Pat. No. 2,941,859).
- the resulting aldimines can reversibly react back to aldehyde and amine in the presence of water.
- aliphatic diisocyanates such as hexamethylene diisocyanate (DE-PS 72 981) has not been able to gain acceptance for toxicological reasons.
- reaction products to be used according to the invention can be obtained from the intermediates obtainable from A, B and optionally C with NCO contents of 3 to 50, preferably 5 to 45, in particular 20 to 45% by weight (based on the intermediate) by subsequently blocking the free ones Obtained isocyanate groups.
- the products according to the invention then - calculated as sodium salt and based on solids - contain 9.7 to 78, preferably 14 to 74, in particular 46.5 to 74% by weight of carbamoyl sulfonate groups.
- Suitable organic polyisocyanates A) are aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic polyisocyanates as described, for example, by W. Siefken in Liebigs Annalen der Chemie 562 , pages 75 to 136.
- Preferred polyisocyanates A) are compounds of the formula Q (NCO) n with an average molecular weight below 800, where n is a number of at least 2, preferably from 2 to 4, Q is an aliphatic C4-C12 hydrocarbon radical, a cycloaliphatic C6-C15 hydrocarbon radical , an araliphatic C7-C15-coblenhydrogen radical or a heterocyclic C2-C12 radical with 1 to 3 heteroatoms from the series oxygen, sulfur, nitrogen mean, for example (i) diisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate , 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-2-isocyanatomethyl
- polyisocyanates produced by trimerization are the trimerizate of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane obtainable by isocyanurate formation and the isocyanurate groups obtainable by trimerization of hexamethylene diisocyanate, optionally in a mixture with 2,4'-diisocyanatotoluene containing polyisocyanates.
- trimerizate of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane obtainable by isocyanurate formation and the isocyanurate groups obtainable by trimerization of hexamethylene diisocyanate, optionally in a mixture with 2,4'-diisocyanatotoluene containing polyisocyanates.
- biuretization Polyisocyanates are tris (isocyanatohexyl) biuret and its mixtures with its higher homologues, as are accessible, for example,
- Particularly preferred polyisocyanates A are those with a molecular weight of 140 to 400 with NCO groups bound to aliphatics or cycloaliphatics, such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethylpentane, 2 , 2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,3- and 1,4-diisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 1-isocyanato-1-methyl-4-isocyanatomethyl-cyclohexane and 4,4'-diisocyanatodicyclohexyl-methane, and any mixtures of such diisocyanates.
- araliphatic polyisocyanates such as the xylylene diisocyanates of
- diisocyanates are preferably used.
- monofunctional aliphatic isocyanates such as butyl isocyanate, hexyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate or dodecyl isocyanate and / or polyisocyanates with an average functionality of 2.2 to 4.2 can also be used.
- the higher-functionality polyisocyanates are preferably essentially composed of trimeric 1,6-diisocyanatohexane or 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and optionally dimeric 1,6-diisocyanatohexane or 1-isocyanato-3 , 3,5-trimethyl-5-isocyanatomethyl-cyclohexane and the correspondingly higher homologues of isocyanurate groups and optionally uretdione groups containing polyisocyanate mixtures with an NCO content of 19 to 24 wt .-%, as obtained by known catalytic trimerization and under isocyanurate Formation of 1,6-diisocyanatohexane or 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane can be obtained and which preferably have an (average) NCO functionality of 3.2 to 4.2.
- polyisocyanates A are polyisocyanates prepared by modifying aliphatic or cycloaliphatic diisocyanates with uretdione and / or isocyanurate, urethane and / or allophanate, biuret or oxadiazine structure, as described, for example, in DE-OS 1 670 666, 3 700 209 and 3 900 053 and are described by way of example in EP 336 205 and 339 396.
- Suitable polyisocyanates are e.g. also the ester group-containing polyisocyanates, e.g.
- triisocyanates accessible by reacting pentaerythritol or trimethylolpropane silyl ethers with isocyanatocaproic acid chloride (cf. DE-OS 3 743 782). It is also possible to use triisocyanates such as e.g. Tris-isocyanatodicyclohexylmethane to use.
- the use of monofunctional and more than difunctional isocyanates is preferably limited to amounts of at most 10 mol%, based on all polyisocyanates A.
- the polyether alcohols B are accessible in a manner known per se by alkoxylation of suitable starter molecules. Any mono- or polyhydric alcohols with a molecular weight of 32 to 250 can be used as starter molecules to produce the polyether alcohols. Monofunctional aliphatic C1-C18, preferably C1-C4 alcohols are preferably used as starter molecules. The use of methanol, butanol, ethylene glycol monomethyl ether or ethylene glycol monobutyl ether as starter is particularly preferred.
- Alkylene oxides suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any order. Any other epoxides such as butylene oxide, dodecene oxide or styrene oxide can also be used. Pure polyethylene oxide alcohols are particularly preferred.
- Ester group-containing polyalkylene oxide alcohols are OH-terminated polyester ethers which are reacted by reacting aliphatic C2-C8 dicarboxylic acids or their esters or acid chlorides with polyethers from the group consisting of polyethylene oxides, polypropylene oxides, their mixtures or mixed polyethers, with 0.8 to 0 per OH equivalent of the polyether 0.99 equivalents of carboxyl groups or their derivatives are used, are available and have an average molecular weight below 10,000, preferably below 3,000.
- the optionally used NCO-redactive components C comprise conventional mono- to tetrafunctional building blocks used in polyurethane chemistry, such as alcohols, amines, amino alcohols and mercaptans with molecular weights below 6,000, preferably below 2,000, such as e.g. Polyesters, polyether esters and polycarbonates, unless they fall under definition B.
- Preferred components C are long-chain, optionally branched, so-called fatty alcohols or fatty amines with 12 to 30 carbon atoms which have a "fatty" or “re-fatty” effect, and esters of natural fatty acids, such as stearic acid, oleic acid, palmitic acid, linoleic acid, linolenic acid, etc., which contain OH groups.
- Very particularly preferred components C are natural fats and oils carrying OH groups, such as castor oil.
- reaction products from components A to D to be used according to the invention can contain up to 20% by weight of incorporated residues of component C.
- Preferred blocking agents D are preferably the sodium salts of sulphurous or disulphurous acid, i.e. Sodium hydrogen sulfite (NaHSO3) or sodium disulfite (Na2S2O5).
- alkali and ammonium salts of these acids namely potassium bisulfite, potassium disulfite, lithium bisulfite, lithium disulfite, ammonium bisulfite, ammonium disulfite and simple tetraalkylammonium salts of these acids, such as, for example, tetramethylammonium bisulfite, can also be used advantageously. Tetraethylammonium bisulfite etc.
- the salts are preferably used as aqueous solutions with solids contents of 5 to 40% by weight.
- reaction products to be used according to the invention can be prepared, for example, as follows: In a first step, the polyisocyanate is reacted with the polyether alcohol B until all OH groups have been urethanized. The NCO-terminated prepolymer thus obtained is then blocked in a second step with alkali metal or ammonium bisulfite or disulfite until all NCO groups have been reacted.
- the entire process is particularly preferably carried out solvent-free as a one-pot process.
- the reaction (1st step) is carried out in the temperature range up to 130 ° C., preferably in the range between 50 ° C. and 120 ° C., particularly preferably between 80 ° C. and 110 ° C.
- the reaction can be followed by titration of the NCO content or by measurement of the IR spectra and evaluation of the carbonyl band at approx. 2 100 cm ⁇ 1 and is complete when the isocyanate content is not more than 0.1% by weight above the value which is to be achieved with complete sales. As a rule, response times of less than 4 hours are sufficient.
- NCO prepolymers thus obtained with NCO contents of 5 to 45% by weight are then in a second step at 0 to 60 ° C, preferably at 10 to 40 ° C, with aqueous solutions of alkali or ammonium sulfites and Water reacted until all NCO groups have reacted. This generally requires reaction times of 1 to 12, preferably 3 to 8 hours.
- the end products are optically clear aqueous solutions, in a few individual cases stable, fine-particle emulsions with average particle diameters below 8000 nanometers. It may be advantageous to first react the NCO prepolymers with 20 to 50% by weight aqueous solutions of the alkali metal or ammonium bisulfites or disulfites and to add the remaining water after 5 to 45 minutes, so that then a solids content of the aqueous preparations of 10 to 50 wt .-%, preferably 25 to 40 wt .-% results.
- the pH should be at least 7.5 to preferably a maximum of 9.5.
- the blocked isocyanate groups react with cross-linking of the collagen (with simultaneous elimination of the bisulfite group).
- All known blunting agents customary in tannery are suitable for basifying the reaction products according to the invention: Sodium carbonate and bicarbonate, magnesium oxide, dolomite, tertiary amines, etc.
- the controlled addition of sodium or potassium hydroxide is generally possible (but not common).
- Magnesium oxide is particularly preferred.
- a low pH is not required, as is customary, for example, in mineral tanning. This can save you the addition of salt (pimples). Nakedness is e.g. decalcified to a pH of 5 to 8 (preferably by 7), the reaction product to be used according to the invention is added and the basification is started after an hour's running time. (In the case of annealed magnesium oxide, the addition can be started immediately).
- the tanning and preferably the simultaneous basification can be completed in 4 to 6 hours.
- the mixture is left to run overnight in a further 2 steps (each after 1 hour running time), rinsing the next morning and continuing as usual.
- the reaction products to be used according to the invention can be used as a replacement for mineral tanning agents. Amounts of 1 to 20% by weight, preferably 3 to 15% by weight, of the reaction product, based on the pelt weight, are generally used.
- the leather tanned with the reaction product with shrinkage temperatures of above 70 ° C., preferably above 75 ° C., serves as a preliminary stage (analogue wet blue) for retanning with synthetic organic polymers (incl. resin tanning agents) or vegetable tanning agents.
- the leathers can of course still be dyed and greased.
- the tanning with the reaction products to be used according to the invention proceeds particularly well at pH values of 4 to 10, preferably 5 to 8. There is no need to pick or pickle. Pickling can also be an advantage to achieve a softer leather; even pimples don't bother.
- reaction products to be used according to the invention can also be used in such a way that they are only tanned up to a shrinkage temperature of 65 to 70 ° C. This gives colorless leather (wet white) which can then be mineral-tanned and retanned with synthetic organic polymers or vegetable tanning agents.
- the percentages in the following examples relate to the weight and to the bare / leather.
- the following examples contain an additional component C or 10 mol% trimerized HDI (22.1% NCO). Production analogous to example 1.
- E.g. Polyisocyanate Moles of polyisocyanate Polyether Mole polyether Mole bisulfite Component C % blocked NCO 26 HDI 0.262 12th 0.047 0.433 A, 17 g 17.0 27 HDI 0.212 12th 0.047 0.191 B, 11 g 7.9 28 HDI plus trim.
- HDI 0.095 0.009 5 0.063 0.152 - 5.8 30th HDI 0.328 12th 0.028 0.626 C, 5.2 g 23.9 31 HDI 0.221 5 0.039 0.210 D, 16 g 9.3 32 HDI 0.179 12th 0.047 0.232 E, 13.4 g 9.0 33 HDI 0.211 1 0.025 0.390 C, 14.1 g 14.9 34 HDI 0.217 8th 0.036 0.390 C 13.9 g 14.9 35 HDI 0.218 5 0.040 0.373 C, 13.8 g 14.4 36 HDI plus trim.
- Example A-1 The procedure was analogous to Example A-1, the reaction product from Example 7 (10% in each case) being used as the active ingredient and the truncating agents used varying.
- E.g. Anesthetic% Final pH Shrink temp. ° C Appearance A-38 3.4% soda 9.1 81 white / transparent A-39 6.6% NaHCO3 9 80 transparent A-40 12.4% triethanolamine 9 76 transparent A-41 2% MgO 9 83 white / transparent
- a ashed bare beef was decalcified as follows: 100% water (35 ° C) and 2% ammonium sulfate; after 30 minutes, 1% Polyzym 202 was added, the mixture was run for 60 minutes (pH 8); then the fleet was drained.
- Pretanning was carried out as follows: 50% water (30 ° C.) and 10% reaction product from example 7, after 90 minutes addition of 0.5% magnesium oxide, after 7 hours addition of further 0.5% magnesium oxide. When left to run overnight, the pH was 7.2.
- the leathers were unloaded, rolled over, beaten on the box overnight, vacuumed the next day, rolled up and dried out hanging.
- the chrome-free leather was full and soft - similar to the chrome-tanned one.
- Both leathers can be dyed very well.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4422569A DE4422569A1 (de) | 1994-06-28 | 1994-06-28 | Bisulfit-blockierte Polyisocyanate als Gerbstoffe |
DE4422569 | 1994-06-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0690135A1 true EP0690135A1 (fr) | 1996-01-03 |
EP0690135B1 EP0690135B1 (fr) | 1999-11-17 |
Family
ID=6521689
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95109198A Expired - Lifetime EP0690135B1 (fr) | 1994-06-28 | 1995-06-14 | Polyisocyanates bloqués par du bisulfite en tant qu'agents de tannage |
Country Status (7)
Country | Link |
---|---|
US (1) | US5618317A (fr) |
EP (1) | EP0690135B1 (fr) |
JP (1) | JPH08199200A (fr) |
BR (1) | BR9502950A (fr) |
CA (1) | CA2152539A1 (fr) |
DE (2) | DE4422569A1 (fr) |
ES (1) | ES2140581T3 (fr) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0814168A1 (fr) * | 1996-06-21 | 1997-12-29 | Bayer Ag | Procédé de tannage du cuir |
EP1647563A2 (fr) | 2004-10-15 | 2006-04-19 | Lanxess Deutschland GmbH | Agents de tannage à base d' isocyanates |
EP2415879A1 (fr) | 2010-08-06 | 2012-02-08 | LANXESS Deutschland GmbH | Compositions comprenant au moins un composé contenant des groupes carbamoylsulfonates et leur utilisation comme agents de tannage |
EP2508626A1 (fr) | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Préparations d'agents de tannage solides particulaires |
EP2508627A1 (fr) | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Matériau solide particulaire à base de composés comprenant des groupes de carbamoylsulfonate |
WO2012150179A1 (fr) * | 2011-05-04 | 2012-11-08 | Lanxess Deutschland Gmbh | Procédé pour conserver des substrats contenant des fibres de collagène |
EP2540753A1 (fr) | 2011-06-29 | 2013-01-02 | LANXESS Deutschland GmbH | Composition à base de composés contenant des groupes de carbamoylsulfonate |
WO2013001077A1 (fr) | 2011-06-29 | 2013-01-03 | Lanxess Deutschland Gmbh | Composition à base de composés contenant des groupes sulfonate de carbamoyle |
EP2557181A1 (fr) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Procédé d'hydrophobisation de substrats contenant des fibres de collagène |
EP2557224A1 (fr) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Procédé de coloration de substrats contenant des fibres de collagène |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6254644B1 (en) * | 1997-02-26 | 2001-07-03 | Bayer Aktiengesellschaft | Biologically degradable leather |
JP5307308B1 (ja) * | 2012-09-18 | 2013-10-02 | 大榮産業株式会社 | ブロックポリイソシアネート組成物、プレポリマー組成物及びそれらの製造方法、並びに、ブロックポリイソシアネート組成物の熱解離性ブロック剤 |
WO2014045620A1 (fr) * | 2012-09-18 | 2014-03-27 | 大榮産業株式会社 | Composition de polyisocyanate bloqué, composition de prépolymère et procédé de fabrication desdites compositions et agent de blocage thermiquement dissociable pour composition de polyisocyanate bloqué |
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DE72981C (de) | E. HOSCHBERGER in Buchholz i. S | Ausrückvorrichtung für Schnuren-Umspinnmascbinen | ||
US2923594A (en) | 1958-05-29 | 1960-02-02 | Ethicon Inc | Method of tanning |
US2941859A (en) | 1959-04-08 | 1960-06-21 | Martin L Fein | Tanning with glutaraldehyde |
DE1670666A1 (de) | 1966-02-02 | 1971-07-01 | Bayer Ag | Verfahren zur Herstellung von Oxadiazinonen mit NCO-Gruppen |
DE2308015A1 (de) | 1973-02-17 | 1974-09-12 | Bayer Ag | Verfahren zur herstellung von polyisocyanaten mit biuretstruktur |
US4106898A (en) * | 1974-04-04 | 1978-08-15 | Bayer Aktiengesellschaft | Leather tanning with oligourethanes |
US4413997A (en) | 1983-02-07 | 1983-11-08 | The United States Of America As Represented By The Secretary Of Agriculture | Dicarbamoylsulfonate tanning agent |
EP0278278A1 (fr) * | 1987-01-29 | 1988-08-17 | Henkel Kommanditgesellschaft auf Aktien | Agent de revêtement et d'apprêt pour le cuir |
DE3743782A1 (de) | 1987-12-23 | 1989-07-13 | Bayer Ag | Ester-urethan-(meth)-acrylsaeurederivate |
DE3900053A1 (de) | 1989-01-03 | 1990-07-12 | Bayer Ag | Verfahren zur herstellung von uretdion- und isocyanuratgruppen aufweisenden polyisocyanaten, die nach diesem verfahren erhaeltlichen polyisocyanate und ihre verwendung in zweikomponenten-polyurethanlacken |
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1994
- 1994-06-28 DE DE4422569A patent/DE4422569A1/de not_active Withdrawn
-
1995
- 1995-06-01 US US08/456,972 patent/US5618317A/en not_active Expired - Fee Related
- 1995-06-14 EP EP95109198A patent/EP0690135B1/fr not_active Expired - Lifetime
- 1995-06-14 ES ES95109198T patent/ES2140581T3/es not_active Expired - Lifetime
- 1995-06-14 DE DE59507234T patent/DE59507234D1/de not_active Expired - Fee Related
- 1995-06-23 CA CA002152539A patent/CA2152539A1/fr not_active Abandoned
- 1995-06-23 JP JP7179594A patent/JPH08199200A/ja active Pending
- 1995-06-27 BR BR9502950A patent/BR9502950A/pt not_active IP Right Cessation
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DE72981C (de) | E. HOSCHBERGER in Buchholz i. S | Ausrückvorrichtung für Schnuren-Umspinnmascbinen | ||
US2923594A (en) | 1958-05-29 | 1960-02-02 | Ethicon Inc | Method of tanning |
US2941859A (en) | 1959-04-08 | 1960-06-21 | Martin L Fein | Tanning with glutaraldehyde |
DE1670666A1 (de) | 1966-02-02 | 1971-07-01 | Bayer Ag | Verfahren zur Herstellung von Oxadiazinonen mit NCO-Gruppen |
DE2308015A1 (de) | 1973-02-17 | 1974-09-12 | Bayer Ag | Verfahren zur herstellung von polyisocyanaten mit biuretstruktur |
US4106898A (en) * | 1974-04-04 | 1978-08-15 | Bayer Aktiengesellschaft | Leather tanning with oligourethanes |
US4413997A (en) | 1983-02-07 | 1983-11-08 | The United States Of America As Represented By The Secretary Of Agriculture | Dicarbamoylsulfonate tanning agent |
EP0278278A1 (fr) * | 1987-01-29 | 1988-08-17 | Henkel Kommanditgesellschaft auf Aktien | Agent de revêtement et d'apprêt pour le cuir |
DE3743782A1 (de) | 1987-12-23 | 1989-07-13 | Bayer Ag | Ester-urethan-(meth)-acrylsaeurederivate |
DE3900053A1 (de) | 1989-01-03 | 1990-07-12 | Bayer Ag | Verfahren zur herstellung von uretdion- und isocyanuratgruppen aufweisenden polyisocyanaten, die nach diesem verfahren erhaeltlichen polyisocyanate und ihre verwendung in zweikomponenten-polyurethanlacken |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0814168A1 (fr) * | 1996-06-21 | 1997-12-29 | Bayer Ag | Procédé de tannage du cuir |
US5820634A (en) * | 1996-06-21 | 1998-10-13 | Bayer Aktiengesellschaft | Process for tanning leather |
EP1647563A2 (fr) | 2004-10-15 | 2006-04-19 | Lanxess Deutschland GmbH | Agents de tannage à base d' isocyanates |
EP2415879A1 (fr) | 2010-08-06 | 2012-02-08 | LANXESS Deutschland GmbH | Compositions comprenant au moins un composé contenant des groupes carbamoylsulfonates et leur utilisation comme agents de tannage |
WO2012016907A1 (fr) | 2010-08-06 | 2012-02-09 | Lanxess Deutschland Gmbh | Compositions contenant au moins un composé renfermant des groupes carbamylsulfonate et utilisation de celles-ci comme agents de tannage |
WO2012136565A1 (fr) | 2011-04-04 | 2012-10-11 | Lanxess Deutschland Gmbh | Préparations tannantes particulaires solides |
EP2508627A1 (fr) | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Matériau solide particulaire à base de composés comprenant des groupes de carbamoylsulfonate |
WO2012136559A1 (fr) | 2011-04-04 | 2012-10-11 | Lanxess Deutschland Gmbh | Matériau particulaire solide à base de composés contenant des groupes carbamoylsulfonate |
EP2508626A1 (fr) | 2011-04-04 | 2012-10-10 | LANXESS Deutschland GmbH | Préparations d'agents de tannage solides particulaires |
CN103502476A (zh) * | 2011-04-04 | 2014-01-08 | 朗盛德国有限责任公司 | 固体颗粒鞣剂配制品 |
CN103502476B (zh) * | 2011-04-04 | 2016-06-01 | 朗盛德国有限责任公司 | 固体颗粒鞣剂配制品 |
WO2012150179A1 (fr) * | 2011-05-04 | 2012-11-08 | Lanxess Deutschland Gmbh | Procédé pour conserver des substrats contenant des fibres de collagène |
EP2540753A1 (fr) | 2011-06-29 | 2013-01-02 | LANXESS Deutschland GmbH | Composition à base de composés contenant des groupes de carbamoylsulfonate |
WO2013001077A1 (fr) | 2011-06-29 | 2013-01-03 | Lanxess Deutschland Gmbh | Composition à base de composés contenant des groupes sulfonate de carbamoyle |
EP2557181A1 (fr) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Procédé d'hydrophobisation de substrats contenant des fibres de collagène |
EP2557224A1 (fr) | 2011-08-12 | 2013-02-13 | LANXESS Deutschland GmbH | Procédé de coloration de substrats contenant des fibres de collagène |
WO2013023980A1 (fr) | 2011-08-12 | 2013-02-21 | Lanxess Deutschland Gmbh | Procédé d'hydrophobisation de substrats contenant des fibres de collagène |
WO2013023979A1 (fr) | 2011-08-12 | 2013-02-21 | Lanxess Deutschland Gmbh | Procédé pour teinter des substrats à base de fibres de collagène |
Also Published As
Publication number | Publication date |
---|---|
CA2152539A1 (fr) | 1995-12-29 |
EP0690135B1 (fr) | 1999-11-17 |
JPH08199200A (ja) | 1996-08-06 |
US5618317A (en) | 1997-04-08 |
BR9502950A (pt) | 1996-03-12 |
DE4422569A1 (de) | 1996-01-04 |
DE59507234D1 (de) | 1999-12-23 |
ES2140581T3 (es) | 2000-03-01 |
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