EP0340530A1 - Agents d'activation ne contenant pas de titane, procédé pour leur préparation et leur utilisation pour activer des surfaces métalliques avant la phosphatation au zinc - Google Patents
Agents d'activation ne contenant pas de titane, procédé pour leur préparation et leur utilisation pour activer des surfaces métalliques avant la phosphatation au zinc Download PDFInfo
- Publication number
- EP0340530A1 EP0340530A1 EP89106998A EP89106998A EP0340530A1 EP 0340530 A1 EP0340530 A1 EP 0340530A1 EP 89106998 A EP89106998 A EP 89106998A EP 89106998 A EP89106998 A EP 89106998A EP 0340530 A1 EP0340530 A1 EP 0340530A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium
- range
- alkali metal
- phosphating
- free
- 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
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- 230000003213 activating effect Effects 0.000 title claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 31
- 239000011701 zinc Substances 0.000 title claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000004913 activation Effects 0.000 claims abstract description 16
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims abstract description 16
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 13
- 239000010959 steel Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 34
- 150000007513 acids Chemical class 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- -1 alkali metal salts Chemical class 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 6
- 239000008397 galvanized steel Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 229910000680 Aluminized steel Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 239000004411 aluminium Substances 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 235000021317 phosphate Nutrition 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229920000137 polyphosphoric acid Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 description 3
- 235000019800 disodium phosphate Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000005341 metaphosphate group Chemical group 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical class [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001463 metal phosphate Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 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 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- NIWQQYJSLXQOCI-UHFFFAOYSA-L [O--].[K+].[Ti+4].[O-]C(=O)C([O-])=O Chemical compound [O--].[K+].[Ti+4].[O-]C(=O)C([O-])=O NIWQQYJSLXQOCI-UHFFFAOYSA-L 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- XNEQAVYOCNWYNZ-UHFFFAOYSA-L copper;dinitrite Chemical compound [Cu+2].[O-]N=O.[O-]N=O XNEQAVYOCNWYNZ-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011975 tartaric acid Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- SCZMHJCEJAGXRV-UHFFFAOYSA-K titanium(4+);phosphate Chemical compound [Ti+4].[O-]P([O-])([O-])=O SCZMHJCEJAGXRV-UHFFFAOYSA-K 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
Definitions
- the invention relates to titanium-free agents for the activation of metal surfaces made of iron or steel, zinc or galvanized steel and aluminum or aluminized steel before phosphating the surfaces mentioned with phosphating baths containing zinc ions, in particular before a so-called low zinc phosphating, in which the ratio of zinc to phosphate ions in the treatment solution is less than 1:12.
- the present invention further relates to a method for producing the titanium-free activating agents and their use.
- the usual materials used for body construction conventionally iron or steel sheets, have recently been phosphated, more and more recently electrolytically galvanized or hot-dip galvanized steel or materials with a surface made of zinc alloys, which contain, for example, iron, nickel, cobalt or aluminum as alloying partners. Corrosion-inhibiting phosphating of such surfaces is common not only in automobile construction, but also in the manufacture of household appliances such as washing machines or refrigerators.
- the workpieces are cleaned, rinsed and activated in order to achieve a thin and uniform phosphate layer during phosphating, which is known to be a prerequisite for good corrosion protection.
- high zinc phosphating processes it was possible to remove adhering oils, greases and other impurities, also from mechanical processing, from the metal surface in one process step and at the same time to activate it for the subsequent step of zinc phosphating.
- Corresponding treatment baths are described, for example, in the context of processes for pretreating metal surfaces before phosphating in DE-PS 2 951 600 and DE-PS 3 213 649.
- the activation of the metal surface has the following goals: Increase in the nucleation rate and thus the number of crystal nuclei in the starting phase of zinc phosphating, which leads to a layer refinement; by forming crystals as close together as possible, the porosity of the desired zinc phosphate layer is reduced. This results in a uniform and closed zinc phosphate layer over the entire metal surface with a low basis weight (specified in grams of metal phosphate per m2 metal surface), whereby low basis weights have proven to be favorable as an adhesive base for paints. Reduction of the minimum phosphating time, ie the time until the metal surface is completely covered with a closed zinc phosphating layer.
- the essential manufacturing step comprises the reaction (sometimes called "aging” in the literature) of suitable titanium compounds (for example titanyl sulfate, potassium hexafluorotitanate, titanium disulfate, titanium dioxide, potassium titanium oxide oxalate) with a large excess of phosphate components (preferably disodium hydrogen phosphate) at a temperature above 70 ° C. and a pH -Value between 6 and 9.
- suitable titanium compounds for example titanyl sulfate, potassium hexafluorotitanate, titanium disulfate, titanium dioxide, potassium titanium oxide oxalate
- phosphate components preferably disodium hydrogen phosphate
- Jernstedt describes activating agents based on zirconium phosphate or reaction products of water-soluble tin and lead compounds with disodium hydrogen phosphate in US Pat. Nos. 2,456,947 and 2,462,196.
- hydrolysis-stable organic titanium compounds are used as activating agents for zinc and zinc -Manganese or manganese surfaces described. They are obtained by reacting a beta-di-ketontitanylacetylacetonate with gluconic acid or gluconates in the presence of a hydrogen halide salt of an aliphatic amino alcohol.
- Another way of increasing the nucleation rate on steel is to treat the surface with dilute aqueous copper sulfate or copper nitrite solutions and with oxalic acid. However, the latter may only cause a weak etching of the iron surface; If a coherent iron oxalate layer is formed, the activation effect disappears (US Pat. No. 2,164,024, German Pat. No. 1,771,924).
- EP-PS 0 056 675 describes a process for pretreating steel wire before zinc phosphating with a bath, which contains sodium salts of oxalic, tartaric or citric acid as activating agents.
- the object of the present invention was to provide titanium-free activating agents.
- the object of the present invention was to provide activating agents which are soluble in clear water and contain a high proportion for activating effective amounts of substances.
- the invention thus relates to titanium-free agents for the activation of metal surfaces made of iron or steel, zinc or galvanized steel and aluminum or aluminized steel the phosphating with phosphating baths containing zinc ions, characterized in that they - 1,1-diphosphonic acids and / or poly (aldehydocarboxylic acids) as complexing agents and - alkali metal phosphates in the ratio of complexing agent to alkali metal phosphate in the range from 0.1: 10 to 1:10 contain.
- the titanium-free agents according to the invention are characterized in that the ratio of complexing agent to alkali metal phosphate is in the range from 0.2: 10 to 0.5: 10.
- the alkali metal phosphates to be reacted with the complexing agents under the conditions of an optionally hydrothermal reaction at a pH in the range from 6 to 12 are mentioned in DE-OS 37 31 049 and correspond to the general formulas (I) to (III), M m H 3-m PO4 (I) M p H n + 2-p P n O 3n + 1 (II) (M q H 1-q PO3) r (III) in which M represents an alkali metal and m 0, 1, 2 or 3, n 2, 3 or 4, p 0, 1, 2 ..., n + 2, q 0 or 1 and r is an integer from 2 to 20.
- orthophosphates of the general formula (I) are used M m H 3-m PO4 (I) in the m for 0, 1, 2 or 3 and M stand for an alkali metal.
- Orthophosphates of the general formula (I) from the group orthophosphoric acid, monoalkali metal dihydrogenphosphate, dialkalimetal monohydrogenphosphate and trialkalimetal orthophosphate are thus used.
- the preferred alkali metal in the orthophosphates of the general formula (I) is sodium.
- the above-mentioned salts of orthophosphoric acid are therefore sodium salts in preferred embodiments of the process.
- polyphosphates of the general formula (II) are used as the phosphate component M p H n + 2-p P n O 3n + 1 (II) in the n for 2, 3 or 4, p for an integer in the range from 0 to (n + 2) and M for an alkali metal stand.
- alkali metal salts are also suitable, in which - compared to the polyphosphoric acids mentioned above - one or more hydrogen atoms are replaced by alkali metal atoms .
- the respective sodium salts are preferably used.
- metaphosphates of the general formula (III) are used as phosphates, (M q H 1-q PO3) r (III) in the M for an alkali metal, r for an integer from 2 to 20 and q for 0 or 1 stand.
- One or more of the hydrogen atoms bonded to an oxygen atom in such polyphosphoric acids can be replaced by one or more alkali metal atoms in such ring-shaped metaphosphates.
- the preferred alkali metal atom is again sodium.
- the reaction can be advantageously carried out in a kneader, especially if the reaction mixture has a high solids content.
- a reaction temperature of 80 ° C is sufficient, but can also be exceeded without damaging the product.
- the preparation can advantageously be carried out in a stirred kettle at boiling temperature under atmospheric pressure with subsequent spray drying.
- poly (aldehydocarboxylic acids) or their alkali metal salts obtainable by the reaction of hydrogen peroxide, acrolein and acrylic acid with a viscosity number in the range from 5 to 50 ml / g, an acid number in the range from 450 to 670, an acid equivalent weight in the range from 125 to 70, - a pour point of less than 0 ° C and - A carboxyl group content in the range of 55 to 90 mol% and - A molecular weight in the range of 1,000 to 20,000 and or 1,1-diphosphonic acids of the general formula (IV) in which R for an unsubstituted or in a para position with halogen, amino, hydroxy or C1 ⁇ 4-alkyl groups, preferably with Cl or NH2, substituted phenyl radical, a straight-chain or branched-chain or cyclic, saturated or mono- or polyunsaturated alkyl radical with 1 to
- Particularly preferred complexing agents used in the present invention are 1,1-diphosphonic acids of the general formula (IV), where R represents an unbranched alkyl radical having 1 to 6 carbon atoms.
- the sodium salts are preferably used as alkali metal salts in the poly (aldehydocarboxylic acids) and the 1,1-diphosphonic acids, so that M in the general formula (IV) is sodium.
- reaction of complexing agents with alkali metal phosphate can usually be carried out to dryness in a kneader or in a stirred kettle with subsequent spray drying.
- a further preferred embodiment of the present invention consists in carrying out the reaction of alkali metal phosphate with complexing agents at temperatures in the range from 75 ° C. to 120 ° C. in a kneader to dryness or in a stirred kettle with subsequent spray drying.
- the process is particularly preferred if the reaction is carried out at temperatures in the range from 80 ° C. to 100 ° C.
- the process according to the invention allows a large variation in the solids content of the reaction. Accordingly, a further preferred embodiment of the process according to the invention is that the solids content in the reaction is in the range from 30 to 85%. A particularly preferred embodiment of the present invention is that the solids content of the reaction in a kneader is in the range from 75 to 85%. When reacting in a stirred tank, it is particularly preferred that the solids content is in the range from 30 to 40%.
- a further preferred embodiment of the process according to the invention consists in that up to 30% by weight of the total amount of complexing agent is used before or during the reaction of the Adds complexing agent with alkali metal phosphate and incorporates the remaining amount into the reaction mixture after a first drying to a residual moisture content of 10 to 20%.
- Activating agents of this type are usually used by adjusting solids contents in the range from 0.001 to 10% by weight of the titanium-free activating agents according to the invention with water directly for activating metal surfaces before zinc phosphating.
- the present invention furthermore relates to the use of the titanium-free activating agents according to the invention prior to phosphating metal surfaces made of iron, steel, zinc, galvanized iron or galvanized steel, aluminum and / or aluminized steel with phosphating baths containing zinc ions.
- a further preferred embodiment of the present invention consists in the use of titanium-free activating agents according to the present invention in the form of aqueous dispersions as activating agents before the low zinc phosphating.
- the poly (aldehydocarboxylic acids) used according to the invention are commercially available and are available from Degussa AG, Frankfurt, for example under the names POC OS 20, POC HS 0010, POC HS 2020, POC HS 5060, POC HS 65 120 and POC AS 0010, POC AS 2020, POC AS 5060 or POC AS 65 120 sold.
- the HS designation relates to the acid form and the AS designation relates to the sodium salt form of the poly (aldehydocarboxylic acids). They can be produced using a special process developed by Degussa, the "oxidative polymerization" of acrolein. Acrolein is aqueous or mixed with acrylic acid Solution treated with hydrogen peroxide.
- the H2O2 acts as an initiator of the polymerization and as a molecular weight regulator.
- some of the aldehyde groups of acrolein are oxidized to carboxyl groups by hydrogen peroxide. This creates polymers with pendant aldehyde and carboxyl groups, namely the poly (aldehydocarboxylic acids).
- the poly (aldehydocarboxylic acids) described above and about their possible uses can be found in Degussa AG's company publication entitled "POC-Environmentally Friendly Polycarboxylic Acids with a Wide Range of Applications" (note: CH 215-3-3-582 Vol).
- the poly (aldehydocarboxylic acids) can be used, for example, as hardness stabilizers with regard to the inhibition of the crystallization of calcium and other alkaline earth metal salts, as deposit inhibitors in seawater desalination, as dispersants for aqueous pigment dispersions with a high solids content, and as builders for detergents and cleaning agents.
- DE-PS 10 71 339 production
- DE-OS 19 04 940 complexing agent
- DE-OS 19 04 941 polyoxycarboxylic acids
- DE-PS 19 42 556 Complexing agent
- DE-OS 21 54 737 rust protection treatment
- DE-OS 23 30 260 and DE-PS 23 57 036 production.
- the general formula (V) represents the basic structure of the poly (aldehydocarboxylic acids) to be used according to the invention.
- the poly (aldehydocarboxylic acids) are predominantly poly (aldehydocarboxylic acids) linked linearly via carbon-carbon bonds with many carboxyl and a few carbonyl side groups and hydroxyl end groups.
- Their chemical constitution is characterized in particular by the general formula (V).
- the average degrees of polymerization are characterized by the viscosity numbers. These are usually between 5 to 50 ml / g, based on 100% solids, measured as a 2% solution in 0.1 N NaBr at 25 ° C. and pH 10 in an Ubbelohde viscometer, capillary Oa.
- the spatial linkage of the monomer units can be assumed to be atactic, the order of the linkage to be statistical.
- the carboxyl group content expressed in mol% COOH, can be calculated from the acid number (DIN 53402) of the dried polymers.
- the acid number of aqueous poly is unsuitable for calculating the molar percentages of COOH, since the technical qualities contain small amounts of formic acid, acetic acid and ⁇ -hydroxypropionic acid as by-products.
- the sodium poly (aldehydocarboxylates) must be converted into the H form by ion exchange before the acid number is determined.
- the agents containing titanium phosphate are at least equivalent if suitable complexing agents are reacted with a large excess of a phosphate component in an aqueous medium at elevated temperature.
- 1-Hydroxyethane-1,1-diphosphonic acid (HEDP) can particularly preferably be used as the complexing agent.
- alkali metal phosphate monomeric or oligomeric orthophosphates are used as alkali salts; the pH of the aqueous reaction mixture is optionally adjusted to the range between 7.5 and 9. With the particularly preferred use of disodium hydrogen phosphate, there is no need to adjust the pH.
- the new activating agents are used in approximately 0.2% by weight aqueous preparation. They then form clear solutions. This is an application technology advantage over conventional agents based on titanium phosphate, which due to their largely insolubility can only be used as cloudy, cloudy suspensions. These usually contain a considerable proportion of coarse and ineffective particles for the activation.
- a decisive step in the production of the new titanium-free activating agents is the reaction of the complexing agent with alkali metal phosphate at a temperature above 70 ° C., preferably between 80 ° C. and 100 ° C. in the presence of water. Simply adding the complexing agent to an aqueous phosphate solution does not lead to the desired result.
- the reaction can advantageously take place in a kneader at high solids contents of the reaction mixture.
- phosphate preferably disodium hydrogenphosphate
- 1 to 4 parts by weight preferably 1 to 2 parts by weight
- the surfaces of steel coupons were measured using standardized phosphating processes in accordance with Table 1 (immersion phosphating, normal zinc process) and 3 (spray phosphating, manganese-modified low-zinc process) phosphated.
- Weight per unit area means the mass per unit area of the metal phosphate layer in grams per square meter, which is determined in accordance with DIN 50 492.
- To determine the bath capacity two liters of a 0.2% strength by weight aqueous preparation of the activating agent were loaded with test sheets, which were then phosphated. Initially and then after every tenth sample sheet, the average basis weight of four successive sample sheets was determined. The average values calculated from this are given in Table 2. The baths were considered exhausted if ten sheets in a row failed during the zinc phosphating places or showed coarse crystalline areas. The bath capacity is given in m2 of activatable area per 2 l of activating bath.
- HEDP 1-hydroxyethane-1,1-diphosphonic acid
- VE demineralized
- Table 2 contains the activation results for immersion phosphating in the normal zinc process.
- Example 3 in Table 2 shows the significant decrease in activation performance when the quantity ratio of complexing agent to phosphate exceeds the preferred value of 5 to 100.
- Table 3 shows how the test was carried out by spraying.
- the commercially available activating agent Fixodine R 6 from Collardin, Cologne was used as a comparative product.
- the results show that the product according to the invention from Example 1 (Table 2) has no loss of performance compared to the standard product: while a weight per unit area of 3.07 g / m 2 was achieved with the commercial product, the product according to the invention gave a weight per unit area of 3.01 g / m2.
- Table 3 Process flow for checking the activation in connection with a "low zinc" phosphating process GRANODINE R SP 2500 / spray application step Process product Conc. (% By weight) Temp.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3814363A DE3814363A1 (de) | 1988-04-28 | 1988-04-28 | Titanfreie aktivierungsmittel, verfahren zu ihrer herstellung und ihre verwendung zur aktivierung von metalloberflaechen vor einer zinkphosphatierung |
DE3814363 | 1988-04-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0340530A1 true EP0340530A1 (fr) | 1989-11-08 |
EP0340530B1 EP0340530B1 (fr) | 1992-06-24 |
Family
ID=6353098
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89106998A Expired - Lifetime EP0340530B1 (fr) | 1988-04-28 | 1989-04-19 | Agents d'activation ne contenant pas de titane, procédé pour leur préparation et leur utilisation pour activer des surfaces métalliques avant la phosphatation au zinc |
Country Status (10)
Country | Link |
---|---|
US (2) | US5039362A (fr) |
EP (1) | EP0340530B1 (fr) |
JP (1) | JPH01316467A (fr) |
AR (1) | AR240485A1 (fr) |
AU (1) | AU608153B2 (fr) |
BR (1) | BR8902023A (fr) |
CA (1) | CA1333989C (fr) |
DE (2) | DE3814363A1 (fr) |
ES (1) | ES2032622T3 (fr) |
MX (1) | MX172303B (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995031588A1 (fr) * | 1994-05-11 | 1995-11-23 | Henkel Kommanditgesellschaft Auf Aktien | Fabrication d'activateurs phosphates destines a la phosphatation par micro-ondes |
US5503733A (en) * | 1992-09-28 | 1996-04-02 | Henkel Kommanditgesellschaft Auf Aktien | Process for phosphating galvanized steel surfaces |
CN103132122A (zh) * | 2011-11-22 | 2013-06-05 | 吴怡岗 | 一种钢丝在线常温电解磷化方法 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4012795A1 (de) * | 1990-04-21 | 1991-10-24 | Metallgesellschaft Ag | Aktivierungsmittel fuer die phosphatierung |
US5628838A (en) * | 1992-01-29 | 1997-05-13 | C.F.P.I Societe Anonyme | Concentrate for activating and defining bath and bath obtained from this concentrate |
US5326408A (en) * | 1993-06-15 | 1994-07-05 | Henkel Corporation | Rapidly dissolving and storage stable titanium phosphate containing activating composition |
CN1214097C (zh) * | 2000-05-31 | 2005-08-10 | 坎梅陶尔股份有限公司 | 处理或预处理容器的方法 |
US20040094236A1 (en) * | 2002-11-14 | 2004-05-20 | Crown Technology, Inc. | Methods for passivating stainless steel |
Citations (3)
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DE1942556A1 (de) * | 1969-08-21 | 1971-03-11 | Gold U Silber Scheide Anstalt | Komplexbildner |
EP0031103A1 (fr) * | 1979-12-21 | 1981-07-01 | Gerhard Collardin GmbH | Procédé pour le traitement préliminaire de surfaces métalliques avant la phosphatation |
EP0180523A1 (fr) * | 1984-10-31 | 1986-05-07 | Compagnie Francaise De Produits Industriels | Procédé perfectionné de phosphatation au zinc, bain d'activation et d'affinage mis en oeuvre dans ce procédé et concentré correspondant |
Family Cites Families (13)
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US2164024A (en) * | 1935-12-07 | 1939-06-27 | Ig Farbenindustrie Ag | Electric arc furnace |
IT429345A (fr) * | 1941-10-25 | 1900-01-01 | ||
IT432445A (fr) * | 1943-07-29 | |||
US2456947A (en) * | 1944-12-21 | 1948-12-21 | Westinghouse Electric Corp | Corrosion resistant coating for metal surfaces |
US3141804A (en) * | 1961-07-18 | 1964-07-21 | Foils Packaging Corp | Dielectric heat sealing |
GB1176066A (en) * | 1967-08-18 | 1970-01-01 | Pyrene Co Ltd | Phosphate Coating of Steel. |
DE1904941A1 (de) * | 1969-02-01 | 1970-08-06 | Degussa | Polyoxycarbonsaeuren |
DE1904940C2 (de) * | 1969-02-01 | 1982-07-22 | Degussa Ag, 6000 Frankfurt | Verwendung von Carboxyl- bzw. Carboxylat- und Hydroxylgruppen aufweisenden Polymeren als Komplexbildner |
DE2330260A1 (de) * | 1973-06-14 | 1975-01-16 | Degussa | Verfahren zur herstellung von polycarboxylaten mit verbesserter biologischer abbaubarkeit |
NL157021B (nl) * | 1973-11-15 | 1978-06-15 | Degussa | Werkwijze ter bereiding van polycarboxylaten met verbeterde biologische afbreekbaarheid. |
US4266677A (en) * | 1979-01-19 | 1981-05-12 | Donaldson Display Company, Inc. | Samples clamp |
IT1165849B (it) * | 1979-05-16 | 1987-04-29 | Fosfa Col Sas Di A Dal Pane & | Procedimento per preparare un prodotto attivatore dei processi di fosfatazione e prodotto ottenuto con lo stesso procedimento |
JPS5855229B2 (ja) * | 1981-01-19 | 1983-12-08 | 日本ペイント株式会社 | リン酸亜鉛処理用表面調整剤 |
-
1988
- 1988-04-28 DE DE3814363A patent/DE3814363A1/de not_active Withdrawn
-
1989
- 1989-04-19 EP EP89106998A patent/EP0340530B1/fr not_active Expired - Lifetime
- 1989-04-19 ES ES198989106998T patent/ES2032622T3/es not_active Expired - Lifetime
- 1989-04-19 DE DE8989106998T patent/DE58901729D1/de not_active Expired - Fee Related
- 1989-04-25 MX MX015793A patent/MX172303B/es unknown
- 1989-04-26 CA CA000597876A patent/CA1333989C/fr not_active Expired - Fee Related
- 1989-04-27 AU AU33789/89A patent/AU608153B2/en not_active Ceased
- 1989-04-28 US US07/344,883 patent/US5039362A/en not_active Expired - Fee Related
- 1989-04-28 BR BR898902023A patent/BR8902023A/pt not_active Application Discontinuation
- 1989-04-28 AR AR313796A patent/AR240485A1/es active
- 1989-04-28 JP JP1111912A patent/JPH01316467A/ja active Pending
-
1991
- 1991-05-10 US US07/698,650 patent/US5112414A/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1942556A1 (de) * | 1969-08-21 | 1971-03-11 | Gold U Silber Scheide Anstalt | Komplexbildner |
EP0031103A1 (fr) * | 1979-12-21 | 1981-07-01 | Gerhard Collardin GmbH | Procédé pour le traitement préliminaire de surfaces métalliques avant la phosphatation |
EP0180523A1 (fr) * | 1984-10-31 | 1986-05-07 | Compagnie Francaise De Produits Industriels | Procédé perfectionné de phosphatation au zinc, bain d'activation et d'affinage mis en oeuvre dans ce procédé et concentré correspondant |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5503733A (en) * | 1992-09-28 | 1996-04-02 | Henkel Kommanditgesellschaft Auf Aktien | Process for phosphating galvanized steel surfaces |
WO1995031588A1 (fr) * | 1994-05-11 | 1995-11-23 | Henkel Kommanditgesellschaft Auf Aktien | Fabrication d'activateurs phosphates destines a la phosphatation par micro-ondes |
CN103132122A (zh) * | 2011-11-22 | 2013-06-05 | 吴怡岗 | 一种钢丝在线常温电解磷化方法 |
CN103132122B (zh) * | 2011-11-22 | 2015-07-22 | 吴怡岗 | 一种钢丝在线常温电解磷化方法 |
Also Published As
Publication number | Publication date |
---|---|
AU3378989A (en) | 1989-11-02 |
AR240485A1 (es) | 1990-04-30 |
MX172303B (es) | 1993-12-13 |
BR8902023A (pt) | 1989-12-05 |
EP0340530B1 (fr) | 1992-06-24 |
DE3814363A1 (de) | 1989-11-09 |
DE58901729D1 (de) | 1992-07-30 |
JPH01316467A (ja) | 1989-12-21 |
US5112414A (en) | 1992-05-12 |
ES2032622T3 (es) | 1993-02-16 |
AU608153B2 (en) | 1991-03-21 |
CA1333989C (fr) | 1995-01-17 |
US5039362A (en) | 1991-08-13 |
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