EP0817872B1 - Verfahren zur phosphatierung mit metallhaltiger nachspülung - Google Patents
Verfahren zur phosphatierung mit metallhaltiger nachspülung Download PDFInfo
- Publication number
- EP0817872B1 EP0817872B1 EP96908083A EP96908083A EP0817872B1 EP 0817872 B1 EP0817872 B1 EP 0817872B1 EP 96908083 A EP96908083 A EP 96908083A EP 96908083 A EP96908083 A EP 96908083A EP 0817872 B1 EP0817872 B1 EP 0817872B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- phosphating
- ions
- solution used
- rinse solution
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000008569 process Effects 0.000 title claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 25
- -1 m-nitrobenzene sulfonate ions Chemical class 0.000 claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 13
- 239000010959 steel Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 239000008397 galvanized steel Substances 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 2
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical compound [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 2
- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical compound [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 229910052744 lithium Inorganic materials 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000003973 paint Substances 0.000 description 21
- 230000007797 corrosion Effects 0.000 description 20
- 238000005260 corrosion Methods 0.000 description 20
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 235000021317 phosphate Nutrition 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 239000010452 phosphate Substances 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910002651 NO3 Inorganic materials 0.000 description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 238000010422 painting Methods 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000009189 diving Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000002161 passivation Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- ONMOULMPIIOVTQ-UHFFFAOYSA-M 3-Nitrobenzene sulphonate Chemical compound [O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 150000003388 sodium compounds Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 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 2
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000680 Aluminized steel Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910004844 Na2B4O7.10H2O Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001499740 Plantago alpina Species 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- RVGMCVRSUKTFHN-UHFFFAOYSA-G [F-].[Zr+4].[Al+3].[F-].[F-].[F-].[F-].[F-].[F-] Chemical class [F-].[Zr+4].[Al+3].[F-].[F-].[F-].[F-].[F-].[F-] RVGMCVRSUKTFHN-UHFFFAOYSA-G 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000004973 alkali metal peroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DYLSCLYVTVPEFF-UHFFFAOYSA-N lithium manganese(2+) Chemical compound [Li+].[Mn+2] DYLSCLYVTVPEFF-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- UJJUJHTVDYXQON-UHFFFAOYSA-N nitro benzenesulfonate Chemical compound [O-][N+](=O)OS(=O)(=O)C1=CC=CC=C1 UJJUJHTVDYXQON-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000005385 peroxodisulfate group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 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 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
Definitions
- the invention relates to methods for phosphating metal surfaces with aqueous, acidic zinc-containing phosphating solutions.
- a rinse with a solution containing lithium, Contains copper and / or silver ions is suitable as a pretreatment of the metal surfaces for a subsequent Painting, especially an electro dip painting.
- the procedure is applicable for the treatment of surfaces made of steel, galvanized or galvanized steel, aluminum, aluminized or alloy aluminized Steel.
- the phosphating of metals pursues the goal on the metal surface to produce firmly adherent metal phosphate layers already improve the corrosion resistance and in Connection with paints and other organic coatings too a significant increase in paint adhesion and resistance to Infiltration under corrosion stress contribute.
- Such phosphating processes have been known for a long time.
- the low-zinc phosphating processes are particularly suitable, where the phosphating solutions are comparatively low levels of zinc ions of e.g. B. 0.5 to 2 g / l.
- the weight ratio of phosphate ions to zinc ions which is usually is in the range> 8 and can take values up to 30.
- phosphate layers have disadvantages in that Nickel and nickel compounds from the point of view of environmental protection and occupational hygiene can be classified as critical.
- Low zinc phosphating processes are increasingly being described the too qualitative without using nickel similar high-quality phosphate layers as the nickel-containing processes to lead.
- nitrite and nitrate Concerns have been raised about possible formation of nitrous gases.
- the phosphating of galvanized steel with nickel-free phosphating baths Corrosion protection and insufficient paint adhesion results if the phosphating baths contain larger quantities (> 0.5 g / l) nitrate.
- DE-A-39 20 296 describes a phosphating process that dispenses with nickel and besides zinc and manganese ions Magnesium ions used.
- the phosphating baths described here contain, in addition to 0.2 to 10 g / l nitrate ions, other accelerators acting oxidizing agents selected from nitrite, chlorate or an organic oxidizing agent.
- EP-A-60 716 discloses low-zinc phosphating baths, which are essential cations zinc and Contain manganese and which contain nickel as an optional component can.
- the necessary accelerator is preferred selected from nitrite, m-nitrobenzenesulfonate or hydrogen peroxide.
- Phosphating baths are also described in EP-A-228 151, which contain zinc and manganese as essential cations.
- the phosphating accelerator is selected from nitrite, nitrate, hydrogen peroxide, m-nitrobenzoate or p-nitrophenol.
- the process of applying the phosphating solution on the metal surfaces and / or other process parameters the phosphate layer on the metal surfaces is not complete closed. Rather, there are more or less large ones "Pores” whose area is on the order of 0.5 to 2% of phosphated surface is located in the course of a so-called "Post-passivation” must be closed to be corrosive To leave influences on the metal surfaces no point of attack. Post-passivation further improves the liability of one then applied paint.
- a rinse solution is known from EP-B-410 497 which contains Al, Zr and contains fluoride ions, the solution being a complex mixture Fluoride or as a solution of aluminum hexafluorozirconate can be understood.
- the total amount of these 3 ions is in the range from 0.1 to 2.0 g / l.
- DE-A-21 00 497 relates to a method for electrophoretic Applying paints to ferrous surfaces, doing the job should be solved, white on the ferrous surfaces or apply other bright colors without discoloration.
- This The object is achieved in that the surfaces that have previously been phosphated can be rinsed with copper-containing solutions. Copper concentrations are between for this rinse solution 0.1 and 10 g / l suggested.
- DE-A-34 00 339 describes also a copper-containing rinse solution for phosphated metal surfaces, with copper contents between 0.01 and 10 g / l is worked. It was not observed that this Rinse solutions in connection with different phosphating processes lead to different results.
- Nickel-free phosphating process in connection with a Chrome-free rinsing currently does not reach all body materials used reliably in the automotive industry the requirements for paint adhesion and corrosion protection. Therefore there is still a need for rinse aid solutions that are related with a nickel- and nitrite-free phosphating and one subsequent cathodic electrocoating the requirements corrosion protection and paint adhesion for different substrate materials reliably meet.
- the invention turns the Task, such a combination of methods from a Environmental and occupational safety optimized phosphating processes and a particularly suitable chrome-free rinse before to provide cathodic electrocoating.
- iron (II) in the concentration range mentioned requires an accelerator that does not react to these ions has an oxidizing effect. Hydroxylamine in particular is an example of this to call.
- the phosphating baths are free of nickel and preferably also of Cobalt. This means that these elements or ions the phosphating baths not be added deliberately. However, it is in the Practice does not rule out that such constituents go beyond that Treating material entered in traces in the phosphating baths become. In particular, it cannot be ruled out that at Phosphating of steel coated with zinc-nickel alloys Nickel ions are introduced into the phosphating solution. However is the expectation of the phosphating baths that under technical conditions under the nickel concentration in the baths 0.01 g / l, in particular below 0.0001 g / l. Preferably included the phosphating baths also do not contain oxo anions from halogens.
- accelerators are in the state of the art Technology known as components of zinc phosphating baths. Below are understood substances that are caused by the pickling attack the hydrogen on the metal surface bind chemically so that they themselves are reduced. Oxidizing Accelerators continue to have the effect of pickling Iron (II) ions released on steel surfaces become trivalent Oxidize stage, so that it as iron (III) phosphate can fail.
- the process sequence according to the invention in the phosphating bath usable accelerators were listed above.
- nitrate ions can be used as co-accelerators in quantities of up to 10 g / l be present, which is particularly the case with phosphating of steel surfaces can have a favorable effect.
- the phosphating solution contains as little nitrate as possible.
- Nitrate concentrations of 0.5 g / l should preferably not be exceeded, since at higher nitrate concentrations the risk of a so-called "Speck formation" exists. These are white, crater-like defects in the phosphate layer meant.
- hydroxylamine is an accelerator particularly preferred. Sharing these two accelerators however, is not advisable since hydroxylamine is made of hydrogen peroxide is decomposed. If you put hydrogen peroxide in free or bound form as an accelerator, so are concentrations from 0.005 to 0.02 g / l of hydrogen peroxide are particularly preferred. Here the hydrogen peroxide of the phosphating solution as such be added. However, it is also possible to add hydrogen peroxide use bound form in the form of compounds in the phosphating bath deliver hydrogen peroxide by hydrolysis reactions.
- persalts such as perborates, Percarbonates, peroxosulfates or peroxodisulfates.
- persalts such as perborates, Percarbonates, peroxosulfates or peroxodisulfates.
- ionic peroxides such as Alkali metal peroxides into consideration.
- Hydroxylamine can be used as a free base, as a hydroxylamine complex or in Form of hydroxylammonium salts can be used.
- the hydroxylammonium salt are the sulfates and the phosphates particularly suitable. In the case of the phosphates are due to the preferred solubility preferred the acid salts.
- Hydroxylamine or its compounds are added to the phosphating bath in such quantities that the calculated concentration of free hydroxylamine between 0.1 and 10 g / l, preferably between 0.2 and 6 g / l and in particular is between 0.3 and 2 g / l.
- hydroxylamine as an accelerator on iron surfaces to particularly favorable spherical and / or leads to columnar phosphate crystals.
- the one to be carried out in sub-step b) Rinsing is a post-passivation of such phosphate layers particularly suitable.
- lithium-containing phosphating baths the preferred ones Concentrations of lithium ions in the range from 0.4 to 1 g / l. Phosphating baths, lithium, are particularly preferred as the only monovalent cation. Depending on what you want Ratio of phosphate ions to divalent cations and However, lithium ions may be required to adjust the desired free acid the phosphating baths further basic Add substances. In this case, ammonia is preferably used a, so that the lithium-containing phosphating baths in addition Contain ammonium ions in the range from about 0.5 to about 2 g / l can.
- the use of basic sodium compounds such as in this case sodium hydroxide solution is less preferred because the presence of sodium ions in the lithium-containing phosphating baths the corrosion protection properties of the layers obtained worsened.
- the free acid preferably by adding basic sodium compounds such as sodium carbonate or sodium hydroxide.
- phosphating baths obtained which, in addition to zinc and possibly lithium manganese (II) contain The manganese content of the phosphating bath should are between 0.2 and 4 g / l, since the lower the manganese content positive influence on the corrosion behavior of the phosphate layers is no longer available and with higher manganese contents no more positive effect occurs. Contents between 0.3 and 2 g / l and especially between 0.5 and 1.5 g / l are preferred.
- the zinc content of the phosphating bath is preferably set to values between 0.45 and 2 g / l.
- the current The zinc content of the working bath increases up to 3 g / l.
- the zinc and manganese ions in the phosphating baths is basically irrelevant. It offers itself in particular, as the zinc and / or manganese source, the oxides and / or to use the carbonates.
- iron (II) ions When using the phosphating process on steel surfaces iron dissolves in the form of iron (II) ions. If the phosphating baths do not contain any substances that are have a strong oxidizing effect, the divalent iron mainly goes into Consequence of air oxidation into the trivalent state so that it can precipitate as iron (III) phosphate. Therefore, in the Phosphate baths build up iron (II) contents that are significantly higher than the Laid down containing baths containing oxidizing agents. This is, for example, in the hydroxylamine-containing phosphating baths the case. In this sense, iron (II) concentrations are up to 50 ppm normal, with values up to in the short term in the production process 500 ppm can occur. For the phosphating process according to the invention such iron (II) concentrations are not harmful.
- the weight ratio of phosphate ions to zinc ions in the phosphating baths can vary within a wide range, provided that it is in the range between 3.7 and 30. A weight ratio between 10 and 20 is particularly preferred.
- the total phosphorus content of the phosphating bath is considered to be present in the form of phosphate ions PO 4 3- . Accordingly, the known fact that the pH values of the phosphating baths, which are usually in the range from about 3 to about 3.4, is only neglected in the form of the triple negative at the pH values of the phosphating baths charged anions. At these pH values, it is rather to be expected that the phosphate is present primarily as a single negatively charged dihydrogenphosphate anion, together with smaller amounts of non-associated phosphoric acid and double negatively charged hydrogenphosphate anions.
- the phosphating can be done in spraying, diving or spray diving respectively.
- the exposure times are in the usual range between about 1 and about 4 minutes.
- the temperature of the phosphating solution is in the range between about 40 and about 60 ° C.
- front phosphating are the usual steps in the prior art cleaning and activation, preferably with activation baths containing titanium phosphate.
- the rinse solution used in sub-step b) preferably has a pH in the range of 3.4 to 6 and a temperature in the range from 20 to 50 ° C.
- the concentrations of the cations in the The aqueous solution used in sub-step b) is preferably in the following areas: lithium (I) 0.02 to 2, in particular 0.2 to 1.5 g / l, copper (II) 0.002 to 1 g / l, in particular 0.01 to 0.1 g / l and silver (I) 0.002 to 1 g / l, in particular 0.01 to 0.1 g / l.
- the metal ions mentioned can be used individually or as a mixture with one another available.
- Rinse solutions containing copper (II) are particularly preferred. contain.
- metal ions mentioned in the rinse solution are introduced is irrelevant in principle, as long as guaranteed is that the metal compounds in the concentration ranges mentioned the metal ions are soluble.
- metal connections should with anions that prevent the tendency to corrode known to promote, such as chloride.
- the metal ions are nitrates or as Carboxylates, especially as acetates.
- phosphates also suitable, provided that they are below the selected concentration and pH conditions are soluble. The same applies to sulfates.
- the metal ions of Lithium, copper and / or silver together in the rinse solutions with hexafluorotitanate and / or, particularly preferably, Hexafluoro zirconia It is preferred that the concentrations of the anions mentioned in the range from 100 to 500 ppm lie.
- the sources of the hexafluoro anions mentioned come from them Acids or their acids under the concentration and pH conditions mentioned water-soluble salts, especially their alkali metal and / or ammonium salts. It is particularly cheap Use hexafluoro anions at least partially in the form of their acids and in the acidic solutions basic compounds of lithium, Dissolve copper and / or silver. For example, come here the hydroxides, oxides or carbonates of the metals mentioned in Consideration. By doing this, you avoid the metals together with any interfering anions.
- the pH can if necessary, adjust with ammonia.
- the rinse solutions can also contain the ions of lithium and copper and / or silver together with ions of cerium (III) and / or cerium (IV) included, with the total concentration of cerium ions in the range from 0.01 to 1 g / l.
- the rinse solution can Copper and / or silver also contain aluminum (III) compounds, the concentration of aluminum in the range of 0.01 to 1 g / l lies.
- the aluminum compounds in particular come on the one hand Polyaluminium compounds such as polymer Aluminum hydroxychloride or polymeric aluminum hydroxysulfate in Consideration (WO 92/15724), or else complex aluminum-zirconium fluorides, as they are known for example from EP-B-410 497.
- the metal surfaces phosphated in sub-step a) can Sub-step b) with the rinse solution by spraying, dipping or Spray diving can be brought into contact with the exposure time should be in the range of 0.5 to 10 minutes and preferably about Is 40 to about 120 seconds. Because of the simpler system technology it is preferable to use the rinse solution in the partial step b) sprayed onto the phosphated metal surface in sub-step a).
- Rinsing off the treatment solution after the end of the exposure period and before the subsequent painting is basically not required.
- phosphated metal surfaces rinsed in sub-step b) can be dried and varnished without further rinsing, for example with a powder coating.
- the procedure is however, especially as a pretreatment before a cathodic one Electro dip coating designed.
- the rinse solution from the metal surfaces rinse off preferably with low salt or desalinated Water.
- the metal surfaces pretreated according to the invention are dried. In the interest of a faster production cycle, however, is omitted preferably such drying.
- the cathodic electrodeposition paint FT 85-7042 gray from BASF was used for painting.
- the corrosion protection test was carried out according to the VDA alternating climate test 621-415.
- the paint infiltration at the Ritz is entered in Table 5.
- a paint adhesion test was carried out according to the VW stone impact test, which was assessed according to the K value. Higher K values mean poorer, lower K values better paint adhesion.
- the results are also shown in Table 5.
- Corrosion protection values and paint adhesion parameters Rinse solution Paint infiltration (mm) K value steel galvanized steel steel galvanized steel completely desalinated water 1.8 4 - 5 7-8 9 Compare 4 1.3 3-4 6 8th Ex. P 1.2 6 Ex. Q 1.0 2.5 - 3.5 6 8th Ex. R 1.2 2.1 - 3 6 8th Ex 1.1 6
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- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Chemically Coating (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Removal Of Specific Substances (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacture And Refinement Of Metals (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19511573A DE19511573A1 (de) | 1995-03-29 | 1995-03-29 | Verfahren zur Phosphatierung mit metallhaltiger Nachspülung |
DE19511573 | 1995-03-29 | ||
PCT/EP1996/001196 WO1996030559A1 (de) | 1995-03-29 | 1996-03-20 | Verfahren zur phosphatierung mit metallhaltiger nachspülung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0817872A1 EP0817872A1 (de) | 1998-01-14 |
EP0817872B1 true EP0817872B1 (de) | 2000-01-19 |
Family
ID=7758087
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96908083A Expired - Lifetime EP0817872B1 (de) | 1995-03-29 | 1996-03-20 | Verfahren zur phosphatierung mit metallhaltiger nachspülung |
Country Status (19)
Country | Link |
---|---|
US (2) | US6090224A (xx) |
EP (1) | EP0817872B1 (xx) |
JP (1) | JP3883571B2 (xx) |
KR (1) | KR100362549B1 (xx) |
CN (1) | CN1079845C (xx) |
AT (1) | ATE189010T1 (xx) |
AU (1) | AU697424B2 (xx) |
BR (1) | BR9607767A (xx) |
CA (1) | CA2216925A1 (xx) |
CZ (1) | CZ287867B6 (xx) |
DE (2) | DE19511573A1 (xx) |
ES (1) | ES2143186T3 (xx) |
HU (1) | HUP9802380A3 (xx) |
PL (1) | PL179316B1 (xx) |
PT (1) | PT817872E (xx) |
SK (1) | SK128997A3 (xx) |
TR (1) | TR199701061T1 (xx) |
WO (1) | WO1996030559A1 (xx) |
ZA (1) | ZA962504B (xx) |
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WO2009020794A2 (en) * | 2007-08-03 | 2009-02-12 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a metal substrate |
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DE19511573A1 (de) * | 1995-03-29 | 1996-10-02 | Henkel Kgaa | Verfahren zur Phosphatierung mit metallhaltiger Nachspülung |
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DE19834796A1 (de) | 1998-08-01 | 2000-02-03 | Henkel Kgaa | Verfahren zur Phosphatierung, Nachspülung und kathodischer Elektrotauchlackierung |
DE19933189A1 (de) * | 1999-07-15 | 2001-01-18 | Henkel Kgaa | Verfahren zur korrosionsschützenden Behandlung oder Nachbehandlung von Metalloberflächen |
DE10056628B4 (de) * | 2000-11-15 | 2004-07-22 | Henkel Kgaa | Fraktionierte Regenerierung eines mit Nickelionen beladenen schwach sauren Ionenaustauschers |
DE102005047424A1 (de) * | 2005-09-30 | 2007-04-05 | Henkel Kgaa | Phosphatierlösung mit Wasserstoffperoxid und chelatbildenden Carbonsäuren |
DE102006052919A1 (de) * | 2006-11-08 | 2008-05-15 | Henkel Kgaa | Zr-/Ti-haltige Phosphatierlösung zur Passivierung von Metallverbundoberflächen |
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DE102010030697A1 (de) * | 2010-06-30 | 2012-01-05 | Henkel Ag & Co. Kgaa | Verfahren zur selektiven Phosphatierung einer Verbundmetallkonstruktion |
EP2405031A1 (de) * | 2010-07-07 | 2012-01-11 | Mattthias Koch | Verfahren zur Beschichtung von Formkörpern sowie beschichteter Formkörper |
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US9273399B2 (en) | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
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-
1995
- 1995-03-29 DE DE19511573A patent/DE19511573A1/de not_active Withdrawn
-
1996
- 1996-03-20 US US08/930,565 patent/US6090224A/en not_active Expired - Fee Related
- 1996-03-20 CZ CZ19973061A patent/CZ287867B6/cs not_active IP Right Cessation
- 1996-03-20 TR TR97/01061T patent/TR199701061T1/xx unknown
- 1996-03-20 HU HU9802380A patent/HUP9802380A3/hu unknown
- 1996-03-20 AT AT96908083T patent/ATE189010T1/de not_active IP Right Cessation
- 1996-03-20 CA CA002216925A patent/CA2216925A1/en not_active Abandoned
- 1996-03-20 DE DE59604232T patent/DE59604232D1/de not_active Expired - Fee Related
- 1996-03-20 ES ES96908083T patent/ES2143186T3/es not_active Expired - Lifetime
- 1996-03-20 WO PCT/EP1996/001196 patent/WO1996030559A1/de active IP Right Grant
- 1996-03-20 JP JP52888296A patent/JP3883571B2/ja not_active Expired - Fee Related
- 1996-03-20 BR BR9607767A patent/BR9607767A/pt not_active Application Discontinuation
- 1996-03-20 CN CN96192795A patent/CN1079845C/zh not_active Expired - Fee Related
- 1996-03-20 PL PL96321960A patent/PL179316B1/pl not_active IP Right Cessation
- 1996-03-20 KR KR1019970706149A patent/KR100362549B1/ko not_active IP Right Cessation
- 1996-03-20 AU AU51464/96A patent/AU697424B2/en not_active Ceased
- 1996-03-20 PT PT96908083T patent/PT817872E/pt unknown
- 1996-03-20 EP EP96908083A patent/EP0817872B1/de not_active Expired - Lifetime
- 1996-03-20 SK SK1289-97A patent/SK128997A3/sk unknown
- 1996-03-28 ZA ZA962504A patent/ZA962504B/xx unknown
-
2000
- 2000-07-17 US US09/617,886 patent/US6395105B1/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009020794A2 (en) * | 2007-08-03 | 2009-02-12 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a metal substrate |
WO2009020794A3 (en) * | 2007-08-03 | 2009-03-26 | Ppg Ind Ohio Inc | Pretreatment compositions and methods for coating a metal substrate |
RU2447193C2 (ru) * | 2007-08-03 | 2012-04-10 | Ппг Индастриз Огайо, Инк. | Композиции для предварительной обработки и способы нанесения покрытия на металлическую подложку |
Also Published As
Publication number | Publication date |
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CN1079845C (zh) | 2002-02-27 |
JP3883571B2 (ja) | 2007-02-21 |
HUP9802380A2 (hu) | 1999-02-01 |
DE59604232D1 (de) | 2000-02-24 |
CZ306197A3 (cs) | 1998-03-18 |
PT817872E (pt) | 2000-07-31 |
CN1179183A (zh) | 1998-04-15 |
US6090224A (en) | 2000-07-18 |
CA2216925A1 (en) | 1996-10-03 |
HUP9802380A3 (en) | 1999-03-29 |
JPH11502569A (ja) | 1999-03-02 |
PL179316B1 (pl) | 2000-08-31 |
SK128997A3 (en) | 1998-12-02 |
WO1996030559A1 (de) | 1996-10-03 |
PL321960A1 (en) | 1998-01-05 |
CZ287867B6 (en) | 2001-02-14 |
TR199701061T1 (xx) | 1998-01-21 |
EP0817872A1 (de) | 1998-01-14 |
US6395105B1 (en) | 2002-05-28 |
DE19511573A1 (de) | 1996-10-02 |
ZA962504B (en) | 1996-09-30 |
ES2143186T3 (es) | 2000-05-01 |
KR19980702742A (ko) | 1998-08-05 |
ATE189010T1 (de) | 2000-02-15 |
MX9707328A (es) | 1998-07-31 |
AU5146496A (en) | 1996-10-16 |
KR100362549B1 (ko) | 2003-02-11 |
AU697424B2 (en) | 1998-10-08 |
BR9607767A (pt) | 1999-01-19 |
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