EP1658392B1 - Couches de conversion colores sur des surfaces metalliques - Google Patents
Couches de conversion colores sur des surfaces metalliques Download PDFInfo
- Publication number
- EP1658392B1 EP1658392B1 EP04764202A EP04764202A EP1658392B1 EP 1658392 B1 EP1658392 B1 EP 1658392B1 EP 04764202 A EP04764202 A EP 04764202A EP 04764202 A EP04764202 A EP 04764202A EP 1658392 B1 EP1658392 B1 EP 1658392B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- concentration
- diphosphonsäure
- total
- treatment solution
- 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
- 229910052751 metal Inorganic materials 0.000 title claims description 36
- 239000002184 metal Substances 0.000 title claims description 36
- 238000006243 chemical reaction Methods 0.000 title description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 34
- -1 tungstate ions Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 13
- 239000000956 alloy Substances 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract 5
- 229920000642 polymer Polymers 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 37
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- 239000012141 concentrate Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 13
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 claims description 10
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 150000004683 dihydrates Chemical class 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 claims description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 2
- 230000009469 supplementation Effects 0.000 claims 1
- 229910001335 Galvanized steel Inorganic materials 0.000 abstract description 3
- 238000007739 conversion coating Methods 0.000 abstract description 3
- 239000008397 galvanized steel Substances 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- 239000010410 layer Substances 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 11
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
- 239000008139 complexing agent Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- ZCOMURCDMLBWOR-UHFFFAOYSA-N (hydroxy-phenyl-phosphonomethyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(O)C1=CC=CC=C1 ZCOMURCDMLBWOR-UHFFFAOYSA-N 0.000 description 6
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 6
- LCKXJCKRKBQVJZ-UHFFFAOYSA-N 2h-1,4-thiazine 1,1-dioxide Chemical compound O=S1(=O)CC=NC=C1 LCKXJCKRKBQVJZ-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- CLIDPHDIUMOTKS-UHFFFAOYSA-N (1,3-dihydroxy-3-phenyl-1-phosphonopropyl)phosphonic acid Chemical compound OP(=O)(O)C(O)(P(O)(O)=O)CC(O)C1=CC=CC=C1 CLIDPHDIUMOTKS-UHFFFAOYSA-N 0.000 description 4
- QJLDGRMIHRXNOS-UHFFFAOYSA-N (1,6-dihydroxy-1-phosphonohexyl)phosphonic acid Chemical compound OCCCCCC(O)(P(O)(O)=O)P(O)(O)=O QJLDGRMIHRXNOS-UHFFFAOYSA-N 0.000 description 4
- YBVPARYLSNJHJI-UHFFFAOYSA-N (1-amino-4-ethyl-4-methyl-3-oxo-1-phosphonohexyl)phosphonic acid Chemical compound CCC(C)(CC)C(=O)CC(N)(P(O)(O)=O)P(O)(O)=O YBVPARYLSNJHJI-UHFFFAOYSA-N 0.000 description 4
- XHAZMZWXAOBLQG-UHFFFAOYSA-N (1-hydroxy-1-phosphonopropyl)phosphonic acid Chemical compound CCC(O)(P(O)(O)=O)P(O)(O)=O XHAZMZWXAOBLQG-UHFFFAOYSA-N 0.000 description 4
- VMFJPPCHDVLGKB-UHFFFAOYSA-N (3-amino-1-hydroxy-3-phenyl-1-phosphonopropyl)phosphonic acid Chemical compound OP(=O)(O)C(O)(P(O)(O)=O)CC(N)C1=CC=CC=C1 VMFJPPCHDVLGKB-UHFFFAOYSA-N 0.000 description 4
- AXZCPOJTZDFVNT-UHFFFAOYSA-N (4,4-dimethyl-3-oxo-1-phosphonohept-1-enyl)phosphonic acid Chemical compound CCCC(C)(C)C(=O)C=C(P(O)(O)=O)P(O)(O)=O AXZCPOJTZDFVNT-UHFFFAOYSA-N 0.000 description 4
- NQQVWXXSIOPAAU-UHFFFAOYSA-N (4-ethyl-1-hydroxy-4-methyl-3-oxo-1-phosphonohexyl)phosphonic acid Chemical compound CCC(C)(CC)C(=O)CC(O)(P(O)(O)=O)P(O)(O)=O NQQVWXXSIOPAAU-UHFFFAOYSA-N 0.000 description 4
- JILWLDBFNHPYQG-UHFFFAOYSA-N (4-ethyl-4-methyl-3-oxo-1-phosphonohex-1-enyl)phosphonic acid Chemical compound CCC(C)(CC)C(=O)C=C(P(O)(O)=O)P(O)(O)=O JILWLDBFNHPYQG-UHFFFAOYSA-N 0.000 description 4
- YMOJUZRGXNRXAD-UHFFFAOYSA-N (cyclohexyl-hydroxy-phosphonomethyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(O)C1CCCCC1 YMOJUZRGXNRXAD-UHFFFAOYSA-N 0.000 description 4
- COKIOUWMXONTKQ-UHFFFAOYSA-N 1-phosphonopropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)P(O)(O)=O COKIOUWMXONTKQ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- UQZJJBYYCNPQNR-UHFFFAOYSA-N [(decylamino)-phosphonomethyl]phosphonic acid Chemical compound CCCCCCCCCCNC(P(O)(O)=O)P(O)(O)=O UQZJJBYYCNPQNR-UHFFFAOYSA-N 0.000 description 4
- RHNGIWBVWPVMNG-UHFFFAOYSA-N [1-(hydroxymethylamino)-1-phosphonoethyl]phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)NCO RHNGIWBVWPVMNG-UHFFFAOYSA-N 0.000 description 4
- UUSRRPIFDSRPAI-UHFFFAOYSA-N [1-amino-3-(dodecylamino)-1-phosphonopropyl]phosphonic acid Chemical compound CCCCCCCCCCCCNCCC(N)(P(O)(O)=O)P(O)(O)=O UUSRRPIFDSRPAI-UHFFFAOYSA-N 0.000 description 4
- SJGAOTDCRVFQOS-UHFFFAOYSA-N [3-(diethylamino)-1-hydroxy-1-phosphonopropyl]phosphonic acid Chemical compound CCN(CC)CCC(O)(P(O)(O)=O)P(O)(O)=O SJGAOTDCRVFQOS-UHFFFAOYSA-N 0.000 description 4
- AZKACZGHQQSQGL-UHFFFAOYSA-N [amino-(4-hydroxyphenyl)-phosphonomethyl]phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)C1=CC=C(O)C=C1 AZKACZGHQQSQGL-UHFFFAOYSA-N 0.000 description 4
- XYIFELBBPMNDSZ-UHFFFAOYSA-N [chloro-(3,4-dimethylphenyl)-phosphonomethyl]phosphonic acid Chemical compound CC1=CC=C(C(Cl)(P(O)(O)=O)P(O)(O)=O)C=C1C XYIFELBBPMNDSZ-UHFFFAOYSA-N 0.000 description 4
- YIEQYXDYRUSSEH-UHFFFAOYSA-N [chloro-(4-chlorophenyl)-phosphonomethyl]phosphonic acid Chemical compound OP(O)(=O)C(Cl)(P(O)(O)=O)C1=CC=C(Cl)C=C1 YIEQYXDYRUSSEH-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000004532 chromating Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- XYJLPCAKKYOLGU-UHFFFAOYSA-N 2-phosphonoethylphosphonic acid Chemical compound OP(O)(=O)CCP(O)(O)=O XYJLPCAKKYOLGU-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BFDMEODWJJUORJ-UHFFFAOYSA-N [dimethylamino(phosphono)methyl]phosphonic acid Chemical compound CN(C)C(P(O)(O)=O)P(O)(O)=O BFDMEODWJJUORJ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 235000013495 cobalt Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005211 surface analysis Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- YHMQQEODLNCQNR-UHFFFAOYSA-N (1,11-dihydroxy-1-phosphonoundecyl)phosphonic acid Chemical compound OCCCCCCCCCCC(O)(P(O)(O)=O)P(O)(O)=O YHMQQEODLNCQNR-UHFFFAOYSA-N 0.000 description 2
- GRTBRLKPTPWXDQ-UHFFFAOYSA-N (1,3-diamino-1-phosphonobutyl)phosphonic acid Chemical compound CC(N)CC(N)(P(O)(O)=O)P(O)(O)=O GRTBRLKPTPWXDQ-UHFFFAOYSA-N 0.000 description 2
- YMWBXNDYONFTRJ-UHFFFAOYSA-N (1,3-diamino-1-phosphonopropyl)phosphonic acid Chemical compound NCCC(N)(P(O)(O)=O)P(O)(O)=O YMWBXNDYONFTRJ-UHFFFAOYSA-N 0.000 description 2
- NKYYWZKYBQLKML-UHFFFAOYSA-N (1,3-dihydroxy-1-phosphonopropyl)phosphonic acid Chemical compound OCCC(O)(P(O)(O)=O)P(O)(O)=O NKYYWZKYBQLKML-UHFFFAOYSA-N 0.000 description 2
- KFPDMAIURCBYRY-UHFFFAOYSA-N (1-amino-1,3-diphosphonopropyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)CCP(O)(O)=O KFPDMAIURCBYRY-UHFFFAOYSA-N 0.000 description 2
- XLIREHXMRXKQIV-UHFFFAOYSA-N (1-amino-1-phosphonobutyl)phosphonic acid Chemical compound CCCC(N)(P(O)(O)=O)P(O)(O)=O XLIREHXMRXKQIV-UHFFFAOYSA-N 0.000 description 2
- TWYYYYAFACTHMV-UHFFFAOYSA-N (1-amino-1-phosphonodecyl)phosphonic acid Chemical compound CCCCCCCCCC(N)(P(O)(O)=O)P(O)(O)=O TWYYYYAFACTHMV-UHFFFAOYSA-N 0.000 description 2
- GPCTYPSWRBUGFH-UHFFFAOYSA-N (1-amino-1-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(N)(C)P(O)(O)=O GPCTYPSWRBUGFH-UHFFFAOYSA-N 0.000 description 2
- KJSDJVZBBZIGKM-UHFFFAOYSA-N (1-amino-1-phosphonohexadecyl)phosphonic acid Chemical compound CCCCCCCCCCCCCCCC(N)(P(O)(O)=O)P(O)(O)=O KJSDJVZBBZIGKM-UHFFFAOYSA-N 0.000 description 2
- SAJOHMPTNBCJQU-UHFFFAOYSA-N (1-amino-1-phosphonohexyl)phosphonic acid Chemical compound CCCCCC(N)(P(O)(O)=O)P(O)(O)=O SAJOHMPTNBCJQU-UHFFFAOYSA-N 0.000 description 2
- PCTMREJZUSEOQD-UHFFFAOYSA-N (1-amino-1-phosphonopropyl)phosphonic acid Chemical compound CCC(N)(P(O)(O)=O)P(O)(O)=O PCTMREJZUSEOQD-UHFFFAOYSA-N 0.000 description 2
- VBNALRAHPZFNBQ-UHFFFAOYSA-N (1-amino-2-chloro-1-phosphonoethyl)phosphonic acid Chemical compound ClCC(N)(P(O)(O)=O)P(O)(O)=O VBNALRAHPZFNBQ-UHFFFAOYSA-N 0.000 description 2
- AYURIJIONUBEGY-UHFFFAOYSA-N (1-amino-2-phenyl-1-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)CC1=CC=CC=C1 AYURIJIONUBEGY-UHFFFAOYSA-N 0.000 description 2
- ILZVLLNQIKWNDM-UHFFFAOYSA-N (1-amino-4,4-dimethyl-3-oxo-1-phosphonodecyl)phosphonic acid Chemical compound CCCCCCC(C)(C)C(=O)CC(N)(P(O)(O)=O)P(O)(O)=O ILZVLLNQIKWNDM-UHFFFAOYSA-N 0.000 description 2
- MIUWJWZLAKNZBM-UHFFFAOYSA-N (1-amino-4,4-dimethyl-3-oxo-1-phosphonoheptyl)phosphonic acid Chemical compound CCCC(C)(C)C(=O)CC(N)(P(O)(O)=O)P(O)(O)=O MIUWJWZLAKNZBM-UHFFFAOYSA-N 0.000 description 2
- RUPZRJCPTQGQRU-UHFFFAOYSA-N (1-hydroxy-1-phosphonobutyl)phosphonic acid Chemical compound CCCC(O)(P(O)(O)=O)P(O)(O)=O RUPZRJCPTQGQRU-UHFFFAOYSA-N 0.000 description 2
- ITCAYUFDTCVNTE-UHFFFAOYSA-N (1-hydroxy-1-phosphonooctyl)phosphonic acid Chemical compound CCCCCCCC(O)(P(O)(O)=O)P(O)(O)=O ITCAYUFDTCVNTE-UHFFFAOYSA-N 0.000 description 2
- QGLGFSYSGKZIMF-UHFFFAOYSA-N (1-hydroxy-1-phosphonopentyl)phosphonic acid Chemical compound CCCCC(O)(P(O)(O)=O)P(O)(O)=O QGLGFSYSGKZIMF-UHFFFAOYSA-N 0.000 description 2
- SOFWQXWMAXQLJC-UHFFFAOYSA-N (1-hydroxy-4,4-dimethyl-3-oxo-1-phosphonoheptyl)phosphonic acid Chemical compound CCCC(C)(C)C(=O)CC(O)(P(O)(O)=O)P(O)(O)=O SOFWQXWMAXQLJC-UHFFFAOYSA-N 0.000 description 2
- PSJKMWOFTYGXGF-UHFFFAOYSA-N (1-methyl-5-oxo-2-phosphonopyrrolidin-2-yl)phosphonic acid Chemical compound CN1C(=O)CCC1(P(O)(O)=O)P(O)(O)=O PSJKMWOFTYGXGF-UHFFFAOYSA-N 0.000 description 2
- FUTVJDIIKIEOFH-UHFFFAOYSA-N (11-amino-1-hydroxy-1-phosphonoundecyl)phosphonic acid Chemical compound NCCCCCCCCCCC(O)(P(O)(O)=O)P(O)(O)=O FUTVJDIIKIEOFH-UHFFFAOYSA-N 0.000 description 2
- ILKULJZMELENNS-UHFFFAOYSA-N (2-amino-1-hydroxy-2-methyl-1-phosphonopropyl)phosphonic acid Chemical compound CC(C)(N)C(O)(P(O)(O)=O)P(O)(O)=O ILKULJZMELENNS-UHFFFAOYSA-N 0.000 description 2
- KBPGKWPDIYMIFV-UHFFFAOYSA-N (2-amino-2-imino-1-phosphonoethyl)phosphonic acid Chemical compound NC(=N)C(P(O)(O)=O)P(O)(O)=O KBPGKWPDIYMIFV-UHFFFAOYSA-N 0.000 description 2
- FNPLDQVMNZFNEG-UHFFFAOYSA-N (3-amino-1-hydroxy-1-phosphonobutyl)phosphonic acid Chemical compound CC(N)CC(O)(P(O)(O)=O)P(O)(O)=O FNPLDQVMNZFNEG-UHFFFAOYSA-N 0.000 description 2
- HEJXJRDSBLXLAG-UHFFFAOYSA-N (5-oxo-2-phosphonopyrrolidin-2-yl)phosphonic acid Chemical compound OP(O)(=O)C1(P(O)(O)=O)CCC(=O)N1 HEJXJRDSBLXLAG-UHFFFAOYSA-N 0.000 description 2
- VDWQXPSMKAUVLF-UHFFFAOYSA-N (amino-cyclohexyl-phosphonomethyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)C1CCCCC1 VDWQXPSMKAUVLF-UHFFFAOYSA-N 0.000 description 2
- IDYCJOKDHJLCGO-UHFFFAOYSA-N (amino-phenyl-phosphonomethyl)phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(N)C1=CC=CC=C1 IDYCJOKDHJLCGO-UHFFFAOYSA-N 0.000 description 2
- JSBMVKVNJQZVEF-UHFFFAOYSA-N 1,2,2-triphosphonoethylphosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)C(P(O)(O)=O)P(O)(O)=O JSBMVKVNJQZVEF-UHFFFAOYSA-N 0.000 description 2
- ZRECPFOSZXDFDT-UHFFFAOYSA-N 1-decylpyrrolidin-2-one Chemical compound CCCCCCCCCCN1CCCC1=O ZRECPFOSZXDFDT-UHFFFAOYSA-N 0.000 description 2
- MXYOPVWZZKEAGX-UHFFFAOYSA-N 1-phosphonoethylphosphonic acid Chemical compound OP(=O)(O)C(C)P(O)(O)=O MXYOPVWZZKEAGX-UHFFFAOYSA-N 0.000 description 2
- XOQVDBCNWPUEPS-UHFFFAOYSA-N 2-(phosphonomethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CP(O)(O)=O XOQVDBCNWPUEPS-UHFFFAOYSA-N 0.000 description 2
- PMGINNPAPWFWMT-UHFFFAOYSA-N 2-chloro-2-phosphonoacetic acid Chemical compound OC(=O)C(Cl)P(O)(O)=O PMGINNPAPWFWMT-UHFFFAOYSA-N 0.000 description 2
- ARRNRHHUNZJPKF-UHFFFAOYSA-N 2-phosphonoethane-1,1,2-tricarboxylic acid Chemical compound OC(=O)C(C(O)=O)C(C(O)=O)P(O)(O)=O ARRNRHHUNZJPKF-UHFFFAOYSA-N 0.000 description 2
- RUQHVTAVRHUGBT-UHFFFAOYSA-N 4,4,4-trifluoro-3-methyl-3-phosphonobutanoic acid Chemical compound FC(F)(F)C(P(O)(O)=O)(C)CC(O)=O RUQHVTAVRHUGBT-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- OGSPWJRAVKPPFI-UHFFFAOYSA-N Alendronic Acid Chemical compound NCCCC(O)(P(O)(O)=O)P(O)(O)=O OGSPWJRAVKPPFI-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- KJZMOIILRJSQBX-UHFFFAOYSA-N [(1-chlorocyclohexa-2,4-dien-1-yl)-phosphonomethyl]phosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)C1(Cl)CC=CC=C1 KJZMOIILRJSQBX-UHFFFAOYSA-N 0.000 description 2
- ZLECTQKMSSBVGC-UHFFFAOYSA-N [(1-hydroxycyclohexa-2,4-dien-1-yl)-phosphonomethyl]phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)C1(O)CC=CC=C1 ZLECTQKMSSBVGC-UHFFFAOYSA-N 0.000 description 2
- PCHYRVJWWOKFPC-UHFFFAOYSA-N [(3,4-dimethylanilino)-phosphonomethyl]phosphonic acid Chemical compound CC1=CC=C(NC(P(O)(O)=O)P(O)(O)=O)C=C1C PCHYRVJWWOKFPC-UHFFFAOYSA-N 0.000 description 2
- WSFMXOGBQIOTBJ-UHFFFAOYSA-N [(4-aminophenyl)-hydroxy-phosphonomethyl]phosphonic acid Chemical compound NC1=CC=C(C(O)(P(O)(O)=O)P(O)(O)=O)C=C1 WSFMXOGBQIOTBJ-UHFFFAOYSA-N 0.000 description 2
- PWQSPBJUQIQAAY-UHFFFAOYSA-N [(4-chlorophenyl)-hydroxy-phosphonomethyl]phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(O)C1=CC=C(Cl)C=C1 PWQSPBJUQIQAAY-UHFFFAOYSA-N 0.000 description 2
- FDOYVDWHMFMETE-UHFFFAOYSA-N [(4-chlorophenyl)-phosphonomethyl]phosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)C1=CC=C(Cl)C=C1 FDOYVDWHMFMETE-UHFFFAOYSA-N 0.000 description 2
- XQVNOYYFZWUDCV-UHFFFAOYSA-N [(4-hydroxyanilino)-phosphonomethyl]phosphonic acid Chemical compound OC1=CC=C(NC(P(O)(O)=O)P(O)(O)=O)C=C1 XQVNOYYFZWUDCV-UHFFFAOYSA-N 0.000 description 2
- YDUAOVIBEJLQGD-UHFFFAOYSA-N [1-(carbamoylamino)-1-phosphonoethyl]phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)NC(N)=O YDUAOVIBEJLQGD-UHFFFAOYSA-N 0.000 description 2
- XXZUNONBFXFHFH-UHFFFAOYSA-N [1-(methylamino)-1-phosphonoethyl]phosphonic acid Chemical compound CNC(C)(P(O)(O)=O)P(O)(O)=O XXZUNONBFXFHFH-UHFFFAOYSA-N 0.000 description 2
- FQBCODHKOPSNSZ-UHFFFAOYSA-N [1-amino-3-(dimethylamino)-1-(hydroxy-oxido-oxoniumylidene-$l^{5}-phosphanyl)propyl]-oxoniophosphinate Chemical compound CN(C)CCC(N)(P(O)(O)=O)P(O)(O)=O FQBCODHKOPSNSZ-UHFFFAOYSA-N 0.000 description 2
- KKUOXKPTDJEXLE-UHFFFAOYSA-N [1-amino-3-(ethylamino)-1-phosphonobutyl]phosphonic acid Chemical compound CCNC(C)CC(N)(P(O)(O)=O)P(O)(O)=O KKUOXKPTDJEXLE-UHFFFAOYSA-N 0.000 description 2
- FHIIZSPHLAMIDZ-UHFFFAOYSA-N [1-amino-3-(methylamino)-1-phosphonopropyl]phosphonic acid Chemical compound CNCCC(N)(P(O)(O)=O)P(O)(O)=O FHIIZSPHLAMIDZ-UHFFFAOYSA-N 0.000 description 2
- RUMIXNAYCNCFSD-UHFFFAOYSA-N [1-hydroxy-2-[2-(2-methoxyethoxy)ethoxy]-1-phosphonoethyl]phosphonic acid Chemical compound COCCOCCOCC(O)(P(O)(O)=O)P(O)(O)=O RUMIXNAYCNCFSD-UHFFFAOYSA-N 0.000 description 2
- UGEPSJNLORCRBO-UHFFFAOYSA-N [3-(dimethylamino)-1-hydroxy-1-phosphonopropyl]phosphonic acid Chemical compound CN(C)CCC(O)(P(O)(O)=O)P(O)(O)=O UGEPSJNLORCRBO-UHFFFAOYSA-N 0.000 description 2
- SUGUCADESZKPDD-UHFFFAOYSA-N [3-(dodecylamino)-1-hydroxy-1-phosphonopropyl]phosphonic acid Chemical compound CCCCCCCCCCCCNCCC(O)(P(O)(O)=O)P(O)(O)=O SUGUCADESZKPDD-UHFFFAOYSA-N 0.000 description 2
- GPLZYWFVMJCFRR-UHFFFAOYSA-N [[4-(aminomethyl)cyclohexyl]-hydroxy-phosphonomethyl]phosphonic acid Chemical compound NCC1CCC(C(O)(P(O)(O)=O)P(O)(O)=O)CC1 GPLZYWFVMJCFRR-UHFFFAOYSA-N 0.000 description 2
- HFICPJYNTPTHQB-UHFFFAOYSA-N [[4-(dimethylamino)phenyl]-hydroxy-phosphonomethyl]phosphonic acid Chemical compound CN(C)C1=CC=C(C(O)(P(O)(O)=O)P(O)(O)=O)C=C1 HFICPJYNTPTHQB-UHFFFAOYSA-N 0.000 description 2
- FRCICXIVPRNPLM-UHFFFAOYSA-N [amino(phosphono)methyl]phosphonic acid Chemical compound OP(=O)(O)C(N)P(O)(O)=O FRCICXIVPRNPLM-UHFFFAOYSA-N 0.000 description 2
- XESGBDAACQDTDT-UHFFFAOYSA-N [amino-(4-aminophenyl)-phosphonomethyl]phosphonic acid Chemical compound NC1=CC=C(C(N)(P(O)(O)=O)P(O)(O)=O)C=C1 XESGBDAACQDTDT-UHFFFAOYSA-N 0.000 description 2
- JLFLQDDIUGOWOO-UHFFFAOYSA-N [amino-phosphono-(3,4,5-trimethoxyphenyl)methyl]phosphonic acid Chemical compound COC1=CC(C(N)(P(O)(O)=O)P(O)(O)=O)=CC(OC)=C1OC JLFLQDDIUGOWOO-UHFFFAOYSA-N 0.000 description 2
- KBQVJQDNMNDQTA-UHFFFAOYSA-N [hydroxy-(4-hydroxyphenyl)-phosphonomethyl]phosphonic acid Chemical compound OC1=CC=C(C(O)(P(O)(O)=O)P(O)(O)=O)C=C1 KBQVJQDNMNDQTA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- ACSIXWWBWUQEHA-UHFFFAOYSA-N clodronic acid Chemical compound OP(O)(=O)C(Cl)(Cl)P(O)(O)=O ACSIXWWBWUQEHA-UHFFFAOYSA-N 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
- 239000013065 commercial product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JOUOJMIHRPQLAA-UHFFFAOYSA-N ethenylphosphonic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(=O)C=C JOUOJMIHRPQLAA-UHFFFAOYSA-N 0.000 description 2
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- PUUSSSIBPPTKTP-UHFFFAOYSA-N neridronic acid Chemical compound NCCCCCC(O)(P(O)(O)=O)P(O)(O)=O PUUSSSIBPPTKTP-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 2
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 description 2
- HJZKOAYDRQLPME-UHFFFAOYSA-N oxidronic acid Chemical compound OP(=O)(O)C(O)P(O)(O)=O HJZKOAYDRQLPME-UHFFFAOYSA-N 0.000 description 2
- 229960004230 oxidronic acid Drugs 0.000 description 2
- XUYJLQHKOGNDPB-UHFFFAOYSA-N phosphonoacetic acid Chemical compound OC(=O)CP(O)(O)=O XUYJLQHKOGNDPB-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- SKEGVBOXIRUYDI-UHFFFAOYSA-N (1,5-diamino-1,5,5-triphosphonopentyl)phosphonic acid trihydrate Chemical compound O.O.O.NC(CCCC(P(O)(=O)O)(P(O)(=O)O)N)(P(O)(=O)O)P(O)(=O)O SKEGVBOXIRUYDI-UHFFFAOYSA-N 0.000 description 1
- YNDMMOPNGZIGKT-UHFFFAOYSA-N (2-amino-1,4-dihydroxy-2-methyl-1-phosphonobutyl)phosphonic acid Chemical compound OCCC(C(P(O)(=O)O)(P(O)(=O)O)O)(C)N YNDMMOPNGZIGKT-UHFFFAOYSA-N 0.000 description 1
- GDRWQOJIKFWLOC-UHFFFAOYSA-N (2-phosphonopyrrolidin-2-yl)phosphonic acid Chemical compound OP(O)(=O)C1(P(O)(O)=O)CCCN1 GDRWQOJIKFWLOC-UHFFFAOYSA-N 0.000 description 1
- SFRLSTJPMFGBDP-UHFFFAOYSA-N 1,2-diphosphonoethylphosphonic acid Chemical compound OP(O)(=O)CC(P(O)(O)=O)P(O)(O)=O SFRLSTJPMFGBDP-UHFFFAOYSA-N 0.000 description 1
- YVPHSTVRTGSOSK-UHFFFAOYSA-N 1,3,3-triphosphonopropylphosphonic acid Chemical compound OP(O)(=O)C(P(O)(O)=O)CC(P(O)(O)=O)P(O)(O)=O YVPHSTVRTGSOSK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BFDGJIBEQVHHLT-UHFFFAOYSA-N 2-methylprop-1-ene-1,3-diol Chemical compound OCC(C)=CO BFDGJIBEQVHHLT-UHFFFAOYSA-N 0.000 description 1
- SXBBIRVIRIHQAM-UHFFFAOYSA-N 2-octadecyl-2-phosphonobutanedioic acid Chemical compound CCCCCCCCCCCCCCCCCCC(P(O)(O)=O)(C(O)=O)CC(O)=O SXBBIRVIRIHQAM-UHFFFAOYSA-N 0.000 description 1
- ZAISDHPZTZIFQF-UHFFFAOYSA-N 2h-1,4-thiazine Chemical compound C1SC=CN=C1 ZAISDHPZTZIFQF-UHFFFAOYSA-N 0.000 description 1
- 229910000680 Aluminized steel Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910003638 H2SiF6 Inorganic materials 0.000 description 1
- 229910003708 H2TiF6 Inorganic materials 0.000 description 1
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- WWSAHSPHJKFXCW-UHFFFAOYSA-N O.CCCC(O)(P(O)(O)=O)P(O)(O)=O.CCCCCCCCCCCCCCCCC Chemical compound O.CCCC(O)(P(O)(O)=O)P(O)(O)=O.CCCCCCCCCCCCCCCCC WWSAHSPHJKFXCW-UHFFFAOYSA-N 0.000 description 1
- ZKETVZPSJPVTMD-UHFFFAOYSA-N O.P(=O)(O)OP(=O)O.CN(C)C Chemical compound O.P(=O)(O)OP(=O)O.CN(C)C ZKETVZPSJPVTMD-UHFFFAOYSA-N 0.000 description 1
- UQRWSQBZBTUYEU-UHFFFAOYSA-N P(=O)(O)OP(=O)O.BrC=1C=C(C=C(C1O)Br)CN Chemical compound P(=O)(O)OP(=O)O.BrC=1C=C(C=C(C1O)Br)CN UQRWSQBZBTUYEU-UHFFFAOYSA-N 0.000 description 1
- MKETZAFPUSEYTN-UHFFFAOYSA-N P(=O)(O)OP(=O)O.C(CCCCCCCCC)NC Chemical compound P(=O)(O)OP(=O)O.C(CCCCCCCCC)NC MKETZAFPUSEYTN-UHFFFAOYSA-N 0.000 description 1
- JWZUBNXOZPDRDK-UHFFFAOYSA-N P(=O)(O)OP(=O)O.CC=1C=C(C=CC1C)CO Chemical compound P(=O)(O)OP(=O)O.CC=1C=C(C=CC1C)CO JWZUBNXOZPDRDK-UHFFFAOYSA-N 0.000 description 1
- SEIHGGBNTYKYOI-UHFFFAOYSA-N P(=O)(O)OP(=O)O.CN(C(=O)NC)C Chemical compound P(=O)(O)OP(=O)O.CN(C(=O)NC)C SEIHGGBNTYKYOI-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- IWIIVNWTDUODAW-UHFFFAOYSA-N [(3,5-dichloro-4-hydroxyphenyl)-hydroxy-phosphonomethyl]phosphonic acid Chemical compound OC1=C(Cl)C=C(C(O)(P(O)(O)=O)P(O)(O)=O)C=C1Cl IWIIVNWTDUODAW-UHFFFAOYSA-N 0.000 description 1
- PILQELKHNZKZID-UHFFFAOYSA-N [(hydroxymethylamino)-phenyl-phosphonomethyl]phosphonic acid Chemical compound OCNC(P(O)(=O)O)(P(O)(=O)O)C1=CC=CC=C1 PILQELKHNZKZID-UHFFFAOYSA-N 0.000 description 1
- HUHUIXFOXUATES-UHFFFAOYSA-N [[methyl(methylcarbamoyl)amino]-phosphonomethyl]phosphonic acid Chemical compound CNC(=O)N(C)C(P(O)(O)=O)P(O)(O)=O HUHUIXFOXUATES-UHFFFAOYSA-N 0.000 description 1
- NQLSAZAZMCKLJN-UHFFFAOYSA-N [dimethylamino(phosphono)methyl]phosphonic acid;hydrate Chemical compound O.CN(C)C(P(O)(O)=O)P(O)(O)=O NQLSAZAZMCKLJN-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- RWMKKWXZFRMVPB-UHFFFAOYSA-N silicon(4+) Chemical compound [Si+4] RWMKKWXZFRMVPB-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- ZEFWRWWINDLIIV-UHFFFAOYSA-N tetrafluorosilane;dihydrofluoride Chemical compound F.F.F[Si](F)(F)F ZEFWRWWINDLIIV-UHFFFAOYSA-N 0.000 description 1
- DXIGZHYPWYIZLM-UHFFFAOYSA-J tetrafluorozirconium;dihydrofluoride Chemical compound F.F.F[Zr](F)(F)F DXIGZHYPWYIZLM-UHFFFAOYSA-J 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 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
- C23C22/05—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 using aqueous solutions
- C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
Definitions
- the invention is in the field of chemical surface treatment of zinc or galvanized steel, aluminum, magnesium or their alloys. It describes chromium-free conversion processes for such metal surfaces, i. H. chemical treatment processes which result in the formation of a surface layer in which both cations of the treated metal surface and ions from the treatment solution are incorporated.
- the chromium-free coating is colored, so that it can be determined by simple visual inspection whether a sufficient conversion layer has been formed.
- the object of this conversion layer is to reduce the tendency of the metal surface to corrode and to produce good adhesion between the metal surface and an organic coating such as a lacquer or an adhesive applied to the conversion layer.
- WO 92/07973 teaches a chromium-free treatment process for aluminum containing, as essential components in acidic aqueous solution, from 0.01 to about 18% by weight of H 2 ZrF 6 and from 0.01 to about 10% by weight of a 3- (NC 1 4- alkyl-N-2-hydroxyethylaminomethyl) -4-hydroxystyrene polymer.
- Optional components are 0.05-10% by weight of dispersed SiO 2 , 0.06-0.6% by weight of a solubilizer for the polymer, and surfactant.
- Said polymer falls under the group of "reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl group-containing amines" described below and usable in the context of the present invention.
- WO 94/28193 describes a process for the pretreatment of surfaces of aluminum or its alloys prior to a second, permanent corrosion-protective conversion treatment, wherein the surfaces in contact with acidic aqueous treatment solutions, the complex fluorides of the elements boron, silicon, titanium, zirconium or hafnium individually or in admixture with one another in concentrations of the fluoro anions of in total between 100 and 4000, preferably 200 to 2000, mg / l and have a pH of between 0.3 and 3.5, preferably between 1 and 3.
- the treatment solutions may additionally contain polymers of the polyacrylate type and / or the reaction products of poly (vinylphenol) with aldehydes and organic hydroxyl-containing amines in concentrations below 500 mg / l, preferably below 200 mg / l.
- Other potential components of the treatment baths are Polyhydroxycarboxylic acids or their anions, in particular gluconate ions, in concentrations up to 500 mg / l.
- WO 95/04169 teaches the treatment of metal surfaces with a treatment solution containing at least the following components: fluorocomplexes of titanium, zirconium, hafnium, silicon, aluminum and boron, metal ions selected from cobalt, magnesium, manganese, zinc, nickel, tin, copper , Zirconium, iron and strontium, phosphates or phosphonates, as well as water-soluble or water-dispersible organic film formers.
- WO 94/25640 discloses a method of producing blue colored conversion layers on zinc / aluminum alloys.
- a treatment solution in contact which has a pH between 3.5 and 6 and which has 0.2 to 3.0 wt .-% molybdenum and a fluoride content of 0.1 to 2.0 wt .-%.
- Molybdenum can be used as molybdate, as phosphomolybdic acid, as molybdenum chloride and the like.
- Fluoride can be used in the form of hydrofluoric acid, simple fluorides, but also complex fluoro acids such as fluorotitanic acid or fluorozirconic acid.
- the treatment solution contains heterooxo anions of molybdenum, tungsten or vanadium with one of the heteroions. Phosphorus, aluminum, silicon, manganese, zirconium, titanium, tin, cerium or nickel.
- the treatment solution contains an organic film former, which can be selected for example from acrylates.
- the heterooxo anions such as, for example, anions of heteropolyacids, can be formed directly in the treatment solution in which the starting materials for this are added, for example molybdate ions and phosphoric acid.
- the treatment solution should preferably contain an etchant for aluminum, for example fluoride, tetrafluoroborate or similar etchant.
- WO 00/26437 The teaching of WO 00/26437 is the way to colorize the conversion layer by an organic dye (Alizerinfarbstoff).
- the conversion layer itself is produced with a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to further inorganic oxides, hydroxides or carbonates or their reaction products with the fluoro acids.
- a treatment solution which contains complex fluorides, for example of titanium and zirconium, in addition to further inorganic oxides, hydroxides or carbonates or their reaction products with the fluoro acids.
- an amino-substituted poly-4-hydroxy-styrene polyvinylphenol
- the metal surfaces may be surfaces of the metals mentioned or their alloys as such, but also surfaces of a substrate such as steel, which is coated with the metals or their alloys. Examples of the latter are electrolytically galvanized or hot dip galvanized steel, aluminized steel, or coated steel as Galvalume ® or Galfan ®, which carry a coating of zinc / aluminum alloys.
- the treatment solution is free of chromium. Furthermore, it preferably also contains no other heavy metal ions than those listed as components a) and b). This reduces the demands on the treatment of wastewater.
- the pH of the treatment solution should not be significantly lower than 1, since lower pH values lead to an increasingly stronger pickling attack on the metal surface.
- the pH is not less than 2 and especially not less than 2.5.
- the formation of the conversion layer is no longer to the desired extent.
- the mentioned essential components a) to d) are all protolytes, that is to say molecules or ions which are capable of reacting with release or uptake of protons in the sense of an acid-base reaction.
- these components will undergo such reactions with one another and with the solvent of water until the appropriate chemical equilibria are achieved.
- pH values it is to be expected that all these protolytes are in a partially protolysed state, irrespective of whether they have been introduced into the treatment solution in the form of their acids or their salts.
- the said pH values which are in the acid range, are introduced by introducing the hexafluorotitanate and / or hexafluorozirconic acids in the form of the free acids.
- An additional acid to adjust the acidic pH is then not required.
- the molybdate and / or tungsten ions are preferably used in the form of their salts, for example as sodium salts.
- the chelating complexing agents and the copolymer of group d) can also be used in the form of free acids or in the form of ammonium or alkali metal salts. This is primarily a matter of commercial availability. Should the desired pH range not be reached automatically when the essential components are mixed with water, the pH value can be adjusted downwards by adding an acid such as nitric acid, for example, by adding an alkali such as sodium hydroxide solution.
- the definition of the chelating complexing agent c) is to be understood as representing a different compound than the copolymer mentioned under d), although this might also have chelating properties. Rather, the chelating complexing agents c) should preferably be non-polymeric molecules.
- the minimum concentration for component a) is preferably 30 mg / l and especially 100 mg / l, for component b) 50 mg / l, especially 100 mg / l, for component c) 5 mg / l, especially 15 mg / l and for component d) 0.2 mg / l, in particular 0.5 mg / l.
- the mentioned preferred minimum concentrations of the individual components are independent of each other. Preferably, however, all 4 components are present at the same time in each case with the minimum concentrations mentioned.
- Component a) is preferably present in a maximum concentration of 1000 mg / l, in particular 500 mg / l, component b) in a maximum concentration of 2000 mg / l , in particular of 1000 mg / l, the component c) in a maximum concentration of 1000 mg / l, preferably 300 mg / l and the component d) in a maximum concentration of 10 mg / l, in particular 5 mg / l.
- a "partial ester” is understood to mean that only a part of the alcohol groups is esterified, the ester formation taking place with non-polymeric carboxylic acids.
- the ester formation can be carried out with monobasic carboxylic acids having 1 to 4 carbon atoms.
- the polymers or copolymers of group f) may be selected, for example, from homopolymers or copolymers of acrylic acid and / or methacrylic acid whose acid groups may be partially replaced by amide groups or esterified with alcohols, in particular with simple alcohols having 1 to 4 carbon atoms.
- Specific examples are homopolymers or copolymers of or with methyl methacrylate, n-butyl acrylate, hydroxyethyl acrylate and glycerol propoxitriacrylate. These specific examples are known, for example, from WO 95/14117.
- the polymers of group f) may further be selected from those containing maleic acid monomers. A specific example of this is a maleic acid-methyl vinyl ether copolymer.
- the treatment solution contains both polymers of group e) and those of group f).
- the polymer of group f) is a maleic acid-methyl vinyl ether copolymer.
- Polymers of group e) generally contain free alcohol groups, those of group f) free carboxylic acid groups. Therefore, these two polymers can be used not only in admixture with each other but in a form in which ester formation has occurred at least partially between the alcohol groups of the polymer e) and the carboxylic acid groups of the polymer f). This is explained in more detail in WO 94/12570. The teaching described therein can also be used in the context of the present invention.
- the treatment solution may contain polymers of group h).
- polymers of group h Such polymers and their use in treatment solutions for the conversion treatment are described in more detail in DE-A-100 05 113 and DE-A-101 31 723.
- the additional polymers can be selected from those of group i), amine-substituted polymers of 4-hydroxystyrene, which are also referred to as polymers of polyvinylphenol. Examples of this can be found in WO 00/26437 and in the literature cited therein, in particular US Pat. No. 5,281,282.
- the additional polymers can be selected from those of group k), as described in more detail in US Pat. No. 5,356,490.
- the chelating complexing agent c) is preferably non-polymeric and preferably selected from molecules having 2 or more phosphonic acid groups, especially from geminal diphosphonic acids, and phosphonocarboxylic acids and their respective anions. (As explained above, in the treatment solution and in the concentrate, depending on the pH, the corresponding acid-base balance will be established between the acid form and the salt form of the complexing agent, regardless of the form in which it has been introduced into the solution or concentrate .)
- the copolymer d) is preferably selected from copolymers of vinylphosphonic acid and one or more unsaturated carboxylic acids selected from acrylic acid, methacrylic acid and maleic acid whose acid groups may be at least partially esterified with alcohols having 1 to 4 carbon atoms.
- a specific example is a vinylphosphonic acid-acrylic acid copolymer, which is available under CAS no. 27936-88-5 is known.
- the molecular weight is in the range of 30,000 to 90,000. This polymer is commercially available, for example, as a 20% aqueous solution having a total phosphorus content of 2.0 ⁇ 0.2% by weight.
- the treatment solution contains an additional polymer or copolymer of group f), which is selected in particular from maleic acid-methyl vinyl ether copolymers and from polymers or copolymers of acrylic acid and / or methacrylic acid whose carboxyl groups are at least partially replaced by amide groups.
- an additional polymer or copolymer of group f which is selected in particular from maleic acid-methyl vinyl ether copolymers and from polymers or copolymers of acrylic acid and / or methacrylic acid whose carboxyl groups are at least partially replaced by amide groups.
- an additional polymer or copolymer of group f which is selected in particular from maleic acid-methyl vinyl ether copolymers and from polymers or copolymers of acrylic acid and / or methacrylic acid whose carboxyl groups are at least partially replaced by amide groups.
- a polymer can also be used its ester with polyvinyl alcohol, which has been described above as a polymer of group g).
- the invention relates to a process for producing colored layers on surfaces of zinc, aluminum, magnesium or their alloys, by spraying or dipping the surfaces with an aqueous treatment solution for a period of time ranging from 2 seconds to 10 minutes one or more of claims 1 to 4 or 6 to 8 in contact, which has a temperature in the range of 10 to 70 ° C.
- the concentration of the individual active ingredients there is a relationship between the concentration of the individual active ingredients and the time: the shorter the treatment time, the more concentrated the treatment solution is preferably chosen.
- Treatment times at the lower end of the specified interval for example in the range of 2 to about 10 seconds, can be used in the treatment of running metal bands.
- treatment times in the range of 0.5 to 3 minutes are preferably selected.
- the temperature of the treatment solution is preferably adjusted to at least 20 ° C. A maximum temperature of 60 ° C is usually sufficient.
- the treatment step according to the invention is usually part of a treatment sequence, as is usual in a conversion treatment of the metal surfaces mentioned before a subsequent coating or bonding.
- a treatment sequence usually begins with a cleaning / degreasing of the metal surfaces, for which example an alkaline cleaner can be used.
- This is followed by one or more rinses with water.
- an acidic treatment step to remove superficial oxides which are not removed during alkaline cleaning.
- This step is also referred to as "deoxidizing" or "pickling” and is used particularly on surfaces of aluminum and its alloys.
- the treatment step according to the invention is then followed by the treatment solution according to the invention. Thereafter, it can be rinsed again with water.
- the method can also be carried out as a "no-rinse” method, ie rinsing with water after the treatment step according to the invention can also be dispensed with.
- a yellowish-colored, corrosion-protected metal surface is obtained which exhibits good adhesion to a subsequently applied layer based on organic polymers, for example a lacquer or an adhesive.
- This surface usually contains 1 to 70 mg of titanium and / or zirconium per m 2 , in particular 3 to 30 mg / m 2 .
- the molybdenum and / or tungsten coating is usually between 2 and 500 mg / m 2 .
- the present invention also includes metal strips, metal sheets or metal parts, which - as explained in more detail above - have surfaces of zinc, aluminum, magnesium or their alloys and wear on these surfaces colored layers that were produced by the method according to the invention.
- the metal strips, metal sheets or metal parts may be coated with a layer based on organic polymers such as a paint or an adhesive.
- the invention also includes metal strips, metal sheets or metal parts with said surfaces which have been treated by the method according to the invention and which have subsequently been coated with a lacquer or bonded to other components.
- these metal strips, metal sheets or metal parts may have a powder coating.
- the inventive method thus provides metal surfaces, which have a good corrosion protection and a good paint adhesion, as the expert knows it as a result of technically very advantageous, for environmental and health reasons, however, undesirable Chromierung.
- the person skilled in the art immediately sees whether a sufficient conversion layer has formed during the treatment, as he is accustomed to from chromating.
- the process according to the invention therefore has the technical advantage over the production of colorless conversion layers that the result of the treatment is immediately visually recognizable without the need for special surface analysis.
- the sheets were rinsed with demineralized water and dried and then painted with a commercial polyester paint (facade quality, white, TGIC-free). This was followed by a paint adhesion test which was customary in practice. The test panels were cross-hatched, stored for 2 hours in boiling demineralized water and then for one hour at room temperature. Then an adhesive tape was glued over the crosshatch area and pulled off again. The proportion of paint removed from the sample sheet was assessed and characterized by cross-cut notes: Gt 0: no loss of paint, Gt 5: substantial loss of paint.
- Treatment solutions, treatment parameters and treatment results (V: comparative solutions not according to the invention, B: examples according to the invention); Concentrations in mg / l in water; Duration of treatment: 1 minute; V1 to V3 and B1 to B8: treatment by spraying, B9: treatment by dipping.
- V1 V2 V3 B1 B2 B3 B4 B5 B6 B7 B8 B9 a) hexafluorotitanic acid 160 160 160 160 160 160 160 160 160 160 b) Sodium molybdate dihydrate 400 400 200 300 400 200 300 400 200 300 200 c) 1-Hydroxyethane-1,1-diphosphonic acid, Na salt 60 30 45 60 30 45 60 30 45 30 d) vinylphosphonic acid-acrylic acid copolymer, CAS no.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
Claims (10)
- Solution aqueuse de traitement pour la production de couches colorées sur des surfaces en zinc, aluminium, magnésium ou leurs alliages, qui présente un pH de 1 à 6 et qui contienta) au total 4 à 4 000 mg/l d'ions hexafluorotitanate et/ou hexafluorozirconate,b) au total 10 à 4 000 mg/l d'ions molybdate et/ou tungsténate, calculé sous forme dihydratée du sel sodique,c) au total 1 à 2 000 mg/l d'un ou de plusieurs complexants formant un chélate,d) 0,04 à 40 mg/l d'un copolymère d'acide alkylènephosphonique ou alkylènephosphinique et d'un ou de plusieurs acides carboxyliques insaturés.
- Solution aqueuse de traitement selon la revendication 1, caractérisée en ce que
la concentration en ions hexafluorotitanate et/ou hexafluorozirconate a) est au total d'au moins 30 mg/l, de préférence d'au moins 100 mg/l et/ou
la concentration en ions molybdate et/ou tungsténate, calculée sous forme dihydratée du sel sodique b) est au total d'au moins 50 mg/l, de préférence d'au moins 100 mg/l et/ou
la concentration totale en l'un ou plusieurs complexants formant un chélate c) est au total d'au moins 5 mg/l, de préférence d'au moins 15 mg/l et/ou
la concentration en copolymère de l'acide alkylènephosphonique ou alkylènephosphinique et d'un ou de plusieurs acides carboxyliques insaturés d) est d'au moins 0,2 mg/l, de préférence d'au moins 0,5 mg/l. - Solution aqueuse de traitement selon l'une ou les deux revendications 1 et 2, caractérisée en ce que
la concentration en ions hexafluorotitanate et/ou hexafluorozirconate a) est au total d'au plus 1 000 mg/l, de préférence d'au plus 500 mg/l et/ou
la concentration en ions molybdate et/ou tungsténate, calculée sous forme dihydratée du sel sodique b) est au total d'au plus 2 000 mg/l, de préférence d'au plus 1 000 mg/l et/ou
la concentration totale en l'un ou plusieurs complexants formant un chélate c) est au total d'au plus 1 000 mg/l, de préférence d'au plus 300 mg/l et/ou
la concentration en copolymère de l'acide alkylènephosphonique ou alkylènephosphinique et d'un ou de plusieurs acides carboxyliques insaturés d) est d'au plus 10 mg/l, de préférence d'au plus 5 mg/l. - Solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 3, caractérisée en ce qu'elle contient en outre un ou plusieurs autres polymères qui ne font pas partie du groupe d) et qui sont choisis parmi :e) le poly(alcool vinylique) ou des esters partiels solubles ou dispersibles dans l'eau de celui-ci en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 20 mg/l et d'au plus de 1 000 mg/l, de préférence d'au plus 500 mg/l, de préférence d'au plus 200 mg/l,f) les polymères ou les copolymères d'acides monocarboxyliques ou dicarboxyliques insaturés ou leurs amides, en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 30 mg/l et d'au plus 2 000 mg/l, de préférence d'au plus 500 mg/l, en particulier d'au plus 300 mg/l,g) les esters des polymères des groupes e) et f) en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 30 mg/l et d'au plus 2 000 mg/l, de préférence d'au plus 500 mg/l, en particulier d'au plus 300 mg/l,h) 0,01 à 20 g/l d'un polymère ou d'un copolymère de la vinylpyrrolidone,i) les polymères substitués par amine du 4-hydroxystyrène en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 30 mg/l et d'au plus 2 000 mg/l, de préférence d'au plus 500 mg/l, en particulier d'au plus 300 mg/l,k) les polymères du diglycidyléther du bisphénol A en une concentration d'au moins 1 mg/l, de préférence d'au moins 10 mg/l, en particulier d'au moins 30 mg/l et d'au plus 2 000 mg/l, de préférence d'au plus 500 mg/l, en particulier d'au plus 300 mg/l.
- Concentrat aqueux destiné à préparer ou à compléter une solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 4, qui contientb) au total 2 à 200 g/l d'ions molybdate et/ou tungsténate, calculé sous forme dihydratée du sel sodique,c) au total 0,5 à 200 g/l d'un ou de plusieurs complexants formant un chélate,d) 0,02 à 5 g/l d'un copolymère d'acide alkylènephosphonique ou alkylènephosphinique et d'un ou de plusieurs acides carboxyliques insaturés.
- Solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 4 ou concentrat selon la revendication 5, caractérisé en ce que le complexant formant un chélate c) est choisi parmi les molécules présentant 2 groupes acide phosphonique ou plus, de préférence parmi les acides diphosphoniques géminés et les acides phosphonocarboxyliques et à chaque fois leurs anions.
- Solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 4 ou concentrat selon la revendication 5, caractérisé en ce que le copolymère d) est choisi parmi les copolymères de l'acide vinylphosphonique et d'un ou de plusieurs acides carboxyliques insaturés choisis parmi l'acide acrylique, méthacrylique et maléique.
- Solution aqueuse de traitement selon la revendication 4, caractérisée en ce qu'elle contient au moins un polymère ou copolymère f) qui est choisi parmi les copolymères de l'acide maléique-méthylvinyléther et parmi les polymères ou copolymères de l'acide acrylique et/ou méthacrylique, dont les groupes carboxyle sont au moins partiellement remplacés par des groupes amide ou leurs esters avec du poly(alcool vinylique) comme polymère g).
- Procédé pour la production de couches colorées sur des surfaces en zinc, aluminium, magnésium ou leurs alliages, les surfaces étant mises en contact pendant un laps de temps situé dans la plage de 2 secondes à 10 minutes dans un procédé de pulvérisation ou d'immersion avec une solution aqueuse de traitement selon l'une ou plusieurs des revendications 1 à 4 ou 6 à 8, qui présente une température dans la plage de 10 à 70°C.
- Bandes métalliques, tôles métalliques ou pièces métalliques qui présentent des surfaces en zinc, aluminium, magnésium ou leurs alliages et qui portent sur ces surfaces des couches colorées qui ont été produites par un procédé selon la revendication 9.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10339165A DE10339165A1 (de) | 2003-08-26 | 2003-08-26 | Farbige Konversionsschichten auf Metalloberflächen |
PCT/EP2004/009212 WO2005021834A1 (fr) | 2003-08-26 | 2004-08-17 | Couches de conversion colorées sur des surfaces métalliques |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1658392A1 EP1658392A1 (fr) | 2006-05-24 |
EP1658392B1 true EP1658392B1 (fr) | 2007-03-14 |
Family
ID=34202034
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04764202A Expired - Lifetime EP1658392B1 (fr) | 2003-08-26 | 2004-08-17 | Couches de conversion colores sur des surfaces metalliques |
Country Status (5)
Country | Link |
---|---|
US (1) | US8293029B2 (fr) |
EP (1) | EP1658392B1 (fr) |
AT (1) | ATE356895T1 (fr) |
DE (2) | DE10339165A1 (fr) |
WO (1) | WO2005021834A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004022565A1 (de) * | 2004-05-07 | 2005-12-22 | Henkel Kgaa | Farbige Konversionsschichten auf Metalloberflächen |
US20070264511A1 (en) * | 2006-05-09 | 2007-11-15 | Roberto Ponzellini | Method and composition for forming a coloured coating on a metallic surface |
US20090242081A1 (en) * | 2008-03-26 | 2009-10-01 | Richard Bauer | Aluminum Treatment Composition |
PL2890829T3 (pl) | 2012-08-29 | 2022-08-29 | Ppg Industries Ohio, Inc. | Kompozycje do obróbki wstępnej cyrkonu zawierające lit, związane z nimi sposoby obróbki substratów metalowych oraz powiązane z nimi powlekane substraty metalowe |
DE102012017438A1 (de) | 2012-09-04 | 2014-03-06 | Carl Freudenberg Kg | Behandlungslösung und Verfahren zur Beschichtung von Metalloberflächen |
WO2015055756A1 (fr) * | 2013-10-17 | 2015-04-23 | Chemetall Gmbh | Procédé de préparation d'articles façonnés métalliques en vue du formage à froid |
US20150315718A1 (en) * | 2014-05-05 | 2015-11-05 | Ppg Industries Ohio, Inc. | Metal pretreatment modification for improved throwpower |
ES2763038T3 (es) | 2015-04-15 | 2020-05-26 | Henkel Ag & Co Kgaa | Revestimientos finos protectores contra corrosión que incorporan polímeros de poliamidoamina |
WO2017046139A1 (fr) * | 2015-09-15 | 2017-03-23 | Chemetall Gmbh | Prétraitement de surfaces en aluminium avec des compositions contenant du zircon et du molybdène |
US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
KR20190043155A (ko) | 2016-08-24 | 2019-04-25 | 피피지 인더스트리즈 오하이오 인코포레이티드 | 금속 기판을 처리하기 위한 알칼리성 조성물 |
EP3847297B1 (fr) * | 2018-09-07 | 2023-11-08 | Chemetall GmbH | Procédé de traitement de surfaces de substrats contenant de l'aluminium |
JP7476173B2 (ja) * | 2018-09-07 | 2024-04-30 | ケメタル ゲゼルシャフト ミット ベシュレンクテル ハフツング | アルミニウム含有基材の表面を処理する方法 |
DE102020117925A1 (de) | 2020-07-07 | 2022-01-13 | Salzgitter Flachstahl Gmbh | Blech mit Haftvermittlerbeschichtung als Halbzeug zur Fertigung von Metall-Thermoplastverbundbauteilen und Verfahren zur Herstellung eines solchen Bleches |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4191596A (en) | 1978-09-06 | 1980-03-04 | Union Carbide Corporation | Method and compositions for coating aluminum |
US5129967A (en) * | 1988-05-03 | 1992-07-14 | Betz Laboratories, Inc. | Composition and method for non-chromate coating of aluminum |
US4992116A (en) * | 1989-04-21 | 1991-02-12 | Henkel Corporation | Method and composition for coating aluminum |
US5089064A (en) | 1990-11-02 | 1992-02-18 | Henkel Corporation | Process for corrosion resisting treatments for aluminum surfaces |
US5281282A (en) * | 1992-04-01 | 1994-01-25 | Henkel Corporation | Composition and process for treating metal |
US5356490A (en) * | 1992-04-01 | 1994-10-18 | Henkel Corporation | Composition and process for treating metal |
DE69330138T3 (de) | 1992-11-30 | 2007-10-11 | Bulk Chemicals, Inc. | Verfahren und zusammensetzungen zur behandlung von metalloberflächen |
JP3325334B2 (ja) * | 1993-04-28 | 2002-09-17 | 日本パーカライジング株式会社 | 溶融亜鉛−アルミニウム合金めっき鋼板の光輝性青色処理方法 |
DE4317217A1 (de) * | 1993-05-24 | 1994-12-01 | Henkel Kgaa | Chromfreie Konversionsbehandlung von Aluminium |
US5427632A (en) | 1993-07-30 | 1995-06-27 | Henkel Corporation | Composition and process for treating metals |
WO1995014117A1 (fr) | 1993-11-16 | 1995-05-26 | Ici Australia Operations Pty. Ltd. | Traitement anticorrosion d'acier possedant des revetements d'aluminium, de zinc ou de leurs alliages |
DE19524828A1 (de) * | 1995-07-07 | 1997-01-09 | Henkel Kgaa | Verfahren zum schwermetallfreien Verdichten anodisierter Metalle mit Lithium- und Fluorid-haltigen Lösungen |
TW460618B (en) | 1998-10-30 | 2001-10-21 | Henkel Corp | Visible chromium- and phosphorus-free conversion coating for aluminum and its alloys |
GB9825043D0 (en) * | 1998-11-16 | 1999-01-13 | Agfa Gevaert Ltd | Production of support for lithographic printing plate |
DE19923084A1 (de) * | 1999-05-20 | 2000-11-23 | Henkel Kgaa | Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren |
DE10005113A1 (de) | 2000-02-07 | 2001-08-09 | Henkel Kgaa | Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen |
JP2001335954A (ja) * | 2000-05-31 | 2001-12-07 | Nippon Parkerizing Co Ltd | 金属表面処理剤、金属表面処理方法及び表面処理金属材料 |
US6540901B2 (en) * | 2000-07-17 | 2003-04-01 | Agfa-Gevaert | Production of support for lithographic printing plate |
JP3844643B2 (ja) | 2000-08-21 | 2006-11-15 | 日本パーカライジング株式会社 | 下地処理剤、及び下地処理方法 |
CA2425403A1 (fr) * | 2000-10-11 | 2003-04-08 | Chemetall Gmbh | Procede de pretraitement et d'enduction subsequente de surfaces metalliques avant le formage a l'aide d'une couche de type peinture et utilisation des substrats ainsi recouverts |
DE10149148B4 (de) * | 2000-10-11 | 2006-06-14 | Chemetall Gmbh | Verfahren zur Beschichtung von metallischen Oberflächen mit einer wässerigen, Polymere enthaltenden Zusammensetzung, die wässerige Zusammensetzung und Verwendung der beschichteten Substrate |
US20020179189A1 (en) * | 2001-02-26 | 2002-12-05 | Nelson Homma | Process and composition for sealing porous coatings containing metal and oxygen atoms |
JP4652592B2 (ja) * | 2001-03-15 | 2011-03-16 | 日本ペイント株式会社 | 金属表面処理剤 |
DE10131723A1 (de) | 2001-06-30 | 2003-01-16 | Henkel Kgaa | Korrosionsschutzmittel und Korrosionsschutzverfahren für Metalloberflächen |
US6679943B1 (en) * | 2002-05-01 | 2004-01-20 | Basf Corporation | Coating containing adhesion promoting additive |
-
2003
- 2003-08-26 DE DE10339165A patent/DE10339165A1/de not_active Withdrawn
-
2004
- 2004-08-17 DE DE502004003236T patent/DE502004003236D1/de not_active Expired - Lifetime
- 2004-08-17 AT AT04764202T patent/ATE356895T1/de not_active IP Right Cessation
- 2004-08-17 WO PCT/EP2004/009212 patent/WO2005021834A1/fr active IP Right Grant
- 2004-08-17 EP EP04764202A patent/EP1658392B1/fr not_active Expired - Lifetime
-
2006
- 2006-01-31 US US11/343,664 patent/US8293029B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
US10920324B2 (en) | 2012-08-29 | 2021-02-16 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
Also Published As
Publication number | Publication date |
---|---|
WO2005021834A1 (fr) | 2005-03-10 |
DE502004003236D1 (de) | 2007-04-26 |
US8293029B2 (en) | 2012-10-23 |
DE10339165A1 (de) | 2005-03-24 |
ATE356895T1 (de) | 2007-04-15 |
US20060173099A1 (en) | 2006-08-03 |
EP1658392A1 (fr) | 2006-05-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69405530T2 (de) | Verfahren und Zusammensetzung zur Metallbehandlung | |
EP1658392B1 (fr) | Couches de conversion colores sur des surfaces metalliques | |
EP0754251B1 (fr) | Procede sans chrome de traitement sans rincage de l'aluminium et de ses alliages et solutions aqueuses appropriees | |
DE60226078T2 (de) | Behandlungsflüssigkeit für die oberflächenbehandlung von auf aluminium oder magnesium basierendem metall und oberflächenbehandlungsverfahren | |
EP1751327A1 (fr) | Couches de conversion colorees sur des surfaces metalliques | |
EP1254279B1 (fr) | Anticorrosif et procede de protection contre la corrosion destine a des surfaces metalliques | |
WO2005061761A1 (fr) | Traitement de conversion en deux etapes | |
EP1402083B1 (fr) | Procédé de protection contre la corrosion pour surfaces métalliques | |
EP0578670B1 (fr) | Procede de phosphatation de surfaces metalliques | |
EP0261704B1 (fr) | Procédé pour produire des revêtements de phosphate sur des surfaces métalliques | |
EP0359296B1 (fr) | Procédé de phosphatation | |
WO1996034995A1 (fr) | Traitement sans chrome ni fluorures de surfaces metalliques | |
DE4241134A1 (de) | Verfahren zur Phosphatierung von Metalloberflächen | |
DE10030462A1 (de) | Haftvermittler in Konversionslösungen | |
DE4031817A1 (de) | Verfahren zur passivierenden nachbehandlung von phosphatierten metalloberflaechen | |
EP0264811B1 (fr) | Procédé d'obtention de revêtements de phosphate | |
DE3820650A1 (de) | Verfahren zum verdichten von anodisierten oxidschichten auf aluminium und aluminiumlegierungen | |
EP0103234A2 (fr) | Procédé de colmatage de couches d'oxyde obtenues par voie anodique sur de l'aluminium ou des alliages d'aluminium | |
EP0815293B1 (fr) | Procede sans chrome permettant d'ameliorer l'adherence d'une peinture ou d'un vernis applique(e) par anodisation en couche mince | |
EP3676419B1 (fr) | Procédé amélioré de phosphatage sans nickel des surfaces métalliques | |
DE4232292A1 (de) | Verfahren zum Phosphatieren von verzinkten Stahloberflächen | |
DE2851432A1 (de) | Kontinuierliches verfahren zum aufbringen eines phosphatbelags auf ein eisenhaltiges oder zinkhaltiges metallsubstrat | |
EP3456864B1 (fr) | Prétraitement d'aluminium, en particulier d'alliages d'aluminium, à deux étapes comprenant le bain de décapage et le traitement de conversion | |
DE3217145A1 (de) | Verfahren zum reinigen, entfetten sowie aktivieren von metalloberflaechen | |
EP4382641A1 (fr) | Procédé de dépôt électrolytique d'une couche de phosphate sur des surfaces de zinc |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20051207 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
DAX | Request for extension of the european patent (deleted) | ||
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 502004003236 Country of ref document: DE Date of ref document: 20070426 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070614 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070625 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070814 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20070814 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 |
|
26N | No opposition filed |
Effective date: 20071217 |
|
BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 20070831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070615 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070817 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080831 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070817 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070614 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070915 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20070314 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20160819 Year of fee payment: 13 Ref country code: DE Payment date: 20160822 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20160822 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502004003236 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20170817 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20180430 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170817 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20180301 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170831 |