EP0757725B1 - Composition et procede pour traiter la surface de metaux alumineux - Google Patents
Composition et procede pour traiter la surface de metaux alumineux Download PDFInfo
- Publication number
- EP0757725B1 EP0757725B1 EP95915455A EP95915455A EP0757725B1 EP 0757725 B1 EP0757725 B1 EP 0757725B1 EP 95915455 A EP95915455 A EP 95915455A EP 95915455 A EP95915455 A EP 95915455A EP 0757725 B1 EP0757725 B1 EP 0757725B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- polymer
- composition
- surface treatment
- seconds
- 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 abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 64
- 150000002739 metals Chemical class 0.000 title claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 36
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 34
- 238000005507 spraying Methods 0.000 claims description 12
- 239000003352 sequestering agent Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims 1
- 230000001939 inductive effect Effects 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 abstract description 94
- 229940085991 phosphate ion Drugs 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 150000002500 ions Chemical class 0.000 description 27
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 24
- 238000005260 corrosion Methods 0.000 description 24
- 230000007797 corrosion Effects 0.000 description 24
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 239000003973 paint Substances 0.000 description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000007921 spray Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910019142 PO4 Inorganic materials 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 12
- -1 phenol compound Chemical class 0.000 description 11
- 229940048086 sodium pyrophosphate Drugs 0.000 description 11
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- 238000009472 formulation Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 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 4
- 238000007654 immersion Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007739 conversion coating Methods 0.000 description 3
- KHEMNHQQEMAABL-UHFFFAOYSA-J dihydroxy(dioxo)chromium Chemical compound O[Cr](O)(=O)=O.O[Cr](O)(=O)=O KHEMNHQQEMAABL-UHFFFAOYSA-J 0.000 description 3
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- XFNGYPLLARFULH-UHFFFAOYSA-N 1,2,4-oxadiazetidin-3-one Chemical compound O=C1NON1 XFNGYPLLARFULH-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical compound [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000010736 Chelating Activity Effects 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- C23C22/07—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 phosphates
- C23C22/23—Condensed phosphates
-
- 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
- C23C22/07—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 phosphates
Definitions
- This invention relates to a novel composition and method for treating the surface of aluminiferous metals in order thereby to provide such surfaces, prior to their being painted, with an excellent corrosion resistance and paint adherence.
- This invention may be effectively applied, inter alia, to the surface treatment of drawn-and-ironed (hereinafter usually abbreviated "Dl") aluminum cans.
- Dl drawn-and-ironed
- the surface treatment composition and method according to the present invention are particularly effective in providing the surface of such cans, prior to the painting or printing thereof, with an excellent corrosion resistance and paint adherence and also with the excellent slideability required for smooth conveyor transport of the can (abbreviated below simply as “slideability").
- Liquid compositions which hereinafter are often called “baths” for brevity, even though they may be used by spraying or other methods of establishing contact than immersion, that are useful for treating the surface of aluminiferous metals, defined as aluminum and its alloys that contain at least 45% by weight of aluminum, may be broadly classified into chromate-type treatment baths and non-chromate-type treatment baths.
- the chromate-type surface treatment baths typically are divided into chromic acid chromate conversion treatment baths and phosphoric acid chromate conversion treatment baths. Chromic acid chromate conversion treatment baths were first used in about 1950 and are still in wide use at present for the surface treatment of, for example, heat exchanger fins and the like.
- Chromic acid chromate conversion treatment baths contain chromic acid (CrO 3 ) and hydrofluoric acid (HF) as their essential components and may also contain a conversion accelerator. These baths form a coating that contains small amounts of hexavalent chromium.
- the phosphoric acid chromate conversion treatment bath was invented in 1945 (see U.S. Patent 2,438,877). This conversion treatment bath contains chromic acid (CrO 3 ), phosphoric acid (H 3 PO 4 ), and hydrofluoric acid (HF) as its essential components.
- the main component in the coating produced by this bath is hydrated chromium phosphate (CrPO 4 •4 H 2 O). Since this conversion coating does not contain hexavalent chromium, this bath is still in wide use at present as, for example, a paint undercoat treatment for the lid and body of beverage cans.
- the treatment bath taught in Japanese Patent Application Laid Open [Kokai or Unexamined] Number Sho 52-131937 [131,937/1977] is typical of the non-chromate-type conversion treatment baths.
- Treatment of aluminiferous metal surfaces with this non-chromate-type conversion treatment bath produces thereon a conversion film whose main component is zirconium and/or titanium oxide.
- the surface of Dl aluminum cans is at present treated mainly with the above-described phosphoric acid chromate surface treatment baths and zirconium-containing non-chromate surface treatment baths.
- the outside bottom surface of Dl aluminum cans is not painted, but is subjected to high-temperature sterilization. If its corrosion resistance is poor, the aluminum will become oxidized at this point and a blackening discoloration will occur, a phenomenon which is generally known as "blackening". In order to prevent blackening, the coating produced by surface treatment must itself, even when unpainted, exhibit a high corrosion resistance.
- This invention relates to a surface treatment agent for metal cans, wherein said surface treatment agent contains water-soluble organic substance selected from phosphate esters, alcohols, monovalent and polyvalent fatty acids, fatty acid derivatives, and mixtures of the preceding. While this method does serve to increase the slideability of aluminum cans, it affords no improvement in corrosion resistance or paint adherence.
- the invention described in Japanese Patent Application Laid Open [Kokai or Unexamined] Number Hei 5-239434 [239,434/1993] is another method directed to improving the slideability of aluminum cans.
- This invention is characterized by the use of phosphate esters. This method does yield an improved slideability, but again it affords no improvements in corrosion resistance or paint adherence.
- the present invention is directed to solving the problems described above for the prior art.
- the present invention introduces a composition and method for treating the surface of aluminiferous metal which are able to provide the surface of aluminiferous metal with an excellent corrosion resistance and paint adherence.
- said composition and method When applied in particular to Dl aluminum cans, said composition and method impart thereto an excellent slideability in combination with an excellent corrosion resistance and paint adherence.
- a composition according to the present invention for treating the surface of aluminiferous metal characteristically comprises, preferably consists essentially of, or more preferably consists of, water and, in parts by weight:
- each polymer molecule (I) must contain at least one Z moiety-substituted phenyl ring. This average value for the number of Z moieties substituted on each phenyl ring in the polymer molecules of total component (C) is hereinafter referred to as the average value for Z moiety substitution.
- compositions according to the invention as described above may be either working compositions, suitable for directly treating aluminiferous metal substrates, or they may be concentrate compositions, which are useful for preparing working compositions, usually by dilution of the concentrate compositions with water, and optionally, adjustment of the pH of the resulting working composition.
- a method according to the present invention for treating the surface of aluminiferous metal characteristically comprises contacting the surface of aluminiferous metal with a surface treatment bath containing the above-described surface treatment composition according to the present invention, then rinsing the treated surface with water, and subsequently drying the surface by heating.
- the bath preferably has a pH value of 6.5 or less, preferably 2.0 to 6.5, the total time of contacting the metal to be treated preferably is from 5 to 60 seconds, and the temperature during its contact with the aluminiferous metal being treated preferably is from 30°C to 65°C.
- the reactivity of the bath may be insufficient below 30°C, preventing the formation of a good-quality film.
- the surface treatment method according to the present invention may be implemented by immersing the aluminiferous metal, preferably for 5 to 60 seconds, in the above described surface treatment bath.
- the surface treatment method according to the present invention may also be implemented by spraying the above-described surface treatment bath onto the surface of the aluminiferous metal, preferably at least twice, and preferably with a nonspray interval of from 2 to 5 seconds between each period of continuous spraying and the next period of continuous spraying if there is one.
- the occurrence of the pH increase in the vicinity of the interface with the surface, which is required for proper coating formation, is less reliable when spray treatment is carried out by continuously spraying the bath, and in some cases a satisfactory film formation will not occur. It is for this reason that use of an intermittent spray is preferred.
- the total of the spray and nonspray interval time periods preferably is from 5 to 60 seconds.
- the reaction may be inadequate and a highly corrosion-resistant coating may not be produced when the total contact time is less than 5 seconds. Lengthy total contact times in excess of 60 seconds usually produce no additional improvements in performance and are more expensive.
- a surface treatment composition according to the present invention is an acidic aqueous solution whose essential ingredients are phosphate ion, condensed phosphate ion, and water-soluble polymer with the above-specified chemical structure.
- Phosphoric acid H 3 PO 4
- sodium phosphate Na 3 PO 4
- the phosphate ion content in the above-described formulation ranges from 1 to 30 parts by weight (hereinafter often abbreviated "pbw"), while the preferred range is from 1 to 5 pbw. Reaction between the surface treatment bath and the metal surface will be insufficient and film formation often will be inadequate when the phosphate ions content in the above-described formulation is less than 1 pbw. While a good-quality film is formed with more than 30 pbw of phosphate ions, the high cost of the resulting treatment bath makes such levels economically undesirable.
- the condensed phosphate ions used in the present invention conform to the general chemical formula H (p+1-q) P p O (3p+1) -q , where p represents a positive integer that is 2 or greater and q represents a positive integer that is from 1 to (p+1); examples are pyrophosphate ions, tripolyphosphate ions, tetrapolyphosphate ions, and the like.
- Either the condensed phosphoric acid or its neutral or acid salt can be used as the condensed phosphate ion source for the surface treatment composition according to the present invention.
- any of pyrophosphoric acid H 4 P 2 O 7
- disodium diacidpyrophosphate Na 2 H 2 P 2 O 7
- trisodium acidpyrophosphate Na 3 HP 2 O 7
- tetrasodium pyrophosphate Na 4 P 2 O 7
- the condensed phosphate ions content in the above-described formulation for the surface treatment composition according to the present invention measured as its stoichiometric equivalent of completely ionized condensed phosphate anions conforming to the formula P p O (3p+1) -(p+2) , where p and q have the same meanings as above, ranges from 0.1 to 10 pbw, while the preferred range is from 0.5 to 3.0 pbw.
- Surface treatment baths prepared using less than 0.1 pbw condensed phosphate ion in the above-described formulation usually have only a weak etching activity and provide inadequate film formation. On the other hand, at more than 10 pbw the etching activity generated by the resulting surface treatment bath is too strong, so that the film-forming reactions are inhibited.
- Polymer according to formula (I) with n less than 2 yields only an insufficient improvement in the corrosion resistance of the resulting surface coating.
- the stability of the corresponding surface treatment composition and surface treatment bath is sometimes inadequate and practical problems often ensue in the case of polymer (I) with n greater than 50.
- the polymer usually is insufficiently water soluble when the average value for Z moiety substitution is below 0.2; this results in an insufficiently stable surface treatment concentrate and/or surface treatment bath.
- the average value for Z moiety substitution exceeds 1.0 (substitution of a phenyl ring by 2 or more moieties Z)
- the resulting polymer becomes so soluble in water that formation of an adequately protective surface film is impeded.
- the alkyl and hydroxyalkyl moieties encompassed by R 1 , R 2 , R 3 , R 4 , and R 5 in formulas (II) and (III) should contain from 1 to 10 carbon atoms each.
- the polymer molecule becomes bulky when this number of carbons exceeds 10; this results in a coarse coating and thereby in an insufficient improvement in the corrosion resistance.
- the content of water-soluble polymer (I) in the above-described formulation for the surface treatment composition according to the present invention ranges from 0.1 to 20 pbw, while the range from 0.5 to 5 pbw is preferred.
- the formation of a coating on the metal surface by the corresponding surface treatment bath often becomes quite problematic when the content of the water-soluble polymer in the above-described formulation is below 0.1 pbw. Values above 20 pbw are economically undesirable due to the increased cost of the surface treatment composition and surface treatment method.
- the pH of the surface treatment composition according to the present invention is not narrowly restricted, but adjustment of the pH to values no greater than 6.5, more preferably also not less than 2.0, is generally preferred.
- the method according to the present invention is implemented by the preparation of a working surface treatment bath using the above-described surface treatment composition (generally by dilution of a concentrate with water).
- the pH of the working surface treatment bath at this point is adjusted if necessary to values no greater than 6.5 and preferably to 2.0 to 6.5.
- the polymer conforming to formula (I) in the surface treatment bath has a pronounced tendency to deposit or precipitate at a surface treatment bath pH above 6.5; this results in an unsatisfactory stability and service life for the treatment bath.
- the pH is below 2.0, the surface treatment bath may etch the metal surface too severely, which can impair formation of the surface coating.
- the pH of the surface treatment bath may be adjusted using an acid, e.g., phosphoric acid, nitric acid, hydrochloric acid, and the like, or by using alkali, e.g., 'sodium hydroxide, sodium carbonate, ammonium hydroxide, and the like.
- Hydrofluoric acid may be used to adjust the pH when waste water treatment presents no problems.
- a precipitate may be produced in some cases due to the formation of a complex between polymer (I) and the aluminum ions.
- An aluminum sequestrant is preferably added to the treatment bath in such cases. Suitable as said aluminum sequestrant are, for example, ethylene diamine tetraacetic acid, Cy-DTA, triethanolamine, gluconic acid, heptogluconic acid, oxalic acid, tartaric acid, malic acid, and organophosphonic acids, but the particular sequestrant selection is not critical. Hydrofluoric acid may be used as the sequestrant when it presents no problems for waste water treatment.
- a process according to the present invention preferably is performed by contacting the surface of aluminiferous metal with a surface treatment bath - prepared as described above - at 30° C to 65° C for a total of 5 to 60 seconds. The process then continues with a water rinse of the film formed on the metal surface and drying by heating.
- a preferred method of preparation of a surface treatment composition according to the present invention will now be briefly summarized.
- the phosphate ions and condensed phosphate ions are first made up in the above-described proportions and dissolved with thorough stirring in the required amount of water according to the preceding specifications.
- the pH of the resulting solution exceeds 7, it is adjusted to less than or equal to 7 using a suitable acid as described above.
- the water-soluble resin specified by the invention is then added while stirring and completely dissolved, and the pH is adjusted to less than or equal to 6.5 as described above.
- the coating formed on the surface of aluminiferous metal is an organic-inorganic composite coating whose main components are phosphate salt and polymer (I). Etching of the metal surface by the phosphate ions and condensed phosphate ions causes a local increase in pH to occur at the interface; this results in deposition of phosphate salt on the metal surface.
- the chelating activity of the amino group in polymer (I) may result in the formation of a coordination compound with the fresh substrate surface exposed by etching.
- the presence of condensed phosphate ions in the surface treatment bath is believed to promote formation of the polymer-metal coordination compound and thereby make possible stable formation of the organic-inorganic composite coating on the surface over a broad pH range.
- An additional polymerization of the polymer present on the surface can be induced by heating the surface coating after its formation.
- the coating is preferably heated in order to produce a higher molecular weight for the polymer on the surface. Suitable heating conditions for this purpose are at least 1 minute and at least 200° C.
- Aluminiferous metal substrates that may be subjected to the method according to the present invention comprise, for example, the sheet, bar, tube, wire, and like shapes, of aluminum and its alloys, e.g., aluminum-manganese alloys, aluminum-magnesium alloys, aluminum-silicon alloys, and the like. There are absolutely no limitations on the dimensions or shape of the aluminiferous metal.
- the polymer composition according to the present invention may contain a preservative or antimold agent. These function to inhibit putrefaction or mold growth when the surface treatment bath is used or stored at low temperatures. Hydrogen peroxide is a specific example in this regard.
- the corrosion resistance of the unpainted parts of the Dl aluminum cans was evaluated based on the degree of discoloration (blackening) after immersion of treated Dl aluminum cans in boiling tap water for 30 minutes. The results of this test are reported on the following scale:
- the paint adherence was tested as follows. The surface of the treated can was coated to a paint film thickness of 5 to 7 micrometers with an epoxy-urea can paint. This was followed by baking for 4 minutes at 215° C. A 5 millimeter (hereinafter usually abbreviated "mm") x 150 mm strip was then cut from the painted can and hot-press bonded with polyamide film to give a test specimen. The test specimen thus prepared was subjected to a 180° peel test, during which the peel strength was measured.
- mm millimeter
- peel strength values in this test are indicative of a better paint adherence, and peel strength values equal to or greater than 4.0 kilograms-force per 5 millimeters of width (hereinafter usually abbreviated as "kgf/5mm") are generally regarded as excellent from the standpoint of practical applications.
- the slideability was evaluated by measuring the static friction coefficient on the outside surface of the can. Lower values for the static friction coefficient are indicative of a better siideability, and values less than or equal to 1.0 are generally regarded as excellent.
- DI aluminum cans fabricated by the DI processing of A3004 aluminum alloy sheet were cleaned by first degreasing with a 60-second spray at 75° C of an 8 % aqueous solution of PALKLINTM 500 acidic degreaser manufactured by Nihon Parkerizing Company, Limited and then rinsing with water. The cleaned surface was subsequently sprayed with Surface Treatment Bath 1 (composition given below) heated to 60° C. The spray treatment consisted of 3 sprays of 5 seconds each separated by 5 second intervals for a total of 25 seconds.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 20 seconds in Surface Treatment Bath 2 (composition given below) heated to 60° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Surface Treatment Bath 2 75 % Aqueous phosphoric acid (H 3 PO 4 ) 10.0 g/L (PO 4 -3 ions: 7.2 g/L) sodium pyrophosphate (Na 4 P 2 O ⁇ 10H 2 O) 3.0 g/L (P 2 O 7 -4 ions: 1.2 g/L) Water-Soluble Polymer 1 0.4 g/L (solids) pH: 3.0 (adjusted with sodium carbonate) Balance: water Water-Soluble Polymer 1 was the same as described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 60 seconds in Surface Treatment Bath 3 (composition given below) heated to 35° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Surface Treatment Bath 3 75 % Aqueous phosphoric acid (H 3 PO 4 ) 20.0 g/L (PO 4 -3 ions: 14.4 g/L) Sodium pyrophosphate (Na 4 P 2 O 7 • 10H 2 O) 6.0 g/L (P 2 O 7 -4 ions: 2.4 g/L) Water-Soluble Polymer 1 8.0 g/L (solids) pH: 6.0 (adjusted with sodium hydroxide) Balance: water Water-Soluble Polymer 1 was the same as described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then sprayed with Surface Treatment Bath 4 (composition given below) heated to 65° C.
- the spray treatment consisted of 3 sprays (6 seconds each) separated by intervals of 2 seconds (total of 22 seconds). This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 30 seconds in Surface Treatment Bath 5 (composition given below) heated to 60° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Surface Treatment Bath 5 75 % Aqueous phosphoric acid (H 3 PO 4 ) 30.0 g/L (PO 4 -3 ions: 21.6 g/L) Sodium tripolyphosphate (Na 5 P 3 O 10 ) 1.2 g/L (P 3 O 10 -5 ions: 0.8 g/L) Water-Soluble Polymer 1 2.0 g/L (solids) pH: 3.5 (adjusted with sodium hydroxide) Balance: water Water-Soluble Polymer 1 was the same as described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then sprayed with Surface Treatment Bath 6 (composition given below) heated to 60° C.
- the spray treatment consisted of 2 sprays of 5 seconds each separated by an interval of 5 seconds for a total of 15 seconds). This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 30 seconds in Surface Treatment Bath 7 (composition given below) heated to 60° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then sprayed with Surface Treatment Bath 8 (composition given below) heated to 60° C.
- the spray treatment consisted of 5 sprays of 4 seconds each separated by intervals of 5 seconds each, for a total of 40 seconds. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Surface Treatment Bath 8 75 % Aqueous phosphoric acid (H 3 PO 4 ) 10.0 g/L (PO 4 -3 ions: 7.2 g/L) Water-Soluble Polymer 1 2.0 g/L (solids) pH: 3.0 (adjusted with sodium carbonate) Balance: water Water-Soluble Polymer 1 was the same as described in Example 1.
- the DI aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 30 seconds in Surface Treatment Bath 9 (composition given below) heated to 60° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Surface Treatment Bath 9 75 % Aqueous phosphoric acid (H 3 PO 4 ) 1.0 g/L (PO 4 -3 ions: 0.72 g/L) Water-Soluble Polymer 1 2.0 g/L (solids) pH: 7.0 (adjusted with sodium hydroxide) Balance: water Water-Soluble Polymer 1 was the same as described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 5 seconds in Surface Treatment Bath 10 (composition given below) heated to 60° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Surface Treatment Bath 10 75 % Aqueous phosphoric acid (H 3 PO 4 ) 10.0 g/L (PO 4 -3 ions: 7.2 g/L) Sodium pyrophosphate (Na 4 P 2 O 7 • 10H 2 O) 1.0 g/L (P 2 O 7 -4 ions: 0.4 g/L) Water-Soluble Polymer 1 0.05 g/L (solids) pH: 4.0 (adjusted with sodium carbonate) Balance: water Water-Soluble Polymer 1 was the same as described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 20 seconds in Surface Treatment Bath 11 (composition given below) heated to 60° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Surface Treatment Bath 11 95 % Aqueous sulfuric acid (H 2 SO 4 ) 2.0 g/L (SO 4 -2 ions: 1.9 g/L) Sodium pyrophosphate (Na 4 P 2 O 7 • 10H 2 O) 1.0 g/L (P 2 O 7 ion: 0.4 g/L) Water-Soluble Polymer 1 0.05 g/L (solids) pH: 3.5 (adjusted with sodium carbonate) Water-Soluble Polymer 1 was the same as described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 30 seconds in Surface Treatment Bath 12 (composition given below) heated to 60° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then immersed for 30 seconds in Surface Treatment Bath 14 (composition given below) heated to 60° C. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Surface Treatment Bath 14 75 % Aqueous phosphoric acid (H 3 PO 4 ) 1.0 g/L (PO 4 -3 ions: 0.72 g/L) Sodium pyrophosphate (Na 4 P 2 O 7 • 10 H 2 O) 1.0 g/L (P 2 O 7 -4 ions: 0.4 g/L) Water-Soluble Polymer 6 2.0 g/L (solids) pH: 4.0 (adjusted with sodium hydroxide) Balance: water Water-Soluble Polymer 6 had the following formula (V) (resin described in Japanese Patent Application Laid Open [Kokai or Unexamined] Number Hei 2-608):
- the Dl aluminum cans were cleaned according to the procedure described in Example 1 and then sprayed with the 2% aqueous solution of a non-chromate surface treatment agent (brand name ALO DINE® 404 non-chromate surface treatment agent, manufactured by Nihon Parkerizing Company, Limited, heated to 40° C.
- This spray treatment consisted of 3 sprays of 5 seconds each separated by 5 second intervals for a total of 25 seconds. This treatment was followed by rinsing with water and drying according to the procedure described in Example 1.
- Examples 1 to 7 which used surface treatment compositions and surface treatment methods according to the present invention, yielded surface-treated metals with an excellent blackening resistance, excellent adherence, and excellent slideability. In contrast to this, satisfactory values could not be simultaneously obtained for all these properties (corrosion resistance, paint adherence, and slideability) in the case of the surface-treated metals afforded by surface treatment baths outside the scope of the present invention (Comparative Examples 1 to 8).
- the surface treatment composition and surface treatment method according to the present invention can produce very corrosion-resistant and highly paint-adherent conversion coatings on the surface of aluminiferous metals prior to the painting thereof.
- application of the surface treatment composition according to the present invention to the treatment of Dl aluminum cans results in the formation on the surface of Dl aluminum cans prior to its painting or printing of a very corrosion-resistant and highly paint-adherent film that also provides the excellent slideability required for smooth conveyor transport of the can.
- the surface treatment composition according to the present invention and the surface treatment bath used in the invention method do not contain chromium or fluorine, they have the excellent advantage of reducing the load on waste water treatment.
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)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Claims (10)
- Composition liquide aqueuse pour traiter la surface de métaux contenant de l'aluminium, en l'état ou après dilution avec de l'eau supplémentaire, ladite composition comprenant de l'eau et:(A) de 1 à 30 parties en masse d'ions phosphate;(B) de 0,1 à 10 parties en masse d'ions phosphate condensés; et(C) de 0,1 à 20 parties en masse d'un ou plusieurs polymères hydrosolubles répondant à la formule générale suivante: dans laquelle:(i) X1 et X2, indépendamment l'un de l'autre et aussi d'une unité du polymère [qui est définie par toute partie du polymère qui répond à la formule générale (I) ci-dessus à ceci près que les crochets et l'indice n sont omis] à une autre unité du polymère, représentent chacun un atome d'hydrogène, un groupe alkyle en C1 à C5 ou un groupe hydroxyalkyle en C1 à C5;(ii) Y1 et Y2, indépendamment l'un de l'autre et aussi d'une unité du polymère [comme défini ci-dessus] à une autre, représentent chacun un atome d'hydrogène ou une entité Z qui répond à l'une ou l'autre des formules générales suivantes: [où R1, R2, R3, R4 et R5, indépendamment les uns des autres, représentent chacun un groupe alkyle en C1 à C10 ou un groupe hydroxyalkyle en C1 à C10];(iii) l'entité Z liée à tout cycle phényle individuel dans la molécule de polymère peut être identique à ou différente de l'entité Z liée à tout autre cycle phényle dans la molécule de polymère;(iv) la valeur moyenne du nombre d'entités Z comme substituants sur chaque cycle phényle dans la molécule de polymère est dans le domaine de 0,2 à 1,0;(v) n est un entier ayant une valeur dans le domaine de 2 à 50; et(vi) chaque molécule de polymère de formule générale I contient au moins une entité Z.
- Composition selon la revendication 1 comprenant de 1 à 5 parties en masse d'ions phosphate, de 0,5 à 3 parties en masse d'ions phosphate condensés et de 0,5 à 5 parties en masse de polymère(s) hydrosoluble(s) répondant à la formule générale (I).
- Composition selon la revendication 1 ou la revendication 2 ayant un pH d'au plus 6,5 et comprenant de 1 à 30 g/l d'ions phosphate, de 0,1 à 10 g/l d'ions phosphate condensés et de 0,1 à 20 g/l de polymère(s) hydrosoluble(s) répondant à la formule (I).
- Composition selon la revendication 3 ayant un pH dans le domaine de 2,0 à 6,5.
- Composition selon l'une quelconque des revendications précédentes qui comprend aussi un séquestrant de l'aluminium.
- Procédé pour traiter une surface de métal contenant de l'aluminium, ledit procédé comprenant les étapes de:(I) mise en contact de la surface du métal contenant de l'aluminium pendant une durée de 5 à 60 secondes à une température dans le domaine de 30°C à 65°C avec une composition liquide aqueuse selon l'une quelconque des revendications précédentes;(II) après l'achèvement de l'étape (I), séparation de la surface du métal contenant de l'aluminium d'avec la composition, et rinçage de la surface à l'eau; et (III) séchage de la surface relevée du métal contenant de l'aluminium provenant de l'étape II par chauffage.
- Procédé selon la revendication 6 dans lequel l'étape (I) est accomplie par immersion de la surface du métal contenant de l'aluminium dans la composition.
- Procédé selon la revendication 6 dans lequel l'étape (I) est accomplie par pulvérisation de la composition sur la surface du métal contenant de l'aluminium.
- Procédé selon la revendication 8 dans lequel:la surface du métal contenant de l'aluminium est soumise à la pulvérisation au moins deux fois; les périodes de contact par pulvérisation sont interrompues par des intervalles sans pulvérisation ayant une durée dans le domaine de 2 à 5 secondes; etla durée totale entre l'accomplissement de la première pulvérisation et la fin de la dernière pulvérisation est dans le domaine de 5 à 60 secondes.
- Procédé selon l'une quelconque des revendications 6 à 9 qui comprend aussi l'étape subséquente d'induire une polymérisation supplémentaire du polymère présent sur la surface traitée par chauffage de celui-ci pendant une durée d'au moins 1 minute à une température d'au moins 200°C.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7721994 | 1994-04-15 | ||
JP77219/94 | 1994-04-15 | ||
JP6077219A JP2771110B2 (ja) | 1994-04-15 | 1994-04-15 | アルミニウム含有金属材料用表面処理組成物および表面処理方法 |
PCT/US1995/003933 WO1995028509A1 (fr) | 1994-04-15 | 1995-04-07 | Composition et procede pour traiter la surface de metaux alumineux |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0757725A1 EP0757725A1 (fr) | 1997-02-12 |
EP0757725A4 EP0757725A4 (fr) | 1997-07-30 |
EP0757725B1 true EP0757725B1 (fr) | 1999-09-08 |
Family
ID=13627747
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95915455A Expired - Lifetime EP0757725B1 (fr) | 1994-04-15 | 1995-04-07 | Composition et procede pour traiter la surface de metaux alumineux |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0757725B1 (fr) |
JP (1) | JP2771110B2 (fr) |
KR (1) | KR0179685B1 (fr) |
CN (1) | CN1092246C (fr) |
AT (1) | ATE184331T1 (fr) |
BR (1) | BR9507365A (fr) |
CA (1) | CA2187795A1 (fr) |
DE (1) | DE69512049T2 (fr) |
ES (1) | ES2136844T3 (fr) |
MY (1) | MY113052A (fr) |
TW (1) | TW404975B (fr) |
WO (1) | WO1995028509A1 (fr) |
ZA (1) | ZA953031B (fr) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997003226A1 (fr) * | 1995-07-10 | 1997-01-30 | Nippon Paint Co., Ltd. | Traitements de surface de metaux, procede de traitement de surface de metaux et materiau metallique ayant subi un traitement de surface |
JP3620893B2 (ja) * | 1995-07-21 | 2005-02-16 | 日本パーカライジング株式会社 | アルミニウム含有金属用表面処理組成物及び表面処理方法 |
US6059896A (en) * | 1995-07-21 | 2000-05-09 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
JP3544761B2 (ja) * | 1995-10-13 | 2004-07-21 | 日本パーカライジング株式会社 | アルミニウム含有金属材料用表面処理組成物および表面処理方法 |
DE19621184A1 (de) * | 1996-05-28 | 1997-12-04 | Henkel Kgaa | Zinkphosphatierung mit integrierter Nachpassivierung |
JPH101782A (ja) * | 1996-06-13 | 1998-01-06 | Nippon Paint Co Ltd | 金属表面処理剤、処理方法及び表面処理された金属材料 |
JPH1046101A (ja) * | 1996-08-01 | 1998-02-17 | Nippon Parkerizing Co Ltd | 金属材料の表面にフィルムラミネート用下地皮膜を形成させた被覆金属材料、およびその製造方法 |
JPH10182916A (ja) * | 1996-10-21 | 1998-07-07 | Nippon Paint Co Ltd | N複素環を含むアクリル樹脂含有金属表面処理組成物、処理方法及び処理金属材料 |
FR2769325B1 (fr) * | 1997-10-08 | 1999-12-03 | Cfpi Ind | Bain acide pour la phosphatation au zinc de substrats metalliques, concentre pour la preparation du bain et procede de phosphatation le mettant en oeuvre |
JPWO2002061175A1 (ja) * | 2001-01-31 | 2004-06-03 | 日本パーカライジング株式会社 | 金属材料用表面処理剤および表面処理方法 |
JP2004076024A (ja) * | 2002-08-09 | 2004-03-11 | Nippon Paint Co Ltd | アルミニウム系基材の処理方法及び製品 |
JP2010013677A (ja) | 2008-07-01 | 2010-01-21 | Nippon Parkerizing Co Ltd | 金属構造物用化成処理液および表面処理方法 |
CN102983419A (zh) * | 2011-09-07 | 2013-03-20 | 崔骥 | 一种接地器件以及接地方法 |
CN106591817B (zh) * | 2016-11-08 | 2019-01-29 | 高林 | 无重金属物排放钢铁表面处理液及其制备方法 |
WO2019074068A1 (fr) * | 2017-10-12 | 2019-04-18 | 日本パーカライジング株式会社 | Agent de traitement de surface, procédé de production de matériau d'alliage d'aluminium pour canettes, ledit matériau d'alliage d'aluminium comportant un film de revêtement traité en surface, et corps de canette d'alliage d'aluminium et couvercle de canette utilisant celui-ci |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4433015A (en) * | 1982-04-07 | 1984-02-21 | Parker Chemical Company | Treatment of metal with derivative of poly-4-vinylphenol |
US4795506A (en) * | 1986-07-26 | 1989-01-03 | Detrex Corporation | Process for after-treatment of metals using 2,2-bis(4-hydroxyphenyl)alkyl poly derivatives |
JPH03207766A (ja) * | 1990-01-10 | 1991-09-11 | Nippon Parkerizing Co Ltd | ぶりきdi缶の表面処理方法 |
AU647498B2 (en) * | 1990-06-19 | 1994-03-24 | Henkel Corporation | Liquid composition and process for treating aluminium or tin cans to impart corrosion resistance and reduced friction coefficient |
JPH04187782A (ja) * | 1990-11-21 | 1992-07-06 | Nippon Parkerizing Co Ltd | ぶりきdi缶用表面処理液 |
-
1994
- 1994-04-15 JP JP6077219A patent/JP2771110B2/ja not_active Expired - Lifetime
-
1995
- 1995-04-07 CA CA002187795A patent/CA2187795A1/fr not_active Abandoned
- 1995-04-07 ES ES95915455T patent/ES2136844T3/es not_active Expired - Lifetime
- 1995-04-07 BR BR9507365A patent/BR9507365A/pt not_active IP Right Cessation
- 1995-04-07 EP EP95915455A patent/EP0757725B1/fr not_active Expired - Lifetime
- 1995-04-07 AT AT95915455T patent/ATE184331T1/de not_active IP Right Cessation
- 1995-04-07 DE DE69512049T patent/DE69512049T2/de not_active Expired - Fee Related
- 1995-04-07 WO PCT/US1995/003933 patent/WO1995028509A1/fr active IP Right Grant
- 1995-04-12 MY MYPI95000943A patent/MY113052A/en unknown
- 1995-04-12 TW TW084103586A patent/TW404975B/zh not_active IP Right Cessation
- 1995-04-12 ZA ZA953031A patent/ZA953031B/xx unknown
- 1995-04-14 CN CN95103820A patent/CN1092246C/zh not_active Expired - Fee Related
- 1995-04-15 KR KR1019950008908A patent/KR0179685B1/ko not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR950029375A (ko) | 1995-11-22 |
CN1112166A (zh) | 1995-11-22 |
DE69512049T2 (de) | 2000-04-27 |
WO1995028509A1 (fr) | 1995-10-26 |
EP0757725A4 (fr) | 1997-07-30 |
KR0179685B1 (ko) | 1999-02-18 |
CA2187795A1 (fr) | 1995-10-26 |
AU685938B2 (en) | 1998-01-29 |
EP0757725A1 (fr) | 1997-02-12 |
JPH07278836A (ja) | 1995-10-24 |
ES2136844T3 (es) | 1999-12-01 |
ATE184331T1 (de) | 1999-09-15 |
DE69512049D1 (de) | 1999-10-14 |
ZA953031B (en) | 1995-12-21 |
AU2232995A (en) | 1995-11-10 |
TW404975B (en) | 2000-09-11 |
MY113052A (en) | 2001-11-30 |
CN1092246C (zh) | 2002-10-09 |
BR9507365A (pt) | 1997-10-07 |
JP2771110B2 (ja) | 1998-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU684929B2 (en) | Composition and process for treating the surface of aluminiferous metals | |
EP0757725B1 (fr) | Composition et procede pour traiter la surface de metaux alumineux | |
US6361833B1 (en) | Composition and process for treating metal surfaces | |
WO1995033869A1 (fr) | Composition et procede de traitement de la surface de metaux alumineux | |
EP0846192B1 (fr) | Composition et procede de traitement de surface de metaux aluminiferes | |
EP0755419B1 (fr) | Composition polymere et procede de traitement de surfaces metalliques | |
MXPA98000581A (en) | Composition and process for treating metal surface aluminife | |
AU4469796A (en) | Low sludging composition and process for treating aluminum and its alloys | |
EP1230422A1 (fr) | Procede et composition de traitement pour des metaux | |
US6059896A (en) | Composition and process for treating the surface of aluminiferous metals | |
EP0558581B1 (fr) | Composition et procede pour le traitement de surfaces | |
EP0533823B1 (fr) | Composition liquide et procede de traitement de boites en aluminium ou en fer blanc destines a ameliorer la resistance a la corrosion et a reduire le coefficient de friction | |
US5370909A (en) | Liquid composition and process for treating aluminum or tin cans to impart corrosion resistance and mobility thereto | |
US6153022A (en) | Composition and process for surface treatment of aluminum and its alloys | |
US5728234A (en) | Composition and process for treating the surface of aluminiferous metals | |
EP0516700B1 (fr) | Procede et composition de traitement de conversion pour aluminium et alliages d'aluminium | |
US6200693B1 (en) | Water-based liquid treatment for aluminum and its alloys | |
AU709612B2 (en) | Composition and process for surface treatment of aluminum and its alloys | |
US5904784A (en) | Composition and method for treating the surface of aluminiferous metals | |
AU685938C (en) | Composition and process for treating the surface of aluminiferous metals | |
US6369149B1 (en) | Aqueous treatment process and bath for aluminiferous surfaces | |
JP3587590B2 (ja) | ぶりきdi缶表面処理用水性組成物および表面処理方法 | |
WO1999002758A1 (fr) | Bain et procede de traitement aqueux pour surfaces aluminiferes | |
US5965205A (en) | Composition and process for treating tinned surfaces | |
WO1998052699A1 (fr) | Traitement liquide a base aqueuse pour l'aluminium et ses alliages |
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: 19961112 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT DE DK ES FR GB IT NL SE |
|
A4 | Supplementary search report drawn up and despatched |
Effective date: 19970617 |
|
AK | Designated contracting states |
Kind code of ref document: A4 Designated state(s): AT DE DK ES FR GB IT NL SE |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
17Q | First examination report despatched |
Effective date: 19980629 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT DE DK ES FR GB IT NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19990908 Ref country code: AT 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: 19990908 |
|
REF | Corresponds to: |
Ref document number: 184331 Country of ref document: AT Date of ref document: 19990915 Kind code of ref document: T |
|
ITF | It: translation for a ep patent filed | ||
REF | Corresponds to: |
Ref document number: 69512049 Country of ref document: DE Date of ref document: 19991014 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2136844 Country of ref document: ES Kind code of ref document: T3 |
|
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: 19991208 |
|
ET | Fr: translation filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20000320 Year of fee payment: 6 |
|
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 |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20011101 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20011101 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20030416 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20030418 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20030430 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20030508 Year of fee payment: 9 |
|
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: 20040407 |
|
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 NON-PAYMENT OF DUE FEES Effective date: 20040410 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041103 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
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: 20041231 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
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 NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20050407 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20040410 |