WO1997013887A1 - Composition and process for surface treatment of aluminum and its alloys - Google Patents
Composition and process for surface treatment of aluminum and its alloys Download PDFInfo
- Publication number
- WO1997013887A1 WO1997013887A1 PCT/US1996/016132 US9616132W WO9713887A1 WO 1997013887 A1 WO1997013887 A1 WO 1997013887A1 US 9616132 W US9616132 W US 9616132W WO 9713887 A1 WO9713887 A1 WO 9713887A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- component
- water
- composition
- surface treatment
- phosphoric acid
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 83
- 238000004381 surface treatment Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims description 34
- 229910052782 aluminium Inorganic materials 0.000 title description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title description 12
- 239000000956 alloy Substances 0.000 title description 5
- 230000008569 process Effects 0.000 title description 5
- 229910045601 alloy Inorganic materials 0.000 title description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- -1 phosphoric acid ions Chemical class 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 235000011007 phosphoric acid Nutrition 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229910001868 water Inorganic materials 0.000 claims description 32
- 238000011282 treatment Methods 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000006467 substitution reaction Methods 0.000 claims description 11
- 150000002739 metals Chemical class 0.000 claims description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002826 nitrites Chemical class 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims 2
- 239000012895 dilution Substances 0.000 claims 2
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 239000003973 paint Substances 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000007739 conversion coating Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 238000005530 etching Methods 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000009471 action Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- 239000002253 acid Chemical class 0.000 description 7
- 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 7
- 239000007921 spray Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 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
- 239000007769 metal material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003352 sequestering agent Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005238 degreasing Methods 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
- 238000005187 foaming Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- KHEMNHQQEMAABL-UHFFFAOYSA-J dihydroxy(dioxo)chromium Chemical compound O[Cr](O)(=O)=O.O[Cr](O)(=O)=O KHEMNHQQEMAABL-UHFFFAOYSA-J 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification 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
- 238000010422 painting Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 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
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 241001600451 Chromis Species 0.000 description 1
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-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
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 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
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000013361 beverage Nutrition 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
- 229940003372 compro Drugs 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical group O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- WIKYUJGCLQQFNW-UHFFFAOYSA-N prochlorperazine Chemical compound C1CN(C)CCN1CCCN1C2=CC(Cl)=CC=C2SC2=CC=CC=C21 WIKYUJGCLQQFNW-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000008237 rinsing water Substances 0.000 description 1
- 239000010731 rolling oil Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—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
- C23C22/08—Orthophosphates
- C23C22/10—Orthophosphates containing oxidants
-
- 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
- C23C22/73—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 characterised by the process
- C23C22/76—Applying the liquid by spraying
Definitions
- the present invention relates to a novel composition and method for the surface treatment of aluminum and its alloys, such as aluminum-manganese al ⁇ loys, aluminum-magnesium alloys, and aluminum-silicon alloys, that contain at least 45 % by weight of aluminum, all of these being jointly hereinafter briefly designated as "aluminiferous metals", in which the surface of an aiuminiferous metal is provided with better corrosion resistance and adhesion to paint or syn ⁇ thetic resin film before said surface is painted or is laminated to a synthetic resin film.
- aluminiferous metals in which the surface of an aiuminiferous metal is provided with better corrosion resistance and adhesion to paint or syn ⁇ thetic resin film before said surface is painted or is laminated to a synthetic resin film.
- Chromate treatments are presently being used for the most part in the in ⁇ dustrial surface treatment of aluminum coils.
- Typical examples of chromate treatments include chromic acid chromate conversion treatments and phosphoric acid chromate conversion treatments.
- Chromic acid chromate conversion treat ⁇ ment solutions were put to practical use around 1950 and are still widely used for fin members and the like in heat exchangers.
- This chemical conversion treat ⁇ ment solution consists primarily of chromic acid (CrO 3 ) and hydrofluoric acid (HF), with a promoter added, and forms a film containing some hexavalent chromium.
- Phosphoric acid chromate conversion treatment solutions are based on the invention in US Patent 2,438,877 from 1945.
- This chemical conversion treatment solution contains chromic acid (CrO 3 ), phosphoric acid (H 3 PO 4 ), and hydrofluoric acid (HF).
- the film that is formed consists primarily of hydrated chromium phosphate (CrPO 4 H 2 O). Since the film does not contain hexavalent chromium, it is widely used at present for the paint undercoating treatment of beverage can bodies, particularly drawn and ironed aluminum cans and lids. However, in the interests of environmental protection, a need has arisen for sur ⁇ face treatment solutions which contain no chromium.
- the present invention is intended to remedy the aforementioned draw ⁇ backs of the conventional technology, and more specifically is intended to offer a novel composition and method for surface treating aluminiferous metals, which allow the surface of an aluminiferous metal to be provided in a short period of time with better corrosion resistance and paint or laminated film adhesion, 5 without the use of chromium, and which also allow a film with better workability to be formed.
- an aqueous liquid surface treatment composition containing phosphoric acid ions, condensed phosphoric acid ions, an oxidizer, o and a water-soluble polymer with a specific structure and that has a pH within a specific range forms a film with better corrosion resistance and paint or lamin- ated film adhesion, as well as better workability, when a surface of an aluminifer ⁇ ous metal is brought into contact with such a surface treatment composition.
- composition according to the invention for the surface treatment of an aluminiferous metal comprises, preferably consists essentially of, or more preferably consists of, water and:
- each of X 1 and X 2 independently of each other and independently from one unit ofthe polymer, said unit being defined as represented by a modification of formula (I) above in which the square brackets and the subscript n are omit ⁇ ted, to another unit of the polymer represents a hydrogen atom, a C, to C 5 alkyl group, or a C, to C 5 hydroxyalkyl group; each of Y 1 and Y 2 independently of one another and independently for each unit of the polymer represents a hydrogen atom or a moiety "Z" which conforms to one ofthe following general formulas (II) and (III):
- each of R ⁇ R 2 , R 3 , R 4 , and R 5 in each of general formulas (II) and (III) independently represents a C, to C 10 alkyl group or a C, to C 10 hydroxyalkyl group; one moiety "Z” may be identical to or may differ from any other moiety "Z” in the polymer molecule, so long as each "Z” con ⁇ forms to one ofthe general formulas (II) and (III); and n represents a posi ⁇ 0 tive integer, which may be the same as or different from the value of n for any other poiymer molecule; in addition, in component (D) as a whole: the average value for the number of Z moieties substituted on each phen ⁇ yl ring in the polymer molecule 1 , which may be referred to hereinafter as "the average value for Z moiety substitution", is from 0.2 to 1.0; the av ⁇ 5 erage value of n, which may be referred to hereinafter as "the average
- 25 mer (D) are present in a weight ratio (A):(B):(C):(D) of 0.1 to 30 : 0.1 to 10 : 0.1
- a composition according to the invention may be immediately suitable for use as such in treating aluminiferous metal, in which instance it is called a working composition, or it may be suitable for diluting with additional water to form a working composition, in which instance it is called a concentrate composition. Some compositions are suitable for both purposes.
- a process for the surface treatment of an aluminiferous metal according to the present invention is characterized by the fact that an aqueous surface treatment solution which contains the aforementioned surface treatment compo ⁇ sition pertaining to the present invention and which has a pH value no more than 6.5 is brought into contact with the surface of an aluminiferous metal, preferably for a total of 1 to 60 seconds, and the surface which has thus contacted prefer ⁇ ably is then rinsed with water, and then is dried and preferably heated.
- Orthophosphoric acid having the chemical formula H 3 PO 4 and herein usually designated simply as "phosphoric acid” unless the context requires differ ⁇ entiating it from other phosphoric acids, and any water soluble salt or acid salt of orthophosphoric acid that does not act adversely to the objects of the in ⁇ vention may be used as a source of component (A) of a composition according to the invention as defined above, and any such salt is to be understood, for the purpose of the preferences indicated below, as contributing its full stoichiometric equivalent as orthophosphate ions (i.e., PO 4 "3 ) to the concentration thereof in any composition according to the invention, irrespective of the actual degree of ionization that may prevail in the composition.
- the phosphoric acid ions content ranges from 0.1 to 30 weight parts, and preferably 0.5 to 5 weight parts, per 0.1 to 20 weight parts of water-soluble polymer (D) in the aforementioned ratio.
- a phosphoric acid ions content of less than 0.1 weight part in the aforementioned blend ratio often results in inadequate reactivity between the surface treatment solution and the surface of the metal substrate being coated, as well as in an inadequately formed film. More than 30 weight parts in this ratio does not harm formation of a favorable conversion coating but is uneconomical because of the higher cost of the treatment solution and lack of any offsetting benefit compared with compositions containing somewhat less of this component.
- one or two or more types selected from among pyrophosphoric acid, tripolyphosphoric acid and tetrapolyphosphoric acid, and the salts of all of these acids can be used to provide the condensed phosphoric acid ions in a water-based composition of this invention, but the invention is not limited to the use of these materials.
- Any water soluble source of any phosphate anions that contain at least two atoms of phosphorus each may be used, and is to be under ⁇ stood for the purposes of the preferences below as supplying its full stoichio ⁇ metric equivalent as condensed phosphate anions to the composition used ac- cording to the invention, irrespective of the actual degree of ionization that exists in the composition.
- pyrophosphoric acid H 4 P 2 O 7
- sodium pyro ⁇ phosphate Na 4 P 2 O 7
- like compounds can be used to provide pyrophosphate ions.
- the content of the condensed phosphoric acid ions component (B) ranges from 0.1 to 10 weight parts, and preferably 0.5 to 3.0 weight parts, per 0.1 to 20 weight parts of water-soluble polymer (D).
- a condensed phosphoric acid ions content of less than 0.1 weight part in the aforementioned ratio normally results in a sur ⁇ face treatment solution with weak etching action, preventing a film from being adequately formed.
- a content of more than 10 weight parts usually results in a surface treatment solution with etching action that is too strong, which inhibits the film-forming reaction.
- the oxidizing agent preferably comprises, more preferably consists essentially of, or still more preferably consists of one or more substances selected from the group consisting of hydrogen peroxide, chlorates, and nitrites; the use of hydrogen per ⁇ oxide is most preferred.
- the content of oxidizing agent component (C) in the aforementioned ratio for the surface treatment composition according to the present invention ranges from 0.1 to 10 weight parts, and preferably 2 to 5 weight parts, per 0.1 to 20 weight parts of water-soluble polymer component (D).
- An oxidizing agent content of less than 0.1 weight part usually results in a treat ⁇ ment solution with weak etching action, preventing an adequate film from being formed. More than 10 weight parts usually results in a treatment solution with etching action that is too strong, which inhibits the film-forming reaction.
- the water-soluble polymer used in the present invention is a water-sol ⁇ uble polymer (a term intended herein to include oligomers) that has an average degree of polymerization of 2 to 50, or preferably of 2 to 20, and that contains, preferably consists essentially of, or more preferably consists of (except for end groups) polymer units as described above in connection with general formula (I).
- the alkyl or hydroxyalkyl groups represented by X 1 and X 2 in general formula (I) have 6 or more carbon atoms, the resulting polymer becomes bulky, usually causing steric hindrance and preventing a compact film with good corrosion resistance from being obtained.
- the resulting polymer When the average value for Z substitutions is less than 0.2, the resulting polymer normally has poor water solubility, and the resulting surface treatment composition stability is usually inadequate.
- the average value for Z moiety substitution is more than 1.0, and thus contains a substantial fraction of benzene rings substituted by two or more Z groups, the polymer usually has such a high water solubility that a composition containing it as component (D) has great difficulty in forming a satisfactorily protective surface film.
- the alkyl or hydroxyalkyl groups expressed by R ⁇ R 2 , R 3 , R 4 , and R 5 in general formulas (II) and (III) have 1 to 10 carbon atoms. A number of carbon atoms of 11 or more usually results in a polymer molecule that is too bulky, leading to a film with poor density and insufficient corrosion resistance.
- the content of the water-soluble polymer component (D), in terms of the aforemen- tioned ratios to other components, is 0.1 to 20 weight parts, and preferably 0.5 to 5 weight parts, per 0.1 to 30 weight parts of phosphoric acid ions (A).
- this ratio is less than 0.1 weight part, it is difficult to form a film on the surface of aluminiferous metals with the surface treatment composition, whereas more than 20 weight parts in this ratio is uneconomical because ofthe higher cost ofthe re- suiting surface treatment and lack of any substantial improvement over the results achieved with a composition according to the invention containing 20 or fewer parts in this ratio.
- the pH of a working surface treatment com ⁇ position is preferably no more than 6.5, and even more preferably is between 2.0 and 6.5.
- the pH of the surface treat- s ment composition is higher than 6.5, the polymer of formula (I) in the resulting surface treatment composition tends to precipitate, impairing the treatment com ⁇ position stability and its use life.
- the pH is lower than 2.0, the etching ac ⁇ tion ofthe surface treatment composition on the surface of the metal material is very strong, making it difficult to form a surface film.
- the pH of the surface treat- o ment composition can be adjusted using an acid such as phosphoric acid, nitric acid, and hydrochloric acid, or an alkali such as sodium hydroxide, sodium car ⁇ bonate, and ammonium hydroxide.
- Hydrofluoric acid may be used to adjust the pH when wastewater disposal is not a problem.
- the s aforementioned surface treatment solution preferably has a pH of 2.0 to 6.5 and contains from 1 to 30 grams per liter (hereinafter usually abbreviated as "g/l") of phosphoric acid ions, from 0.1 to 10 g/l of condensed phosphoric acid ions, from 0.1 to 10 g/l of oxidizing agent, and from 0.1 to 20 g/l of water-soluble polymer component (D) as described above.
- g/l grams per liter
- concentration of phosphoric acid 0 ions in a surface treatment composition according to the invention is lower than 0.1 g/l, a surface film is usually inadequately formed, whereas more than 30 g/l is uneconomical because of higher costs.
- the etching action ofthe result ⁇ ing surface treatment composition is usually too weak, and a surface film is in- 5 adequately formed, whereas more than 10 g/l results in a surface treatment com ⁇ position with etching properties that are so strong that the film-forming reaction is hindered.
- the oxidizing agent concentration is lower than 0.1 g/l, the etching action of the resulting surface treatment composition is weak, usually preventing the formation of an adequate film, whereas more than 10 g/l results 0 in a surface treatment composition with etching action that is too high, which hinders the film-forming reaction.
- the concentration of the water-soluble polymer component (D) is lower than 0.1 g/l, the resulting surface treatment composition usually has inadequate film formability, whereas more than 20 g/l is economically disadvantageous because of higher costs.
- an aluminum sequestering agent should be added to the surface treatment composition.
- useful aluminum sequestering agents in ⁇ clude, but are not limited to, ethylene diamine tetra-acetic acid, 1 ,2-cyclohexane- diamine tetra-acetic acid, triethanolamine, gluconic acid, heptogluconic acid, ox ⁇ alic acid, tartaric acid, malic acid, and organophosphonic acids.
- hydrofluoric acid poses no problems for wastewater treatment, it may be used as a sequestering agent.
- a working surface treatment compo- sition as described above is brought into contact, preferably for a total of 1 to 60 seconds and independently preferably at a temperature within a range from 30 to 65 °C, with a surface of an aluminiferous metal.
- the film formed on the sur ⁇ face of the metal material is then preferably rinsed with water, and thereafter preferably is heated and dried.
- Contact between the aluminiferous metal and a working composition may be established by any convenient method, among which immersion of the substrate in a bath of the working composition and spraying the working composition on the metal are most common.
- a contact time of less than 1 second usually results in inadequate formation of a corrosion- resistant film, whereas a contact time of more than 60 seconds yields no greater benefits and thus leads to less operational efficiency.
- the surface treatment composition When a spray treatment is used, the surface treatment composition some ⁇ times foams and thus causes problems in the film that is formed. Although the presence or absence of foaming and the extent of such foaming depends largely on the spraying equipment and conditions, a defoaming agent should be added to the surface treatment composition when foaming is not suitably avoided by modification of the spraying equipment and conditions.
- the adhesion between the resulting film and the paint or laminated film should not be compro ⁇ mised.
- the film formed on the surface ofthe aluminiferous metal in a process ac- cording to the invention is believed to be a film of an organic-inorganic composite consisting primarily of phosphates and water-soluble polymer (resin) (D).
- the metal substrate is etched by the ions of the phosphoric acid and condensed phosphoric acid, at which time the pH becomes elevated in some areas at the interface, resulting in the precipitation of phosphates on the surface.
- the amino groups (included in the groups Z) of the water-soluble polymer (D) have chelat ⁇ ing action, and are believed to form a type ot coordination compound with the re ⁇ generated surface of the metal substrate produced by the etching.
- the organic-inorganic composite film is basically formed as a result of the two afore ⁇ mentioned actions, the additional presence of the condensed phosphoric acid ions in the surface treatment composition appears to allow some water-soluble polymer-metal coordination compound(s) to be more readily formed, thereby al ⁇ lowing a stable organic-inorganic complex film to be formed on the metal surface within a wide pH range.
- the film can be and preferably is heated to allow the polymer from compon ⁇ ent (D) of the working composition according to the invention that was used, and that was inco ⁇ orated into the coating film formed on the surface, to undergo fur ⁇ ther polymerization on the surface. At least one minute at 200 °C (in the normal ambient natural atmosphere) is sufficient for the heating conditions.
- a preferred expanded treatment process step sequence, using a surface treatment composition according to the present invention, is outlined below.
- the surface of the metal material is preferably cleaned so that it is degreased of oil such as rolling oil or the like remaining on the surface of the aluminiferous metal that is being treated. No particular restrictions are imposed on the type of degreasing agent or the degreasing method used in this step.
- the degreased material is then preferably rinsed with water.
- the rinsing is intended to remove the de ⁇ greasing composition from the surface; therefore, any rinsing method may be used, provided that the degreasing composition is removed from the surface.
- the surface treatment of the method according to the present invention is then implemented.
- the surface ofthe aluminiferous metal being treated is the prefer ⁇ ably further rinsed with water.
- This rinsing is intended to remove the surface treatment composition, so any rinsing method may be used, provided that the unreacted surface treatment composition is removed from the surface.
- the heating and drying are intended to dry off the rinsing water, with no narrow re ⁇ strictions imposed on the method, drying temperature, drying time, or the like, although hot air drying or the like is generally useful for industrial purposes.
- the surface of the aluminiferous metal that has been surface treated is then painted or laminated with film.
- the coating formed by a method according to the present invention has good adhesion to paint or laminated films. Since the coating formed by means of the present invention is also flexible, it also has excellent performance after processing such as folding or drawing.
- the aluminiferous metals used in the method according to the present in- vention include forms such as sheets, bars, tubes, wires, and the like. No re ⁇ strictions whatever are imposed on the dimensions and configuration of the met ⁇ al, although the method according to the present invention is especially effective when used on aluminiferous metal coils.
- the corrosion resistance of aluminum materials was evaluated by the following test: Treated aluminum ob ⁇ jects were bent into the shape of a U around a round bar with a diameter of 1 millimeter (hereinafter usually abbreviated as "mm”); these were immersed for 30 minutes in boiling tap water; and the degree of discoloration (darkening) in the bent parts was visually assessed. No darkening was rated as “O”, partial darkening was rated as “ ⁇ ”, and total darkening was rated as "x".
- Paint adhesion was tested in the following manner: Polyvinyl chloride paint for cans was painted to a thickness of between 5 and 10 micrometres (hereinafter usually abbreviated as " ⁇ m") on the surface of treated aluminum, fol- lowed by 1 minute of baking at 260 °C; the samples were cut into rectangles 5 x 150 mm; the painted surfaces were thermally bonded via a polyamide film to form test pieces; the bonded surfaces were separated by the 180 degree peel test method; and the peel strength was evaluated at that time. The greater the peel strength, the better the paint adhesion. In general, a peel strength of 4.0 kilograms-force (hereinafter usually abbreviated as "kgf) or more per 5 mm of width is considered excellent for practical purposes.
- kgf 4.0 kilograms-force
- Used surface treatment composition waste was diluted twenty-fold with water, and the concentration of hexavalent chromium in the thus formed compo- sition was measured. For the purposes of environmental protection, no chromi ⁇ um should be detected.
- JIS Japanese Indus ⁇ trial Standard
- A5182 An aluminum-magnesium alloy sheet (alloy according to Japanese Indus ⁇ trial Standard, hereinafter usually abbreviated as "JIS", A5182) was degreased by spraying with a 2 % aqueous solution of an alkaline degreaser (trade name: O 97/13887 PC17US96/16132
- FINECLEANER® 4377K by Nihon Parkerizing
- the sheet was then sprayed for 3 seconds at 60 °C with Surface Treatment Composition 1 having the ingredients noted below, with the balance being water; it was then rinsed with tap water, then sprayed and washed for 10 seconds with deionized water having a specific resistivity of at least 3,000,000 ohm-centimeters, and was then dried for 2 minutes in a hot air drying furnace at 80 °C.
- composition 1 75 % Phosphoric acid (i.e., H 3 PO 4 ) 10.0 g/l (P0 4 3 : 7.2 g/l) Sodium pyrophosphate (i.e., Na 4 P 2 O 7 *10H 2 O) 3.0 g/l (P 2 O 7 4 : 1.2 g/l) 31 % Hydrogen peroxide in water 10.0 g/l (H 2 O 2 : 3.1 g/l) Polymer (1) - solids part 2.0 g/l pH 4.0 (Adjusted with sodium hydroxide)
- Aluminum alloy materials were degreased and rinsed clean in the same manner as in Example 1 , and they were then treated by immersion for 10 sec ⁇ onds at 40 °C using Surface Treatment Composition 2 having the ingredients shown below, with the balance being water. This treatment was followed by rinsing and drying under the same conditions as in Example 1.
- Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1 , were then spray treated for 1 second at 65 ⁇ C using Surface Treatment Composition 3 containing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in Example 1.
- Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1 , were then spray treated for 30 seconds at 40 °C using Surface Treatment Composition 4 containing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in Example 1.
- Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 5 seconds at 50 °C using
- composition 5 containing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in
- Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1 , and they were then spray treated for 5 seconds at 50 °C using Surface Treatment Composition C1 having the ingredients set forth be ⁇ low, with the balance being water. This treatment was followed by rinsing and drying under the same conditions as in Example 1.
- Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1 , were then spray treated for 2 seconds at 50 °C using a 5 % aqueous solution of a commercially available phosphoric acid chromate type of chemical conversion composition (tradename: ALCHROME® K 702, by Nihon Parkerizing). The treatment was followed by rinsing and drying under the same conditions as in Example 1.
- a commercially available phosphoric acid chromate type of chemical conversion composition (tradename: ALCHROME® K 702, by Nihon Parkerizing). The treatment was followed by rinsing and drying under the same conditions as in Example 1.
- Comparative Example 3 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 10 seconds at 50 °C using a 6 % aqueous solution of a commercially available zirconium phosphate type of chemical conversion composition (tradename: AEROSILTM 404, by Nihon Par ⁇ kerizing). The treatment was followed by rinsing and drying under the same con- ditions as in Example 1.
- AEROSILTM 404 commercially available zirconium phosphate type of chemical conversion composition
- Table 1 shows the results obtained in the evaluations of the above noted Examples 1 through 5 and Comparative Examples 1 through 3.
- the surface treatment composition contained no condensed phosphoric acid ions or oxidizing agent, resulting in a film with in ⁇ adequate corrosion resistance and paint adhesion.
- Comparative Examples 2 and 3 conventional surface treatment compositions were used, resulting in films with low corrosion resistance.
- the wastewater con ⁇ tained hexavalent chromium, while in Comparative Example 3, the paint adhe ⁇ sion was poor.
- the surface treat ⁇ ment composition and method according to the present invention allow a chem ⁇ ical conversion film with better corrosion resistance and paint adhesion to be formed on the surfaces of aluminiferous metals before they are painted.
- the surface treatment composition and method according to the present invention are non-chromium and non-fluorine types, and have the exceptional merit of al ⁇ leviating the burden of wastewater disposal.
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)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
An aqueous liquid surface treatment composition having a pH value not more than 6.5 and containing phosphoric acid ions, condensed phosphoric acid ions, an oxidizing agent, and a water-soluble polymer consisting, except for end groups, of polymer units expressed by formula (I), in a weight ratio of 0.1 to 30 : 0.1 to 10 : 0.1 to 10 : 0.1 to 20 respectively, when brought into contact with an aluminiferous metal surface, rapidly forms on the surface a conversion coating that has good corrosion resistance and adhesion to subsequently applied organic coatings such as paint and is less easily damaged by mechanical stresses than prior art conversion coatings.
Description
Description
COMPOSITION AND PROCESS FOR SURFACE TREATMENT OF ALUMINUM
AND ITS ALLOYS
Technical Field
The present invention relates to a novel composition and method for the surface treatment of aluminum and its alloys, such as aluminum-manganese al¬ loys, aluminum-magnesium alloys, and aluminum-silicon alloys, that contain at least 45 % by weight of aluminum, all of these being jointly hereinafter briefly designated as "aluminiferous metals", in which the surface of an aiuminiferous metal is provided with better corrosion resistance and adhesion to paint or syn¬ thetic resin film before said surface is painted or is laminated to a synthetic resin film. One field in which the present invention may be particularly effectively ap- plied is the surface treatment of aluminiferous coils. Background Art
Chromate treatments are presently being used for the most part in the in¬ dustrial surface treatment of aluminum coils. Typical examples of chromate treatments include chromic acid chromate conversion treatments and phosphoric acid chromate conversion treatments. Chromic acid chromate conversion treat¬ ment solutions were put to practical use around 1950 and are still widely used for fin members and the like in heat exchangers. This chemical conversion treat¬ ment solution consists primarily of chromic acid (CrO3) and hydrofluoric acid (HF), with a promoter added, and forms a film containing some hexavalent chromium. Phosphoric acid chromate conversion treatment solutions are based on the invention in US Patent 2,438,877 from 1945. This chemical conversion treatment solution contains chromic acid (CrO3), phosphoric acid (H3PO4), and hydrofluoric acid (HF). The film that is formed consists primarily of hydrated chromium phosphate (CrPO4 H2O). Since the film does not contain hexavalent chromium, it is widely used at present for the paint undercoating treatment of beverage can bodies, particularly drawn and ironed aluminum cans and lids. However, in the interests of environmental protection, a need has arisen for sur¬ face treatment solutions which contain no chromium. In recent years, the paint-
ing or lamination following such surface treatment has been followed by an in¬ creasingly wide range of shaping processes, with the need for increasingly strin¬ gent levels of processing, but films made from inorganic systems such as chro¬ mate suffer from problems; e.g., the film is broken when bent sharply, prevent- 5 ing adequate performance from being realized, and the like. There is thus strong demand for the development of a technique for forming a flexible film with better corrosion resistance and/or adhesion in articles of manufacture that are shaped after the conversion coating is formed.
Treatment solutions or methods intended to provide the surface of alumin- 0 iferous metals with corrosion resistance and paint adhesion using a water-solu¬ ble resin have been proposed in Japanese Laid-Open Patent Applications 61-91369, 1-172406, 1-177379, 1-177380, 2-608, 2-609, and others. In these conventional treatment methods, the metal surface is treated with a solution con¬ taining a derivative of a polyhydric phenol compound. Problems in these con- s ventional methods, however, are that it is difficult to form a sufficiently stable film in a short period of time on the surface of aluminiferous metal materials, and adequate corrosion resistance cannot be obtained. Disclosure of the Invention
Problems to Be Solved bv the Invention o The present invention is intended to remedy the aforementioned draw¬ backs of the conventional technology, and more specifically is intended to offer a novel composition and method for surface treating aluminiferous metals, which allow the surface of an aluminiferous metal to be provided in a short period of time with better corrosion resistance and paint or laminated film adhesion, 5 without the use of chromium, and which also allow a film with better workability to be formed.
Summary of the Invention
It has been found that an aqueous liquid surface treatment composition containing phosphoric acid ions, condensed phosphoric acid ions, an oxidizer, o and a water-soluble polymer with a specific structure and that has a pH within a specific range forms a film with better corrosion resistance and paint or lamin-
ated film adhesion, as well as better workability, when a surface of an aluminifer¬ ous metal is brought into contact with such a surface treatment composition.
More particularly, a composition according to the invention for the surface treatment of an aluminiferous metal comprises, preferably consists essentially of, or more preferably consists of, water and:
(A) a component of ions of orthophosphoric acid;
(B) a component of ions of condensed phosphoric acid(s);
(C) a component of oxidizing agent; and
(D) a component of molecules of water-soluble polymer and/or oligomers conforming, except for end groups, to the following general formula (I):
in which each of X1 and X2 independently of each other and independently from one unit ofthe polymer, said unit being defined as represented by a modification of formula (I) above in which the square brackets and the subscript n are omit¬ ted, to another unit of the polymer represents a hydrogen atom, a C, to C5 alkyl group, or a C, to C5 hydroxyalkyl group; each of Y1 and Y2 independently of one another and independently for each unit of the polymer represents a hydrogen atom or a moiety "Z" which conforms to one ofthe following general formulas (II) and (III):
in which each of R\ R2, R3, R4, and R5 in each of general formulas (II) and (III) independently represents a C, to C10 alkyl group or a C, to C10 hydroxyalkyl group; one moiety "Z" may be identical to or may differ from any other moiety "Z" in the polymer molecule, so long as each "Z" con¬ forms to one ofthe general formulas (II) and (III); and n represents a posi¬ 0 tive integer, which may be the same as or different from the value of n for any other poiymer molecule; in addition, in component (D) as a whole: the average value for the number of Z moieties substituted on each phen¬ yl ring in the polymer molecule1, which may be referred to hereinafter as "the average value for Z moiety substitution", is from 0.2 to 1.0; the av¬ 5 erage value of n, which may be referred to hereinafter as "the average degree of polymerization", is from 2 to 50, and, because it is an average, need not be an integer; and, optionally, one or both of the following components:
(E) a component of aluminum sequestering agent that is not part of any of 0 the previously recited components; and
(F) a component of antifoam agent that is not part of any of the previously re¬ cited components, and in the composition as a whole, the aforementioned phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble poly¬
25 mer (D) are present in a weight ratio (A):(B):(C):(D) of 0.1 to 30 : 0.1 to 10 : 0.1
1For example, if a polymer with an average degree of polymerization of 10, which contains 20 benzene rings, has only 10 of these 20 benzene rings each substituted with one group Z, the mean group Z substitution rate of the polymer is:
{(1 10) + (0 χ 10')}/20 = 0.5
to 10 : 0.1 to 20. A composition according to the invention may be immediately suitable for use as such in treating aluminiferous metal, in which instance it is called a working composition, or it may be suitable for diluting with additional water to form a working composition, in which instance it is called a concentrate composition. Some compositions are suitable for both purposes.
A process for the surface treatment of an aluminiferous metal according to the present invention is characterized by the fact that an aqueous surface treatment solution which contains the aforementioned surface treatment compo¬ sition pertaining to the present invention and which has a pH value no more than 6.5 is brought into contact with the surface of an aluminiferous metal, preferably for a total of 1 to 60 seconds, and the surface which has thus contacted prefer¬ ably is then rinsed with water, and then is dried and preferably heated. Detailed Description of the Invention. Including Preferred Embodiments Orthophosphoric acid, having the chemical formula H3PO4 and herein usually designated simply as "phosphoric acid" unless the context requires differ¬ entiating it from other phosphoric acids, and any water soluble salt or acid salt of orthophosphoric acid that does not act adversely to the objects of the in¬ vention may be used as a source of component (A) of a composition according to the invention as defined above, and any such salt is to be understood, for the purpose of the preferences indicated below, as contributing its full stoichiometric equivalent as orthophosphate ions (i.e., PO4 "3) to the concentration thereof in any composition according to the invention, irrespective of the actual degree of ionization that may prevail in the composition. The phosphoric acid ions content ranges from 0.1 to 30 weight parts, and preferably 0.5 to 5 weight parts, per 0.1 to 20 weight parts of water-soluble polymer (D) in the aforementioned ratio. A phosphoric acid ions content of less than 0.1 weight part in the aforementioned blend ratio often results in inadequate reactivity between the surface treatment solution and the surface of the metal substrate being coated, as well as in an inadequately formed film. More than 30 weight parts in this ratio does not harm formation of a favorable conversion coating but is uneconomical because of the higher cost of the treatment solution and lack of any offsetting benefit compared
with compositions containing somewhat less of this component.
Similarly, one or two or more types selected from among pyrophosphoric acid, tripolyphosphoric acid and tetrapolyphosphoric acid, and the salts of all of these acids, can be used to provide the condensed phosphoric acid ions in a water-based composition of this invention, but the invention is not limited to the use of these materials. Any water soluble source of any phosphate anions that contain at least two atoms of phosphorus each may be used, and is to be under¬ stood for the purposes of the preferences below as supplying its full stoichio¬ metric equivalent as condensed phosphate anions to the composition used ac- cording to the invention, irrespective of the actual degree of ionization that exists in the composition. For example, pyrophosphoric acid (H4P2O7), sodium pyro¬ phosphate (Na4P2O7) and like compounds can be used to provide pyrophosphate ions. In a surface treatment composition according to the present invention, the content of the condensed phosphoric acid ions component (B) ranges from 0.1 to 10 weight parts, and preferably 0.5 to 3.0 weight parts, per 0.1 to 20 weight parts of water-soluble polymer (D). A condensed phosphoric acid ions content of less than 0.1 weight part in the aforementioned ratio normally results in a sur¬ face treatment solution with weak etching action, preventing a film from being adequately formed. A content of more than 10 weight parts usually results in a surface treatment solution with etching action that is too strong, which inhibits the film-forming reaction.
In a surface treatment composition according to the present invention, the oxidizing agent preferably comprises, more preferably consists essentially of, or still more preferably consists of one or more substances selected from the group consisting of hydrogen peroxide, chlorates, and nitrites; the use of hydrogen per¬ oxide is most preferred. The content of oxidizing agent component (C) in the aforementioned ratio for the surface treatment composition according to the present invention ranges from 0.1 to 10 weight parts, and preferably 2 to 5 weight parts, per 0.1 to 20 weight parts of water-soluble polymer component (D). An oxidizing agent content of less than 0.1 weight part usually results in a treat¬ ment solution with weak etching action, preventing an adequate film from being
formed. More than 10 weight parts usually results in a treatment solution with etching action that is too strong, which inhibits the film-forming reaction.
The water-soluble polymer used in the present invention is a water-sol¬ uble polymer (a term intended herein to include oligomers) that has an average degree of polymerization of 2 to 50, or preferably of 2 to 20, and that contains, preferably consists essentially of, or more preferably consists of (except for end groups) polymer units as described above in connection with general formula (I).
When the alkyl or hydroxyalkyl groups represented by X1 and X2 in general formula (I) have 6 or more carbon atoms, the resulting polymer becomes bulky, usually causing steric hindrance and preventing a compact film with good corrosion resistance from being obtained.
When the average value for Z substitutions is less than 0.2, the resulting polymer normally has poor water solubility, and the resulting surface treatment composition stability is usually inadequate. When the average value for Z moiety substitution is more than 1.0, and thus contains a substantial fraction of benzene rings substituted by two or more Z groups, the polymer usually has such a high water solubility that a composition containing it as component (D) has great difficulty in forming a satisfactorily protective surface film.
The alkyl or hydroxyalkyl groups expressed by R\ R2, R3, R4, and R5 in general formulas (II) and (III) have 1 to 10 carbon atoms. A number of carbon atoms of 11 or more usually results in a polymer molecule that is too bulky, leading to a film with poor density and insufficient corrosion resistance.
In a surface treatment composition according to the present invention, the content of the water-soluble polymer component (D), in terms of the aforemen- tioned ratios to other components, is 0.1 to 20 weight parts, and preferably 0.5 to 5 weight parts, per 0.1 to 30 weight parts of phosphoric acid ions (A). When this ratio is less than 0.1 weight part, it is difficult to form a film on the surface of aluminiferous metals with the surface treatment composition, whereas more than 20 weight parts in this ratio is uneconomical because ofthe higher cost ofthe re- suiting surface treatment and lack of any substantial improvement over the results achieved with a composition according to the invention containing 20 or
fewer parts in this ratio.
Although not narrowly limited, the pH of a working surface treatment com¬ position according to the present invention is preferably no more than 6.5, and even more preferably is between 2.0 and 6.5. When the pH of the surface treat- s ment composition is higher than 6.5, the polymer of formula (I) in the resulting surface treatment composition tends to precipitate, impairing the treatment com¬ position stability and its use life. When the pH is lower than 2.0, the etching ac¬ tion ofthe surface treatment composition on the surface of the metal material is very strong, making it difficult to form a surface film. The pH of the surface treat- o ment composition can be adjusted using an acid such as phosphoric acid, nitric acid, and hydrochloric acid, or an alkali such as sodium hydroxide, sodium car¬ bonate, and ammonium hydroxide. Hydrofluoric acid may be used to adjust the pH when wastewater disposal is not a problem.
In a surface treatment method according to the present invention, the s aforementioned surface treatment solution preferably has a pH of 2.0 to 6.5 and contains from 1 to 30 grams per liter (hereinafter usually abbreviated as "g/l") of phosphoric acid ions, from 0.1 to 10 g/l of condensed phosphoric acid ions, from 0.1 to 10 g/l of oxidizing agent, and from 0.1 to 20 g/l of water-soluble polymer component (D) as described above. When the concentration of phosphoric acid 0 ions in a surface treatment composition according to the invention is lower than 0.1 g/l, a surface film is usually inadequately formed, whereas more than 30 g/l is uneconomical because of higher costs. When the concentration of the con¬ densed phosphoric acid ions is lower than 0.1 g/l, the etching action ofthe result¬ ing surface treatment composition is usually too weak, and a surface film is in- 5 adequately formed, whereas more than 10 g/l results in a surface treatment com¬ position with etching properties that are so strong that the film-forming reaction is hindered. When the oxidizing agent concentration is lower than 0.1 g/l, the etching action of the resulting surface treatment composition is weak, usually preventing the formation of an adequate film, whereas more than 10 g/l results 0 in a surface treatment composition with etching action that is too high, which hinders the film-forming reaction. When the concentration of the water-soluble
polymer component (D) is lower than 0.1 g/l, the resulting surface treatment composition usually has inadequate film formability, whereas more than 20 g/l is economically disadvantageous because of higher costs.
When aluminum ions that have eluted from the aluminiferous metal be- come mixed with the surface treatment composition, the water-soluble polymer (D) and the metal ions sometimes form a complex and produce precipitation. In such instances, an aluminum sequestering agent should be added to the surface treatment composition. Examples of useful aluminum sequestering agents in¬ clude, but are not limited to, ethylene diamine tetra-acetic acid, 1 ,2-cyclohexane- diamine tetra-acetic acid, triethanolamine, gluconic acid, heptogluconic acid, ox¬ alic acid, tartaric acid, malic acid, and organophosphonic acids. When the use of hydrofluoric acid poses no problems for wastewater treatment, it may be used as a sequestering agent.
In a method ofthe present invention, a working surface treatment compo- sition as described above is brought into contact, preferably for a total of 1 to 60 seconds and independently preferably at a temperature within a range from 30 to 65 °C, with a surface of an aluminiferous metal. The film formed on the sur¬ face of the metal material is then preferably rinsed with water, and thereafter preferably is heated and dried. Contact between the aluminiferous metal and a working composition may be established by any convenient method, among which immersion of the substrate in a bath of the working composition and spraying the working composition on the metal are most common. A contact time of less than 1 second usually results in inadequate formation of a corrosion- resistant film, whereas a contact time of more than 60 seconds yields no greater benefits and thus leads to less operational efficiency.
When a spray treatment is used, the surface treatment composition some¬ times foams and thus causes problems in the film that is formed. Although the presence or absence of foaming and the extent of such foaming depends largely on the spraying equipment and conditions, a defoaming agent should be added to the surface treatment composition when foaming is not suitably avoided by modification of the spraying equipment and conditions. The type of defoaming
9 16132
agent, the amount used, and so forth are not narrowly limited, but the adhesion between the resulting film and the paint or laminated film should not be compro¬ mised.
The film formed on the surface ofthe aluminiferous metal in a process ac- cording to the invention is believed to be a film of an organic-inorganic composite consisting primarily of phosphates and water-soluble polymer (resin) (D). The metal substrate is etched by the ions of the phosphoric acid and condensed phosphoric acid, at which time the pH becomes elevated in some areas at the interface, resulting in the precipitation of phosphates on the surface. The amino groups (included in the groups Z) of the water-soluble polymer (D) have chelat¬ ing action, and are believed to form a type ot coordination compound with the re¬ generated surface of the metal substrate produced by the etching. Although the organic-inorganic composite film is basically formed as a result of the two afore¬ mentioned actions, the additional presence of the condensed phosphoric acid ions in the surface treatment composition appears to allow some water-soluble polymer-metal coordination compound(s) to be more readily formed, thereby al¬ lowing a stable organic-inorganic complex film to be formed on the metal surface within a wide pH range.
After a coating film has been formed in a process according to the inven- tion, the film can be and preferably is heated to allow the polymer from compon¬ ent (D) of the working composition according to the invention that was used, and that was incoφorated into the coating film formed on the surface, to undergo fur¬ ther polymerization on the surface. At least one minute at 200 °C (in the normal ambient natural atmosphere) is sufficient for the heating conditions. A preferred expanded treatment process step sequence, using a surface treatment composition according to the present invention, is outlined below.
(1) Surface cleaning/degreasing (any acidic, alkaline, or solvent type);
(2) Rinsing with water;
(3) Surface treatment (by method of the present invention); (4) Rinsing with water;
(5) Deionized water rinsing;
(6) Heating and drying;
(7) Painting or film lamination.
Before the method of the present invention is implemented, the surface of the metal material is preferably cleaned so that it is degreased of oil such as rolling oil or the like remaining on the surface of the aluminiferous metal that is being treated. No particular restrictions are imposed on the type of degreasing agent or the degreasing method used in this step. The degreased material is then preferably rinsed with water. The rinsing is intended to remove the de¬ greasing composition from the surface; therefore, any rinsing method may be used, provided that the degreasing composition is removed from the surface. The surface treatment of the method according to the present invention is then implemented. The surface ofthe aluminiferous metal being treated is the prefer¬ ably further rinsed with water. This rinsing is intended to remove the surface treatment composition, so any rinsing method may be used, provided that the unreacted surface treatment composition is removed from the surface. The heating and drying are intended to dry off the rinsing water, with no narrow re¬ strictions imposed on the method, drying temperature, drying time, or the like, although hot air drying or the like is generally useful for industrial purposes. The surface of the aluminiferous metal that has been surface treated is then painted or laminated with film. The coating formed by a method according to the present invention has good adhesion to paint or laminated films. Since the coating formed by means of the present invention is also flexible, it also has excellent performance after processing such as folding or drawing.
The aluminiferous metals used in the method according to the present in- vention include forms such as sheets, bars, tubes, wires, and the like. No re¬ strictions whatever are imposed on the dimensions and configuration of the met¬ al, although the method according to the present invention is especially effective when used on aluminiferous metal coils.
The present invention is described in further detail below with reference to specific working and comparison examples.
Examples and Comparison Examples Methods of Evaluation
(1) Corrosion Resistance
The corrosion resistance of aluminum materials (resistance to darkening from boiling water) was evaluated by the following test: Treated aluminum ob¬ jects were bent into the shape of a U around a round bar with a diameter of 1 millimeter (hereinafter usually abbreviated as "mm"); these were immersed for 30 minutes in boiling tap water; and the degree of discoloration (darkening) in the bent parts was visually assessed. No darkening was rated as "O", partial darkening was rated as "Δ", and total darkening was rated as "x".
(2) Paint Adhesion
Paint adhesion was tested in the following manner: Polyvinyl chloride paint for cans was painted to a thickness of between 5 and 10 micrometres (hereinafter usually abbreviated as "μm") on the surface of treated aluminum, fol- lowed by 1 minute of baking at 260 °C; the samples were cut into rectangles 5 x 150 mm; the painted surfaces were thermally bonded via a polyamide film to form test pieces; the bonded surfaces were separated by the 180 degree peel test method; and the peel strength was evaluated at that time. The greater the peel strength, the better the paint adhesion. In general, a peel strength of 4.0 kilograms-force (hereinafter usually abbreviated as "kgf) or more per 5 mm of width is considered excellent for practical purposes.
(3) Wastewater Disposability
Used surface treatment composition waste was diluted twenty-fold with water, and the concentration of hexavalent chromium in the thus formed compo- sition was measured. For the purposes of environmental protection, no chromi¬ um should be detected.
Example 1
An aluminum-magnesium alloy sheet (alloy according to Japanese Indus¬ trial Standard, hereinafter usually abbreviated as "JIS", A5182) was degreased by spraying with a 2 % aqueous solution of an alkaline degreaser (trade name:
O 97/13887 PC17US96/16132
FINECLEANER® 4377K, by Nihon Parkerizing) for 5 seconds at 60 °C, and was then rinsed clean with water. The sheet was then sprayed for 3 seconds at 60 °C with Surface Treatment Composition 1 having the ingredients noted below, with the balance being water; it was then rinsed with tap water, then sprayed and washed for 10 seconds with deionized water having a specific resistivity of at least 3,000,000 ohm-centimeters, and was then dried for 2 minutes in a hot air drying furnace at 80 °C.
Surface Treatment Composition 1 75 % Phosphoric acid (i.e., H3PO4) 10.0 g/l (P04 3 : 7.2 g/l) Sodium pyrophosphate (i.e., Na4P2O7*10H2O) 3.0 g/l (P2O7 4 : 1.2 g/l) 31 % Hydrogen peroxide in water 10.0 g/l (H2O2: 3.1 g/l) Polymer (1) - solids part 2.0 g/l pH 4.0 (Adjusted with sodium hydroxide)
Water Soluble Polymer (1) was according to general formula (I) when: the average value of n = 5; each of X1 and X2 represents a hydrogen atom; each of Y1 and Y2 represents a -CH2N(CH3)2 moiety or hydrogen atom; and the average Z moiety substitution number = 0.50
Example 2
Aluminum alloy materials were degreased and rinsed clean in the same manner as in Example 1 , and they were then treated by immersion for 10 sec¬ onds at 40 °C using Surface Treatment Composition 2 having the ingredients shown below, with the balance being water. This treatment was followed by rinsing and drying under the same conditions as in Example 1.
Surface Treatment Composition 2 75 % Phosphoric acid (i.e., H3PO4) 10.0 g/l (P04 3 : 7.2 g/l) Sodium pyrophosphate (i.e., Na4P2O7 «10H2O) 3.0 g/l (P2O7 4.- 1.2 g/l) 31 % Hydrogen peroxide in water 15.0 g/l (H202: 4.6 g/l) Polymer (2) - solids part 0.4 g/l pH 3.0 (Adjusted with sodium carbonate) Water soluble polymer (2) was according to general formula (I) when: the
average value of n = 5; each of X1 and X2 = a -C2H5 moiety; each of Y and Y2 = a -CH2N(CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0.25.
Example 3
Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1 , were then spray treated for 1 second at 65 βC using Surface Treatment Composition 3 containing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in Example 1.
Surface Treatment Composition 3 75 % Phosphoric acid (i.e., H3PO4) 20.0 g/l (PO4 3-: 14.4 g/l) Sodium pyrophosphate (i.e., Na4P2O7 »10H2O) 6.0 g/l (P2O7 4-: 2.4 g/l) 31 % Hydrogen Peroxide in water 15.0 g/l (H2O2: 4.6 g/l) Polymer (3) - solids part 8.0 g/l pH 4.0 (Adjusted with sodium hydroxide) Water soluble polymer (3) was according to general formula (I) when: the aver¬ age value of n = 15; each of X1 and X2 = a -C2H5 moiety; each of Y1 and Y2 = a -CH2N(CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 1.0.
Example 4
Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1 , were then spray treated for 30 seconds at 40 °C using Surface Treatment Composition 4 containing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in Example 1.
Surface Treatment Composition 4
75 % Phosphoric acid (i.e., H3PO4) 20.0 g/l (PO4 3-: 14.4 g/l) Sodium tripolyphosphate (i.e., Na5P3O10) 1.2 g/l (P3O10 : 0.8 g/l) 43 % Sodium chlorate in water 10.0 g/l (NaCIO3: 4.3 g/1) Polymer (4) - solids part 1.0 g/l
pH 4.0 (Adjusted with aqueous ammonia) Water soluble polymer (4) was according to general formula (I) when: the average value of n = 15; each of X1 and X2 represents a hydrogen atom; each of Y1 and Y2 represents a -CH2N(CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0.50
Example 5
Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 5 seconds at 50 °C using
Surface Treatment Composition 5 containing the ingredients shown below, with the balance being water, then rinsed and dried under the same conditions as in
Example 1.
Surface Treatment Composition 5
75 % Phosphoric acid (i.e., H3PO4) 20.0 g/l (PO4 3-: 14.4 g/l)
Pyrophosphoric acid (i.e., H4P2O7) 1.0 g/l (P2O7 4 : 0.98 g/l) 31 % Hydrogen Peroxide in water 5.0 g/l (H2O2: 1.6 g/l)
Polymer (5) - solids part 1.0 g/l pH 3.5 (Adjusted with aqueous ammonia)
Water soluble polymer (5) was according to general formula (I) when: the average value of n = 20; each of X1 and X2 = a hydrogen atom; each of Y1 and Y2 = a -CH2N(CH2CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0.75.
Comparative Example 1
Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1 , and they were then spray treated for 5 seconds at 50 °C using Surface Treatment Composition C1 having the ingredients set forth be¬ low, with the balance being water. This treatment was followed by rinsing and drying under the same conditions as in Example 1.
Surface Treatment Composition C1 — with no condensed phosphoric acid ions or oxidizing agent 75 % Phosphoric acid (i.e., H3PO4) 20.0 g/l (P04 3": 14.4 g/l)
Polymer (6) - solids part 1.0 g/l pH 3.5 (Adjusted with aqueous ammonia) Water soluble polymer (6) was according to general formula (I) when: the average value of n = 10; each of X1 and X2 = a hydrogen atom; each of Y1 and Y2 = a -CH2N(CH2CH2CH2OH)2 moiety or a hydrogen atom; and the average value for Z moiety substitution = 0.75.
Comparative Example 2
Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1 , were then spray treated for 2 seconds at 50 °C using a 5 % aqueous solution of a commercially available phosphoric acid chromate type of chemical conversion composition (tradename: ALCHROME® K 702, by Nihon Parkerizing). The treatment was followed by rinsing and drying under the same conditions as in Example 1.
Comparative Example 3 Aluminum alloy sheets were degreased and rinsed clean in the same manner as in Example 1, were then spray treated for 10 seconds at 50 °C using a 6 % aqueous solution of a commercially available zirconium phosphate type of chemical conversion composition (tradename: AEROSIL™ 404, by Nihon Par¬ kerizing). The treatment was followed by rinsing and drying under the same con- ditions as in Example 1.
Table 1 shows the results obtained in the evaluations of the above noted Examples 1 through 5 and Comparative Examples 1 through 3.
O 97/13887 PC17US96/16132
Table 1
It is apparent from the results in Table 1 that Examples 1 through 5 which used a method according to the present invention had better corrosion resist¬ ance, adhesion, and wastewater disposability.
In Comparative Example 1 , the surface treatment composition contained no condensed phosphoric acid ions or oxidizing agent, resulting in a film with in¬ adequate corrosion resistance and paint adhesion. In Comparative Examples 2 and 3, conventional surface treatment compositions were used, resulting in films with low corrosion resistance. In Comparative Example 2, the wastewater con¬ tained hexavalent chromium, while in Comparative Example 3, the paint adhe¬ sion was poor. Benefits of the Invention
It is apparent from the aforementioned description that the surface treat¬ ment composition and method according to the present invention allow a chem¬ ical conversion film with better corrosion resistance and paint adhesion to be formed on the surfaces of aluminiferous metals before they are painted. The surface treatment composition and method according to the present invention are non-chromium and non-fluorine types, and have the exceptional merit of al¬ leviating the burden of wastewater disposal.
Claims
1. A liquid composition of matter suitable for use as such, after dilution with water, or both as such and after dilution with water for the surface treatment of aluminiferous metals, said composition comprising water and:
(A) a component of ions of orthophosphoric acid;
(B) a component of ions of condensed phosphoric acid(s);
(C) a component of oxidizing agent; and
(D) a component of molecules of water-soluble polymers, oligomers, or both polymers and oligomers, each of said molecules conforming, except for end groups, to the following general formula (I):
in which each of X1 and X2 independently of each other and independently from one unit of the molecule, said unit being defined as represented by a modi¬ fication of formula (I) above in which the square brackets and the subscript n are omitted, to another unit of the molecule represents a hydrogen atom, a C, to C5 alkyl group, or a C, to C5 hydroxyalkyl group; each of Y1 and Y2 independently of one another and independently for each unit of the polymer represents a hydrogen atom or a moiety "Z" which conforms to one of the following general formulas (II) and (III):
in which each of R\ R2, R3, R4, and R5 in each of general formulas (II) and (III) independently represents a C, to C10 alkyl group or a C to C10 hydroxyalkyl group; one moiety "Z" may be identical to or may differ from any other moiety "Z" in the same or another molecule, so long as each "Z" moiety conforms to one of the general formulas (II) and (III); and n repre¬ sents a positive integer, which may be the same as or different from the value of n for any other molecule in component (D); and in component (D) as a whole: the average value for the number of Z moieties substituted on each phenyl ring in the polymer molecule, which may be referred to hereinafter as ' he average value for Z moiety substitution", is from 0.2 to
1.0; the average value of n, which may be referred to hereinafter as "the average degree of polymerization", is from 2 to 50, and, because it is an average, need not be an integer, in said composition as a whole, the aforementioned phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble poly¬ mer (D) being present in a weight ratio (A):(B):(C):(D) of 0.1 to 30 : 0.1 to 10 : 0.1 to 10 : 0.1 to 20.
2. A composition as defined in claim 1 , wherein the oxidizing agent compon¬ ent includes at least one material selected from the group consisting of hydrogen peroxide, chlorates, and nitrites.
3. A composition as defined in claim 2, wherein phosphoric acid ions (A), condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble poly¬ mer (D) are present in a weight ratio (A):(B):(C):(D) of 0.5 to 5 : 0.5 to 3.0 : 2 to 5 : 0.5 to 5.
4. A composition as defined in claim 1 , wherein phosphoric acid ions (A),
condensed phosphoric acid ions (B), oxidizing agent (C), and water-soluble poly¬ mer (D) are present in a weight ratio (A):(B):(C):(D) of 0.5 to 5 : 0.5 to 3.0 : 2 to 5 : 0.5 to 5.
5. A method for the treatment of an aluminiferous metal surface, comprising a step of bringing the aluminiferous metal surface into contact with an aqueous liquid surface treatment composition which contains a composition as defined in any of claims 1 through 4 and has a pH value not more than 6.5.
6. A method according to claim 5, wherein the contact between the aluminif¬ erous metal surface and the aqueous liquid surface treatment composition is maintained for a time from 1 to 60 seconds at a temperature from 35 to 65 °C, and the surface which has thus been brought into contact is rinsed with water after discontinuance of the contact and is subsequently dried.
7. A method according to claim 6, wherein the dried surface formed has been or is subsequently heated to a temperature of at least 200 °C for a time of at least 1 minute in the ambient atmosphere.
8. A method according to claim 6 or 7, wherein the surface treatment com¬ position has a pH from 2.0 to 6.5 and comprises: from 1 to 30 g/l of component (A); from 0.1 to 10 g/l of component (B); from 0.1 to 10 g/l of component (C); and from 0.1 to 20 g/l of component (D).
9. A method according to claim 5, wherein the surface treatment composi¬ tion has a pH from 2.0 to 6.5 and comprises: from 1 to 30 g/l of component (A); from 0.1 to 10 g/l of component (B); from 0.1 to 10 g/l of component (C); and from 0.1 to 20 g/l of component (D).
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96934123A EP0859871A4 (en) | 1995-10-13 | 1996-10-15 | Composition and process for surface treatment of aluminum and its alloys |
| BR9611045A BR9611045A (en) | 1995-10-13 | 1996-10-15 | Liquid composition and treatment process of an aluminum metal surface |
| AU72616/96A AU709612B2 (en) | 1995-10-13 | 1996-10-15 | Composition and process for surface treatment of aluminum and its alloys |
| US09/051,583 US6153022A (en) | 1995-10-13 | 1996-10-15 | Composition and process for surface treatment of aluminum and its alloys |
| NZ319963A NZ319963A (en) | 1995-10-13 | 1996-10-15 | Composition and process for surface treatment of aluminum and its alloys |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7/265501 | 1995-10-13 | ||
| JP26550195A JP3544761B2 (en) | 1995-10-13 | 1995-10-13 | Surface treatment composition for aluminum-containing metal material and surface treatment method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997013887A1 true WO1997013887A1 (en) | 1997-04-17 |
Family
ID=17418054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1996/016132 WO1997013887A1 (en) | 1995-10-13 | 1996-10-15 | Composition and process for surface treatment of aluminum and its alloys |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0859871A4 (en) |
| JP (1) | JP3544761B2 (en) |
| KR (1) | KR970021375A (en) |
| CN (1) | CN1081663C (en) |
| AR (1) | AR003859A1 (en) |
| AU (1) | AU709612B2 (en) |
| BR (1) | BR9611045A (en) |
| CA (1) | CA2232998A1 (en) |
| NZ (1) | NZ319963A (en) |
| TW (1) | TW375659B (en) |
| WO (1) | WO1997013887A1 (en) |
| ZA (1) | ZA968625B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0812933A3 (en) * | 1996-06-13 | 1998-08-19 | Nippon Paint Co., Ltd. | Surface-treated metal material and metal surface treatment method |
| EP0951581A4 (en) * | 1996-08-01 | 1999-11-03 | ||
| WO1999066104A3 (en) * | 1998-06-19 | 2000-03-30 | Alcoa Inc | Method for inhibiting stains on aluminum product surfaces |
| EP0949353A4 (en) * | 1997-10-03 | 2000-12-20 | Nihon Parkerizing | SURFACE TREATMENT COMPOSITION FOR METAL MATERIALS AND TREATMENT METHOD |
| EP1221497A3 (en) * | 1998-06-19 | 2003-12-03 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
| US11807942B2 (en) | 2015-05-01 | 2023-11-07 | Novelis Inc. | Continuous coil pretreatment process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4550956B2 (en) * | 1999-08-10 | 2010-09-22 | 新日本製鐵株式会社 | Painted metal plate with excellent anticorrosion paint and corrosion resistance |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714752A (en) * | 1986-07-26 | 1987-12-22 | Detrex Corporation | 2,2-bis (4 hydroxyphenyl) alkyl poly derivatives for use in after-treatment of conversion coated metals |
| US5356491A (en) * | 1990-11-21 | 1994-10-18 | Henkel Corporation | Composition and method for treating tin plated steel surface |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963596A (en) * | 1987-12-04 | 1990-10-16 | Henkel Corporation | Treatment and after-treatment of metal with carbohydrate-modified polyphenol compounds |
| JPH03207766A (en) * | 1990-01-10 | 1991-09-11 | Nippon Parkerizing Co Ltd | Surface treatment method for tin DI cans |
| WO1991019828A1 (en) * | 1990-06-19 | 1991-12-26 | Henkel Corporation | Liquid composition and process for treating aluminium or tin cans to impart corrosion resistance and reduced friction coefficient |
| US5427632A (en) * | 1993-07-30 | 1995-06-27 | Henkel Corporation | Composition and process for treating metals |
| JP2771110B2 (en) * | 1994-04-15 | 1998-07-02 | 日本パーカライジング株式会社 | Surface treatment composition for aluminum-containing metal material and surface treatment method |
| JP3587590B2 (en) * | 1995-07-21 | 2004-11-10 | 日本パーカライジング株式会社 | Aqueous composition for tinplate DI can surface treatment and surface treatment method |
-
1995
- 1995-10-13 JP JP26550195A patent/JP3544761B2/en not_active Expired - Fee Related
-
1996
- 1996-10-09 KR KR1019960044679A patent/KR970021375A/en not_active Abandoned
- 1996-10-11 TW TW085112427A patent/TW375659B/en active
- 1996-10-11 AR ARP960104707A patent/AR003859A1/en unknown
- 1996-10-11 ZA ZA9608625A patent/ZA968625B/en unknown
- 1996-10-11 CN CN96112741A patent/CN1081663C/en not_active Expired - Fee Related
- 1996-10-15 CA CA002232998A patent/CA2232998A1/en not_active Abandoned
- 1996-10-15 AU AU72616/96A patent/AU709612B2/en not_active Ceased
- 1996-10-15 WO PCT/US1996/016132 patent/WO1997013887A1/en not_active Application Discontinuation
- 1996-10-15 BR BR9611045A patent/BR9611045A/en not_active Application Discontinuation
- 1996-10-15 EP EP96934123A patent/EP0859871A4/en not_active Withdrawn
- 1996-10-15 NZ NZ319963A patent/NZ319963A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4714752A (en) * | 1986-07-26 | 1987-12-22 | Detrex Corporation | 2,2-bis (4 hydroxyphenyl) alkyl poly derivatives for use in after-treatment of conversion coated metals |
| US5356491A (en) * | 1990-11-21 | 1994-10-18 | Henkel Corporation | Composition and method for treating tin plated steel surface |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP0859871A4 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0812933A3 (en) * | 1996-06-13 | 1998-08-19 | Nippon Paint Co., Ltd. | Surface-treated metal material and metal surface treatment method |
| US6013377A (en) * | 1996-06-13 | 2000-01-11 | Nippon Paint Co., Ltd. | Surface-treated metal material and metal surface treatment method |
| EP0951581A4 (en) * | 1996-08-01 | 1999-11-03 | ||
| EP0949353A4 (en) * | 1997-10-03 | 2000-12-20 | Nihon Parkerizing | SURFACE TREATMENT COMPOSITION FOR METAL MATERIALS AND TREATMENT METHOD |
| US6180177B1 (en) | 1997-10-03 | 2001-01-30 | Nihon Parkerizing Co., Ltd. | Surface treatment composition for metallic material and method for treatment |
| WO1999066104A3 (en) * | 1998-06-19 | 2000-03-30 | Alcoa Inc | Method for inhibiting stains on aluminum product surfaces |
| EP1221497A3 (en) * | 1998-06-19 | 2003-12-03 | Alcoa Inc. | Method for inhibiting stains on aluminum product surfaces |
| US11807942B2 (en) | 2015-05-01 | 2023-11-07 | Novelis Inc. | Continuous coil pretreatment process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1081663C (en) | 2002-03-27 |
| ZA968625B (en) | 1997-08-14 |
| JP3544761B2 (en) | 2004-07-21 |
| NZ319963A (en) | 1999-07-29 |
| TW375659B (en) | 1999-12-01 |
| AU7261696A (en) | 1997-04-30 |
| CA2232998A1 (en) | 1997-04-17 |
| CN1154390A (en) | 1997-07-16 |
| MX9802196A (en) | 1998-08-30 |
| AU709612B2 (en) | 1999-09-02 |
| JPH09111466A (en) | 1997-04-28 |
| EP0859871A4 (en) | 2001-04-18 |
| AR003859A1 (en) | 1998-09-09 |
| BR9611045A (en) | 1999-07-06 |
| KR970021375A (en) | 1997-05-28 |
| EP0859871A1 (en) | 1998-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU635019B2 (en) | A method and composition for coating aluminum | |
| AU684929B2 (en) | Composition and process for treating the surface of aluminiferous metals | |
| WO1995033869A1 (en) | Composition and method for treating the surface of aluminiferous metals | |
| WO2001048264A1 (en) | Composition and process for treating metal surface and resulting article | |
| US5125989A (en) | Method and composition for coating aluminum | |
| JP3333611B2 (en) | Hexavalent chromium-free chemical conversion surface treatment agent for aluminum and aluminum alloys | |
| WO2001086016A2 (en) | Metal surface treatment agent | |
| KR20040074012A (en) | Rust prevention coating agent and method of rust-proofing | |
| EP0757725B1 (en) | Composition and process for treating the surface of aluminiferous metals | |
| US6153022A (en) | Composition and process for surface treatment of aluminum and its alloys | |
| MXPA98000581A (en) | Composition and process for treating metal surface aluminife | |
| JPH0931404A (en) | Surface treatment composition for aluminum-containing metal and surface treatment method | |
| AU709612B2 (en) | Composition and process for surface treatment of aluminum and its alloys | |
| EP1120478A2 (en) | Dry-in-place zinc phosphating compositions and processes | |
| EP0558581B1 (en) | Composition and method for treating tin plated steel surface | |
| US6059896A (en) | Composition and process for treating the surface of aluminiferous metals | |
| EP0533823B1 (en) | Liquid composition and process for treating aluminium or tin cans to impart corrosion resistance and reduced friction coefficient | |
| US5904784A (en) | Composition and method for treating the surface of aluminiferous metals | |
| JPH09111465A (en) | Aluminum-containing metal material surface treatment method | |
| US5728234A (en) | Composition and process for treating the surface of aluminiferous metals | |
| JP3587590B2 (en) | Aqueous composition for tinplate DI can surface treatment and surface treatment method | |
| MXPA98002196A (en) | Composition and process for treatment of aluminum surface and its alloys | |
| AU685938C (en) | Composition and process for treating the surface of aluminiferous metals | |
| US5965205A (en) | Composition and process for treating tinned surfaces | |
| WO1998052699A1 (en) | Water-based liquid treatment for aluminum and its alloys |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU BR CA MX NZ US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: PA/a/1998/002196 Country of ref document: MX |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 319963 Country of ref document: NZ |
|
| ENP | Entry into the national phase |
Ref document number: 2232998 Country of ref document: CA Ref country code: CA Ref document number: 2232998 Kind code of ref document: A Format of ref document f/p: F |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 09051583 Country of ref document: US |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 1996934123 Country of ref document: EP |
|
| WWP | Wipo information: published in national office |
Ref document number: 1996934123 Country of ref document: EP |
|
| WWW | Wipo information: withdrawn in national office |
Ref document number: 1996934123 Country of ref document: EP |