JP2015038255A - Protective film formation method of metal and protective film formation treatment agent - Google Patents
Protective film formation method of metal and protective film formation treatment agent Download PDFInfo
- Publication number
- JP2015038255A JP2015038255A JP2014240540A JP2014240540A JP2015038255A JP 2015038255 A JP2015038255 A JP 2015038255A JP 2014240540 A JP2014240540 A JP 2014240540A JP 2014240540 A JP2014240540 A JP 2014240540A JP 2015038255 A JP2015038255 A JP 2015038255A
- Authority
- JP
- Japan
- Prior art keywords
- protective film
- metal
- zinc
- aluminum
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 230000001681 protective effect Effects 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000011282 treatment Methods 0.000 title claims description 43
- 230000015572 biosynthetic process Effects 0.000 title abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011651 chromium Substances 0.000 claims abstract description 24
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 239000011135 tin Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 150000002739 metals Chemical class 0.000 claims abstract description 4
- -1 nitrate ions Chemical class 0.000 claims description 39
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 24
- 229910052749 magnesium Inorganic materials 0.000 claims description 24
- 150000007524 organic acids Chemical class 0.000 claims description 17
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 229910052721 tungsten Inorganic materials 0.000 claims description 14
- 239000010937 tungsten Substances 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- 238000005238 degreasing Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 235000005985 organic acids Nutrition 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- 230000007797 corrosion Effects 0.000 abstract description 46
- 238000005260 corrosion Methods 0.000 abstract description 46
- 238000000576 coating method Methods 0.000 abstract description 24
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 8
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000003973 paint Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 12
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000007747 plating Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 238000004512 die casting Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 229910000861 Mg alloy Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052845 zircon Inorganic materials 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
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- 150000002681 magnesium compounds Chemical class 0.000 description 2
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- 229920005672 polyolefin resin Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 239000010959 steel Substances 0.000 description 2
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- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
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- 229940009827 aluminum acetate Drugs 0.000 description 1
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- 229940063656 aluminum chloride Drugs 0.000 description 1
- 229940010048 aluminum sulfate Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 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
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- DJZHPOJZOWHJPP-UHFFFAOYSA-N magnesium;dioxido(dioxo)tungsten Chemical compound [Mg+2].[O-][W]([O-])(=O)=O DJZHPOJZOWHJPP-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Description
本発明は、種々の金属の保護皮膜形成方法及び保護皮膜形成処理剤に関する。 The present invention relates to various metal protective film forming methods and protective film forming treatment agents.
一般的に、亜鉛、アルミニウム及びマグネシウム等は多くの工業材料として使用されており、様々な分野で利用されている。しかしながら、これらの材料はそのまま使用すると錆と呼ばれる水酸化物を形成し、強度や外観が大きく低下する。そのため通常は、その表面に保護皮膜を形成させることが一般的である。このような保護皮膜形成としては、クロメート皮膜処理が一般的に知られている。クロメート皮膜処理は更に電解クロメート処理、塗布型クロメート処理、及び、反応型クロメート処理の３種類に分類される。これらのクロメート処理は、保護皮膜としての効果の他に、良好な外観や良好な塗装密着性が得られるため、多くの工業分野で利用されている。 In general, zinc, aluminum, magnesium, and the like are used as many industrial materials and are used in various fields. However, if these materials are used as they are, hydroxides called rust are formed, and the strength and appearance are greatly reduced. Therefore, usually, a protective film is generally formed on the surface. As such a protective film formation, a chromate film treatment is generally known. The chromate film treatment is further classified into three types: electrolytic chromate treatment, coating chromate treatment, and reactive chromate treatment. These chromate treatments are used in many industrial fields because they provide a good appearance and good paint adhesion in addition to the effect as a protective film.
しかしながら、クロメート処理は、いずれも有害な六価クロムを使用するため、処理液のみならず処理品からも溶出する六価クロムが人体や環境へ悪影響があるとして、近年大きな問題となっている。これは、クロメート皮膜が皮膜中の六価クロムにより耐食性を発揮する皮膜である以上、如何ともしがたい問題である。 However, since all chromate treatment uses harmful hexavalent chromium, the hexavalent chromium eluted from not only the treatment liquid but also the treated product has a serious problem in recent years because it has an adverse effect on the human body and the environment. This is a problem that cannot be solved as long as the chromate film is a film that exhibits corrosion resistance due to hexavalent chromium in the film.
そこで、この六価クロメートに代わる化成皮膜の開発が行われ、以下に示すように多くの発明が出願されている。現行の六価クロメート代替皮膜は三価クロム皮膜と完全クロムフリー皮膜に大別されるが、六価クロメートに比較すると外観、耐食性、塗装密着性で劣る傾向があり、多くの企業が三価クロム皮膜と完全クロムフリー皮膜の更なる性能向上に向け、研究を重ねているのが現状である。 Then, the chemical conversion film which replaces this hexavalent chromate has been developed, and many inventions have been filed as shown below. Current hexavalent chromate alternative coatings are roughly divided into trivalent chromium coatings and complete chromium-free coatings, but they tend to be inferior in appearance, corrosion resistance, and paint adhesion compared to hexavalent chromate. Currently, research is being conducted to further improve the performance of coatings and complete chromium-free coatings.
六価クロムフリー金属保護皮膜において、外観、耐食性及び塗装密着性の全てに優れた保護形成は存在せず、耐食性が優れていても外観や塗装密着性に問題が確認される等、改善が必要な状況である。このような背景下、本発明は、金属表面、特に、亜鉛または亜鉛合金表面、アルミニウムまたはアルミニウム合金表面、マグネシウムまたはマグネシウム合金表面上に、外観、耐食性及び塗装密着性全てに優れた六価クロムフリー金属保護皮膜を形成する方法及び保護被膜形成処理剤を提供するものである。 Hexavalent chromium-free metal protective film does not have excellent protective formation in all aspects of appearance, corrosion resistance, and paint adhesion, and needs to be improved, such as confirmation of problems in appearance and paint adhesion even with excellent corrosion resistance It is a situation. Under such a background, the present invention is a hexavalent chromium-free material having excellent appearance, corrosion resistance and coating adhesion on a metal surface, particularly zinc or zinc alloy surface, aluminum or aluminum alloy surface, magnesium or magnesium alloy surface. A method for forming a metal protective film and a protective film forming treatment agent are provided.
本発明者らは上記課題を解決するために鋭意検討した結果、（Ａ）三価クロム、（Ｂ）ジルコニウムイオン、（Ｃ）塩素イオン、硫酸イオン及び硝酸イオンからなる群のうちの１種以上、（Ｄ）芳香族スルホン酸、及び、（Ｅ）フッ素イオンを含有する液体組成物により処理を行うことで、被処理金属上に外観、耐食性及び塗装密着性に優れた保護皮膜が形成されることを見出した。また上記構成組成液に更に（Ｆ）珪酸化合物、芳香族スルホン酸以外の有機酸、亜鉛、マグネシウム、アルミニウム、コバルト、ニッケル、バナジウム及びタングステンからなる群のうちの１種以上を添加することで、更に耐食性が良好な保護皮膜が形成されることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found that one or more members selected from the group consisting of (A) trivalent chromium, (B) zirconium ion, (C) chlorine ion, sulfate ion and nitrate ion. (D) A protective film excellent in appearance, corrosion resistance and coating adhesion is formed on the metal to be treated by treatment with a liquid composition containing aromatic sulfonic acid and (E) fluorine ion. I found out. Further, by adding one or more members selected from the group consisting of (F) silicic acid compounds, organic acids other than aromatic sulfonic acids, zinc, magnesium, aluminum, cobalt, nickel, vanadium, and tungsten to the above constituent composition liquid, Furthermore, it discovered that the protective film with favorable corrosion resistance was formed.
以上の知見を基礎として完成した本発明は一側面において、（Ａ）三価クロム、（Ｂ）ジルコニウムイオン、（Ｃ）塩素イオン、硫酸イオン及び硝酸イオンからなる群のうちの１種以上、（Ｄ）芳香族スルホン酸、及び、（Ｅ）フッ素イオンを含有する液体組成物を含む処理液に、亜鉛、アルミニウム、銅、ニッケル、クロム、鉄、錫及びこれらの合金からなる群のうちの１種以上の金属を浸漬させることで、前記金属に保護皮膜を形成する金属の保護皮膜形成方法である。 In one aspect, the present invention completed on the basis of the above knowledge is one or more members selected from the group consisting of (A) trivalent chromium, (B) zirconium ion, (C) chlorine ion, sulfate ion and nitrate ion, ( One of the group consisting of zinc, aluminum, copper, nickel, chromium, iron, tin, and alloys thereof in a treatment liquid containing D) an aromatic sulfonic acid and (E) a liquid composition containing fluorine ions It is a method for forming a protective film of a metal in which a protective film is formed on the metal by immersing more than one kind of metal.
本発明に係る金属の保護皮膜形成方法の一実施形態においては、前記液体組成物が、更に（Ｆ）珪酸化合物、芳香族スルホン酸以外の有機酸、亜鉛、マグネシウム、アルミニウム、コバルト、ニッケル、バナジウム及びタングステンからなる群のうちの１種以上を含む。 In one embodiment of the metal protective film forming method according to the present invention, the liquid composition further comprises (F) a silicic acid compound, an organic acid other than an aromatic sulfonic acid, zinc, magnesium, aluminum, cobalt, nickel, vanadium. And one or more of the group consisting of tungsten.
本発明に係る金属の保護皮膜形成方法の更に別の一実施形態においては、前記保護皮膜の形成後に、更にケイ素、樹脂及びワックスからなる群のうちの一種以上を含有するコーティング剤にて後処理を行う。 In yet another embodiment of the method for forming a protective film for a metal according to the present invention, after the formation of the protective film, it is further post-treated with a coating agent containing at least one member selected from the group consisting of silicon, resin and wax. I do.
本発明に係る金属の保護皮膜形成方法の更に別の一実施形態においては、前記保護皮膜の形成前に、被処理金属に、脱脂、活性化又は表面調整のための前処理を行う。 In still another embodiment of the method for forming a protective film for a metal according to the present invention, pretreatment for degreasing, activation, or surface adjustment is performed on the metal to be processed before the formation of the protective film.
本発明は他の側面において、（Ａ）三価クロム、（Ｂ）ジルコニウムイオン、（Ｃ）塩素イオン、硫酸イオン及び硝酸イオンからなる群のうちの１種以上、（Ｄ）芳香族スルホン酸、及び、（Ｅ）フッ素イオンを含有する、亜鉛、アルミニウム、銅、ニッケル、クロム、鉄、錫及びこれらの合金からなる群のうちの１種以上の金属を浸漬させて前記金属に保護皮膜を形成するための保護皮膜形成処理剤である。 In another aspect, the present invention provides (A) trivalent chromium, (B) zirconium ion, (C) one or more members selected from the group consisting of chlorine ion, sulfate ion and nitrate ion, (D) aromatic sulfonic acid, And (E) one or more metals selected from the group consisting of zinc, aluminum, copper, nickel, chromium, iron, tin and alloys thereof containing fluorine ions are immersed to form a protective film on the metal. This is a protective film forming treatment agent.
本発明に係る保護皮膜形成処理剤の一実施形態においては、更に（Ｆ）珪酸化合物、芳香族スルホン酸以外の有機酸、亜鉛、マグネシウム、アルミニウム、コバルト、ニッケル、バナジウム及びタングステンからなる群のうちの１種以上を含む。 In one embodiment of the protective film-forming treatment agent according to the present invention, (F) a group consisting of silicic acid compound, organic acid other than aromatic sulfonic acid, zinc, magnesium, aluminum, cobalt, nickel, vanadium and tungsten One or more of these.
本発明によれば、被処理金属表面に、有害な六価クロムを含有せず、且つ、均一で良好な外観と耐食性と塗装密着性とを兼ね備えた皮膜を形成することができる。 According to the present invention, it is possible to form a film that does not contain harmful hexavalent chromium and has a uniform and good appearance, corrosion resistance, and coating adhesion on the surface of the metal to be treated.
（被処理金属）
本発明の保護皮膜を形成する被処理金属としては、亜鉛、アルミニウム、マグネシウム、銅、ニッケル、クロム、鉄、錫及びこれらの合金が挙げられる。本発明の保護皮膜は、特に亜鉛めっき、亜鉛合金めっき、亜鉛ダイキャスト、アルミニウム、ダイキャストを含むアルミニウム合金、マグネシウム、ダイキャストを含むマグネシウム合金に対し効果的に作用する。
(Metal to be treated)
Examples of the metal to be treated for forming the protective film of the present invention include zinc, aluminum, magnesium, copper, nickel, chromium, iron, tin, and alloys thereof. The protective film of the present invention effectively acts particularly on zinc plating, zinc alloy plating, zinc die cast, aluminum, aluminum alloy including die cast, magnesium, and magnesium alloy including die cast.
反応の詳細な機構については、三価クロムとジルコニウムとが強固な皮膜骨格を形成し、各種アニオンと芳香族スルホン酸とフッ素イオンが皮膜形成速度を促進するものと考えられ、この５成分が同時に存在することにより、相乗的に皮膜形成が促進され、強固な皮膜が形成されるものと考えられる。また、珪酸化合物、芳香族スルホン酸以外の有機酸または有機酸塩、亜鉛、マグネシウム、アルミニウム、コバルト、ニッケル、バナジウム、タングステンといった物質を添加することにより更に耐食性が良好となる。金属カチオンについては皮膜骨格形成成分として作用し、また珪酸化合物や有機酸については皮膜形成の更なる促進の他に、皮膜成分としても作用することで耐食性の向上に寄与しているものと推測される。 Regarding the detailed mechanism of the reaction, it is considered that trivalent chromium and zirconium form a strong film skeleton, and various anions, aromatic sulfonic acids and fluorine ions accelerate the film formation rate. By being present, it is considered that film formation is synergistically promoted and a strong film is formed. Further, the addition of substances such as silicic acid compounds, organic acids or organic acid salts other than aromatic sulfonic acids, zinc, magnesium, aluminum, cobalt, nickel, vanadium, and tungsten further improves the corrosion resistance. It is presumed that the metal cation acts as a film skeleton-forming component, and the silicic acid compound and organic acid contribute to the improvement of corrosion resistance by acting as a film component in addition to further promotion of film formation. The
（三価クロム源）
保護皮膜の構成成分である三価クロム源としては、硝酸クロム、硫酸クロム、塩化クロム、リン酸クロム、酢酸クロム等の三価クロム塩、及び、クロム酸や重クロム酸等の六価クロムを還元剤により三価に還元した三価クロム等の三価クロム化合物が利用できる。三価クロムの化合物であれば、上記以外の物質でも三価クロムの供給源として利用できる。これら三価クロム化合物は一種または二種以上を使用することができる。三価クロムの濃度としてはクロム濃度として０．００１〜１００ｇ／Ｌが好ましく、０．０１〜５０ｇ／Ｌであるのがより好ましい。三価クロムの濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。三価クロム濃度が０．００１ｇ／Ｌより低下すると耐食性の低下を招き、１００ｇ／Ｌを超えるとコストメリットの観点から好ましくない。
(Trivalent chromium source)
The trivalent chromium source, which is a component of the protective film, includes trivalent chromium salts such as chromium nitrate, chromium sulfate, chromium chloride, chromium phosphate and chromium acetate, and hexavalent chromium such as chromic acid and dichromic acid. Trivalent chromium compounds such as trivalent chromium reduced to trivalent by a reducing agent can be used. If it is a compound of trivalent chromium, substances other than the above can be used as a source of trivalent chromium. These trivalent chromium compounds can be used alone or in combination of two or more. The concentration of trivalent chromium is preferably 0.001 to 100 g / L, more preferably 0.01 to 50 g / L as the chromium concentration. A good chemical conversion film can be formed when the concentration of trivalent chromium is within the above range, and a stable appearance, corrosion resistance, and coating adhesion can be obtained. If the trivalent chromium concentration is lower than 0.001 g / L, the corrosion resistance is lowered, and if it exceeds 100 g / L, it is not preferable from the viewpoint of cost merit.
（ジルコニウム源）
ジルコニウム源としては、オキシ塩化ジルコニウム、硫酸ジルコニウム、硝酸ジルコニウム、酸化ジルコニウム、ジルコンフッ化アンモニウム、ジルコンフッ化水素酸、ジルコニウムゾル等のジルコニウム化合物が利用できる。ジルコニウムの化合物であれば、上記以外の物質でもジルコニウムの供給源として利用できる。これらジルコニウム化合物は、一種又は二種以上を使用することができる。当該化合物のジルコニウム濃度としては、０．００１〜５０ｇ／Ｌが好ましく、０．０１〜２０ｇ／Ｌであるのがより好ましい。ジルコニウム濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性及び塗装密着性が得られる。ジルコニウム濃度が０．００１ｇ／Ｌより低下すると耐食性と塗装密着性の低下を招き、５０ｇ／Ｌを超えるとコストメリットの低下と共に、処理液中に沈殿が発生しやすくなり好ましくない。
(Zirconium source)
Zirconium compounds such as zirconium oxychloride, zirconium sulfate, zirconium nitrate, zirconium oxide, zircon ammonium fluoride, zircon hydrofluoric acid, and zirconium sol can be used as the zirconium source. If it is a compound of zirconium, substances other than the above can be used as a supply source of zirconium. One or two or more of these zirconium compounds can be used. The zirconium concentration of the compound is preferably 0.001 to 50 g / L, and more preferably 0.01 to 20 g / L. A favorable chemical conversion film can be formed when the zirconium concentration is within the above range, and a stable appearance, corrosion resistance and paint adhesion can be obtained. If the zirconium concentration is lower than 0.001 g / L, the corrosion resistance and paint adhesion are reduced, and if it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur in the treatment liquid.
（塩素イオン、硫酸イオン及び硝酸イオンの供給源）
塩素イオン、硫酸イオン及び硝酸イオンの供給源としては、塩酸、硫酸、硝酸や塩化ナトリウム、硫酸ナトリウム、硝酸ナトリウム等の各無機酸塩が利用できる。硫酸クロム、塩化クロム、硝酸クロム、硫酸ジルコニウム、塩化ジルコニウム、硝酸ジルコニウム等のクロム化合物やジルコニウム化合物に含有される各種アニオンも供給源として利用できる。塩素イオン、硫酸イオン及び硝酸イオンの化合物であれば、上記以外の物質も塩素イオン、硫酸イオ及び硝酸イオンの供給源として利用できる。塩素イオン、硫酸イオン及び硝酸イオンは、一種または二種以上を使用することができる。塩素イオン、硫酸イオン及び硝酸イオンの濃度は、０．００１〜２００ｇ／Ｌが好ましく、０．０１〜１００ｇ／Ｌであるのがより好ましい。塩素イオン、硫酸イオン及び硝酸イオンの濃度が上記範囲内であれば、良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。塩素イオン、硫酸イオン及び硝酸イオンの濃度が０．００１ｇ／Ｌより低下すると耐食性と塗装密着性の低下を招き、２００ｇ／Ｌを超えるとコストメリットの低下と共に、処理外観でムラが発生しやすくなり好ましくない。
(Chlorine ion, sulfate ion and nitrate ion source)
As a supply source of chlorine ions, sulfate ions and nitrate ions, inorganic acid salts such as hydrochloric acid, sulfuric acid, nitric acid, sodium chloride, sodium sulfate, sodium nitrate and the like can be used. Various anions contained in chromium compounds and zirconium compounds such as chromium sulfate, chromium chloride, chromium nitrate, zirconium sulfate, zirconium chloride, and zirconium nitrate can also be used as a supply source. As long as it is a compound of chloride ion, sulfate ion and nitrate ion, other substances than the above can also be used as a supply source of chloride ion, sulfate ion and nitrate ion. Chlorine ion, sulfate ion and nitrate ion can be used singly or in combination. The concentration of chloride ion, sulfate ion and nitrate ion is preferably 0.001 to 200 g / L, and more preferably 0.01 to 100 g / L. If the concentration of chloride ion, sulfate ion and nitrate ion is within the above range, a good chemical conversion film can be formed, and a stable appearance, corrosion resistance and coating adhesion can be obtained. If the concentration of chloride ion, sulfate ion and nitrate ion is lower than 0.001 g / L, corrosion resistance and paint adhesion will be reduced. It is not preferable.
（芳香族スルホン酸源）
芳香族スルホン酸源としては、ベンゼンスルホン酸、トルエンスルホン酸、ニトロベンゼンスルホン酸やこれら芳香族スルホン酸の塩等が利用できる。芳香族スルホン酸の化合物であれば、上記以外の物質でも芳香族スルホン酸の供給源として利用できる。これら芳香族スルホン酸は一種または二種以上を使用することができる。芳香族スルホン酸の濃度は、０．００１〜１００ｇ／Ｌが好ましく、０．０１〜５０ｇ／Ｌであるのがより好ましい。芳香族スルホン酸濃度が上記範囲内であれば、良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。芳香族スルホン酸が０．００１ｇ／Ｌより低下すると耐食性の低下を招き、１００ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Aromatic sulfonic acid source)
As the aromatic sulfonic acid source, benzenesulfonic acid, toluenesulfonic acid, nitrobenzenesulfonic acid, salts of these aromatic sulfonic acids, and the like can be used. If it is a compound of aromatic sulfonic acid, substances other than the above can be used as a source of aromatic sulfonic acid. These aromatic sulfonic acids can be used alone or in combination of two or more. The concentration of the aromatic sulfonic acid is preferably 0.001 to 100 g / L, and more preferably 0.01 to 50 g / L. When the aromatic sulfonic acid concentration is within the above range, a good chemical conversion film can be formed, and a stable appearance, corrosion resistance, and coating adhesion can be obtained. If the aromatic sulfonic acid is lower than 0.001 g / L, the corrosion resistance is lowered, and if it exceeds 100 g / L, the cost merit is lowered and precipitation is likely to occur.
（フッ素イオン源）
フッ素イオン源としては、フッ化水素、フッ化ナトリウム、酸性フッ化ナトリウム、フッ化アンモニウム、酸性フッ化アンモニウム、フッ化カリウム、ケイフッ化物、ジルコンフッ化アンモニウム、ホウフッ化物等のフッ素化合物が使用できる。フッ素イオンの化合物であれば、上記以外の物質でもフッ素イオンの供給源として利用できる。これらフッ素化合物は一種または二種以上を使用することができる。フッ素イオンの濃度は、０．００１〜８０ｇ／Ｌが好ましく、０．０１〜４０ｇ／Ｌであるのがより好ましい。フッ素イオン濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。フッ素イオンが０．００１ｇ／Ｌより低下すると耐食性と塗装密着性の低下を招き、８０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Fluorine ion source)
As the fluorine ion source, fluorine compounds such as hydrogen fluoride, sodium fluoride, sodium acid fluoride, ammonium fluoride, ammonium acid fluoride, potassium fluoride, silicofluoride, zircon ammonium fluoride, and borofluoride can be used. If it is a compound of a fluorine ion, substances other than the above can be used as a source of fluorine ion. One or two or more of these fluorine compounds can be used. The concentration of fluorine ions is preferably 0.001 to 80 g / L, and more preferably 0.01 to 40 g / L. A favorable chemical conversion film can be formed within the above-mentioned range of fluorine ion concentration, and a stable appearance, corrosion resistance, and coating adhesion can be obtained. When the fluorine ion is lower than 0.001 g / L, the corrosion resistance and the coating adhesion are deteriorated, and when it exceeds 80 g / L, the cost merit is lowered and precipitation is easily generated, which is not preferable.
（珪酸化合物源）
珪酸化合物源としては珪酸ナトリウム、珪酸カリウム、オルソ珪酸塩、メタ珪酸塩、コロイダルシリカ等の珪酸化合物が使用できる。珪酸の化合物であれば、上記以外の物質でも珪酸化合物の供給源として利用できる。これら珪酸化合物は一種または二種以上を使用することができる。珪酸化合物の濃度は、０．００１〜２０ｇ／Ｌが好ましく、０．０１〜１０ｇ／Ｌであるのがより好ましい。珪酸濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。珪酸化合物が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、２０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Silicic acid compound source)
As the silicate compound source, silicate compounds such as sodium silicate, potassium silicate, orthosilicate, metasilicate and colloidal silica can be used. If it is a compound of a silicic acid, substances other than the above can be used as a supply source of a silicic acid compound. These silicic acid compounds can be used alone or in combination of two or more. The concentration of the silicic acid compound is preferably 0.001 to 20 g / L, and more preferably 0.01 to 10 g / L. An excellent chemical conversion film can be formed within the above-mentioned range of the silicic acid concentration, and a stable appearance, corrosion resistance, and paint adhesion can be obtained. When the silicic acid compound is lower than 0.001 g / L, it is difficult to obtain an effect of improving the corrosion resistance. When the silicic acid compound exceeds 20 g / L, the cost merit is lowered and precipitation is likely to occur.
（芳香族スルホン酸以外の有機酸）
芳香族スルホン酸以外の有機酸としては、ギ酸、酢酸、プロピオン酸、グルコン酸、酪酸、シュウ酸、マロン酸、琥珀酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、安息香酸、フタル酸、酒石酸、グリコール酸、ジグリコール酸、乳酸、グリシン、クエン酸、リンゴ酸、エチレンジアミン四酢酸、ニトリロ三酢酸やこれらの有機酸塩等が利用できる。有機酸の化合物であれば、上記以外の物質でも有機酸の供給源として利用できる。これら有機酸は一種または二種以上を使用することができる。有機酸の濃度は、０．００１〜２００ｇ／Ｌが好ましく、０．０１〜１００ｇ／Ｌの範囲であるのがより好ましい。有機酸濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。有機酸濃度が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、１００ｇ／Ｌを超えるとコストメリットの低下と共に、廃水処理性低下するため好ましくない。
(Organic acids other than aromatic sulfonic acids)
Organic acids other than aromatic sulfonic acids include formic acid, acetic acid, propionic acid, gluconic acid, butyric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, benzoic acid, phthalic acid, Tartaric acid, glycolic acid, diglycolic acid, lactic acid, glycine, citric acid, malic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, and organic acid salts thereof can be used. If it is a compound of an organic acid, substances other than those described above can be used as a source of the organic acid. These organic acids can be used alone or in combination of two or more. The concentration of the organic acid is preferably 0.001 to 200 g / L, and more preferably 0.01 to 100 g / L. A favorable chemical film can be formed within the above-mentioned range of the organic acid concentration, and a stable appearance, corrosion resistance, and paint adhesion can be obtained. When the organic acid concentration is lower than 0.001 g / L, it is difficult to obtain an effect of improving the corrosion resistance. When the organic acid concentration exceeds 100 g / L, the cost merit is lowered and the wastewater treatment property is lowered.
（亜鉛源）
亜鉛源としては、酸化亜鉛、硝酸亜鉛、硫酸亜鉛、塩化亜鉛、酢酸亜鉛、炭酸亜鉛等の亜鉛化合物が利用できる。亜鉛の化合物であれば、上記以外の物質でも亜鉛の供給源として利用できる。これら亜鉛化合物は一種または二種以上を使用することができる。亜鉛濃度は、０．００１〜５０ｇ／Ｌが好ましく、０．０１〜３０ｇ／Ｌであるのがより好ましい。亜鉛濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。亜鉛濃度が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、５０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Zinc source)
As the zinc source, zinc compounds such as zinc oxide, zinc nitrate, zinc sulfate, zinc chloride, zinc acetate and zinc carbonate can be used. If it is a compound of zinc, substances other than the above can be used as a source of zinc. These zinc compounds can be used alone or in combination of two or more. The zinc concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A good chemical conversion film can be formed when the zinc concentration is within the above range, and a stable appearance, corrosion resistance, and paint adhesion can be obtained. If the zinc concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the corrosion resistance, and if it exceeds 50 g / L, the cost merit is lowered and precipitation is likely to occur, which is not preferable.
（マグネシウム源）
マグネシウム源としては、硝酸マグネシウム、硫酸マグネシウム、塩化マグネシウム、酢酸マグネシウム、炭酸マグネシウム等のマグネシウム化合物が利用できる。マグネシウムの化合物であれば、上記以外の物質でもマグネシウムの供給源として利用できる。これらマグネシウム化合物は一種または二種以上を使用することができる。マグネシウム濃度は、０．００１〜５０ｇ／Ｌが好ましく、０．０１〜３０ｇ／Ｌの範囲であるのがより好ましい。マグネシウム濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。マグネシウム濃度が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、５０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Magnesium source)
As the magnesium source, magnesium compounds such as magnesium nitrate, magnesium sulfate, magnesium chloride, magnesium acetate, and magnesium carbonate can be used. If it is a compound of magnesium, substances other than the above can be used as a source of magnesium. These magnesium compounds can be used alone or in combination of two or more. The magnesium concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A good chemical conversion film can be formed when the magnesium concentration is within the above range, and a stable appearance, corrosion resistance, and paint adhesion can be obtained. When the magnesium concentration is lower than 0.001 g / L, it is difficult to obtain an effect of improving corrosion resistance.
（アルミニウム源）
アルミニウム源としては、硝酸アルミニウム、硫酸アルミニウム、塩化アルミニウム、酢酸アルミニウム、炭酸アルミニウム、コロイダルアルミナ等のアルミニウム化合物が利用できる。アルミニウムの化合物であれば、上記以外の物質でもアルミニウムの供給源として利用できる。これらアルミニウム化合物は一種または二種以上を使用することができる。アルミニウム濃度として０．００１〜５０ｇ／Ｌが好ましく、０．０１〜３０ｇ／Ｌであるのがより好ましい。アルミニウム濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。アルミニウム濃度が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、５０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Aluminum source)
As the aluminum source, aluminum compounds such as aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate, aluminum carbonate and colloidal alumina can be used. A substance other than the above can be used as an aluminum supply source as long as it is an aluminum compound. These aluminum compounds can be used alone or in combination of two or more. The aluminum concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A favorable chemical conversion film can be formed when the aluminum concentration is within the above range, and a stable appearance, corrosion resistance, and paint adhesion can be obtained. When the aluminum concentration is lower than 0.001 g / L, it is difficult to obtain an effect of improving the corrosion resistance, and when it exceeds 50 g / L, the cost merit is lowered and precipitation is likely to occur, which is not preferable.
（コバルト源）
コバルト源としては、硝酸コバルト、硫酸コバルト、塩化コバルト、酢酸コバルト、炭酸コバルト等のコバルト化合物が利用できる。これらコバルト化合物は一種または二種以上を使用することができる。コバルトの化合物であれば、上記以外の物質でもコバルトの供給源として利用できる。コバルト濃度は、０．００１〜５０ｇ／Ｌが好ましく、０．０１〜３０ｇ／Ｌであるのがより好ましい。コバルト濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。コバルト濃度が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、５０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Cobalt source)
As the cobalt source, cobalt compounds such as cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt acetate, and cobalt carbonate can be used. These cobalt compounds can be used alone or in combination of two or more. If it is a compound of cobalt, substances other than the above can be used as a source of cobalt. The cobalt concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A good chemical conversion film can be formed when the cobalt concentration is within the above range, and a stable appearance, corrosion resistance, and paint adhesion can be obtained. When the cobalt concentration is lower than 0.001 g / L, it is difficult to obtain an effect of improving the corrosion resistance, and when it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur, which is not preferable.
（ニッケル源）
ニッケル源としては、硝酸ニッケル、硫酸ニッケル、塩化ニッケル、酢酸ニッケル、炭酸ニッケル、スルファミン酸ニッケル等のニッケル化合物が利用できる。ニッケルの化合物であれば、上記以外の物質でもニッケルの供給源として利用できる。これらニッケル化合物は一種または二種以上を使用することができる。ニッケル濃度は、０．００１〜５０ｇ／Ｌが好ましく、０．０１〜３０ｇ／Ｌであるのがより好ましい。ニッケル濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。ニッケル濃度が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、５０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Nickel source)
As the nickel source, nickel compounds such as nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, nickel carbonate and nickel sulfamate can be used. If it is a compound of nickel, substances other than the above can be used as a nickel supply source. These nickel compounds can be used alone or in combination of two or more. The nickel concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A favorable chemical conversion film can be formed when the nickel concentration is within the above range, and a stable appearance, corrosion resistance, and coating adhesion can be obtained. When the nickel concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the corrosion resistance, and when it exceeds 50 g / L, the cost merit is lowered and precipitation is likely to occur.
（バナジウム源）
バナジウム源としては、硝酸バナジウム、硫酸バナジウム、塩化バナジウム、バナジン酸、メタバナジン酸カリウム、メタバナジン酸アンモニウム等のバナジウム化合物が利用できる。バナジウムの化合物であれば、上記以外の物質でもバナジウムの供給源として利用できる。これらバナジウム化合物は一種または二種以上を使用することができる。バナジウム濃度は、０．００１〜５０ｇ／Ｌが好ましく、０．０１〜３０ｇ／Ｌであるのがより好ましい。バナジウム濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。バナジウム濃度が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、５０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Vanadium source)
As the vanadium source, vanadium compounds such as vanadium nitrate, vanadium sulfate, vanadium chloride, vanadic acid, potassium metavanadate, and ammonium metavanadate can be used. If it is a compound of vanadium, substances other than the above can be used as a supply source of vanadium. These vanadium compounds can be used alone or in combination of two or more. The vanadium concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A good chemical conversion film can be formed within the above range of vanadium concentration, and a stable appearance, corrosion resistance, and coating adhesion can be obtained. If the vanadium concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the corrosion resistance, and if it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur, which is not preferable.
（タングステン源）
タングステン源としては、タングステン酸ナトリウム、タングステン酸アンモニウム、タングステン酸カリウム、タングステン酸マグネシウム等のタングステン化合物が利用できる。タングステンの化合物であれば、上記以外の物質でもタングステンの供給源として利用できる。これらタングステン化合物は一種または二種以上を使用することができる。タングステン濃度として０．００１〜５０ｇ／Ｌが好ましく、０．０１〜３０ｇ／Ｌであるのがより好ましい。タングステン濃度が上記範囲内で良好な化成皮膜が形成でき、安定な外観、耐食性、塗装密着性が得られる。タングステン濃度が０．００１ｇ／Ｌより低下すると耐食性の向上効果が得られにくく、５０ｇ／Ｌを超えるとコストメリットの低下と共に、沈殿が発生しやすくなり好ましくない。
(Tungsten source)
As the tungsten source, tungsten compounds such as sodium tungstate, ammonium tungstate, potassium tungstate, and magnesium tungstate can be used. Any material other than those described above can be used as a tungsten supply source as long as it is a compound of tungsten. One or two or more of these tungsten compounds can be used. The tungsten concentration is preferably 0.001 to 50 g / L, and more preferably 0.01 to 30 g / L. A good chemical conversion film can be formed when the tungsten concentration is within the above range, and a stable appearance, corrosion resistance, and paint adhesion can be obtained. If the tungsten concentration is lower than 0.001 g / L, it is difficult to obtain an effect of improving the corrosion resistance, and if it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur.
皮膜形成に用いる処理液のｐＨは、ｐＨ０．５〜６．０の範囲が好ましく、より好ましくは１．５〜４．５である。ｐＨが０．５より低い場合は被処理金属の表面が粗面化しやすく、６．０より高い場合は皮膜化成速度が低下するとともに処理液に沈殿が生じやすくなるため好ましくない。なお、処理液のｐＨ調整剤としては、塩酸、硫酸、硝酸の無機酸や、苛性ソーダ、苛性カリ、アンモニア水のアルカリを用いることができる。 The pH of the treatment liquid used for film formation is preferably in the range of pH 0.5 to 6.0, more preferably 1.5 to 4.5. When the pH is lower than 0.5, the surface of the metal to be treated is easily roughened, and when the pH is higher than 6.0, the film formation rate is lowered and precipitation is likely to occur in the treatment liquid, which is not preferable. In addition, as a pH adjuster of a process liquid, hydrochloric acid, a sulfuric acid, the inorganic acid of nitric acid, caustic soda, caustic potash, and the alkali of aqueous ammonia can be used.
保護皮膜の厚さは約０．０２〜２μｍであり、より好ましくは０．０４〜０．５μｍである。膜厚が０．０２μｍ未満では十分な耐食性が得られず、０．５μｍ超では塗装密着性が低下する場合がある。 The thickness of the protective film is about 0.02 to 2 μm, more preferably 0.04 to 0.5 μm. If the film thickness is less than 0.02 μm, sufficient corrosion resistance cannot be obtained, and if it exceeds 0.5 μm, the coating adhesion may decrease.
（保護皮膜形成方法）
本発明の保護皮膜の形成は、被処理金属を上記処理剤に浸漬させることにより行う。更に保護皮膜形成後に必要に応じて水洗と乾燥等の処理を行ってもよい。また、塗布や吹き付け工程による皮膜形成も可能である。保護膜形成の前に、被処理金属の表面に、必要に応じて脱脂、活性化又は表面調整のための前処理を行ってもよい。処理液での処理温度は１０〜８０℃の範囲が好ましく、より好ましくは２０〜５０℃である。処理温度が１０℃より低い場合は化成皮膜の反応速度が低下し、８０℃より高い場合は蒸発による処理液面の低下が生じるため好ましくない。処理液での処理時間は５〜６００秒の範囲が好ましく、より好ましくは１０〜１２０秒である。処理時間が５秒より短い場合は皮膜化成が不十分となり、６００秒より長い場合は表面が白くボケるといった外観不良が発生しやすくなるため好ましくない。
(Protective film formation method)
The protective coating of the present invention is formed by immersing the metal to be treated in the treatment agent. Furthermore, you may perform processing, such as washing and drying, as needed after formation of a protective film. Moreover, the film formation by an application | coating or spraying process is also possible. Prior to the formation of the protective film, a pretreatment for degreasing, activation, or surface adjustment may be performed on the surface of the metal to be treated as necessary. The treatment temperature in the treatment liquid is preferably in the range of 10 to 80 ° C, more preferably 20 to 50 ° C. When the treatment temperature is lower than 10 ° C., the reaction rate of the chemical conversion film is lowered, and when the treatment temperature is higher than 80 ° C., the treatment liquid level is lowered by evaporation, which is not preferable. The treatment time with the treatment liquid is preferably in the range of 5 to 600 seconds, more preferably 10 to 120 seconds. When the treatment time is shorter than 5 seconds, film formation is insufficient, and when it is longer than 600 seconds, appearance defects such as white blurring of the surface are likely to occur.
保護皮膜形成処理を行う際、あらかじめ被処理金属の脱脂、活性化、表面調整を行うことで、本発明の処理外観、耐食性及び塗装密着性を向上させることが可能である。脱脂に関しては被処理金属により適した工程があるが、亜鉛めっきや亜鉛合金めっきに関してはめっき後に硝酸活性を行い、その後、保護皮膜形成処理を行うことが適している。亜鉛ダイキャストやアルミニウム、アルミニウム合金に関しては脱脂や必要に応じて活性処理を行い、その後に保護皮膜形成処理を行うことが適している。マグネシウムやマグネシウム合金に関しては、脱脂、活性化又は表面調整の後に保護皮膜形成処理を行うことが適している。これらの前処理に関しては、各被処理金属に応じて適宜行うことで本発明に係る保護皮膜形成処理の性能を引き出すことが可能である。 When performing the protective film forming treatment, it is possible to improve the appearance of the treatment, the corrosion resistance, and the coating adhesion of the present invention by previously degreasing, activating, and adjusting the surface of the metal to be treated. For degreasing, there are processes that are more suitable for the metal to be treated, but for zinc plating and zinc alloy plating, it is suitable to perform nitric acid activity after plating and then to perform a protective film forming treatment. For zinc die-casting, aluminum, and aluminum alloys, it is suitable to perform degreasing and activation treatment as necessary, followed by protective film formation treatment. For magnesium and magnesium alloys, it is suitable to perform a protective film forming treatment after degreasing, activation or surface conditioning. About these pre-processing, it is possible to draw out the performance of the protective film formation processing which concerns on this invention by performing suitably according to each to-be-processed metal.
保護皮膜形成処理を実施後に、ケイ素、樹脂及びワックスからなる群のうちの一種以上を含有するコーティング剤にて後処理を行っても良い。これらコーティング剤に特に限定はなくアクリル樹脂、オレフィン樹脂アルキド樹脂、尿素樹脂、エポキシ樹脂、メラミン樹脂、フッ素樹脂、ポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、メタクリル樹脂、フェノール樹脂、ポリエステル樹脂、ポリウレタン、ポリアミド、ポリカーボネート等の樹脂類やケイ酸塩、コロイダルシリカ等を成分とするコーティング剤を用いても良い。これらの樹脂濃度は、０．０１〜８００ｇ／Ｌが好ましいが、適切な濃度は樹脂の種類により異なる。コーティング剤としては、具体的には、コスマーコート（商品名、関西ペイント（株））、ハイシール２７２（商品名、日本表面化学（株））、ストロンＪコート（商品名、日本表面化学（株））、トライナーＴＲ−１７０（商品名、日本表面化学（株））、フィニガード（商品名、Coventya社）等が挙げられる。アクリル樹脂としては、具体的には、ヒロタイト（商品名、日立化成（株））、アロセット（商品名、（株）日本触媒）等があり、オレフィン樹脂については、フローセン（商品名、住友精化（株））、ＰＥＳ（商品名、日本ユニカー（株））、ケミパール（商品名、三井化学（株））、サンファイン（商品名、旭化成（株））等が挙げられる。 After performing the protective film forming treatment, a post-treatment may be performed with a coating agent containing one or more members selected from the group consisting of silicon, resin, and wax. There are no particular limitations on these coating agents, acrylic resin, olefin resin alkyd resin, urea resin, epoxy resin, melamine resin, fluororesin, polyethylene, polyvinyl chloride, polystyrene, polypropylene, methacrylic resin, phenol resin, polyester resin, polyurethane, polyamide A coating agent containing resin such as polycarbonate, silicate, colloidal silica or the like may be used. These resin concentrations are preferably 0.01 to 800 g / L, but the appropriate concentration varies depending on the type of resin. Specific examples of the coating agent include Cosmar Coat (trade name, Kansai Paint Co., Ltd.), Hi Seal 272 (trade name, Nippon Surface Chemistry Co., Ltd.), Stron J Coat (trade name, Nihon Surface Chemical Co., Ltd.) ), Triner TR-170 (trade name, Nippon Surface Chemistry Co., Ltd.), Finigard (trade name, Coventya) and the like. Specific examples of acrylic resins include hirotite (trade name, Hitachi Chemical Co., Ltd.) and alloset (trade name, Nippon Shokubai Co., Ltd.). Co., Ltd.), PES (trade name, Nippon Unicar Co., Ltd.), Chemipearl (trade name, Mitsui Chemicals Co., Ltd.), Sun Fine (trade name, Asahi Kasei Co., Ltd.) and the like.
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 EXAMPLES Examples of the present invention will be described below, but these are provided for better understanding of the present invention and are not intended to limit the present invention.
試験片として、鋼板に電気亜鉛めっき、鋼板に電気亜鉛鉄合金めっき（鉄共析率０．３ｗｔ％）、亜鉛ダイキャストＺＤＣ２、アルミニウム板Ａ１１００、アルミニウムダイキャストＡＤＣ２、アルミニウム鋳物ＡＣ４Ｃ、アルミニウム合金板Ａ６０６３、マグネシウム展伸材ＡＺ３１、マグネシウム展伸材ＡＺ６１、マグネシウムダイキャストＡＺ９１Ｄといった各種の標準被処理金属試験片を用いた。亜鉛めっきと亜鉛鉄合金めっきとは、めっき後に水洗、硝酸活性（６７．５％硝酸５ｍＬ/Ｌ、室温５秒）、水洗を行い、各実施例条件で処理、水洗後に乾燥した。亜鉛ダイキャスト、アルミニウム板、アルミニウム鋳物、アルミニウム合金板、アルミニウムダイキャストにつては、脱脂（日本表面化学（株）製ケイクリン６を３０ｍＬ／Ｌ、５０℃、５分）を行い、水洗、各実施例条件で処理、水洗後に乾燥した。マグネシウム展伸材、マグネシウムダイキャストについては脱脂（日本表面化学（株）製Ｓ−０７１７を３０ｇ／Ｌ、５５℃、５分）、水洗、活性化（日本表面化学（株）製ＭＥ−４１０を５０ｍＬ／Ｌ、４５℃、２分）、水洗、表面調整（日本表面化学（株）製ＭＤ−４２０を１００ｍＬ／Ｌ、５５℃、２分）、水洗の工程後、各実施例条件で処理、水洗後に乾燥した。各処理液のｐＨ調整は硝酸とアンモニア水を使用した。実施例４３〜４８に関しては保護皮膜形成処理後に水洗を行い、その後コーティング処理を行い、乾燥した。コーティング処理にはハイシール２７２（日本表面化学（株）製、ポリアクリル樹脂型コーティング剤）とストロンＪコート（日本表面化学（株）製、水分散型シリカ型コーティング剤）、ケミパールＷ４１０（三井化学（株）製、オレフィン樹脂）を使用した。耐食性の評価はＪＩＳ Ｚ ２７３１に従う塩水噴霧試験を行った。塗装密着性試験は、試験片表面にエポキシ系塗料を塗布し、焼き付け乾燥した後碁盤目状にクロスカットを入れ、沸騰水に３０分浸漬後、セロハンテープを圧着させ、これを垂直方向に剥離し評価した。
試験条件及び評価結果を表１〜１０に示す。
As test specimens, electrogalvanized steel sheets, electrogalvanized iron alloy plated steel sheets (iron eutectoid rate 0.3 wt%), zinc die cast ZDC2, aluminum plate A1100, aluminum die cast ADC2, aluminum casting AC4C, aluminum alloy plate A6063 Various standard treated metal specimens such as magnesium expanded material AZ31, magnesium expanded material AZ61, and magnesium die cast AZ91D were used. Zinc plating and zinc iron alloy plating were washed with water after plating, nitric acid activity (67.5% nitric acid 5 mL / L, room temperature 5 seconds), washed with water, treated under the conditions of each example, and dried after washing with water. For zinc die-casting, aluminum plate, aluminum casting, aluminum alloy plate, aluminum die-casting, degreasing (Nihon Surface Chemicals Co., Ltd. Kakerin 6 at 30 mL / L, 50 ° C, 5 minutes), washing with water, and carrying out each It processed on the example conditions, and it dried after washing with water. For magnesium wrought material and magnesium die-casting, degreasing (Nihon Surface Chemicals Co., Ltd. S-0717 30 g / L, 55 ° C., 5 minutes), washing and activation (Nihon Surface Chemicals Co., Ltd. ME-410) 50 mL / L, 45 ° C., 2 minutes), washing with water, surface conditioning (MD-420 manufactured by Nippon Surface Chemical Co., Ltd., 100 mL / L, 55 ° C., 2 minutes) It was dried after washing with water. Nitric acid and aqueous ammonia were used to adjust the pH of each treatment solution. In Examples 43 to 48, washing with water was performed after the protective film formation treatment, followed by coating treatment and drying. For coating treatment, Hi-Seal 272 (manufactured by Nippon Surface Chemical Co., Ltd., polyacrylic resin type coating agent) and Stron J Coat (manufactured by Nippon Surface Chemical Co., Ltd., water-dispersed silica type coating agent), Chemipearl W410 (Mitsui Chemicals ( Co., Ltd., olefin resin) was used. The corrosion resistance was evaluated by a salt spray test according to JIS Z2731. In the coating adhesion test, an epoxy paint is applied to the surface of the test piece, baked and dried, then cross-cut into a grid pattern, immersed in boiling water for 30 minutes, cellophane tape is crimped, and this is peeled off vertically. And evaluated.
Test conditions and evaluation results are shown in Tables 1-10.
上記碁盤目試験評価は、以下の基準による。
Ａ：はく離無し
Ｂ：はく離５％未満
Ｃ：はく離１０％未満
Ｄ：はく離５０％未満
Ｅ：はく離５０％以上
また、上記塩水噴霧試験評価は、以下の基準による。
Ａ：３６０時間白錆発生無し
Ｂ：２４０時間白錆発生無し
Ｃ：１６８時間白錆発生無し
Ｄ：７２時間白錆発生無し
Ｅ：４８時間白錆発生
Ｆ：２４時間白錆発生
The cross-cut test evaluation is based on the following criteria.
A: No peeling B: Peeling less than 5% C: Peeling less than 10% D: Peeling less than 50% E: Peeling 50% or more The above-described salt spray test evaluation is based on the following criteria.
A: 360 hours no white rust occurrence B: 240 hours no white rust occurrence C: 168 hours no white rust occurrence D: 72 hours no white rust occurrence E: 48 hours white rust occurrence F: 24 hours white rust occurrence
（評価）
実施例の結果から、（Ａ）三価クロム、（Ｂ）ジルコニウムイオン、（Ｃ）塩素イオン、硫酸イオン及び硝酸イオンからなる群のうちの１種以上、（Ｄ）芳香族スルホン酸、及び、（Ｅ）フッ素イオンを含有する液体組成物により保護皮膜を形成することにより、優れた外観・耐食性・塗装密着性が得られることが確認された。更に（Ｆ）珪酸化合物、芳香族スルホン酸以外の有機酸、亜鉛、マグネシウム、アルミニウム、コバルト、ニッケル、バナジウム及びタングステンからなる群のうちの１種以上を液体組成物に添加することで耐食性がより良好となることが確認された。一方、比較例の結果からは、上記成分（Ａ）〜（Ｅ）のうちどれか一つが不足しても優れた耐食性が得られないことが確認された。また、上記成分（Ａ）〜（Ｅ）のうちどれか一つが不足している液体組成物に上記成分（Ｆ）を添加しても、実施例に匹敵する耐食性を得るには至らないことが確認された。
(Evaluation)
From the results of the examples, (A) trivalent chromium, (B) zirconium ion, (C) one or more members selected from the group consisting of chlorine ion, sulfate ion and nitrate ion, (D) aromatic sulfonic acid, and (E) It was confirmed that excellent appearance, corrosion resistance, and coating adhesion can be obtained by forming a protective film from a liquid composition containing fluorine ions. Furthermore, the corrosion resistance is further improved by adding at least one of the group consisting of (F) silicic acid compound, organic acid other than aromatic sulfonic acid, zinc, magnesium, aluminum, cobalt, nickel, vanadium and tungsten to the liquid composition. It was confirmed to be good. On the other hand, from the result of the comparative example, it was confirmed that even if any one of the components (A) to (E) is insufficient, excellent corrosion resistance cannot be obtained. Moreover, even if the component (F) is added to the liquid composition in which any one of the components (A) to (E) is insufficient, the corrosion resistance comparable to the examples may not be obtained. confirmed.
Claims (6)
（Ｂ）ジルコニウムイオン、
（Ｃ）塩素イオン、硫酸イオン及び硝酸イオンからなる群のうちの１種以上、
（Ｄ）芳香族スルホン酸、及び、
（Ｅ）フッ素イオン
を含有する液体組成物を含む処理液に、亜鉛、アルミニウム、銅、ニッケル、クロム、鉄、錫及びこれらの合金からなる群のうちの１種以上の金属を浸漬させることで、前記金属に保護皮膜を形成する金属の保護皮膜形成方法。 (A) Trivalent chromium,
(B) zirconium ion,
(C) one or more members selected from the group consisting of chloride ions, sulfate ions and nitrate ions,
(D) an aromatic sulfonic acid, and
(E) By immersing one or more metals from the group consisting of zinc, aluminum, copper, nickel, chromium, iron, tin, and alloys thereof in a treatment liquid containing a liquid composition containing fluorine ions. The metal protective film forming method of forming a protective film on the metal.
（Ｂ）ジルコニウムイオン、
（Ｃ）塩素イオン、硫酸イオン及び硝酸イオンからなる群のうちの１種以上、
（Ｄ）芳香族スルホン酸、及び、
（Ｅ）フッ素イオン
を含有する、亜鉛、アルミニウム、銅、ニッケル、クロム、鉄、錫及びこれらの合金からなる群のうちの１種以上の金属を浸漬させて前記金属に保護皮膜を形成するための保護皮膜形成処理剤。 (A) Trivalent chromium,
(B) zirconium ion,
(C) one or more members selected from the group consisting of chloride ions, sulfate ions and nitrate ions,
(D) an aromatic sulfonic acid, and
(E) In order to form a protective film on the metal by immersing one or more metals selected from the group consisting of zinc, aluminum, copper, nickel, chromium, iron, tin and alloys thereof containing fluorine ions Protective film forming treatment agent.
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