JP2015232155A - Alumite member, manufacturing method of alumite member and treatment agent - Google Patents
Alumite member, manufacturing method of alumite member and treatment agent Download PDFInfo
- Publication number
- JP2015232155A JP2015232155A JP2014118679A JP2014118679A JP2015232155A JP 2015232155 A JP2015232155 A JP 2015232155A JP 2014118679 A JP2014118679 A JP 2014118679A JP 2014118679 A JP2014118679 A JP 2014118679A JP 2015232155 A JP2015232155 A JP 2015232155A
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- aluminum
- anodizing
- alumite
- base material
- 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
- 238000011282 treatment Methods 0.000 title claims description 177
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000005260 corrosion Methods 0.000 claims abstract description 74
- 230000007797 corrosion Effects 0.000 claims abstract description 74
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 61
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 55
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011651 chromium Substances 0.000 claims abstract description 36
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 36
- 239000010941 cobalt Substances 0.000 claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 35
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 29
- 239000010407 anodic oxide Substances 0.000 claims abstract 2
- 238000007743 anodising Methods 0.000 claims description 85
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000012360 testing method Methods 0.000 claims description 19
- 239000003973 paint Substances 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 13
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000005238 degreasing Methods 0.000 claims description 10
- -1 fluorine ions Chemical class 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000004043 dyeing Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229910001430 chromium ion Inorganic materials 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- 150000002222 fluorine compounds Chemical class 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000003518 caustics Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000010186 staining Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 abstract description 54
- 239000002585 base Substances 0.000 description 25
- 239000000126 substance Substances 0.000 description 17
- 239000002987 primer (paints) Substances 0.000 description 15
- 238000002048 anodisation reaction Methods 0.000 description 14
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 238000013461 design Methods 0.000 description 12
- 229940078494 nickel acetate Drugs 0.000 description 12
- 229960005069 calcium Drugs 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000005211 surface analysis Methods 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004020 luminiscence type Methods 0.000 description 8
- 238000013507 mapping Methods 0.000 description 7
- 238000010422 painting Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 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 5
- 230000002378 acidificating effect Effects 0.000 description 5
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 235000014443 Pyrus communis Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 239000000470 constituent Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229910052845 zircon Inorganic materials 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
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 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 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 238000005237 degreasing agent Methods 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
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 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 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000013615 primer Substances 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- 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 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 description 1
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 1
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011469 Crying Diseases 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
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 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
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- 229940010048 aluminum sulfate Drugs 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 230000004888 barrier function Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 229960004256 calcium citrate Drugs 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229940095626 calcium fluoride Drugs 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- CNYFJCCVJNARLE-UHFFFAOYSA-L calcium;2-sulfanylacetic acid;2-sulfidoacetate Chemical compound [Ca+2].[O-]C(=O)CS.[O-]C(=O)CS CNYFJCCVJNARLE-UHFFFAOYSA-L 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 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
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- 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 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 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
- 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
- 229910000152 cobalt phosphate 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
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 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
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 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
- 238000004512 die casting Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 239000002932 luster Substances 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
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 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
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-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
- 231100000989 no adverse effect Toxicity 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 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
- 238000010979 pH adjustment Methods 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 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
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 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
- 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
- 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 1
Abstract
Description
本発明は、アルマイト部材、アルマイト部材の製造方法及び処理剤に関する。 The present invention relates to an anodized member, an alumite member manufacturing method, and a treatment agent.
アルミニウムまたはアルミニウム合金の表面処理技術の一つとして、アルマイト（陽極酸化）処理が古くから行われている。アルマイト処理は陽極電解によりアルミニウムまたはアルミニウム合金の表面に多孔質層とバリア層からなる酸化膜を形成させ、その後に多孔質層に生じる孔を封孔することでアルミニウム部材に耐食性を付与させる技術である。また、アルマイト処理後に染料等の着色剤に浸漬させ、多孔質層の孔に染料を染み込ませ、その後に封孔処理を行うことで優れた色調と耐食性を付与させることが可能な技術でもある。染料を選択することで多くの色調が得られ、更に耐食性も優れていることから、アルマイト処理は古くから工業分野で広く利用されている。 As one of the surface treatment techniques for aluminum or aluminum alloy, anodization (anodization) treatment has been performed for a long time. Anodizing is a technology that provides an aluminum member with corrosion resistance by forming an oxide film consisting of a porous layer and a barrier layer on the surface of aluminum or an aluminum alloy by anodic electrolysis, and then sealing the holes generated in the porous layer. is there. Moreover, it is also a technique which can give the outstanding color tone and corrosion resistance by immersing in coloring agents, such as dye, after alumite treatment, making a dye soak into the hole of a porous layer, and performing sealing treatment after that. Since many colors are obtained by selecting a dye and the corrosion resistance is also excellent, the alumite treatment has been widely used in the industrial field for a long time.
ここで、封孔処理に関しては、アルマイト処理後の素材を純水や酢酸ニッケル水溶液に浸漬し、純水なら沸騰水で３０分以上、酢酸ニッケル水溶液でも９０℃以上で１５分以上行うことでアルマイトの多孔質層の孔を封孔させるのが一般的な技術となっている。この封孔処理を行うことで優れた耐食性を得ることができる。ただし、染色した場合、沸騰水での封孔は泣き出しと呼ばれる染料の流出が起きることから、酢酸ニッケル水溶液で封孔するのが一般的である。しかしながら、この封孔処理は、純水なら沸騰水で３０分以上、酢酸ニッケル水溶液でも９０℃以上で１５分以上行う必要があり、工業的にはこの温度を維持するためのコストと、封孔にかかる時間が問題となっている。温度を低下させることと時間を短縮させることで、生産性の向上とコスト低減を果たすことができるのである。また封孔処理を行ったアルマイト処理品の耐食性を塩水噴霧試験で評価した場合、ＡＤＣ１２材上では２４〜４８時間で白錆が発生するため、更なる耐食性向上を果たすための検討も行われている。 Here, with respect to the sealing treatment, the alumite-treated material is immersed in pure water or a nickel acetate aqueous solution. If pure water is used, boiling water is used for 30 minutes or more, and nickel acetate aqueous solution is used for 90 minutes or more for 15 minutes or more. It is a common technique to seal the pores of the porous layer. By performing this sealing treatment, excellent corrosion resistance can be obtained. However, in the case of dyeing, since sealing with boiling water causes dye outflow called crying out, sealing with a nickel acetate aqueous solution is common. However, this sealing treatment needs to be performed for 30 minutes or more with boiling water for pure water, and 15 minutes or more for 90 ° C. or more with an aqueous nickel acetate solution. Industrially, the cost for maintaining this temperature, and sealing The time it takes is a problem. By reducing the temperature and shortening the time, productivity can be improved and costs can be reduced. In addition, when the corrosion resistance of the alumite-treated product subjected to sealing treatment is evaluated by a salt spray test, white rust is generated on the ADC12 material in 24 to 48 hours. Therefore, studies for further improving the corrosion resistance are also performed. Yes.
アルマイトの封孔処理の低温化、またアルマイトの耐食性を向上させる手段は既に検討されている。しかしながら、耐食性を向上させ、また同時に封孔処理の低温・短時間化を果たせる技術は得られていない。例えば、特許文献１にはアルマイトの部材を浸漬し、電圧を印加する方法が開示されている。この方法では新たな電気設備を追加する事が必須となり、従来の浸漬及びスプレーといった簡潔な処理ではなく、経済的、生産性の面で好ましいものではない。 Means for lowering the alumite sealing treatment and improving the corrosion resistance of the alumite have already been studied. However, no technology has been obtained that can improve the corrosion resistance and at the same time reduce the sealing process temperature and time. For example, Patent Document 1 discloses a method of immersing an alumite member and applying a voltage. In this method, it is indispensable to add new electric equipment, and it is not preferable in terms of economy and productivity, rather than a simple process such as conventional dipping and spraying.
特許文献２では、フルオロアルキル基を有するアクリル酸、メタクリル酸のフッ素化ポリマー又はコポリマーを含有し、更にリチウムイオン、マグネシウムイオンを含有する溶液にてｐＨ５．５〜８．５、７５℃以上にて処理する方法が開示されている。ニッケルは含有していないが、処理温度が高温である。 Patent Document 2 contains a fluorinated polymer or copolymer of acrylic acid or methacrylic acid having a fluoroalkyl group, and a solution containing lithium ions and magnesium ions at pH 5.5 to 8.5 at 75 ° C. or higher. A method of processing is disclosed. Although nickel is not contained, the processing temperature is high.
特許文献３にはアルミニウムまたはアルミニウム合金上の保護皮膜に関する記載があるが、アルマイト上への転用を試みたものの耐食性を得ることはできなかった。 Patent Document 3 describes a protective film on aluminum or an aluminum alloy. However, although it was tried to divert to alumite, corrosion resistance could not be obtained.
特許文献４にはα−アミノ酸及び金属を含む溶液で封孔処理を行う方法が開示されているが、処理温度が５０℃以上とやや高温である上、耐食性も高いものではなかった。 Patent Document 4 discloses a method of performing a sealing treatment with a solution containing an α-amino acid and a metal, but the treatment temperature is slightly higher than 50 ° C. and the corrosion resistance is not high.
特許文献５にはリチウムイオン及びフッ化物イオンを含有する溶液を用いる方法が開示されているが、その処理後に二段処理として従来の沸騰水封孔と同等の８０〜１００℃の溶液への処理が必要で、経済的、工程的に好ましいものではなく、また、耐食性を得ることはできなかった。 Patent Document 5 discloses a method using a solution containing lithium ions and fluoride ions, but after the treatment, it is treated as a two-stage treatment into a solution at 80 to 100 ° C. equivalent to the conventional boiling water sealing. Is not preferable in terms of economy and process, and corrosion resistance could not be obtained.
特許文献６、７には、汚染物の付着を抑えるための組成が開示されているが、どちらも７０℃以上の処理温度が必要であり、経済的に好ましいものではない。 Patent Documents 6 and 7 disclose compositions for suppressing the adhesion of contaminants, but both require a treatment temperature of 70 ° C. or higher and are not economically preferable.
特許文献８には、染色したアルマイトを水溶性カチオンポリマー水溶液にて処理することにより、染料の固着を強固にし、その後にマグネシウム塩及び／またはカルシウム塩を含む封孔処理液によって封孔する方法が開示されているが、二段処理を必要とし、封孔処理の処理温度が８０℃以上と高いため経済的に好ましくない。 Patent Document 8 discloses a method in which dyed alumite is treated with a water-soluble cationic polymer aqueous solution to firmly fix the dye, and then sealed with a sealing treatment solution containing magnesium salt and / or calcium salt. Although disclosed, two-stage treatment is required, and the treatment temperature of the sealing treatment is as high as 80 ° C. or higher, which is not economically preferable.
非特許文献１には低温封孔処理も記載されているが、エージング（安定化のための放置）に時間がかかり、また低温クラックを生じ耐食性が劣る。また封孔処理後に湯洗を必須とするため、処理工程の短縮化には対応できない。 Non-Patent Document 1 also describes low-temperature sealing treatment, but it takes time for aging (leaving for stabilization), and low-temperature cracks are generated, resulting in poor corrosion resistance. Moreover, since hot water washing is essential after the sealing treatment, it cannot cope with shortening of the treatment process.
本発明は、上記課題に鑑み、優れた封孔性と耐食性を有するアルマイト部材を提供することを課題とする。 In view of the above problems, an object of the present invention is to provide an alumite member having excellent sealing properties and corrosion resistance.
本発明者らは、従来技術の抱える前記問題点であるアルマイトの耐食性向上の手段について鋭意検討した。その結果、アルマイト処理品の表面に陽極酸化皮膜とコバルト及び／又はクロムが存在するアルミニウム部材を提供することで優れた封孔性と耐食性を有する処理物が得られることを見出した。それと同時に、従来の酢酸ニッケル封孔処理に比べ低温・短時間処理も可能となり、大幅な作業性向上やコストメリットを得ることにも成功した。また、アルマイト後の処理においてジルコニウム、カルシウム、亜鉛、バナジウム、ニッケル、チタン、マグネシウム、アルミニウムを添加することによって、耐食性を低下させることなく、処理後の処理材が落ち着いた外観となり意匠性を持たせ又、耐光性を向上させることを見出した。 The present inventors diligently studied means for improving the corrosion resistance of alumite, which is the above-mentioned problem of the prior art. As a result, it has been found that a processed product having excellent sealing properties and corrosion resistance can be obtained by providing an aluminum member having an anodized film and cobalt and / or chromium on the surface of an alumite-treated product. At the same time, compared to the conventional nickel acetate sealing treatment, low-temperature and short-time treatment is possible, and it has succeeded in greatly improving workability and cost merit. In addition, by adding zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum in the post-anodite treatment, the treated material will have a calm appearance and no design, without reducing the corrosion resistance. Moreover, it discovered that light resistance was improved.
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、アルミニウム基材又はアルミニウム合金基材の表面に、陽極酸化皮膜と、コバルト及び／又はクロムとが存在するアルマイト部材であり、前記アルマイト部材の表面から前記アルミニウム基材又はアルミニウム合金基材方向にかけて、前記酸化皮膜全域又は０．０１μｍ以上の厚み領域で前記コバルト又はクロムが存在し、厚み方向で、前記アルマイト部材の表面から３μｍの間において、前記コバルトの存在比率が０．５質量％以上４０質量％以下、及び／又は、前記クロムの存在比率が１質量％以上４０質量％以下であるアルマイト部材である。 The present invention completed on the basis of the above knowledge is, in one aspect, an anodized member in which an anodized film and cobalt and / or chromium are present on the surface of an aluminum base material or an aluminum alloy base material. From the surface to the aluminum substrate or aluminum alloy substrate direction, the cobalt or chromium is present in the whole oxide film or in a thickness region of 0.01 μm or more, and in the thickness direction, between 3 μm from the surface of the anodized member, In the anodized member, the abundance ratio of the cobalt is 0.5 mass% or more and 40 mass% or less, and / or the abundance ratio of the chromium is 1 mass% or more and 40 mass% or less.
本発明のアルマイト部材は更に別の一実施形態において、アルマイト処理後に染色処理されている。 In yet another embodiment, the anodized member of the present invention is dyed after anodized.
本発明のアルマイト部材は更に別の一実施形態において、前記アルマイト部材の表面が、ケイ素、樹脂及びワックスからなる群のうち一種以上を含有するコーティング、プライマー、塗装、クリアコートのいずれか一種以上の処理がされている。 In yet another embodiment of the anodized member of the present invention, the surface of the anodized member includes at least one of a coating, a primer, a paint, and a clear coat containing at least one of the group consisting of silicon, resin, and wax. It has been processed.
本発明のアルマイト部材は更に別の一実施形態において、更に、ジルコニウム、カルシウム、亜鉛、バナジウム、ニッケル、チタン、マグネシウム、及び、アルミニウムからなる群のうち一種類以上の金属のイオンを含有する。 In yet another embodiment, the alumite member of the present invention further contains ions of one or more kinds of metals from the group consisting of zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum.
本発明は別の一側面において、アルミニウム基材又はアルミニウム合金基材の表面に、コバルト及び／又はクロムが存在し、塩水噴霧試験で４８時間以上の耐食性を有するアルマイト部材である。 Another aspect of the present invention is an alumite member in which cobalt and / or chromium is present on the surface of an aluminum base material or an aluminum alloy base material and has a corrosion resistance of 48 hours or more in a salt spray test.
本発明は更に別の一側面において、アルミニウム基材又はアルミニウム合金基材の表面に、コバルト及び／又はクロムが存在し、且つ、ニッケルを含まず、塩水噴霧試験で４８時間以上の耐食性を有するアルマイト部材である。 In yet another aspect of the present invention, alumite having cobalt and / or chromium present on the surface of an aluminum base material or aluminum alloy base material and not containing nickel and having a corrosion resistance of 48 hours or more in a salt spray test. It is a member.
本発明のアルマイト部材は更に別の一実施形態において、前記塩水噴霧試験で７２時間以上の耐食性を有する。 In yet another embodiment, the alumite member of the present invention has a corrosion resistance of 72 hours or more in the salt spray test.
本発明は更に別の一側面において、アルミニウム基材又はアルミニウム合金基材の表面に、陽極酸化前処理、陽極酸化処理、陽極酸化後処理、乾燥処理をこの順で行う本発明のアルマイト部材の製造方法である。 In another aspect of the present invention, the surface of the aluminum base material or aluminum alloy base material is subjected to anodizing pretreatment, anodizing treatment, post-anodizing treatment, and drying treatment in this order. Is the method.
本発明は更に別の一側面において、アルミニウム基材又はアルミニウム合金基材の表面に、陽極酸化前処理、陽極酸化処理、陽極酸化後処理、湯洗、乾燥処理をこの順で行う本発明のアルマイト部材の製造方法である。 In yet another aspect of the present invention, the alumite of the present invention wherein the surface of the aluminum base material or aluminum alloy base material is subjected to anodization pretreatment, anodization treatment, post-anodization treatment, hot water washing, and drying treatment in this order. It is a manufacturing method of a member.
本発明のアルマイト部材の製造方法は一実施形態において、前記陽極酸化前処理を、脱脂、エッチング、脱スマット、研磨処理、及び、梨地処理から選択される一つ以上の工程で行う。 In one embodiment of the method for producing an alumite member of the present invention, the anodizing pretreatment is performed in one or more steps selected from degreasing, etching, desmutting, polishing treatment, and satin treatment.
本発明のアルマイト部材の製造方法は別の一実施形態において、前記陽極酸化後処理を、５〜７０℃、ｐＨ２〜７、１〜９００秒の処理条件で行う。 In another embodiment of the method for producing an alumite member of the present invention, the post-anodizing treatment is performed under conditions of 5 to 70 ° C., pH 2 to 7, and 1 to 900 seconds.
本発明のアルマイト部材の製造方法は更に別の一実施形態において、前記陽極酸化後処理を、浸漬又はスプレー噴霧にて行う。 In still another embodiment of the method for producing an anodized member of the present invention, the post-anodizing treatment is performed by dipping or spraying.
本発明のアルマイト部材の製造方法は更に別の一実施形態において、前記陽極酸化処理と、前記陽極酸化後処理との間に、染色処理を行う。 In still another embodiment of the method for producing an alumite member of the present invention, a dyeing process is performed between the anodizing process and the post-anodizing process.
本発明のアルマイト部材の製造方法は更に別の一実施形態において、前記陽極酸化後処理と、前記乾燥処理との間に、ケイ素、樹脂及びワックスからなる群のうち一種以上を含有するコーティング、プライマー、塗装、クリアコートのいずれか一種以上の処理を行う。 In yet another embodiment of the method for producing an alumite member of the present invention, a coating or primer containing at least one of the group consisting of silicon, resin and wax between the post-anodizing treatment and the drying treatment Apply at least one of painting, clear coating.
本発明は更に別の一側面において、本発明のアルマイト部材を得るために、アルミニウム基材又はアルミニウム合金基材の表面に陽極酸化皮膜を形成した後の陽極酸化後処理において用いられる処理剤であり、コバルトイオン及び／又はクロムイオンと、フッ素イオンとを含有する処理剤である。 In another aspect of the present invention, there is provided a treating agent used in post-anodizing post-treatment after forming an anodized film on the surface of an aluminum base material or aluminum alloy base material in order to obtain the alumite member of the present invention. , A treatment agent containing cobalt ions and / or chromium ions and fluorine ions.
本発明の処理剤は一実施形態において、更に、ジルコニウム、カルシウム、亜鉛、バナジウム、ニッケル、チタン、マグネシウム、及び、アルミニウムからなる群のうち一種類以上の金属のイオンを含有する。 In one embodiment, the treatment agent of the present invention further contains ions of one or more kinds of metals from the group consisting of zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum.
本発明の処理剤は一実施形態において、本発明のアルマイト部材を得るために、アルミニウム基材又はアルミニウム合金基材の表面に陽極酸化皮膜を形成する前の陽極酸化前処理において用いられる処理剤であり、苛性アルカリ、シリカ、硝酸、鉱酸、有機酸、フッ素化合物、及び、界面活性剤を含有する処理剤である。 In one embodiment, the treatment agent of the present invention is a treatment agent used in an anodization pretreatment before forming an anodized film on the surface of an aluminum substrate or an aluminum alloy substrate in order to obtain the anodized member of the present invention. Yes, it is a processing agent containing caustic, silica, nitric acid, mineral acid, organic acid, fluorine compound, and surfactant.
本発明によれば、アルミニウムまたはアルミニウム合金で優れた耐食性と封孔性を有するアルマイト処理部材を得ることが出来る。更に従来の酢酸ニッケル封孔処理に比べ低温かつ短時間で処理が可能であり、生産性向上とコストメリットが期待できる。 According to the present invention, an alumite-treated member having excellent corrosion resistance and sealing properties can be obtained from aluminum or an aluminum alloy. Furthermore, compared with the conventional nickel acetate sealing treatment, the treatment can be performed at a low temperature and in a short time, and productivity improvement and cost merit can be expected.
（アルマイト部材）
本発明のアルマイト部材は、アルミニウム基材又はアルミニウム合金基材の表面に、陽極酸化皮膜と、コバルト及び／又はクロムとが存在する。アルマイト部材の高耐食性が得られる詳細な機構については、分析結果から、このように基材の表面に、陽極酸化皮膜と、コバルト及び／又はクロムとが存在することで、封孔すると同時に皮膜を形成しており、耐食性と封孔性に優れたアルマイト部材が得られる。
(Anodized materials)
In the alumite member of the present invention, an anodized film and cobalt and / or chromium are present on the surface of an aluminum base or aluminum alloy base. As for the detailed mechanism for obtaining the high corrosion resistance of the alumite member, from the analysis results, the presence of the anodized film and cobalt and / or chromium on the surface of the substrate in this way allows the film to be sealed at the same time as sealing. An alumite member that is formed and excellent in corrosion resistance and sealing properties is obtained.
本発明のアルマイト部材は、アルマイト部材の表面からアルミニウム基材又はアルミニウム合金基材方向にかけて、酸化皮膜全域又は０．０１μｍ以上の厚み領域でコバルトが存在し、厚み方向で、アルマイト部材の表面から３μｍの間において、コバルトの存在比率が０．５質量％以上４０質量％以下、及び／又は、クロムの存在比率が１質量％以上４０質量％以下である。厚み方向で、アルマイト部材の表面から３μｍの間に当該コバルトの存在比率及びクロムの存在比率は、アルマイト部材の表面全域に亘っていなくてもよい。当該存在比率を充足する領域は、少なくとも、優れた封孔性と耐食性が必要な領域に設けていればよい。このような構成であれば、皮膜自体が安定化し、優れた耐食性、外観及び塗装密着性が得られる。また、厚み方向で、アルマイト部材の表面から３μｍの間において、コバルトの存在比率が１質量％以上１１質量％以下であるのがより好ましく、１質量％以上７質量％以下であるのがより好ましい。また、厚み方向で、アルマイト部材の表面から３μｍの間において、クロムの存在比率が５質量％以上３０質量％以下であるのがより好ましく、５質量％以上２５質量％以下であるのがより好ましい。 In the anodized member of the present invention, cobalt exists in the entire oxide film or in a thickness region of 0.01 μm or more from the surface of the anodized member toward the aluminum base material or aluminum alloy base material, and 3 μm from the surface of the anodized member in the thickness direction. Between, the abundance ratio of cobalt is 0.5 mass% or more and 40 mass% or less, and / or the abundance ratio of chromium is 1 mass% or more and 40 mass% or less. In the thickness direction, the abundance ratio of cobalt and the abundance ratio of chromium do not need to cover the entire surface of the alumite member between 3 μm from the surface of the alumite member. The region satisfying the abundance ratio may be provided at least in a region that requires excellent sealing properties and corrosion resistance. With such a configuration, the coating itself is stabilized, and excellent corrosion resistance, appearance, and paint adhesion can be obtained. Further, in the thickness direction, the abundance ratio of cobalt is more preferably 1% by mass or more and 11% by mass or less, and more preferably 1% by mass or more and 7% by mass or less, between 3 μm from the surface of the alumite member. . Further, in the thickness direction, the abundance ratio of chromium is more preferably 5% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 25% by mass or less, between 3 μm from the surface of the anodized member. .
本発明のアルマイト部材は、別の一側面において、アルミニウム基材又はアルミニウム合金基材の表面に、コバルト及び／又はクロムが存在し、塩水噴霧試験で４８時間以上、好ましくは７２時間以上、より好ましくは１２０時間以上の耐食性を有するアルマイト部材である。また、本発明のアルマイト部材は、更に別の一側面において、アルミニウム基材又はアルミニウム合金基材の表面に、コバルト及び／又はクロムが存在し、且つ、ニッケルを含まず、塩水噴霧試験で４８時間以上、好ましくは７２時間以上、より好ましくは１２０時間以上の耐食性を有するアルマイト部材である。 In another aspect of the alumite member of the present invention, cobalt and / or chromium is present on the surface of the aluminum base material or aluminum alloy base material, and the salt spray test is 48 hours or longer, preferably 72 hours or longer, more preferably. Is an anodized member having corrosion resistance of 120 hours or more. In addition, in another aspect of the anodized member of the present invention, cobalt and / or chromium is present on the surface of the aluminum base material or aluminum alloy base material, nickel is not included, and a salt spray test is performed for 48 hours. The anodized member having a corrosion resistance of 72 hours or longer, more preferably 120 hours or longer, preferably above.
（被処理金属基材）
本発明の高耐食性を形成する被処理金属基材としては、アルミニウム部材、展伸材やダイキャストを含むアルミニウム合金部材に対し効果的に作用する。本発明のアルマイト部材は、当該アルミニウム基材又はアルミニウム合金基材の表面に、陽極酸化前処理、陽極酸化処理、陽極酸化後処理、乾燥処理をこの順で行うことで作製される。
(Treatment metal substrate)
As a to-be-processed metal base material which forms the high corrosion resistance of this invention, it acts effectively with respect to the aluminum alloy member containing an aluminum member, a extending | stretching material, and die-casting. The anodized member of the present invention is produced by performing anodizing pretreatment, anodizing treatment, post-anodizing treatment, and drying treatment in this order on the surface of the aluminum substrate or aluminum alloy substrate.
（陽極酸化前処理）
被処理金属基材に対し、まず、陽極酸化前処理を行う。陽極酸化前処理の処理剤は、苛性アルカリ、シリカ、硝酸、鉱酸、有機酸、フッ素化合物、及び、界面活性剤を含有するのが好ましい。このような構成であれば、油や離型剤や汚れの除去が可能で、後の工程で均一なアルマイト外観や良好な耐食性が得られる。
(Anodic oxidation pretreatment)
First, anodizing pretreatment is performed on the metal substrate to be treated. The treatment agent for the anodization pretreatment preferably contains caustic, silica, nitric acid, mineral acid, organic acid, fluorine compound, and surfactant. With such a configuration, it is possible to remove oil, a release agent and dirt, and a uniform alumite appearance and good corrosion resistance can be obtained in a later step.
（陽極酸化前処理の脱脂）
陽極酸化前処理として脱脂を行うことで、本発明のアルマイト部材の処理外観、耐食性および塗装密着性を向上させることができる。脱脂には酸性タイプやアルカリタイプの脱脂剤が使用できる。脱脂時間に関しては部材の油付着度合いにより処理条件を変化させる必要があるが、脱脂時間が短い場合は脱脂不良となり、最終的な処理物で外観ムラや優れた耐食性が得られなくなる。
(Degreasing pre-anodizing treatment)
By performing degreasing as an anodizing pretreatment, it is possible to improve the treated appearance, corrosion resistance and paint adhesion of the anodized member of the present invention. An acid type or alkaline type degreasing agent can be used for degreasing. Regarding the degreasing time, it is necessary to change the processing conditions depending on the degree of oil adhesion of the member. However, if the degreasing time is short, the degreasing is poor and the final processed product cannot obtain uneven appearance and excellent corrosion resistance.
（陽極酸化前処理のエッチング）
陽極酸化前処理としてエッチングを行うことで、本発明のアルマイト部材の処理外観、染色性、耐食性および塗装密着性を向上させることが可能である。離型剤などが付着している部材ではエッチングにより離型剤の除去が可能である。酸やアルカリを用いたエッチング処理を行うことで離型剤が除去でき、耐食性が向上する。離型剤等の除去が不十分であった場合、最終的な処理物で外観ムラや優れた耐食性が得られなくなる。
(Etching of pre-anodizing treatment)
By performing etching as the pre-anodizing treatment, it is possible to improve the treated appearance, dyeability, corrosion resistance and paint adhesion of the anodized member of the present invention. For a member to which a release agent or the like is attached, the release agent can be removed by etching. By performing an etching process using acid or alkali, the release agent can be removed, and the corrosion resistance is improved. If the removal of the release agent or the like is insufficient, the final processed product cannot obtain uneven appearance and excellent corrosion resistance.
（陽極酸化前処理の脱スマット）
処理物表面にスマットが発生した場合には、脱スマット処理（例えば、硝酸につけることでスマット（しみ）を除く処理）が可能である。陽極酸化前処理として脱スマット処理を行うことで、本発明のアルマイト部材の処理外観、染色性、耐食性および塗装密着性を向上させることが可能である。脱スマット処理が不十分であった場合には最終的な処理物で外観ムラや優れた耐食性が得られなくなる。
(Desmutting of anodizing pretreatment)
When smut is generated on the surface of the processed material, desmutting treatment (for example, treatment by removing it from nitric acid by applying it to nitric acid) is possible. By performing desmutting treatment as anodizing pretreatment, it is possible to improve the treated appearance, dyeability, corrosion resistance and paint adhesion of the anodized member of the present invention. If the desmutting process is insufficient, the final processed product cannot have uneven appearance and excellent corrosion resistance.
（陽極酸化前処理の研磨処理）
陽極酸化前処理として研磨処理を行うことで、本発明のアルマイト部材の処理外観、染色性、耐食性および塗装密着性を向上させることが可能である。特に処理物の意匠性や湯じわ除去等の効果を得ることが可能となる。酸性型やアルカリ性型研磨剤を使用でき、また化学研磨処理や電解研磨処理を行うことが出来る。
(Anodic oxidation pretreatment polishing process)
By performing a polishing treatment as a pretreatment for anodization, it is possible to improve the treatment appearance, dyeability, corrosion resistance and paint adhesion of the anodized member of the present invention. In particular, it is possible to obtain effects such as design properties of the processed material and removal of hot water wrinkles. An acidic type or alkaline type polishing agent can be used, and chemical polishing treatment or electrolytic polishing treatment can be performed.
（陽極酸化前処理の梨地処理）
陽極酸化前処理として梨地処理（艶等を無くす処理）を行うことで、本発明のアルマイト部材の処理外観、染色性、耐食性および塗装密着性を向上させることが可能である。特に処理物の意匠性や湯じわ除去等の効果を得るため、梨地処理を行うことが可能である。酸性型やアルカリ性型梨地剤を使用でき、また化学梨地処理や電解梨地処理を行うことが出来る。
(Satin finish for anodizing pretreatment)
By performing a satin treatment (a treatment for eliminating luster or the like) as an anodizing pretreatment, it is possible to improve the treatment appearance, dyeability, corrosion resistance and paint adhesion of the anodized member of the present invention. In particular, it is possible to perform a satin treatment in order to obtain effects such as design properties of the processed material and removal of hot water wrinkles. Acidic or alkaline pear finishes can be used, and chemical pear finish or electrolytic pear finish can be performed.
（アルミニウム陽極酸化処理）
上記陽極酸化前処理後の金属基材を、アルマイト処理液の処理浴に浸漬することで、アルミニウム陽極酸化処理を行う。陽極酸化処理による酸化膜の膜厚は１〜７０μｍが好ましく、５〜３０μｍがより好ましい。１μｍ以下であると耐食性が低下するとともに染色処理が困難となり、７０μｍ以上では生産性が低下するため好ましくない。１μｍ以上の膜厚が得られるのであればアルマイト処理液や温度・電圧等は自由に選択することができる。一般的なアルマイトや硬質アルマイトの浴に用いる処理液となる硫酸、硫酸アンモニウム、硫酸水素ナトリウム、硫酸水素アンモニウム、燐酸、燐酸ナトリウム、硼酸、硼砂、炭酸アンモニウム、クロム酸、重クロム酸、スルファミン酸、シュウ酸、酒石酸、マレイン酸、クエン酸、クエン酸アンモニウム、蟻酸、アンモニア水、水酸化ナトリウム、フッ化アンモニウム、フェリシアン化カリウム、ジメチルスルホキシド、ホルムアミド、過酸化水素水、チタン酸シュウ酸カリウム、スルホサリチル酸、スルホフタル酸、スルホイソフタル酸、フェノールスルホン酸等を含有し、−５〜２５０℃で使用される処理剤を利用できる。
(Aluminum anodizing treatment)
An aluminum anodizing treatment is performed by immersing the metal substrate after the anodizing pretreatment in a treatment bath of an alumite treatment solution. The thickness of the oxide film formed by anodization is preferably 1 to 70 μm, more preferably 5 to 30 μm. If it is 1 μm or less, the corrosion resistance is lowered and the dyeing process becomes difficult, and if it is 70 μm or more, the productivity is lowered, which is not preferable. As long as a film thickness of 1 μm or more can be obtained, the alumite treatment solution, temperature, voltage, and the like can be freely selected. Sulfuric acid, ammonium sulfate, sodium hydrogensulfate, ammonium hydrogensulfate, phosphoric acid, sodium phosphate, boric acid, borax, ammonium carbonate, chromic acid, dichromic acid, sulfamic acid, sulphur, which are treatment liquids used in general anodized and hard anodized baths Acid, tartaric acid, maleic acid, citric acid, ammonium citrate, formic acid, aqueous ammonia, sodium hydroxide, ammonium fluoride, potassium ferricyanide, dimethyl sulfoxide, formamide, hydrogen peroxide, potassium titanate oxalate, sulfosalicylic acid, sulfophthalate A treatment agent containing acid, sulfoisophthalic acid, phenolsulfonic acid and the like and used at −5 to 250 ° C. can be used.
（アルミニウム陽極酸化処理後の染色処理）
陽極酸化処理と、陽極酸化後処理との間に、染色処理を行うことが出来る。このとき、その後のアルミニウム陽極酸化後処理を行うことで、泣き出しと呼ばれる染料の流出もなく、良好な外観と耐食性を得ることが可能である。染色処理を行うことで、本発明のアルマイト部材の処理外観を向上させることが可能である。
(Dyeing after aluminum anodizing)
A dyeing process can be performed between the anodizing process and the post-anodizing process. At this time, it is possible to obtain good appearance and corrosion resistance by performing post-treatment of the subsequent aluminum anodic oxidation without causing the dye to flow out. By performing the dyeing process, it is possible to improve the processing appearance of the anodized member of the present invention.
（陽極酸化後処理）
アルミニウム陽極酸化処理の後、陽極酸化後処理を行う。陽極酸化後処理は、処理液中に浸漬することで、又は、処理液をスプレー噴霧で行うことができる。処理工場に適した処理法を選択することで、本発明の処理外観、耐食性および塗装密着性を向上させることが可能である。
(Anodic oxidation post-treatment)
After the aluminum anodizing treatment, post-anodizing treatment is performed. The post-anodizing treatment can be performed by dipping in the treatment liquid or by spraying the treatment liquid. By selecting a treatment method suitable for the treatment plant, it is possible to improve the treatment appearance, corrosion resistance and paint adhesion of the present invention.
（陽極酸化後処理の処理液の温度）
陽極酸化後処理の処理液の温度は５〜７０℃の範囲が好ましく、２０〜５０℃の範囲であるのがより好ましい。処理温度が上記範囲内で良好な皮膜が得られ、良好な外観、封孔性、耐食性が得られる。処理温度が５℃以下の場合は反応速度の低下により皮膜を得るのに時間がかかり、７０℃以上の場合は維持コストの面から好ましくはない。
(Temperature of anodized post-treatment liquid)
The temperature of the treatment liquid for the post-anodizing treatment is preferably in the range of 5 to 70 ° C, and more preferably in the range of 20 to 50 ° C. A good film can be obtained within the above processing temperature range, and good appearance, sealing properties and corrosion resistance can be obtained. When the treatment temperature is 5 ° C. or lower, it takes time to obtain a film due to a decrease in the reaction rate.
（陽極酸化後処理の処理液のｐＨ）
陽極酸化後処理の処理液のｐＨは２〜７の範囲が好ましく、処理ｐＨ３〜５の範囲であるのがより好ましい。処理ｐＨが上記範囲内で良好な皮膜が得られ、良好な外観、封孔性、耐食性が得られる。処理ｐＨが２以下の場合は部材の研磨過剰が生じ処理外観ムラや耐食性の低下を招き、処理ｐＨが７以上では反応速度の低下と処理液に沈殿が生じやすくなり、また強アルカリであることから好ましくない。ｐＨ調整が必要な場合は硝酸と苛性ソーダで行うことが出来るが、この他に硫酸、塩酸、苛性カリ、アンモニア水等も使用できる。
(PH of treatment solution for post-anodizing treatment)
The pH of the treatment liquid for the post-anodizing treatment is preferably in the range of 2 to 7, and more preferably in the range of treatment pH of 3 to 5. When the treatment pH is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. When the treatment pH is 2 or less, the member is excessively polished, resulting in uneven processing appearance and reduced corrosion resistance. When the treatment pH is 7 or more, the reaction rate is lowered and precipitation tends to occur in the treatment solution, and it is strongly alkaline. Is not preferable. When pH adjustment is necessary, nitric acid and caustic soda can be used. In addition, sulfuric acid, hydrochloric acid, caustic potash, aqueous ammonia and the like can also be used.
（陽極酸化後処理の時間）
陽極酸化後処理の時間は１〜９００秒の範囲が好ましく、２〜３００秒の範囲であることがより好ましい。処理時間が上記範囲内で良好な皮膜が得られ、良好な外観、封孔性、耐食性が得られる。処理時間が１秒以下では反応不足による耐食性の低下を招き、９００秒以上では処理過剰による処理概観ムラを招くとともに生産性も低下するため好ましくない。
(Time of post-anodizing treatment)
The time for the post-anodizing treatment is preferably in the range of 1 to 900 seconds, and more preferably in the range of 2 to 300 seconds. When the treatment time is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. If the treatment time is 1 second or less, the corrosion resistance is lowered due to insufficient reaction, and if it is 900 seconds or more, the processing is not uniform due to excessive treatment and the productivity is also lowered.
（陽極酸化後処理剤）
本発明で用いる陽極酸化後処理剤は、コバルトイオン及び／又はクロムイオンと、フッ素イオンとを含有する。
(Anodizing post-treatment agent)
The anodizing post-treatment agent used in the present invention contains cobalt ions and / or chromium ions and fluorine ions.
（陽極酸化後処理剤−コバルトイオン源）
陽極酸化後処理剤の構成成分であるコバルトイオンのイオン源としては、硝酸コバルト、硫酸コバルト、塩化コバルト、リン酸コバルト、酢酸コバルト、フッ化コバルト、水酸化コバルト等のコバルト化合物が利用できる。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。これらコバルトの化合物は一種または二種以上を使用することができる。当該化合物のコバルトイオン濃度は０．００１〜５０ｇ／Ｌが好ましく、０．０１〜２０ｇ／Ｌであるのがより好ましい。コバルト濃度が上記範囲内で良好な皮膜が得られ、良好な外観、封孔性、耐食性が得られる。コバルト濃度が０．００１ｇ／Ｌより低下すると耐食性と封孔性の低下を招き、５０ｇ／Ｌを超えるとコストメリットの低下と共に、処理液中で沈殿が発生しやすくなり好ましくない。
(Anodizing post-treatment agent-Cobalt ion source)
Cobalt compounds such as cobalt nitrate, cobalt sulfate, cobalt chloride, cobalt phosphate, cobalt acetate, cobalt fluoride, and cobalt hydroxide can be used as an ion source of cobalt ions, which are constituents of the anodizing post-treatment agent. If it is a compound of cobalt, substances other than the above can be used as a source of cobalt. These cobalt compounds may be used alone or in combination of two or more. The cobalt ion concentration of the compound is preferably 0.001 to 50 g / L, and more preferably 0.01 to 20 g / L. A good film can be obtained when the cobalt concentration is within the above range, and good appearance, sealing properties and corrosion resistance can be obtained. When the cobalt concentration is lower than 0.001 g / L, the corrosion resistance and the sealing performance are lowered, and when it exceeds 50 g / L, the cost merit is lowered and precipitation is likely to occur in the treatment liquid.
（陽極酸化後処理剤−クロムイオン源）
陽極酸化後処理剤の構成成分であるクロムイオンのイオン源としては、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、水酸化クロム等の３価クロム塩、およびクロム酸や重クロム酸等の６価クロムを還元剤により３価に還元した３価クロム等のクロム化合物が利用できる。３価クロムの化合物であれば、上記以外の物質でも３価クロムの供給源として利用できる。これらクロムの化合物は一種または二種以上を使用することができる。当該化合物のクロムイオン濃度は０．００１〜５０ｇ／Ｌが好ましく、０．０１〜２０ｇ／Ｌであるのがより好ましい。クロム濃度が上記範囲内で良好な皮膜が得られ、良好な外観、封孔性、耐食性が得られる。クロム濃度が０．００１ｇ／Ｌより低下すると耐食性と封孔性の低下を招き、５０ｇ／Ｌを超えるとコストメリットの低下と共に、処理液中で沈殿が発生しやすくなり好ましくない。
(Anodizing post-treatment agent-chromium ion source)
The ion source of chromium ion, which is a constituent of the anodizing post-treatment agent, includes trivalent chromium salts such as chromium nitrate, chromium sulfate, chromium chloride, chromium phosphate, chromium acetate, chromium hydroxide, and chromic acid and heavy chromium. A chromium compound such as trivalent chromium obtained by reducing hexavalent chromium such as an acid to trivalent with 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 chromium compounds can be used singly or in combination of two or more. The chromium ion concentration of the compound is preferably 0.001 to 50 g / L, and more preferably 0.01 to 20 g / L. When the chromium concentration is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. When the chromium concentration is lower than 0.001 g / L, the corrosion resistance and the sealing performance are lowered, and when it exceeds 50 g / L, the cost merit is lowered and precipitation is likely to occur in the treatment liquid.
（陽極酸化後処理剤−フッ素イオン源）
陽極酸化後処理剤の構成成分であるフッ素イオンのイオン源としては、フッ化水素、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、酸性フッ化カリウム、フッ化ナトリウム、酸性フッ化ナトリウム、フッ化コバルト、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利用できる。フッ素化合物であれば、上記以外の物質でもフッ素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。当該化合物のフッ素イオンの濃度としては０．０１〜１００ｇ／Ｌが好ましく、０．１〜５０ｇ／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皮膜が得られ、良好な外観、封孔性、耐食性が得られる。フッ素イオン濃度が０．０１ｇ／Ｌより低下すると耐食性と封孔性の低下を招き、１００ｇ／Ｌを超えるとコストメリットの低下と共に、処理液中で沈殿が発生しやすくなり好ましくない。
(Anodizing post-treatment agent-Fluorine ion source)
Sources of fluorine ions, which are constituents of the anodizing post-treatment agent, include hydrogen fluoride, ammonium fluoride, acidic ammonium fluoride, potassium fluoride, acidic potassium fluoride, sodium fluoride, acidic sodium fluoride, fluoride. Fluorine compounds such as cobalt fluoride, zircon ammonium fluoride, and borofluoride can be used. If it is a fluorine compound, substances other than those described above can be used as the fluorine supply source. One or two or more of these fluorine compounds can be used. The fluorine ion concentration of the compound is preferably 0.01 to 100 g / L, more preferably 0.1 to 50 g / L. When the fluorine ion concentration is within the above range, a good film is obtained, and good appearance, sealing properties and corrosion resistance are obtained. When the fluorine ion concentration is lower than 0.01 g / L, the corrosion resistance and the sealing performance are lowered, and when it exceeds 100 g / L, the cost merit is lowered and precipitation is likely to occur in the treatment liquid.
（陽極酸化後処理剤−ジルコニウム源）
また、陽極酸化後処理剤がジルコニウム源を含んでも良い。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皮膜が得られ、良好な外観、封孔性、耐食性が得られる。ジルコニウム濃度が０．００１ｇ／Ｌより低下すると意匠性、耐光性が得られにくく、５０ｇ／Ｌを超えるとコストメリットの低下と共に、処理液中に沈殿が発生しやすくなり好ましくない。
(Anodizing post-treatment agent-zirconium source)
Further, the post-anodizing treatment agent may contain a 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 good film is obtained when the zirconium concentration is within the above range, and good appearance, sealing properties and corrosion resistance are obtained. If the zirconium concentration is lower than 0.001 g / L, it is difficult to obtain design properties and light resistance, and if it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur in the treatment liquid.
（陽極酸化後処理剤−カルシウム源）
また、陽極酸化後処理剤がカルシウム源を含んでも良い。カルシウム源としては、フッ化カルシウム、硫酸カルシウム、クエン酸カルシウム、乳酸カルシウム、チオグリコール酸カルシウム、タングステン酸カルシウム等のカルシウム化合物が利用できる。これらカルシ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。当該化合物のカルシウム濃度としては、０．０１〜１０ｇ／Ｌが好ましく、０．１〜１ｇ／Ｌであるのがより好ましい。カルシウム濃度が上記範囲内で良好な皮膜が得られ、良好な外観、封孔性、耐食性が得られる。カルシウム濃度が０．０１ｇ／Ｌより低下すると意匠性、耐光性向上効果が得られにくく、１０ｇ／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。
(Anodizing post-treatment agent-calcium source)
Further, the post-anodizing treatment agent may contain a calcium source. As the calcium source, calcium compounds such as calcium fluoride, calcium sulfate, calcium citrate, calcium lactate, calcium thioglycolate, and calcium tungstate can be used. These calcium compounds can be used alone or in combination of two or more. The calcium concentration of the compound is preferably 0.01 to 10 g / L, and more preferably 0.1 to 1 g / L. A good film can be obtained when the calcium concentration is within the above range, and good appearance, sealing properties and corrosion resistance can be obtained. If the calcium concentration is lower than 0.01 g / L, it is difficult to obtain the effect of improving the design and light resistance, and if it exceeds 10 g / L, the cost merit is reduced and precipitation is likely to occur in the treatment liquid.
（陽極酸化後処理剤−亜鉛源）
また、陽極酸化後処理剤が亜鉛源を含んでも良い。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皮膜が得られ、良好な外観、封孔性、耐食性が得られる。亜鉛濃度が０．００１ｇ／Ｌより低下すると意匠性、耐光性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。
(Anodizing post-treatment agent-zinc source)
Further, the post-anodizing treatment agent may contain a 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. When the zinc concentration is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. When the zinc concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design property and light resistance.
（陽極酸化後処理剤−バナジウム源）
また、陽極酸化後処理剤がバナジウム源を含んでも良い。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皮膜が得られ、良好な外観、封孔性、耐食性が得られる。バナジウム濃度が０．００１ｇ／Ｌより低下すると意匠性、耐光性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。
(Anodizing post-treatment agent-vanadium source)
The post-anodizing treatment agent may contain a 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 film is obtained when the vanadium concentration is within the above range, and good appearance, sealing properties and corrosion resistance are obtained. When the vanadium concentration is lower than 0.001 g / L, it is difficult to obtain an effect of improving the design and light resistance.
（陽極酸化後処理剤−ニッケル源）
また、陽極酸化後処理剤がニッケル源を含んでも良い。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、燐酸ニッケル、スルファミン酸ニッケル、酢酸ニッケル、フッ化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、０．００１〜２０ｇ／Ｌが好ましく、０．０１〜１０ｇ／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皮膜が得られ、良好な外観、封孔性、耐食性が得られる。ニッケル濃度が０．００１ｇ／Ｌより低下すると意匠性、耐光性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。
(Anodizing post-treatment agent-nickel source)
Further, the post-anodizing treatment agent may contain a nickel source. As the nickel source, nickel compounds such as nickel nitrate, nickel sulfate, nickel chloride, nickel phosphate, nickel sulfamate, nickel acetate and nickel fluoride 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 20 g / L, and more preferably 0.01 to 10 g / L. A good film is obtained when the nickel concentration is within the above range, and good appearance, sealing properties and corrosion resistance are obtained. When the nickel concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design and light resistance, and when it exceeds 20 g / L, the cost merit is reduced and precipitation is likely to occur.
（陽極酸化後処理剤−チタン源）
また、陽極酸化後処理剤がチタン源を含んでも良い。チタン源としては、塩化チタン、シュウ酸チタンカリウム、チタンフッ化アンモン、フッ化チタンカリウム、硫酸チタン等のチタン化合物が利用できる。これらチタ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。チタン濃度は、０．０１〜５０ｇ／Ｌが好ましく、０．１〜２０ｇ／Ｌであるのがより好ましい。チタン濃度が上記範囲内で良好な皮膜が得られ、良好な外観、封孔性、耐食性が得られる。チタン濃度が０．００１ｇ／Ｌより低下すると意匠性、耐光性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。
(Anodizing post-treatment agent-titanium source)
Further, the post-anodizing treatment agent may contain a titanium source. As the titanium source, titanium compounds such as titanium chloride, potassium titanium oxalate, ammonium titanium fluoride, potassium titanium fluoride, and titanium sulfate can be used. These titanium compounds can be used alone or in combination of two or more. The titanium concentration is preferably 0.01 to 50 g / L, and more preferably 0.1 to 20 g / L. When the titanium concentration is within the above range, a good film can be obtained, and good appearance, sealing properties and corrosion resistance can be obtained. When the titanium concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design and light resistance, and when it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur.
（陽極酸化後処理剤−マグネシウム源）
また、陽極酸化後処理剤がマグネシウム源を含んでも良い。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皮膜が得られ、良好な外観、封孔性、耐食性が得られる。マグネシウム濃度が０．００１ｇ／Ｌより低下すると意匠性、耐光性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。
(Anodizing post-treatment agent-magnesium source)
Further, the post-anodizing treatment agent may contain a 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 film is obtained when the magnesium concentration is within the above range, and good appearance, sealing properties and corrosion resistance are obtained. When the magnesium concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design and light resistance, and when it exceeds 50 g / L, the cost merit is reduced and precipitation is likely to occur.
（陽極酸化後処理剤−アルミニウム源）
また、陽極酸化後処理剤がアルミニウム源を含んでも良い。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、コル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。アルミニウム濃度が上記範囲内で良好な皮膜が得られ、良好な外観、封孔性、耐食性が得られる。アルミニウム濃度が０．００１ｇ／Ｌより低下すると意匠性、耐光性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。
(Anodizing post-treatment agent-aluminum source)
Further, the post-anodizing treatment agent may contain an aluminum source. As the aluminum source, aluminum compounds such as aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum acetate, aluminum carbonate, and corydal 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. When the aluminum concentration is within the above range, a good film is obtained, and good appearance, sealing properties and corrosion resistance are obtained. If the aluminum concentration is lower than 0.001 g / L, it is difficult to obtain the effect of improving the design and light resistance.
（陽極酸化後処理の後湯洗）
陽極酸化後処理の後に湯洗を行うことも可能である。湯洗の有無で外観や耐食性に影響はないが、湯洗を行うことで洗浄能力が向上するとともに、部材の温度が上昇しその後の乾燥工程での乾燥を容易に、短時間で行うことができる。温度や時間に指定はないが、４０〜８０℃、１０秒〜５分浸漬が量産性に優れている。
(After anodizing and post-treatment)
It is also possible to perform hot water washing after the post-anodizing treatment. The appearance and corrosion resistance are not affected by the presence or absence of hot water washing, but the washing ability is improved by washing with hot water, and the temperature of the member rises, so that the drying in the subsequent drying process can be easily performed in a short time. it can. Although there is no designation for temperature or time, immersion at 40 to 80 ° C. for 10 seconds to 5 minutes is excellent in mass productivity.
(陽極酸化後処理の後のコーティング、プライマー、塗装、クリアコート）
陽極酸化後処理の後に、ケイ素、樹脂及びワックスからなる群のうち一種以上を含有するコーティング、プライマー、塗装、クリアコートのいずれか一つ以上の処理を行っても良い。当該コーティングは、主に耐食性を付与することができる。当該プライマーは、主に塗装の下地として使用され、密着性を付与することができる。当該塗装は主に色調を制御するために使用される。当該クリアコートは、主にワックスのような艶出しのために使用される。これらコーティング、プライマー、塗装、クリアコートに特に限定はなく、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、プライマー、塗装、クリアコートを用いても良い。これらの濃度は、０．０１〜８００ｇ／Ｌが好ましいが、適切な濃度は成分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、ＧＸ−２３５Ｔ（商品名、日本表面化学（株））、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））、エポキシ樹脂としてはＡＬプライマー（商品名、イサム塗料（株））、イサムエポロ５００（商品名、イサム塗料（株））等が、挙げられる。また、電着塗装を行うことも出来る。
(Coating, primer, painting, clear coating after post-anodizing treatment)
After the post-anodizing treatment, any one or more of coating, primer, painting, and clear coating containing at least one of the group consisting of silicon, resin, and wax may be performed. The coating can mainly impart corrosion resistance. The primer is mainly used as a base for painting and can impart adhesion. The paint is mainly used to control the color tone. The clear coat is mainly used for polishing such as wax. There is no particular limitation on these coatings, primers, paints, clear coats, acrylic resin, olefin resin, alkyd resin, urea resin, epoxy resin, melamine resin, fluororesin, polyethylene, polyvinyl chloride, polystyrene, polypropylene, methacrylic resin, phenol Coatings, primers, paints, and clear coats containing resin, polyester resin, polyurethane, polyamide, polycarbonate, and other resins, silicates, colloidal silica, and the like may be used. These concentrations are preferably from 0.01 to 800 g / L, but the appropriate concentration depends on the type of component. 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 the acrylic resin include GX-235T (trade name, Nippon Surface Chemical Co., Ltd.), hirotite (trade name, Hitachi Chemical Co., Ltd.), alloset (trade name, Nippon Shokubai Co., Ltd.), and the like. Yes, for olefin resin, Frocene (trade name, Sumitomo Seika Co., Ltd.), PES (trade name, Nippon Unicar Co., Ltd.), Chemipearl (trade name, Mitsui Chemicals), Sun Fine (trade name, Asahi Kasei Co., Ltd. and epoxy resins include AL primer (trade name, Isamu Paint Co., Ltd.), Isamu Epolo 500 (trade name, Isamu Paint Co., Ltd.) and the like. Electrodeposition coating can also be performed.
（乾燥処理）
陽極酸化後処理の後、或いは、上記コーティング、プライマー、塗装又はクリアコートが行われた場合はそれらの後に、乾燥処理を行う。
(Drying process)
A drying process is performed after the anodizing post-treatment or after the coating, primer, painting or clear coating.
（乾燥温度）
乾燥温度は部材を乾燥させることができれば制限はないが、２０〜２００℃の範囲が好ましく、６０〜１２０℃の範囲であることがより好ましい。乾燥温度が２０℃より低い場合は乾燥時間がかかり生産性を低下させ、また２００℃以上の場合はコストが上昇するため好ましくない。
(Drying temperature)
The drying temperature is not limited as long as the member can be dried, but is preferably in the range of 20 to 200 ° C, and more preferably in the range of 60 to 120 ° C. When the drying temperature is lower than 20 ° C., it takes a long time to reduce the productivity, and when it is 200 ° C. or higher, the cost increases.
（乾燥時間）
乾燥時間は部材を乾燥させることができれば制限はないが、１〜２０分の範囲が好ましく、５〜１５分の範囲であることがより好ましい。乾燥時間が１分より短い場合は乾燥不足を招きやすく、また２０分以上の場合は生産性が低下するため好ましくない。
(Drying time)
The drying time is not limited as long as the member can be dried, but is preferably in the range of 1 to 20 minutes, more preferably in the range of 5 to 15 minutes. When the drying time is shorter than 1 minute, insufficient drying tends to occur, and when it is 20 minutes or longer, productivity is lowered, which is not preferable.
以下に、本発明の実施例によって本発明をさらに詳しく説明するが、本発明は、これらの実施例によってなんら限定されるものではない。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
処理対象の金属基材（素材）としては、アルミニウム基材としてＡ１１００を用い、アルミニウム合金基材としてＡＤＣ１２材及びＡ５０５２材を用いた。一連の実験工程は、脱脂、アルカリエッチング、脱スマット処理、アルミニウム陽極酸化処理、必要に応じ染色処理、アルミニウム陽極酸化後の処理、必要に応じコーティング・プライマー・塗装・クリアコート処理、乾燥の順で、指定がない限り浸漬処理を行った。これら各工程の間には全て水洗を行った。ただし、コーティング・プライマー・塗装・クリアコート後の水洗は行わず乾燥した。脱脂はケイクリン６（日本表面化学株式会社製非鉄用脱脂剤）５０ｍＬ／Ｌ、５０℃、５分の条件で行った。アルカリエッチングは苛性ソーダ５０ｇ／Ｌ、６０℃、３０秒の条件で行った。脱スマット処理は６７．５％硝酸３００ｍＬ／Ｌ、室温、１分の条件で行った。研磨処理はケミライト５３（日本表面化学株式会社製化学研磨剤）９５０ｍＬ／Ｌ、６７．５％硝酸５０ｍＬ／Ｌ、１００℃、３０秒で行った。梨地処理はアルエッチ８３（日本表面化学株式会社製化学梨地剤）１５０ｇ／Ｌ、６５℃、２分で行った。 As a metal base material (material) to be processed, A1100 was used as the aluminum base material, and ADC12 material and A5052 material were used as the aluminum alloy base material. The series of experimental steps are degreasing, alkaline etching, desmutting, aluminum anodizing, dyeing treatment as necessary, treatment after aluminum anodizing, coating / primer / painting / clear coat treatment as necessary, and drying. Unless otherwise specified, immersion treatment was performed. All these steps were washed with water. However, it was dried without washing after coating, primer, painting and clear coating. Degreasing was carried out under the conditions of Keiclin 6 (Nippon Surface Chemicals non-ferrous degreasing agent) 50 mL / L, 50 ° C., 5 minutes. Alkaline etching was performed under the conditions of caustic soda 50 g / L, 60 ° C., and 30 seconds. The desmutting treatment was performed under conditions of 67.5% nitric acid 300 mL / L at room temperature for 1 minute. The polishing treatment was performed at Chemilite 53 (Chemical Abrasive manufactured by Nippon Surface Chemical Co., Ltd.) 950 mL / L, 67.5% nitric acid 50 mL / L, 100 ° C., 30 seconds. The satin treatment was performed at Alec 83 (Chemical pear finish manufactured by Nippon Surface Chemical Co., Ltd.) 150 g / L at 65 ° C. for 2 minutes.
アルマイト処理（陽極酸化処理）は９８％精製硫酸１５０ｍＬ／Ｌ、１６Ｖ、１．３Ａ／ｄｍ2、素材毎に渦電流膜厚計で１０μｍの膜厚になるよう時間を調整した。染色処理はジャスコカラーＢＬ（日本表面化学株式会社製の黒色染料）１０ｇ／Ｌ、６０℃、ｐＨ４．２、１０分の条件で行った。アルミニウム陽極酸化後の処理のスプレー処理は１．３ｋｇｆ／ｃｍ2で行った。アルミニウム陽極酸化後の処理の後の湯洗は４５℃、１分で行った。湯洗を行う場合はアルミニウム陽極酸化後の処理、水洗、湯洗、乾燥の工程で処理した。ストロンＪコート（日本表面化学株式会社製のシリカ系コーティング剤）は濃度原液、４０℃、１０秒で行った。ハイシール２７２（日本表面化学株式会社製のアクリル系コーティング剤）は５００ｍＬ／Ｌ、室温、１０秒で処理した。ＧＸ−２３５Ｔ（日本表面化学株式会社製のアクリル系クリアコート）は１００ｍＬ／Ｌ、室温、１０秒で処理した。ハイポンファインプライマーII（日本ペイント株式会社製の変性エポキシ樹脂プライマー）は濃度原液、室温でバーコーター塗布（Ｎｏ．３で約７μｍ）を行った。ファインウレタンＵ１００（日本ペイント株式会社製のウレタン塗料）は濃度原液、室温でバーコーター塗布（Ｎｏ．３で約７μｍ）を行った。比較例１〜３の酢酸ニッケル封孔剤はアルシール８７（日本表面化学株式会社製）６ｇ／Ｌ、９０℃、ｐＨ５．９、１５分処理で行った。乾燥は８０℃、１０分の条件で行った。なお、比較例２は、（２）陽極酸化処理を行わず、（１）前処理、水洗、（３）陽極酸化後処理、水洗、乾燥をこの順で処理した。比較例１４の電解処理は、−５Ｖ処理の陰極電解処理（陽極カーボン板）によって行った。比較例１７は、（３）陽極酸化後処理で、１度目にＮｏ.４０の処理液の組成での処理、水洗、２度目に純水で処理、乾燥をこの順で処理した。 Alumite treatment (anodization treatment) was adjusted to a thickness of 10 μm with 98% purified sulfuric acid 150 mL / L, 16 V, 1.3 A / dm 2 and eddy current film thickness for each material. The dyeing treatment was performed under the conditions of Jusco Color BL (black dye manufactured by Nippon Surface Chemical Co., Ltd.) 10 g / L, 60 ° C., pH 4.2, 10 minutes. The spray treatment after the aluminum anodization was performed at 1.3 kgf / cm 2 . The hot water washing after the treatment after aluminum anodization was performed at 45 ° C. for 1 minute. When performing hot water washing, it processed in the process of the process after aluminum anodizing, water washing, hot water washing, and drying. Stron J coat (silica-based coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was performed at a stock concentration of 40 ° C. for 10 seconds. High seal 272 (acrylic coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was treated at 500 mL / L at room temperature for 10 seconds. GX-235T (acrylic clear coat manufactured by Nippon Surface Chemical Co., Ltd.) was treated at 100 mL / L at room temperature for 10 seconds. Hypon Fine Primer II (modified epoxy resin primer manufactured by Nippon Paint Co., Ltd.) was applied in a stock solution at a room temperature and a bar coater was applied (about 7 μm in No. 3). Fine urethane U100 (urethane paint manufactured by Nippon Paint Co., Ltd.) was applied as a concentrated stock solution and a bar coater was applied at room temperature (about 7 μm for No. 3). The nickel acetate sealing agent in Comparative Examples 1 to 3 was processed by Alseal 87 (Nihon Surface Chemical Co., Ltd.) 6 g / L, 90 ° C., pH 5.9, and 15 minutes. Drying was performed at 80 ° C. for 10 minutes. In Comparative Example 2, (2) Anodizing treatment was not performed, and (1) pretreatment, water washing, (3) post-anodizing treatment, water washing, and drying were carried out in this order. The electrolytic treatment of Comparative Example 14 was performed by -5 V cathodic electrolysis (anode carbon plate). Comparative Example 17 was (3) post-anodizing post-treatment, the first treatment with the composition of No. 40 treatment solution, the water treatment, the second treatment with pure water, and the drying treatment in this order.
耐食性試験はＪＩＳ Ｚ ２３７１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樹脂を塗布し、焼付け乾燥した後に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、これを垂直方向にはく離し評価した。コート処理を行った実施例に関しては、そのまま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、これを垂直方向にはく離し評価した。コバルトとクロムは、堀場製作所社製マーカス型高周波グロー放電発光分析装置ＧＤ−Ｐｒｏｆｉｌｅｒ２を用いて、グロー放電発光表面分析で、酸化皮膜全域又は０．０１μｍ以上の厚み領域に存在しているかを確認し、さらに、サンプルの表面から深さ方向で０μｍ、０．５μｍ、１μｍ、１．５μｍ、２μｍ、２．５μｍ、３μｍの各部分を測定し各存在比率（質量％）を求め、その平均を算出した。（３）アルミニウム陽極酸化後の処理後にコーティング、プライマー、塗装、クリアコートを行った実施例１２〜１７に関しては、コーティング、プライマー、塗装、クリアコートの前にグロー放電発光表面分析によりコバルトとクロムを分析した。インク試験はＪＩＳ Ｈ ８６８３−１に従う試験を行った。 The corrosion resistance test was a salt spray test according to JIS Z 2371. In the coating adhesion test, an epoxy resin is applied to the surface of the test piece, baked and dried, cross-cut in a grid pattern, immersed in boiling water for 30 minutes, cellophane tape is crimped, and peeled off in the vertical direction. evaluated. Regarding the examples subjected to the coating treatment, a cross cut was put in a grid pattern as it was, and after immersion in boiling water for 30 minutes, a cellophane tape was pressure-bonded and peeled in the vertical direction for evaluation. Cobalt and chromium are checked by glow discharge emission surface analysis using a Marcus type high-frequency glow discharge emission analyzer GD-Profiler2 manufactured by HORIBA, Ltd. to confirm whether they are present in the entire oxide film or in a thickness region of 0.01 μm or more. Furthermore, each part of 0 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, and 3 μm is measured in the depth direction from the surface of the sample to obtain each abundance ratio (mass%), and the average is calculated. did. (3) Regarding Examples 12 to 17 in which coating, primer, coating, and clear coating were performed after the treatment after aluminum anodization, cobalt and chromium were added by glow discharge emission surface analysis before coating, primer, coating, and clear coating. analyzed. The ink test was a test according to JIS H 8683-1.
試験条件、薬剤組成、および評価結果を下記表に示す。表中の（１）は陽極酸化前処理に関連する条件、（２）はアルミニウム陽極酸化処理に関連する条件、（３）は陽極酸化後処理に関連する条件を記している。 Test conditions, drug composition, and evaluation results are shown in the following table. In the table, (1) indicates conditions related to the anodizing pretreatment, (2) indicates conditions related to the aluminum anodizing treatment, and (3) describes conditions related to the postanodizing treatment.
外観の評価は、サンプル表面について、目視で行った。
塩水噴霧試験評価(耐食性評価)は、以下の基準による。
Ａ：１００８時間後白錆発生無し
Ｂ：４８時間後白錆発生
Ｃ：２４時間後白錆発生
塗装密着性を判断する表中の碁盤目試験評価は、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
封孔性を示すインク試験は、以下の基準による。
Ａ：インク残り無し
Ｂ：インク残り有り
The appearance was evaluated visually on the sample surface.
The salt spray test evaluation (corrosion resistance evaluation) is based on the following criteria.
A: No white rust generation after 1008 hours B: White rust generation after 48 hours C: White rust generation after 24 hours Cross-cut test evaluation in the table for judging coating adhesion 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 more than 50% An ink test showing sealing properties is based on the following criteria.
A: No ink remaining B: Ink remaining
（評価）
実験結果から、陽極酸化皮膜とコバルト及び／またはクロムが存在するアルミニウム部材を生成することで、優れた外観・耐食性・塗装密着性・封孔性が得られることが確認された。更にジルコニウム、カルシウム、亜鉛、バナジウム、ニッケル、チタン、マグネシウム、アルミニウムからなる群のうち一種類以上の金属イオンを含有するアルミニウム陽極酸化後の処理剤を用いることで、更に意匠性が向上したが、耐食性に悪影響は無かった。一方比較例からは、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。また従来処理品となる比較例１の酢酸ニッケル封孔処理品と比較しても、低温・短時間処理で優れた耐食性が得られた。
(Evaluation)
From the experimental results, it was confirmed that excellent appearance, corrosion resistance, paint adhesion, and sealing properties can be obtained by producing an anodized film and an aluminum member containing cobalt and / or chromium. Furthermore, by using the treatment agent after aluminum anodization containing one or more kinds of metal ions out of the group consisting of zirconium, calcium, zinc, vanadium, nickel, titanium, magnesium, and aluminum, the design is further improved. There was no adverse effect on corrosion resistance. On the other hand, it was confirmed from the comparative examples that the corrosion resistance comparable to the examples was not obtained. Even when compared with the nickel acetate sealing treatment product of Comparative Example 1 which is a conventional treatment product, excellent corrosion resistance was obtained at low temperature and short time treatment.
実施例１〜１１０はいずれも、酸化皮膜全域又は０．０１μｍ以上の厚み領域にコバルト又はクロムが存在していることが確認された。
図１に比較例１の、図２に実施例１のグロー放電発光表面分析結果を示す。これらはどちらもＡＤＣ１２材の処理品である。ＡＤＣ１２材には銅やシリカも含有されているが、表が重なり見にくくなるため、本発明に関係のない元素は省略している。まず比較例１は酢酸ニッケルを用いた従来技術の封孔処理である。この封孔処理はアルマイト多孔質層の孔内で皮膜の体積膨張を伴う水和封反応（Ｉ）と水酸化ニッケルを析出させる析出反応（II）の二種類の反応機構によりアルマイト多孔質層の封孔が行われていると推測されている。グロー放電発光表面分析結果からこの酢酸ニッケルを用いた封孔処理は表層から０．０１μｍより浅い位置でニッケルが多く析出しており、表層の浅い位置で封孔が行われていることが推測できる。
Ａｌ2Ｏ3 ＋ Ｈ2Ｏ → Ａｌ2Ｏ3・Ｈ2Ｏ （ベーマイト） （Ｉ）
Ｎｉ（ＣＨ3ＣＯＯ) 2 +２Ｈ2Ｏ→ Ｎｉ（ＯＨ）2 ＋ ２ＣＨ3ＣＯＯＨ （II）
一方、本発明である実施例１のグロー放電発光表面分析結果からは、成分となるコバルトとクロムが４μｍ以上まで非常に厚く存在していることが確認できる
In each of Examples 1-110, it was confirmed that cobalt or chromium was present in the entire oxide film or in a thickness region of 0.01 μm or more.
FIG. 1 shows the results of glow discharge luminescence surface analysis of Comparative Example 1 and FIG. 2 of Example 1 of glow discharge. These are both processed products of ADC12 material. Although the ADC12 material also contains copper and silica, the elements that are not related to the present invention are omitted because the tables are difficult to see. First, Comparative Example 1 is a prior art sealing process using nickel acetate. This sealing treatment is carried out by two types of reaction mechanisms: the hydration sealing reaction (I) accompanied by the volume expansion of the film in the pores of the alumite porous layer and the precipitation reaction (II) that precipitates nickel hydroxide. It is presumed that sealing has been performed. From the results of glow discharge luminescence surface analysis, it can be inferred that a large amount of nickel is deposited at a position shallower than 0.01 μm from the surface layer in this sealing treatment using nickel acetate, and the sealing is performed at a shallow position on the surface layer. .
Al 2 O 3 + H 2 O → Al 2 O 3 .H 2 O (Boehmite) (I)
Ni (CH 3 COO) 2 + 2H 2 O → Ni (OH) 2 + 2CH 3 COOH (II)
On the other hand, from the glow discharge luminescence surface analysis result of Example 1 which is the present invention, it can be confirmed that the components cobalt and chromium are very thick up to 4 μm or more.
また、図３に実施例２のグロー放電発光表面分析結果を示す。比較例１は酢酸ニッケルを用いた従来技術の封孔処理であり、比較例１のＡＤＣ１２材と同様にニッケルは表層のみに存在している。実施例２のグロー放電発光表面分析結果からは、成分となるコバルトとクロムが４μｍ以上まで非常に厚く存在していることが確認できる。Ａ１１００等の展伸材は耐食性が得られやすい素材であり、実施例２は４０℃１８０秒処理である。実施例２と比較例３の４０℃１８０秒処理同士の耐食性を考慮すると、本発明の優位性が改めて証明できる。 FIG. 3 shows the results of glow discharge luminescence surface analysis of Example 2. Comparative Example 1 is a prior art sealing treatment using nickel acetate. Like the ADC12 material of Comparative Example 1, nickel is present only on the surface layer. From the results of glow discharge luminescence surface analysis of Example 2, it can be confirmed that the components cobalt and chromium are very thick up to 4 μm or more. A wrought material such as A1100 is a material that is easy to obtain corrosion resistance, and Example 2 is treated at 40 ° C. for 180 seconds. Considering the corrosion resistance between the treatments at 40 ° C. for 180 seconds in Example 2 and Comparative Example 3, the superiority of the present invention can be proved again.
また図４〜９に、実施例１のＦＥ−ＳＥＭ−ＥＤＸ断面元素マッピング写真を示す。ここからもアルマイト皮膜の内部にまでコバルトとクロムが存在していることが確認できる。図９よりフッ素はグロー放電発光表面分析結果では検出されない元素であるが、ＦＥ−ＳＥＭ−ＥＤＸ断面元素マッピングでは検出される物質であり、アルマイト皮膜の内部にまで存在していることが確認できる。この皮膜の詳細な反応機構は不明だが、一般的な６価クロメートやクロム皮膜等の化成皮膜の厚みは０．０１〜０．８μｍが一般的であり、この０．０１μｍ以上に厚く存在するコバルトとクロムの皮膜が本発明では得られるため、優れた耐食性が得られるものと推測される。 Moreover, the FE-SEM-EDX cross-section element mapping photograph of Example 1 is shown in FIGS. From here, it can be confirmed that cobalt and chromium are present even inside the anodized film. From FIG. 9, it is confirmed that fluorine is an element that is not detected in the glow discharge luminescence surface analysis result, but is a substance that is detected in the FE-SEM-EDX cross-section element mapping and exists even inside the alumite film. Although the detailed reaction mechanism of this film is unknown, the thickness of a chemical conversion film such as a general hexavalent chromate or chromium film is generally 0.01 to 0.8 μm, and cobalt exists thicker than 0.01 μm. It is presumed that excellent corrosion resistance can be obtained because a chromium film is obtained in the present invention.
Claims (17)
前記アルマイト部材の表面から前記アルミニウム基材又はアルミニウム合金基材方向にかけて、前記酸化皮膜全域又は０．０１μｍ以上の厚み領域で前記コバルト又はクロムが存在し、
厚み方向で、前記アルマイト部材の表面から３μｍの間において、前記コバルトの存在比率が０．５質量％以上４０質量％以下、及び／又は、前記クロムの存在比率が１質量％以上４０質量％以下であるアルマイト部材。 An anodized member in which an anodized film and cobalt and / or chromium are present on the surface of an aluminum substrate or an aluminum alloy substrate;
From the surface of the anodized member toward the aluminum base material or aluminum alloy base material, the cobalt or chromium is present in the entire oxide film or in a thickness region of 0.01 μm or more,
In the thickness direction, the abundance ratio of cobalt is 0.5 mass% or more and 40 mass% or less and / or the abundance ratio of chromium is 1 mass% or more and 40 mass% or less between 3 μm from the surface of the anodized member. An anodized member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014118679A JP6528051B2 (en) | 2014-06-09 | 2014-06-09 | Alumite member, method of manufacturing alumite member and treating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014118679A JP6528051B2 (en) | 2014-06-09 | 2014-06-09 | Alumite member, method of manufacturing alumite member and treating agent |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2019039029A Division JP2019081963A (en) | 2019-03-04 | 2019-03-04 | Anodized aluminum member, and manufacturing method and treatment agent of anodized aluminum member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015232155A true JP2015232155A (en) | 2015-12-24 |
| JP6528051B2 JP6528051B2 (en) | 2019-06-12 |
Family
ID=54933782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014118679A Active JP6528051B2 (en) | 2014-06-09 | 2014-06-09 | Alumite member, method of manufacturing alumite member and treating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6528051B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019098303A1 (en) | 2017-11-17 | 2019-05-23 | Nok株式会社 | Sealing member |
| CN110760912A (en) * | 2018-07-27 | 2020-02-07 | 比亚迪股份有限公司 | Surface treatment method for metal having anodic oxide film, and metal |
| JP2020063504A (en) * | 2018-10-19 | 2020-04-23 | 日本表面化学株式会社 | Method for producing alumite member, alumite member and treating agent |
| KR102350114B1 (en) * | 2020-08-03 | 2022-01-10 | 김근호 | Eco-friendly aluminum electrolytic chromate treatment method |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5253740A (en) * | 1975-10-30 | 1977-04-30 | Hokusei Aluminium Co Ltd | Process for coloring aluminum or its alloy |
| JPS52130447A (en) * | 1976-04-26 | 1977-11-01 | Hokusei Aluminium Co Ltd | Pigmentation method of aluminum and aluminum alloy |
| JPS57192291A (en) * | 1981-05-19 | 1982-11-26 | Sankyo Alum Ind Co Ltd | Surface treatment of aluminum for patterning |
| JPS62202098A (en) * | 1986-02-28 | 1987-09-05 | Nikka Chem Ind Co Ltd | Low temperature treating agent for sealing of anodized aluminum film |
| JPH03277797A (en) * | 1990-03-27 | 1991-12-09 | Okuno Seiyaku Kogyo Kk | Sealing treatment of aluminum anodically oxidized film |
| JPH06264292A (en) * | 1992-08-10 | 1994-09-20 | Kobe Steel Ltd | Anodic oxidation treatment of mg and mg alloy |
| JPH08109494A (en) * | 1994-10-14 | 1996-04-30 | Shin Nikkei Co Ltd | Formation of composite film of aluminum or aluminum alloy |
| JPH0958690A (en) * | 1995-08-11 | 1997-03-04 | Hidan:Kk | Cosmetic container utilizing color alloy |
| JP2001179154A (en) * | 1999-12-24 | 2001-07-03 | Nippon Light Metal Co Ltd | Dyed material and dyeing method and device for dyeing object |
| JP2002505715A (en) * | 1997-06-14 | 2002-02-19 | クラリアント インターナショナル リミティド | Method for coloring aluminum oxide layer |
| JP2004003025A (en) * | 2002-05-22 | 2004-01-08 | United Technol Corp <Utc> | Surface treatment imparting corrosion resistance for adhesion of adhesive for structure of metal |
| JP2006517613A (en) * | 2003-01-23 | 2006-07-27 | ユナイテッド ステイツ オブ アメリカ アズ レプレゼンテッド バイ ザ セクレタリー オブ ザ ネイビー エト アル． | Pretreatment of aluminum and aluminum alloys |
| JP2008144281A (en) * | 2008-02-27 | 2008-06-26 | Isle Coat Ltd | Multifunctional composite coating for protection based on lightweight alloy |
| JP2008530361A (en) * | 2005-02-15 | 2008-08-07 | ユナイテッド ステイツ オブ アメリカ アズ レプレゼンテッド バイ ザ セクレタリー オブ ザ ネイビー エト アル． | Composition for coating chromium-zirconium on metal substrate and preparation method thereof |
| JP2010248545A (en) * | 2009-04-13 | 2010-11-04 | Okuno Chem Ind Co Ltd | Sealing method for anodized film of aluminum alloy |
| JP2010270350A (en) * | 2009-05-19 | 2010-12-02 | Nikon Corp | Method of coloring anodized coating and colored member |
| WO2013025352A1 (en) * | 2011-08-18 | 2013-02-21 | Apple Inc. | Anodization and plating surface treatments |
-
2014
- 2014-06-09 JP JP2014118679A patent/JP6528051B2/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5253740A (en) * | 1975-10-30 | 1977-04-30 | Hokusei Aluminium Co Ltd | Process for coloring aluminum or its alloy |
| JPS52130447A (en) * | 1976-04-26 | 1977-11-01 | Hokusei Aluminium Co Ltd | Pigmentation method of aluminum and aluminum alloy |
| JPS57192291A (en) * | 1981-05-19 | 1982-11-26 | Sankyo Alum Ind Co Ltd | Surface treatment of aluminum for patterning |
| JPS62202098A (en) * | 1986-02-28 | 1987-09-05 | Nikka Chem Ind Co Ltd | Low temperature treating agent for sealing of anodized aluminum film |
| JPH03277797A (en) * | 1990-03-27 | 1991-12-09 | Okuno Seiyaku Kogyo Kk | Sealing treatment of aluminum anodically oxidized film |
| JPH06264292A (en) * | 1992-08-10 | 1994-09-20 | Kobe Steel Ltd | Anodic oxidation treatment of mg and mg alloy |
| JPH08109494A (en) * | 1994-10-14 | 1996-04-30 | Shin Nikkei Co Ltd | Formation of composite film of aluminum or aluminum alloy |
| JPH0958690A (en) * | 1995-08-11 | 1997-03-04 | Hidan:Kk | Cosmetic container utilizing color alloy |
| JP2002505715A (en) * | 1997-06-14 | 2002-02-19 | クラリアント インターナショナル リミティド | Method for coloring aluminum oxide layer |
| JP2001179154A (en) * | 1999-12-24 | 2001-07-03 | Nippon Light Metal Co Ltd | Dyed material and dyeing method and device for dyeing object |
| JP2004003025A (en) * | 2002-05-22 | 2004-01-08 | United Technol Corp <Utc> | Surface treatment imparting corrosion resistance for adhesion of adhesive for structure of metal |
| JP2006517613A (en) * | 2003-01-23 | 2006-07-27 | ユナイテッド ステイツ オブ アメリカ アズ レプレゼンテッド バイ ザ セクレタリー オブ ザ ネイビー エト アル． | Pretreatment of aluminum and aluminum alloys |
| JP2008530361A (en) * | 2005-02-15 | 2008-08-07 | ユナイテッド ステイツ オブ アメリカ アズ レプレゼンテッド バイ ザ セクレタリー オブ ザ ネイビー エト アル． | Composition for coating chromium-zirconium on metal substrate and preparation method thereof |
| JP2008144281A (en) * | 2008-02-27 | 2008-06-26 | Isle Coat Ltd | Multifunctional composite coating for protection based on lightweight alloy |
| JP2010248545A (en) * | 2009-04-13 | 2010-11-04 | Okuno Chem Ind Co Ltd | Sealing method for anodized film of aluminum alloy |
| JP2010270350A (en) * | 2009-05-19 | 2010-12-02 | Nikon Corp | Method of coloring anodized coating and colored member |
| WO2013025352A1 (en) * | 2011-08-18 | 2013-02-21 | Apple Inc. | Anodization and plating surface treatments |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019098303A1 (en) | 2017-11-17 | 2019-05-23 | Nok株式会社 | Sealing member |
| CN110760912A (en) * | 2018-07-27 | 2020-02-07 | 比亚迪股份有限公司 | Surface treatment method for metal having anodic oxide film, and metal |
| CN110760912B (en) * | 2018-07-27 | 2021-08-10 | 比亚迪股份有限公司 | Surface treatment method for metal having anodic oxide film, and metal |
| JP2020063504A (en) * | 2018-10-19 | 2020-04-23 | 日本表面化学株式会社 | Method for producing alumite member, alumite member and treating agent |
| KR102350114B1 (en) * | 2020-08-03 | 2022-01-10 | 김근호 | Eco-friendly aluminum electrolytic chromate treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6528051B2 (en) | 2019-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6884336B2 (en) | Color finishing method | |
| US5132003A (en) | Process for surface treatment of aluminum or aluminum alloy | |
| ES2234870T3 (en) | PROCEDURE FOR THE UPPER TREATMENT OF ALUMINUM OR ALUMINUM ALLOYS THROUGH FORMULATIONS CONTAINING ALCANOSULPHONIC ACID. | |
| US20080149492A1 (en) | Surface dyeing process for metal articles | |
| JP6528051B2 (en) | Alumite member, method of manufacturing alumite member and treating agent | |
| JP6518877B1 (en) | Method for producing anodized member, alumite member and treating agent | |
| US20110303545A1 (en) | Method for treating surface of magnesium-based metal to give metallic texture thereof | |
| KR20090007081A (en) | Conductivity anodizing method | |
| JP2009513824A (en) | Method for improving the corrosion resistance and light fastness of painted aluminum oxide layers | |
| JP6281101B2 (en) | Metal protective film forming method and protective film forming treatment agent | |
| JP2005187925A (en) | Metal surface treating agent, metal surface treatment solution, corrosion-resistant colored film deposited thereby, corrosion-resistant colored component with corrosion-resistant colored film, and corrosion-resistant colored component manufacturing method | |
| EP1233084A2 (en) | "Anodizing process, with low environmental impact, for a workpiece of aluminium or aluminium alloys" | |
| JP2006312754A (en) | Treatment method for surface of anodized aluminum | |
| US20050056546A1 (en) | Aluminum vehicle body | |
| JP2012036469A (en) | Method for forming protective film on metal and treatment agent for forming protective film | |
| TWI238858B (en) | Process for the production of gold-colored surfaces of aluminum or aluminum alloys by means of silver salt-containing formulations | |
| CN112111736A (en) | Metal surface treatment liquid and metal surface treatment method | |
| Yerokhin et al. | Anodising of light alloys | |
| JP2019081963A (en) | Anodized aluminum member, and manufacturing method and treatment agent of anodized aluminum member | |
| CN216585268U (en) | Anodized aluminum alloy rim | |
| KR101923897B1 (en) | Anodizing method of subject | |
| CN113897606A (en) | Metal coloring liquid for chemical conversion treatment and metal coloring treatment method | |
| JP5648245B2 (en) | Method for forming chromium-free metal protective film and treatment agent for forming chromium-free metal protective film | |
| JP6695767B2 (en) | Method for manufacturing aluminum coating material | |
| JP2009270190A (en) | Surface treatment method capable of embodying coloring and luster on magnesium-based metallic member |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20161228 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170915 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170926 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20171106 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180410 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180606 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20181204 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190304 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20190311 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190319 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190401 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6528051 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |