JP5952485B2 - アルミニウム含有亜鉛系めっき鋼板及びその製造方法 - Google Patents
アルミニウム含有亜鉛系めっき鋼板及びその製造方法 Download PDFInfo
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- JP5952485B2 JP5952485B2 JP2015502783A JP2015502783A JP5952485B2 JP 5952485 B2 JP5952485 B2 JP 5952485B2 JP 2015502783 A JP2015502783 A JP 2015502783A JP 2015502783 A JP2015502783 A JP 2015502783A JP 5952485 B2 JP5952485 B2 JP 5952485B2
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- steel sheet
- plated steel
- aluminum
- cobalt
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- 229910052782 aluminium Inorganic materials 0.000 title claims description 125
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 125
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 13
- 239000008397 galvanized steel Substances 0.000 title claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 174
- 239000010959 steel Substances 0.000 claims description 174
- 239000011701 zinc Substances 0.000 claims description 101
- 238000007747 plating Methods 0.000 claims description 99
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 98
- 229910052725 zinc Inorganic materials 0.000 claims description 98
- 238000000576 coating method Methods 0.000 claims description 88
- 239000011248 coating agent Substances 0.000 claims description 87
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 72
- 229910017052 cobalt Inorganic materials 0.000 claims description 67
- 239000010941 cobalt Substances 0.000 claims description 67
- 150000007514 bases Chemical group 0.000 claims description 54
- 229910052723 transition metal Inorganic materials 0.000 claims description 48
- 150000003624 transition metals Chemical class 0.000 claims description 41
- 150000001869 cobalt compounds Chemical class 0.000 claims description 40
- 239000011651 chromium Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- -1 transition metal basic compound Chemical class 0.000 claims description 22
- 229910052804 chromium Inorganic materials 0.000 claims description 20
- 150000002222 fluorine compounds Chemical class 0.000 claims description 17
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- WBFZBNKJVDQAMA-UHFFFAOYSA-D dipotassium;zirconium(4+);pentacarbonate Chemical compound [K+].[K+].[Zr+4].[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O WBFZBNKJVDQAMA-UHFFFAOYSA-D 0.000 claims description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 claims description 3
- ZQVHTTABFLHMPA-UHFFFAOYSA-N 2-(4-chlorophenoxy)-5-nitropyridine Chemical compound N1=CC([N+](=O)[O-])=CC=C1OC1=CC=C(Cl)C=C1 ZQVHTTABFLHMPA-UHFFFAOYSA-N 0.000 claims 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims 2
- GQJPVGNFTLBCIQ-UHFFFAOYSA-L sodium;zirconium(4+);carbonate Chemical compound [Na+].[Zr+4].[O-]C([O-])=O GQJPVGNFTLBCIQ-UHFFFAOYSA-L 0.000 claims 2
- 230000007797 corrosion Effects 0.000 description 52
- 238000005260 corrosion Methods 0.000 description 52
- 229910052751 metal Inorganic materials 0.000 description 28
- 239000002184 metal Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 22
- 239000003513 alkali Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 18
- 238000011282 treatment Methods 0.000 description 17
- 229910052726 zirconium Inorganic materials 0.000 description 17
- 238000002845 discoloration Methods 0.000 description 15
- 239000012528 membrane Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 238000009833 condensation Methods 0.000 description 13
- 230000005494 condensation Effects 0.000 description 13
- 150000003755 zirconium compounds Chemical class 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 230000008859 change Effects 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229910052758 niobium Inorganic materials 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 8
- 229910052712 strontium Inorganic materials 0.000 description 8
- 150000003609 titanium compounds Chemical class 0.000 description 8
- 229910052720 vanadium Inorganic materials 0.000 description 8
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 8
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- RGRFMLCXNGPERX-UHFFFAOYSA-L oxozirconium(2+) carbonate Chemical compound [Zr+2]=O.[O-]C([O-])=O RGRFMLCXNGPERX-UHFFFAOYSA-L 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001845 chromium compounds Chemical class 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005078 molybdenum compound Substances 0.000 description 3
- 150000002752 molybdenum compounds Chemical class 0.000 description 3
- 150000002822 niobium compounds Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000012756 surface treatment agent Substances 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 150000003682 vanadium compounds Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 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 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 150000003623 transition metal 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
- AFINAILKDBCXMX-PBHICJAKSA-N (2s,3r)-2-amino-3-hydroxy-n-(4-octylphenyl)butanamide Chemical compound CCCCCCCCC1=CC=C(NC(=O)[C@@H](N)[C@@H](C)O)C=C1 AFINAILKDBCXMX-PBHICJAKSA-N 0.000 description 1
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- XVWFIMLHNWYMKY-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;cobalt Chemical compound [Co].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O XVWFIMLHNWYMKY-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- JZDMNWBZPLJKBT-UHFFFAOYSA-N F.[Zr] Chemical compound F.[Zr] JZDMNWBZPLJKBT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- NYAWADGYOWCCLK-UHFFFAOYSA-N [Na].[Zr] Chemical compound [Na].[Zr] NYAWADGYOWCCLK-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- XNLPZZOCLLAQIM-UHFFFAOYSA-N acetyl acetate;vanadium Chemical compound [V].CC(=O)OC(C)=O XNLPZZOCLLAQIM-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000137 annealing Methods 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
- 239000010953 base metal Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000009717 reactive processing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- UYLYBEXRJGPQSH-UHFFFAOYSA-N sodium;oxido(dioxo)niobium Chemical compound [Na+].[O-][Nb](=O)=O UYLYBEXRJGPQSH-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/66—Treatment of aluminium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
Landscapes
- Chemical & Material Sciences (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Coating With Molten Metal (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
Description
前記皮膜が、
コバルト及びクロムを除く遷移金属の塩基性化合物と、
金属コバルト、もしくは金属コバルト及びコバルト化合物とを含有し、
前記めっき鋼板の片面あたりの前記皮膜の付着量が、0.01〜0.8g/m2の範囲内であり、
前記めっき鋼板の片面あたりの、前記皮膜の、コバルトを除く遷移金属質量換算付着量が4〜400mg/m2の範囲内であり、
前記めっき鋼板の片面あたりの、前記皮膜のコバルト質量換算付着量が0.1〜20mg/m2の範囲内であることを特徴とする。めっき鋼板の片面あたりの皮膜の付着量とは、皮膜がめっき鋼板の一つの面のみに形成されている場合はその面における皮膜の単位面積あたりの質量のことであり、皮膜がめっき鋼板の一つの面とその反対側の面の両方に形成されている場合は、各面における皮膜の単位面積あたりの質量のことである。コバルトを除く遷移金属質量換算付着量とは、皮膜中に存在するコバルト以外の遷移金属原子の総質量から導出される、皮膜の単位面積あたりの質量である。遷移金属原子は、単体であるか化合物中に存在するかを問わない。コバルト質量換算付着量とは、皮膜中に存在するコバルト原子の総質量から導出される、皮膜の単位面積あたりの質量である。コバルト原子は、単体であるか化合物中に存在するかを問わない。
(1)供試材
板厚0.8mmのSPCC(JIS G3141)を、レスカ社製の溶融めっきシミュレーターでN2−H2雰囲気中で800℃、60秒加熱還元処理し、溶融金属浴温まで冷却した後、表1に示すめっき組成を有する合金めっき鋼材(めっき鋼板)を製造した。めっき付着量は片面で60g/m2とした。
前項で作製しためっき鋼板の表面をアルカリ脱脂することで、めっき鋼板の表面を清浄化した。アルカリ脱脂にあたっては、シリケート系アルカリ脱脂剤である日本パーカライジング株式会社製「パルクリーンN364S」を、濃度2%、温度60℃に調整し、これをめっき鋼板の表面に向けて10秒間スプレー噴射した。続いて、めっき鋼板の表面を水道水で洗浄した後に、このめっき鋼板を水切りロールで絞り、更にめっき鋼板を50℃で30秒間加熱乾燥した。
塩基性化合物(A)として、下記表2に示す(a1)〜(a7)を準備した。
表4及び表5に示す所定の塩基性化合物(A)、所定のコバルト化合物(B)、及び脱イオン水を配合し、更に必要に応じてアンモニア若しくは硝酸アンモニウムを加えてpHを調整することで、実施例1〜63及び比較例1〜9で使用する水系表面調整剤を得た。
両末端にカルボキシル基を持つ数平均分子量1000のポリエステル樹脂120部、両末端に水酸基を持つ数平均分子量1000のポリエチレングリコール90部、2,2一ジメチロールプロピオン酸12部、ジシクロヘキシルメタンジイソシアネート80部、N−メチル−2−ピロリドン120部と反応させることにより得られるプレポリマーを脱イオン水に分散させることにより、カルボン酸当量として0.30mg当量/g、酸アミド当量として0.79mg当量/g、樹脂/N−メチルピロリドンが2.5mg等量/gの試作ウレタン樹脂を得た。
室温にて、蒸留水中にチタンフッ化水素酸3.0g/L、ジルコニウムフッ化水素酸2.0g/L、30%過酸化水素水1.8g/L、ピロリン酸1.8g/Lを加え、水酸化ナトリウムにてpHを3.5に調整後45℃に加温し、表面調整剤を調整した。
室温にて、蒸留水1000部の中にバナジウムアセチルアセテート0.1部、バナジールアセチルセトネート1部、20%のジルコンフッ化水素酸を1.5部、25%アンモニア水にてpHを5.8に調整した表面調整剤を調整した。
No.16(比較例13)、No.19(比較例14)及びNo.20(比較例15)のめっき鋼板について、皮膜を形成させないで後述の評価を行った。
表4及び5に示す各実施例及び比較例のアルミニウム含有亜鉛系めっき鋼板(比較例13〜15は皮膜なし)を切断して、150mm×70mmの寸法の試験板に製作し、以下の試験を実施した。各評価方法は次のとおりである。
試験板に対し、塩水噴霧試験法(JIS−Z−2371)に基づいて、塩水噴霧を72時間及び120時間実施した。続いて、白錆発生面積を目視により確認し、下記評価基準にて評価した。尚、耐食性評価において72時間で「3」以上の判定であれば一時防錆用途としての実用レベルである。120時間で「3」以上の判定であれば、より耐食性の要求が高い一時防錆として適用できるレベルである。
4;白錆発生面積率3%未満。
3;白錆発生面積率3%以上10%未満。
2;白錆発生面積率10%以上30%未満。
1;白錆発生面積率30%以上。
試験板を、沸騰した脱イオン水中にて、30分間静置した。続いて、変色発生面積を目視により確認し、下記評価基準にて評価した。尚、耐黒変性評価において「3」以上の判定であれば実用レベルである。
4;変化なし。
3;変色発生面積率3%未満。
2;変色発生面積率3%以上30%未満。
1;変色発生面積率30%以上。
アルカリ脱脂剤である日本パーカライジング株式会社製「パルクリーンN364S」を、濃度2%、温度60℃に調整し、試験板の表面に向けて2分間スプレー噴射し、脱イオン水にて水洗した後、ドライヤーで乾燥した。続いて、変色発生面積率を目視により確認し、下記評価基準にて評価した。尚、耐アルカリ性評価において「3」以上の判定であれば実用レベルである。
4;変色発生面積率3%未満。
3;変色発生面積率3%以上10%未満。
2;変色発生面積率10%以上30%未満。
1;変色発生面積率30%以上。
試験板の表面に、脱イオン水を1ml滴下し、完全に水が蒸発するまで常温にて1日静置した。この試験後の変色度合いを目視により確認し、下記評価基準にて評価した。尚、耐結露性評価として「3」以上の判定であれば実用レベルである。
4;変化なし。
3;変色発生面積率1%未満。
2;変色発生面積率1%以上30%未満。
1;変色発生面積率30%以上。
下記条件下で試験板の皮膜上に塗装を施して塗装板を得た。
(1)アルキッド系塗料:大日本塗料(株)商標名デリコン#700、塗装:バーコート法、焼き付け条件:140℃×20分、乾燥塗膜厚25μm。
(2)クリヤー系塗装:大日本塗料(株)商標名Vフロン#2000FC2、塗装:バーコート法、焼き付け条件:200℃×20分、乾燥塗膜厚20μm。
4:100個。
3:98個以上100個未満。
2:50個以上98個未満。
1:50個未満。
試験板を、200℃にて20分間加熱を行った。
ΔE={(ΔL*)2+(Δa*)2+(Δb*)2}1/2
ΔL*=L1*−L2*、Δa*=a1*−a2*、Δb*=b1*−b2*
尚、ΔEは加熱処理試験前と加熱処理後の試験板との間の色差であり、L1*、a1*、及びb1*はそれぞれ処理前の試験板のL*、a*、及びb*の測定値であり、L2*、a2*、及びb2*はそれぞれ処理後の試験板のL*、a*、及びb*の測定値である。
4:ΔEが2未満。
3:ΔEが2以上5未満。
2:ΔEが5以上10未満。
1:ΔEが10以上。
各実施例のアルミニウム含有亜鉛系めっき鋼板における皮膜の、X線光電子分光分析をおこなった。その結果、水酸化コバルト及び酸化コバルトが皮膜の表面付近に存在し、且つ金属コバルトが皮膜の表面から内部にわたって存在していることが、確認された。遷移金属の酸化物及び水酸化物も、皮膜の表面から内部にわたって存在していることが、確認された。
Claims (9)
- めっき鋼板と、前記めっき鋼板を覆う皮膜とを備え、
前記皮膜が、
コバルト及びクロムを除く遷移金属の塩基性化合物と、
金属コバルト、もしくは金属コバルト及びコバルト化合物とを含有し、
前記めっき鋼板が、亜鉛とアルミニウムとを含有するめっき層を備え、前記めっき層中のアルミニウムの割合が1質量%以上、75質量%以下の範囲内であり、
前記遷移金属の塩基性化合物が、炭酸ジルコニウムアンモニウム、炭酸ジルコニウムカリウム、炭酸ジルコニウムナトリウム、炭酸ジルコニウムのジエタノールアミン塩、モリブデン酸アンモニウム、塩化ニオブ(V)、及び塩化バナジウム(III)からなる群から選択される一種以上の化合物を含み、
前記めっき鋼板の片面あたりの、前記皮膜の付着量が、0.01〜0.8g/m2の範囲内であり、
前記めっき鋼板の片面あたりの、前記皮膜の、コバルトを除く遷移金属質量換算付着量が4〜400mg/m2の範囲内であり、
前記めっき鋼板の片面あたりの、前記皮膜のコバルト質量換算付着量が0.1〜20mg/m2の範囲内であり、
前記皮膜中のリン化合物及びフッ素化合物の合計量の割合が、1質量%以下である
ことを特徴とするアルミニウム含有亜鉛系めっき鋼板。 - 前記皮膜のコバルト質量換算付着量が0.5mg/m2よりも大きく20mg/m2以下の範囲内であることを特徴とする請求項1に記載のアルミニウム含有亜鉛系めっき鋼板。
- 前記めっき層がマグネシウムを含有し、
前記めっき層中のマグネシウムの割合が0質量%を超えて6.0質量%以下の範囲内であることを特徴とする請求項1に記載のアルミニウム含有亜鉛系めっき鋼板。 - 前記めっき層が、Siを、前記めっき層中のアルミニウムに対して、質量割合で、0.1%以上、10%以下の範囲内で含むことを特徴とする請求項1に記載のアルミニウム含有亜鉛系めっき鋼板。
- 前記めっき層が、0質量%を超えて1質量%以下の範囲内のNi及び0質量%を超えて1質量%以下の範囲内のCrのうち、一種類以上を含有することを特徴とする請求項1に記載のアルミニウム含有亜鉛系めっき鋼板。
- 前記めっき層が、0質量%を超えて0.5質量%以下の範囲内のCa、0質量%を超えて0.5質量%以下の範囲内のSr、0質量%を超えて0.5質量%以下の範囲内のY、0質量%を超えて0.5質量%以下の範囲内のLa及び0質量%を超えて0.5質量%以下の範囲内のCeのうち、一種類以上を含有することを特徴とする請求項1に記載のアルミニウム含有亜鉛系めっき鋼板。
- コバルト及びクロムを除く遷移金属の塩基性化合物(A)、コバルト化合物(B)、及び水を含有し、pH7.5〜10の範囲内である水系表面調整剤を、めっき鋼板に塗布し、前記めっき鋼板上の前記水系表面調整剤を乾燥することで皮膜を形成する工程を含み、
前記めっき鋼板が、亜鉛とアルミニウムとを含有するめっき層を備え、前記めっき層中のアルミニウムの割合が1質量%以上、75質量%以下の範囲内であり、
前記遷移金属の塩基性化合物が、炭酸ジルコニウムアンモニウム、炭酸ジルコニウムカリウム、炭酸ジルコニウムナトリウム、炭酸ジルコニウムのジエタノールアミン塩、モリブデン酸アンモニウム、塩化ニオブ(V)、及び塩化バナジウム(III)からなる群から選択される一種以上の化合物を含み、
前記皮膜中のリン化合物及びフッ素化合物の合計量の割合が、1質量%以下であることを特徴とするアルミニウム含有亜鉛系めっき鋼板の製造方法。 - 前記めっき鋼板上の前記水系表面調整剤を乾燥するときの、前記めっき鋼板の到達板温を、40〜200℃の範囲内にすることを特徴とする請求項7に記載のアルミニウム含有亜鉛系めっき鋼板の製造方法。
- 前記塩基性化合物(A)の総量に対する、前記コバルト化合物(B)に含まれるコバルト原子の質量比の値が、1/10〜1/1000の範囲内であることを特徴とする請求項7に記載のアルミニウム含有亜鉛系めっき鋼板の製造方法。
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