JP7417888B2 - Zinc-based composite plating solution, method for forming zinc-based composite plating film, and method for forming composite oxide film - Google Patents
Zinc-based composite plating solution, method for forming zinc-based composite plating film, and method for forming composite oxide film Download PDFInfo
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- JP7417888B2 JP7417888B2 JP2019127225A JP2019127225A JP7417888B2 JP 7417888 B2 JP7417888 B2 JP 7417888B2 JP 2019127225 A JP2019127225 A JP 2019127225A JP 2019127225 A JP2019127225 A JP 2019127225A JP 7417888 B2 JP7417888 B2 JP 7417888B2
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- film
- zinc
- composite plating
- based composite
- metal
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- 238000007747 plating Methods 0.000 title claims description 253
- 239000002131 composite material Substances 0.000 title claims description 223
- 238000000034 method Methods 0.000 title claims description 56
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title description 187
- 229910052725 zinc Inorganic materials 0.000 title description 187
- 239000011701 zinc Substances 0.000 title description 187
- 239000007769 metal material Substances 0.000 claims description 87
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 82
- 239000000203 mixture Substances 0.000 claims description 75
- 229910052751 metal Inorganic materials 0.000 claims description 74
- 239000002184 metal Substances 0.000 claims description 74
- 239000011592 zinc chloride Substances 0.000 claims description 41
- 235000005074 zinc chloride Nutrition 0.000 claims description 41
- 229910044991 metal oxide Inorganic materials 0.000 claims description 30
- 150000004706 metal oxides Chemical class 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 25
- 229910052719 titanium Inorganic materials 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 229910007567 Zn-Ni Inorganic materials 0.000 claims description 15
- 229910007614 Zn—Ni Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000010408 film Substances 0.000 description 257
- 239000000243 solution Substances 0.000 description 97
- 238000012360 testing method Methods 0.000 description 75
- 238000005260 corrosion Methods 0.000 description 41
- 230000007797 corrosion Effects 0.000 description 41
- 150000002736 metal compounds Chemical class 0.000 description 38
- -1 V 2 O 5 Inorganic materials 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- 239000001257 hydrogen Substances 0.000 description 27
- 229910052739 hydrogen Inorganic materials 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- 235000002639 sodium chloride Nutrition 0.000 description 23
- 150000003839 salts Chemical class 0.000 description 22
- 239000010936 titanium Substances 0.000 description 22
- 239000008119 colloidal silica Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- 150000004767 nitrides Chemical class 0.000 description 19
- 229920002545 silicone oil Polymers 0.000 description 19
- 229910052782 aluminium Inorganic materials 0.000 description 16
- 150000002902 organometallic compounds Chemical class 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 14
- 230000035699 permeability Effects 0.000 description 14
- 150000001247 metal acetylides Chemical class 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 238000009713 electroplating Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 230000002265 prevention Effects 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000013522 chelant Substances 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000314 lubricant Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011817 metal compound particle Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
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- 235000015165 citric acid Nutrition 0.000 description 3
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- XRASGLNHKOPXQL-UHFFFAOYSA-L azane 2-oxidopropanoate titanium(4+) dihydrate Chemical compound N.N.O.O.[Ti+4].CC([O-])C([O-])=O.CC([O-])C([O-])=O XRASGLNHKOPXQL-UHFFFAOYSA-L 0.000 description 2
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- 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
- 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
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
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- ULFQGKXWKFZMLH-UHFFFAOYSA-N iridium tantalum Chemical compound [Ta].[Ir] ULFQGKXWKFZMLH-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 235000019388 lanolin Nutrition 0.000 description 1
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 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
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 description 1
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- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
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- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 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
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical class [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- NRKQBMOGOKEWPX-UHFFFAOYSA-N vanadyl nitrate Inorganic materials [O-][N+](=O)O[V](=O)(O[N+]([O-])=O)O[N+]([O-])=O NRKQBMOGOKEWPX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- GTQFPPIXGLYKCZ-UHFFFAOYSA-L zinc chlorate Chemical compound [Zn+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O GTQFPPIXGLYKCZ-UHFFFAOYSA-L 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、亜鉛系複合めっき液、亜鉛系複合めっき皮膜の形成方法、及び複合酸化物皮膜の形成方法に関する。 The present invention relates to a zinc-based composite plating solution, a method for forming a zinc-based composite plating film, and a method for forming a composite oxide film.
近年、自動車部品、航空機部品をはじめとする各種金属材料は軽量化や高機能化が進んでおり、それに伴い、金属部材の表面に形成される亜鉛めっき皮膜の薄膜化が望まれている。 In recent years, various metal materials such as automobile parts and aircraft parts have become lighter and more functional, and as a result, there is a desire for thinner galvanized films formed on the surfaces of metal members.
しかしながら、亜鉛めっき皮膜の防食性能は膜厚に比例して向上するため、亜鉛めっき皮膜を薄膜化すると金属材料の長期信頼性が劣るという問題がある。 However, since the anticorrosion performance of a galvanized film improves in proportion to the film thickness, there is a problem in that when the galvanized film is made thinner, the long-term reliability of the metal material is degraded.
防食性能の向上を目的として、Ｚｎ－Ｎｉ、Ｚｎ－Ｍｎ等の合金めっき、亜鉛複合めっきが用いられている。これらの中でも酸性Ｚｎ－Ｎｉ合金めっき浴は、電流効率が高く、水素脆性が小さいなどの点から防錆皮膜薄膜化の検討浴として注目されている。 For the purpose of improving anticorrosion performance, alloy plating such as Zn-Ni, Zn-Mn, etc., and zinc composite plating are used. Among these, acidic Zn--Ni alloy plating baths are attracting attention as a bath for thinning rust preventive coatings because of their high current efficiency and low hydrogen embrittlement.
酸性Ｚｎ－Ｎｉ合金めっき浴として、Ｐ、Ｃｏ、Ｃｒ等の金属が混入しためっき液が提案されている（例えば、特許文献１参照）。 As an acidic Zn--Ni alloy plating bath, a plating solution containing metals such as P, Co, and Cr has been proposed (see, for example, Patent Document 1).
しかしながら、特許文献１に記載の酸性浴Ｚｎ－Ｎｉ合金めっき浴は、皮膜の密着性、、均一性、及び付き廻り性が検討されておらず、これらの特定が十分でないという問題がある。 However, the acid bath Zn--Ni alloy plating bath described in Patent Document 1 has a problem in that the adhesion, uniformity, and coverage of the film have not been studied, and these are not sufficiently specified.
特に、皮膜の均一性及び付き廻り性は、酸化亜鉛、硫酸亜鉛を用いた従来のジンケート浴（亜鉛酸浴）が優れているが、ジンケート浴は電流効率が劣り、タクト（生産効率）が低い。このため、亜鉛酸によらず、ジンケート浴と同等の皮膜の均一性及び付き廻り性を示す亜鉛系複合めっき皮膜を形成することができるめっき液が望ましい。 In particular, conventional zincate baths (zinc acid baths) using zinc oxide and zinc sulfate are excellent in film uniformity and coverage, but zincate baths have poor current efficiency and low tact (production efficiency). . For this reason, it is desirable to have a plating solution that can form a zinc-based composite plating film that exhibits the same film uniformity and coverage as a zincate bath, without relying on zinc acid.
また、亜鉛めっき皮膜では、めっき皮膜を形成する際に発生した水素が、めっき皮膜中に吸蔵されることがある。めっき皮膜中に水素が吸蔵されると、めっき皮膜が形成された被めっき物の延性、靭性、強度が低下する、いわゆる水素脆化を生じるという問題がある。水素脆化は、高い耐久性が要求される航空機部品で特に問題となる。 Further, in the case of a galvanized film, hydrogen generated during formation of the plating film may be occluded in the plating film. When hydrogen is occluded in a plating film, there is a problem in that so-called hydrogen embrittlement occurs, in which the ductility, toughness, and strength of the plated object on which the plating film is formed are reduced. Hydrogen embrittlement is a particular problem in aircraft parts that require high durability.
従って、金属材料に亜鉛系複合めっき皮膜を形成することにより、金属材料に優れた耐食性を付与することができ、形成される亜鉛系複合めっき皮膜の水素透過性が向上し、且つ、形成される亜鉛系複合めっき皮膜の付き廻り性に優れた亜鉛系複合めっき液の開発が求められており、当該亜鉛系複合めっき液を用いた亜鉛系複合めっき皮膜の形成方法、及び複合酸化物皮膜の形成方法の開発が求められている。 Therefore, by forming a zinc-based composite plating film on a metal material, it is possible to impart excellent corrosion resistance to the metal material, and the hydrogen permeability of the formed zinc-based composite plating film is improved. There is a need for the development of a zinc-based composite plating solution with excellent coverage of the zinc-based composite plating film, and a method for forming a zinc-based composite plating film using the zinc-based composite plating solution, and a method for forming a composite oxide film. Development of methods is required.
本発明は、金属材料に亜鉛系複合めっき皮膜を形成することにより、金属材料に優れた耐食性を付与することができ、密着性及び均一性に優れた亜鉛系複合めっき皮膜を形成することができ、形成される亜鉛系複合めっき皮膜の水素透過性が向上し、且つ、形成される亜鉛系複合めっき皮膜の付き廻り性に優れた亜鉛系複合めっき液、当該亜鉛系複合めっき液を用いた亜鉛系複合めっき皮膜の形成方法、及び複合酸化物皮膜の形成方法を提供することを目的とする。 The present invention can impart excellent corrosion resistance to metal materials by forming a zinc-based composite plating film on metal materials, and can form a zinc-based composite plating film with excellent adhesion and uniformity. , a zinc-based composite plating solution that improves the hydrogen permeability of the zinc-based composite plating film that is formed and has excellent coverage of the zinc-based composite plating film that is formed, and zinc using the zinc-based composite plating solution. The present invention aims to provide a method for forming a composite plating film and a method for forming a composite oxide film.
本発明者は、鋭意研究を重ねた結果、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５である亜鉛系複合めっき液によれば、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of extensive research, the present inventor found that (A) zinc chloride, and (B) at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides. However, the present inventors have discovered that the above object can be achieved by using a zinc-based composite plating solution having a pH of 1 to 5.5, and have completed the present invention.
即ち、本発明は、下記の亜鉛系複合めっき液、亜鉛系複合めっき皮膜の形成方法、及び複合酸化物皮膜の形成方法に関する。
１．亜鉛系複合めっき皮膜を形成するための亜鉛系複合めっき液であって、
（Ａ）亜鉛の塩化物、並びに、
（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物
を含有し、ｐＨが１～５．５である、
ことを特徴とする亜鉛系複合めっき液。
２．前記金属化合物は、Ａｌ、Ｓｉ、Ｔｉ、Ｐ、Ｃｅ、Ｃｏ、Ｃｒ、Ｖ、Ｗ、Ｚｒ、Ｆｅ、Ｂｉ及びＳｎからなる群より選択される少なくとも１種の金属の金属化合物である、項１に記載の亜鉛系複合めっき液。
３．前記金属化合物の平均粒子径は、０．００１～１．０μｍである、項１又は２に記載の亜鉛系複合めっき液。
４．前記金属化合物の含有量は、０．１～２００ｇ／Ｌである、項１～３のいずれかに記載の亜鉛系複合めっき液。
５．亜鉛系複合めっき皮膜の形成方法であって、
被めっき物を亜鉛系複合めっき液に浸漬する工程１を有し、
前記亜鉛系複合めっき液は、
（Ａ）亜鉛の塩化物、並びに、
（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物
を含有し、ｐＨが１～５．５である、
ことを特徴とする亜鉛系複合めっき皮膜の形成方法。
６．複合酸化物皮膜の形成方法であって、
（１）金属材料を亜鉛系複合めっき液に浸漬して亜鉛系複合めっき皮膜を形成する工程１、
（２）前記亜鉛系複合めっき皮膜の表面に皮膜形成組成物を塗布して皮膜形成組成物層を形成する工程２、及び
（３）前記皮膜形成組成物層を加熱して、前記金属材料の表面に、当該金属材料側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜を形成する工程３
を含み、
前記亜鉛系複合めっき液は、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５であり、
前記皮膜形成組成物は、（ａ）アルコキシシランオリゴマー、及び（ｂ）溶媒を含有し、前記溶媒は、水及び／又は水溶性有機溶媒である、
ことを特徴とする複合酸化物皮膜の形成方法。
７．金属材料上に、前記金属材料の表面側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜が積層されている、物品。
That is, the present invention relates to the following zinc-based composite plating solution, method for forming a zinc-based composite plating film, and method for forming a composite oxide film.
1. A zinc-based composite plating solution for forming a zinc-based composite plating film,
(A) Zinc chloride, and
(B) contains at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides, and has a pH of 1 to 5.5;
A zinc-based composite plating solution characterized by:
2. Item 1, wherein the metal compound is a metal compound of at least one metal selected from the group consisting of Al, Si, Ti, P, Ce, Co, Cr, V, W, Zr, Fe, Bi, and Sn. Zinc-based composite plating solution described in .
3. Item 3. The zinc-based composite plating solution according to item 1 or 2, wherein the metal compound has an average particle diameter of 0.001 to 1.0 μm.
4. Item 4. The zinc-based composite plating solution according to any one of Items 1 to 3, wherein the content of the metal compound is 0.1 to 200 g/L.
5. A method for forming a zinc-based composite plating film, the method comprising:
A step 1 of immersing the object to be plated in a zinc-based composite plating solution,
The zinc-based composite plating solution is
(A) Zinc chloride, and
(B) contains at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides, and has a pH of 1 to 5.5;
A method for forming a zinc-based composite plating film, characterized by:
6. A method for forming a composite oxide film, the method comprising:
(1) Step 1 of immersing the metal material in a zinc-based composite plating solution to form a zinc-based composite plating film,
(2) Step 2 of applying a film-forming composition to the surface of the zinc-based composite plating film to form a film-forming composition layer, and (3) heating the film-forming composition layer to form a film-forming composition layer on the surface of the metal material. Step 3 of forming a composite oxide film having a zinc-based composite plating film, a chemical conversion film, and a siliceous film on the surface in this order from the metal material side.
including;
The zinc-based composite plating solution contains (A) zinc chloride, and (B) at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides, and has a pH of 1 to 5.5,
The film-forming composition contains (a) an alkoxysilane oligomer and (b) a solvent, where the solvent is water and/or a water-soluble organic solvent.
A method for forming a composite oxide film, characterized by the following.
7. An article in which a composite oxide film having a zinc-based composite plating film, a chemical conversion film, and a siliceous film in this order is laminated on a metal material from the surface side of the metal material.
本発明の亜鉛系複合めっき液は、金属材料に亜鉛系複合めっき皮膜を形成することにより、金属材料に優れた耐食性を付与することができ、密着性及び均一性に優れた亜鉛系複合めっき皮膜を形成することができ、形成される亜鉛系複合めっき皮膜の水素透過性が向上し、且つ、形成される亜鉛系複合めっき皮膜の付き廻り性に優れている。また、本発明の亜鉛系複合めっき皮膜の形成方法は、金属材料を亜鉛系複合めっき液に浸漬する工程１を有しており、金属材料に亜鉛系複合めっき皮膜を形成することにより、金属材料に優れた耐食性を付与することができ、密着性及び均一性に優れた亜鉛系複合めっき皮膜を形成することができ、形成される亜鉛系複合めっき皮膜の水素透過性が向上し、且つ、形成される亜鉛系複合めっき皮膜の付き廻り性に優れている。更に、本発明の複合酸化物皮膜の形成方法は、金属材料の表面に、当該金属材料側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜を形成することができ、金属材料に、更に優れた耐食性を付与することができる。 The zinc-based composite plating solution of the present invention can impart excellent corrosion resistance to metal materials by forming a zinc-based composite plating film on metal materials, and provides a zinc-based composite plating film with excellent adhesion and uniformity. can be formed, the hydrogen permeability of the zinc-based composite plating film to be formed is improved, and the zinc-based composite plating film to be formed has excellent coverage. Further, the method for forming a zinc-based composite plating film of the present invention includes step 1 of immersing a metal material in a zinc-based composite plating solution, and by forming a zinc-based composite plating film on the metal material, It is possible to form a zinc-based composite plating film with excellent corrosion resistance and excellent adhesion and uniformity, and the hydrogen permeability of the formed zinc-based composite plating film is improved. The zinc-based composite plating film has excellent coverage. Furthermore, the method for forming a composite oxide film of the present invention can form a composite oxide film having a zinc-based composite plating film, a chemical conversion film, and a siliceous film in this order from the metal material side on the surface of a metal material. It is possible to impart even better corrosion resistance to metal materials.
１．亜鉛系複合めっき液
本発明の亜鉛系複合めっき液は、亜鉛系複合めっき皮膜を形成するための亜鉛系複合めっき液であって、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５であることを特徴とする。上記構成を備える本発明の亜鉛系複合めっき液は、（Ａ）亜鉛の塩化物を含有し、且つ、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有するので、金属材料に複合酸化皮膜を形成して、当該金属材料に優れた耐食性を付与することができ、密着性及び均一性に優れた亜鉛系複合めっき皮膜を形成することができ、且つ、形成される亜鉛系複合めっき皮膜の付き廻り性に優れている。このため、本発明の亜鉛系複合めっき液を用いて形成した亜鉛系複合めっき皮膜は、薄くても耐食性、密着性及び均一性に優れており、薄膜化が可能である。このため、本発明の亜鉛系複合めっき液は、ｐＨを１～５．５とすることにより、亜鉛系複合めっき皮膜を薄膜化しても、金属材料に優れた耐食性を付与することができ、密着性及び均一性に優れた亜鉛系複合めっき皮膜を形成することができ、且つ、形成される亜鉛系複合めっき皮膜の付き廻り性に優れている。また、本発明の亜鉛系複合めっき液は、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、且つ、ｐＨが１～５．５であるので、被めっき物の表面に形成された亜鉛系複合めっき皮膜の水素透過性が向上する。このため、めっき皮膜が形成された被めっき物の水素脆化が抑制される。
1. Zinc-based composite plating solution The zinc-based composite plating solution of the present invention is a zinc-based composite plating solution for forming a zinc-based composite plating film, and comprises (A) zinc chloride and (B) metal oxide. , a metal compound selected from the group consisting of metal carbides and metal nitrides, and has a pH of 1 to 5.5. The zinc-based composite plating solution of the present invention having the above structure contains (A) zinc chloride, and (B) at least one member selected from the group consisting of metal oxides, metal carbides, and metal nitrides. Because it contains a metal compound, it is possible to form a composite oxide film on a metal material, imparting excellent corrosion resistance to the metal material, and forming a zinc-based composite plating film with excellent adhesion and uniformity. The zinc-based composite plating film formed has excellent coverage. Therefore, the zinc-based composite plating film formed using the zinc-based composite plating solution of the present invention has excellent corrosion resistance, adhesion, and uniformity even if it is thin, and can be made into a thin film. Therefore, by adjusting the pH of the zinc-based composite plating solution of the present invention to 1 to 5.5, even if the zinc-based composite plating film is made thin, it can impart excellent corrosion resistance to metal materials and provide adhesion. It is possible to form a zinc-based composite plating film with excellent properties and uniformity, and the formed zinc-based composite plating film has excellent coverage. Further, the zinc-based composite plating solution of the present invention contains (B) at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides, and has a pH of 1 to 5. 5, the hydrogen permeability of the zinc-based composite plating film formed on the surface of the object to be plated is improved. Therefore, hydrogen embrittlement of the plated object on which the plating film is formed is suppressed.
以下、本発明について詳細に説明する。 The present invention will be explained in detail below.
（Ａ）亜鉛の塩化物
亜鉛の塩化物としては、亜鉛元素及び塩素原子を含んでいれば特に限定されず、塩化亜鉛、塩素酸亜鉛等が挙げられる。これらの中でも、水等の溶媒に溶解し易く、汎用性、安全性の点で塩化亜鉛が好ましい。
(A) Zinc chloride Zinc chloride is not particularly limited as long as it contains a zinc element and a chlorine atom, and examples thereof include zinc chloride, zinc chlorate, and the like. Among these, zinc chloride is preferred because it is easily soluble in solvents such as water and is versatile and safe.
亜鉛系複合めっき液中の亜鉛の塩化物の含有量は３０ｇ／Ｌ以上が好ましく、７０ｇ／Ｌ以上がより好ましい。また、亜鉛系複合めっき液中の亜鉛の塩化物の含有量は１５０ｇ／Ｌ以下が好ましく、１００ｇ／Ｌ以下がより好ましい。亜鉛の塩化物の含有量の上限が上記範囲であると、亜鉛系複合めっき液の安定性・電流効率がより一層向上する。また、亜鉛の塩化物の含有量の下限が上記範囲であると、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。 The content of zinc chloride in the zinc-based composite plating solution is preferably 30 g/L or more, more preferably 70 g/L or more. Further, the content of zinc chloride in the zinc-based composite plating solution is preferably 150 g/L or less, more preferably 100 g/L or less. When the upper limit of the zinc chloride content is within the above range, the stability and current efficiency of the zinc-based composite plating solution are further improved. In addition, when the lower limit of the zinc chloride content is within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved. do.
本発明の亜鉛系複合めっき液は、上述の亜鉛の塩化物を含有することにより、塩化浴であることが好ましい。本明細書において塩化浴とは、亜鉛の塩化物、及びその他の塩化物を含有するめっき液である。 The zinc-based composite plating solution of the present invention is preferably a chloride bath by containing the above-mentioned zinc chloride. In this specification, a chloride bath is a plating solution containing zinc chloride and other chlorides.
（Ｂ）金属化合物
金属化合物に含まれる金属としては特に限定されず、例えば、Ａｌ、Ｓｉ、Ｔｉ、Ｐ、Ｃｅ、Ｃｏ、Ｃｒ、Ｖ、Ｗ、Ｚｒ、Ｆｅ、Ｂｉ、Ｓｎ等が挙げられる。これらの中でも、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する点で、Ａｌ、Ｓｉ、Ｔｉ、Ｐ、Ｃｅ、Ｃｏ、Ｃｒ、Ｖ、Ｗ、Ｚｒ、Ｆｅが好ましく、Ａｌ、Ｓｉ、Ｔｉ、Ｃｅ、Ｃｒ、Ｖ、Ｗ、Ｚｒがより好ましく、Ｓｉ、Ｔｉ，Ａｌが更に好ましく、Ｓｉが特に好ましい。
(B) Metal Compound The metal contained in the metal compound is not particularly limited, and examples thereof include Al, Si, Ti, P, Ce, Co, Cr, V, W, Zr, Fe, Bi, and Sn. Among these, Al, Si, Ti, P, Ce, Co, Cr, V, W, Zr, and Fe are preferred, Al, Si, Ti, Ce, Cr, V, W, and Zr are more preferred, Si, Ti, and Al are still more preferred, and Si is particularly preferred.
上記金属は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 The above metals may be used alone or in combination of two or more.
金属化合物は、上記金属の金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物である。上記以外の金属化合物を用いると、金属材料の耐食性を向上させることができず、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性が十分でない。また、上記以外の金属化合物を用いると、めっき皮膜が形成された被めっき物の水素透過性が十分でない。金属化合物は、より一層亜鉛系複合めっき皮膜の均一性、付き廻り性が向上し、且つ、亜鉛系複合めっき皮膜の水素透過性がより一層向上する点で、金属酸化物、金属炭化物が好ましく、金属酸化物がより好ましい。 The metal compound is at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides of the above metals. If a metal compound other than the above is used, the corrosion resistance of the metal material cannot be improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film will not be sufficient. Furthermore, if a metal compound other than those mentioned above is used, the hydrogen permeability of the plated object on which the plating film is formed will not be sufficient. The metal compound is preferably a metal oxide or metal carbide, since the uniformity and coverage of the zinc-based composite plating film are further improved, and the hydrogen permeability of the zinc-based composite plating film is further improved. Metal oxides are more preferred.
金属酸化物としては、例えば、ＳｉＯ２、Ｃｒ２Ｏ３、Ａｌ２Ｏ３、Ｖ２Ｏ５、ＺｒＯ２、ＴｉＯ２等が挙げられる。 Examples of the metal oxide include SiO 2 , Cr 2 O 3 , Al 2 O 3 , V 2 O 5 , ZrO 2 , TiO 2 and the like.
金属炭化物としては、例えば、ＳｉＣ、ＣｒＣ、Ａｌ４Ｃ３、ＶＣ、ＺｒＣ、ＴｉＣ等が挙げられる。 Examples of the metal carbide include SiC, CrC, Al 4 C 3 , VC, ZrC, and TiC.
金属窒化物としては、例えば、ＳｉＮ、ＣｒＮ、ＡｌＮ、ＶＮ、ＺｒＮ、ＴｉＮ等が挙げられる。 Examples of metal nitrides include SiN, CrN, AlN, VN, ZrN, and TiN.
金属化合物は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 The metal compounds may be used alone or in combination of two or more.
金属化合物は、亜鉛系複合めっき液中で粒子の形状で含有されることが好ましい。金属化合物の粒子の平均粒子径は、０．００１μｍ以上が好ましく、０．００５μｍ以上がより好ましく、０．０１μｍ以上が更に好ましい。また、金属化合物の粒子の平均粒子径は、２．０μｍ以下が好ましく、１．０μｍ以下がより好ましく、０．５μｍ以下が更に好ましく、０．１μｍ以下が特に好ましい。金属化合物の粒子の平均粒子径の上限が上記範囲であると、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。また、金属化合物の粒子の平均粒子径の下限が上記範囲であると、亜鉛系複合めっき液の安定性がより一層向上し、且つ、亜鉛系複合めっき皮膜の水素透過性がより一層向上する。 The metal compound is preferably contained in the form of particles in the zinc-based composite plating solution. The average particle diameter of the metal compound particles is preferably 0.001 μm or more, more preferably 0.005 μm or more, and even more preferably 0.01 μm or more. Further, the average particle diameter of the metal compound particles is preferably 2.0 μm or less, more preferably 1.0 μm or less, even more preferably 0.5 μm or less, and particularly preferably 0.1 μm or less. When the upper limit of the average particle diameter of the metal compound particles is within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved. . Furthermore, when the lower limit of the average particle diameter of the metal compound particles is within the above range, the stability of the zinc-based composite plating solution is further improved, and the hydrogen permeability of the zinc-based composite plating film is further improved.
本明細書において、金属化合物の平均粒子径は、動的光散乱法により測定時間１２０秒、粒子屈折率１．８１、粒子形状 非球形、溶媒屈折率１．３３３の条件で測定される平均粒子径である。 In this specification, the average particle diameter of the metal compound is the average particle size measured by a dynamic light scattering method under the conditions of a measurement time of 120 seconds, a particle refractive index of 1.81, a non-spherical particle shape, and a solvent refractive index of 1.333. It is the diameter.
亜鉛系複合めっき液中の金属化合物の含有量は０．１ｇ／Ｌ以上が好ましく、１０ｇ／Ｌ以上がより好ましく、３０ｇ／Ｌ以上が更に好ましい。また、亜鉛系複合めっき液中の金属化合物の含有量は２００ｇ／Ｌ以下が好ましく、１００ｇ／Ｌ以下がより好ましく、６０ｇ／Ｌ以下が更に好ましい。金属化合物の含有量の上限が上記範囲であると、亜鉛系複合めっき液の安定性がより一層向上する。また、金属化合物の含有量の下限が上記範囲であると、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上し、且つ、亜鉛系複合めっき皮膜の水素透過性がより一層向上する。 The content of the metal compound in the zinc-based composite plating solution is preferably 0.1 g/L or more, more preferably 10 g/L or more, and even more preferably 30 g/L or more. Moreover, the content of the metal compound in the zinc-based composite plating solution is preferably 200 g/L or less, more preferably 100 g/L or less, and even more preferably 60 g/L or less. When the upper limit of the content of the metal compound is within the above range, the stability of the zinc-based composite plating solution is further improved. In addition, when the lower limit of the content of the metal compound is within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved, Moreover, the hydrogen permeability of the zinc-based composite plating film is further improved.
（Ｃ）亜鉛の塩化物以外の塩化物
本発明の亜鉛系複合めっき液は、上記（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物の他に、（Ｃ）亜鉛の塩化物以外の塩化物を含有していてもよい。本発明の亜鉛系複合めっき液が亜鉛の塩化物以外の塩化物を含有することにより、めっき皮膜の均一性、付き廻り性、析出電流効率がより一層向上する。
(C) Chloride other than zinc chloride The zinc-based composite plating solution of the present invention is selected from the group consisting of the above (A) zinc chloride, and (B) metal oxide, metal carbide, and metal nitride. In addition to the at least one metal compound mentioned above, (C) a chloride other than zinc chloride may be contained. By containing a chloride other than zinc chloride in the zinc-based composite plating solution of the present invention, the uniformity, coverage, and deposition current efficiency of the plating film are further improved.
亜鉛の塩化物以外の塩化物としては特に限定されず、塩化ニッケル、塩化カリウム、塩化アンモニウム、塩化ナトリウム等が挙げられる。これらの中でも、水への溶解性、汎用性、めっき液の安定性により一層優れる点で、塩化ニッケル、塩化カリウム、塩化アンモニウムが好ましい。 Chlorides other than zinc chloride are not particularly limited, and include nickel chloride, potassium chloride, ammonium chloride, sodium chloride, and the like. Among these, nickel chloride, potassium chloride, and ammonium chloride are preferred because they are more excellent in water solubility, versatility, and stability of the plating solution.
上記亜鉛の塩化物以外の塩化物は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 Chlorides other than the zinc chloride mentioned above may be used alone or in combination of two or more.
亜鉛系複合めっき液中の亜鉛の塩化物以外の塩化物の含有量は１００ｇ／Ｌ以上が好ましく、１１０ｇ／Ｌ以上がより好ましく、１２０ｇ／Ｌ以上が更に好ましい。また、亜鉛系複合めっき液中の亜鉛の塩化物以外の塩化物の含有量は２００ｇ／Ｌ以下が好ましく、１９０ｇ／Ｌ以下がより好ましく、１８０ｇ／Ｌ以下が更に好ましい。亜鉛の塩化物以外の塩化物の含有量の上限が上記範囲であると、亜鉛系複合めっき液の安定性がより一層向上する。また、亜鉛の塩化物以外の塩化物の含有量の下限が上記範囲であると、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。 The content of chlorides other than zinc chloride in the zinc-based composite plating solution is preferably 100 g/L or more, more preferably 110 g/L or more, and even more preferably 120 g/L or more. Further, the content of chlorides other than zinc chloride in the zinc-based composite plating solution is preferably 200 g/L or less, more preferably 190 g/L or less, and even more preferably 180 g/L or less. When the upper limit of the content of chlorides other than zinc chloride is within the above range, the stability of the zinc-based composite plating solution is further improved. In addition, when the lower limit of the content of chlorides other than zinc chloride is within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are improved. will further improve.
その他の成分
本発明の亜鉛系複合めっき液は、上記（Ａ）亜鉛の塩化物、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物、並びに、必要に応じて添加される（Ｃ）亜鉛の塩化物以外の塩化物の他に、その他の成分を含有していてもよい。このようなその他の成分としては、ベンゼルアセトン、ベンズアルデヒド、クエン酸、芳香族アルデヒド、ニコチンアミド、コハク酸、ポリエチレングリコール（ＰＥＧ）、ゼラチン、ポリアルキレンポリアミン・エピクロルヒドリン反応生成物、ポリオキシエチレン・ポリオキシプロピレン共重合体（ＰＯＥ／ＰＯＰ共重合体）、ポリエチレングリコールノニルフェニルエーテル（ＰＥＧＮＰＥ）等が挙げられる。
Other components The zinc-based composite plating solution of the present invention comprises at least one metal compound selected from the group consisting of (A) zinc chloride, (B) metal oxide, metal carbide, and metal nitride, and In addition to chlorides other than (C) zinc chloride, which are added as necessary, other components may be contained. These other ingredients include benzyl acetone, benzaldehyde, citric acid, aromatic aldehydes, nicotinamide, succinic acid, polyethylene glycol (PEG), gelatin, polyalkylene polyamine epichlorohydrin reaction products, polyoxyethylene poly Examples include oxypropylene copolymer (POE/POP copolymer), polyethylene glycol nonylphenyl ether (PEGNPE), and the like.
本発明の亜鉛系複合めっき液のｐＨは、１～５．５である、ｐＨが１未満であるとめっき析出性、めっき外観に劣る。ｐＨが５．５を超えると、金属材料の耐食性が劣り、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性が低下し、且つ、亜鉛系複合めっき皮膜の水素透過性が十分でない。上記ｐＨは１．０以上が好ましく、１．５以上がより好ましい。また、上記ｐＨは３．０以下が好ましく、２．０以下がより好ましい。 The pH of the zinc-based composite plating solution of the present invention is 1 to 5.5. If the pH is less than 1, the plating precipitation property and the plating appearance are poor. If the pH exceeds 5.5, the corrosion resistance of the metal material will be poor, the adhesion, uniformity, and coverage of the zinc-based composite plating film will be reduced, and the hydrogen permeability of the zinc-based composite plating film will be insufficient. The above pH is preferably 1.0 or higher, more preferably 1.5 or higher. Further, the above pH is preferably 3.0 or less, more preferably 2.0 or less.
上記ｐＨは、ｐＨ調整剤により調整することができる。ｐＨを低く調整する際のｐＨ調整剤としては、塩酸、希硫酸等が挙げられる。これらの中でも、より一層汎用性に優れる点で、塩酸が好ましい。ｐＨを高く調整する際のｐＨ調整剤としては、水酸化ナトリウム水溶液、アンモニア水溶液等が挙げられる。これらの中でも、より一層反応性に優れる点で、アンモニア水溶液が好ましい。 The above pH can be adjusted with a pH adjuster. Examples of pH adjusting agents used to lower the pH include hydrochloric acid and dilute sulfuric acid. Among these, hydrochloric acid is preferred because it is more versatile. Examples of the pH adjuster for adjusting the pH to a high level include a sodium hydroxide aqueous solution and an ammonia aqueous solution. Among these, ammonia aqueous solution is preferred because it has even better reactivity.
以上説明した本発明の亜鉛系複合めっき液によれば、亜鉛系複合めっき皮膜を形成することができる。本発明の亜鉛系複合めっき液を用いて金属材料に亜鉛系複合めっき皮膜を形成することにより、金属材料に優れた耐食性を付与することができ、密着性及び均一性に優れた亜鉛系複合めっき皮膜を形成することができ、且つ、形成される亜鉛系複合めっき皮膜の付き廻り性に優れている。また、本発明の亜鉛系複合めっき液により形成された亜鉛系複合めっき皮膜は、水素透過性に優れている。 According to the zinc-based composite plating solution of the present invention described above, a zinc-based composite plating film can be formed. By forming a zinc-based composite plating film on metal materials using the zinc-based composite plating solution of the present invention, it is possible to impart excellent corrosion resistance to metal materials, and zinc-based composite plating with excellent adhesion and uniformity. It is possible to form a film, and the formed zinc-based composite plating film has excellent coverage. Furthermore, the zinc-based composite plating film formed using the zinc-based composite plating solution of the present invention has excellent hydrogen permeability.
２．亜鉛系複合めっき皮膜の形成方法
本発明の亜鉛系複合めっき皮膜の形成方法は、金属材料を亜鉛系複合めっき液に浸漬する工程１を有し、前記亜鉛系複合めっき液は、
（Ａ）亜鉛の塩化物、並びに、
（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物
を含有し、ｐＨが１～５．５であることを特徴とする亜鉛系複合めっき皮膜の形成方法である。
2. Method for forming a zinc-based composite plating film The method for forming a zinc-based composite plating film of the present invention includes step 1 of immersing a metal material in a zinc-based composite plating solution, the zinc-based composite plating solution comprising:
(A) Zinc chloride, and
(B) A zinc-based composite plating film containing at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides, and having a pH of 1 to 5.5. This is the formation method.
工程１
工程１は、金属材料を亜鉛系複合めっき液に浸漬する工程である。
Process 1
Step 1 is a step of immersing the metal material in a zinc-based composite plating solution.
金属材料を形成する金属としては、被めっき物として工業的に用いられる金属材料を形成する金属であれば特に限定されず、例えば、亜鉛、アルミニウム、マグネシウム、コバルト、ニッケル、鉄、銅、錫、金、これらの合金などの各種の金属材料を処理対象物とすることができる。これらの中でも、より一層汎用性・加工性に優れる点で、ニッケル、亜鉛、鉄、アルミニウムが好ましい。 The metal forming the metal material is not particularly limited as long as it forms a metal material that is used industrially as an object to be plated, and examples thereof include zinc, aluminum, magnesium, cobalt, nickel, iron, copper, tin, Various metal materials such as gold and alloys thereof can be used as objects to be processed. Among these, nickel, zinc, iron, and aluminum are preferable because they are more excellent in versatility and workability.
上記金属材料は、処理液と十分に接触できるように処理対象物の表面部分に存在すればよい。例えば、上記した金属材料のみからなる物品でもよく、該金属材料とその他の材料、例えば、セラミックス材料、プラスチックス材料等と組み合わせた複合品であってもよい。更に、上記した金属によりめっき皮膜を表面に形成しためっき処理品であってもよい。例えば、亜鉛めっき又は亜鉛合金めっきを形成した鋼板を被処理物とすることができる。 The metal material may be present on the surface of the object to be treated so as to be able to sufficiently contact the treatment liquid. For example, it may be an article made only of the above-mentioned metal materials, or it may be a composite article in which the metal material is combined with other materials such as ceramic materials, plastic materials, etc. Furthermore, it may be a plated product in which a plating film is formed on the surface using the above-mentioned metal. For example, a steel plate coated with zinc or zinc alloy can be used as the object to be treated.
金属材料は、装飾性を付与するために、黒色化処理が施されていてもよい。黒化処理としては、金属材料を、無機酸及び／又は有機酸を用いて所定のｐＨ範囲に調整された黒化処理液に浸漬する方法が挙げられる。なお、黒色化処理を施すと、一般に金属材料の表面の防錆性は低下する傾向にある。 The metal material may be subjected to a blackening treatment to give it decorative properties. Examples of the blackening treatment include a method in which the metal material is immersed in a blackening treatment liquid whose pH is adjusted to a predetermined pH range using an inorganic acid and/or an organic acid. Note that when blackening treatment is applied, the rust prevention properties of the surface of the metal material generally tend to decrease.
具体的な無機酸としては、塩酸、硫酸、硝酸、リン酸、フッ化水素酸、ホウ酸などを例示できる。具体的な有機酸としては、ギ酸、酢酸等の脂肪族モノカルボン酸；シュウ酸、マロン酸、コハク酸等の脂肪族ジカルボン酸；グルコン酸等の脂肪族ヒドロキシモノカルボン酸；リンゴ酸等の脂肪族ヒドロキシジカルボン酸；クエン酸等の脂肪族ヒドロキシトリカルボン酸；チオグリコール酸等のカルボン酸を例示できる。これらの無機酸及び有機酸は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 Specific examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, and boric acid. Specific organic acids include aliphatic monocarboxylic acids such as formic acid and acetic acid; aliphatic dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid; aliphatic hydroxymonocarboxylic acids such as gluconic acid; and fatty acids such as malic acid. Examples include group hydroxydicarboxylic acids; aliphatic hydroxytricarboxylic acids such as citric acid; and carboxylic acids such as thioglycolic acid. These inorganic acids and organic acids may be used alone or in combination of two or more.
上記金属材料の表面は、クロム、コバルト及びニッケルを含まない黒色化処理液で処理されていることが好ましい。金属材料の表面がこのような黒色化処理液で処理されることにより、環境への負担を抑制することができ、欧州等のこれらの金属の使用が規制されている地域においても本発明の処理方法を好適に行うことができる。 The surface of the metal material is preferably treated with a blackening treatment liquid that does not contain chromium, cobalt, and nickel. By treating the surface of metal materials with such a blackening treatment liquid, the burden on the environment can be reduced, and the treatment of the present invention can be applied even in regions such as Europe where the use of these metals is regulated. The method can be suitably carried out.
黒色化処理液の液温としては、１０～８０℃が好ましく、３０～６０℃がより好ましい。また、金属材料の浸漬時間は、１０秒～２０分が好ましく、３０秒～１０分がより好ましい。 The temperature of the blackening treatment liquid is preferably 10 to 80°C, more preferably 30 to 60°C. Further, the immersion time of the metal material is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 10 minutes.
亜鉛系複合めっき液としては、上記説明した本発明の亜鉛系複合めっき液を用いればよい。 As the zinc-based composite plating solution, the above-described zinc-based composite plating solution of the present invention may be used.
金属材料を浸漬する際の亜鉛系複合めっき液の温度は３５℃以上が好ましく、４０℃以上がより好ましい。亜鉛系複合めっき液の温度の下限が上記範囲であることにより、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。また、金属材料を浸漬する際の亜鉛系複合めっき液の温度は５０℃以下が好ましく、４５℃以下がより好ましい。亜鉛系複合めっき液の温度の上限が上記範囲であることにより金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。 The temperature of the zinc-based composite plating solution when immersing the metal material is preferably 35°C or higher, more preferably 40°C or higher. By setting the lower limit of the temperature of the zinc-based composite plating solution within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved. . Further, the temperature of the zinc-based composite plating solution when immersing the metal material is preferably 50°C or lower, more preferably 45°C or lower. By setting the upper limit of the temperature of the zinc-based composite plating solution within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved.
金属材料を亜鉛系複合めっき液に浸漬する際の浸漬時間は５分以上が好ましく、１０分以上がより好ましい。浸漬時間の下限が上記範囲であることにより、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。また、金属材料を亜鉛系複合めっき液に浸漬する際の浸漬時間は２０分以下が好ましく、１５分以下がより好ましい。浸漬時間の上限が上記範囲であることにより金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。 The immersion time when the metal material is immersed in the zinc-based composite plating solution is preferably 5 minutes or more, more preferably 10 minutes or more. When the lower limit of the immersion time is within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved. Moreover, the immersion time when immersing the metal material in the zinc-based composite plating solution is preferably 20 minutes or less, more preferably 15 minutes or less. By setting the upper limit of the immersion time within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved.
工程１を電解めっきで行う場合、電流密度は１Ａ／ｄｍ２以上が好ましく、２Ａ／ｄｍ２以上がより好ましい。電流密度の下限が上記範囲であることにより、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。また、電流密度は５Ａ／ｄｍ２以下が好ましく、３Ａ／ｄｍ２以下がより好ましい。亜鉛系複合めっき液の温度の上限が上記範囲であることにより金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。 When step 1 is performed by electrolytic plating, the current density is preferably 1 A/dm 2 or more, more preferably 2 A/dm 2 or more. When the lower limit of the current density is within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved. Further, the current density is preferably 5 A/dm 2 or less, more preferably 3 A/dm 2 or less. By setting the upper limit of the temperature of the zinc-based composite plating solution within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved.
工程１を電解めっきで行う場合、電解めっきで使用する陽極としては、ニッケル、亜鉛極板等の可溶性陽極；白金－チタン、イリジウム－タンタル等の不溶性陽極等を、１種類又は２種類以上用いることができる。 When step 1 is performed by electrolytic plating, one or more types of anodes used in electrolytic plating include soluble anodes such as nickel and zinc plates; insoluble anodes such as platinum-titanium and iridium-tantalum. Can be done.
工程１では、亜鉛系複合めっき液を空気撹拌してもよい。亜鉛系複合めっき液を空気撹拌することにより、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。 In step 1, the zinc-based composite plating solution may be stirred with air. By air stirring the zinc-based composite plating solution, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved.
空気撹拌の方法としては特に限定されず、亜鉛系複合めっき液に従来公知の方法により空気を送り込む方法が挙げられる。空気撹拌の空気の量は１．０Ｌ／ｍｉｎ以上が好ましく、１．５Ｌ／ｍｉｎ以上がより好ましい。空気撹拌の空気の量の下限が上記範囲であることにより、金属材料の耐食性をより一層向上させることができ、亜鉛系複合めっき皮膜の密着性、均一性、付き廻り性がより一層向上する。また、空気撹拌の空気の量は３．０Ｌ／ｍｉｎ以下が好ましく、２．０Ｌ／ｍｉｎ以下がより好ましい。空気撹拌の空気の量の上限が上記範囲であることにより亜鉛系複合めっき皮膜の均一性、付き廻り性がより一層向上する。 The air agitation method is not particularly limited, and may include a method of feeding air into the zinc-based composite plating solution by a conventionally known method. The amount of air for air stirring is preferably 1.0 L/min or more, more preferably 1.5 L/min or more. By setting the lower limit of the amount of air for air agitation within the above range, the corrosion resistance of the metal material can be further improved, and the adhesion, uniformity, and coverage of the zinc-based composite plating film are further improved. Further, the amount of air for air stirring is preferably 3.0 L/min or less, more preferably 2.0 L/min or less. By setting the upper limit of the amount of air in the air agitation within the above range, the uniformity and coverage of the zinc-based composite plating film are further improved.
以上説明した工程１により、金属材料の表面に亜鉛系複合めっき皮膜が形成される。 Through step 1 explained above, a zinc-based composite plating film is formed on the surface of the metal material.
３．複合酸化物皮膜の形成方法
本発明の複合酸化物皮膜の形成方法は、
（１）金属材料を亜鉛系複合めっき液に浸漬して亜鉛系複合めっき皮膜を形成する工程１、
（２）前記亜鉛系複合めっき皮膜の表面に皮膜形成組成物を塗布して皮膜形成組成物層を形成する工程２、及び
（３）前記皮膜形成組成物層を加熱して、前記金属材料の表面に、当該金属材料側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜を形成する工程３を含み、
前記亜鉛系複合めっき液は、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５であり、
前記皮膜形成組成物は、（ａ）アルコキシシランオリゴマー、及び（ｂ）溶媒を含有し、前記溶媒は、水及び／又は水溶性有機溶媒である複合酸化物皮膜の形成方法である。
3. Method for forming a complex oxide film The method for forming a complex oxide film of the present invention is as follows:
(1) Step 1 of immersing the metal material in a zinc-based composite plating solution to form a zinc-based composite plating film,
(2) Step 2 of applying a film-forming composition to the surface of the zinc-based composite plating film to form a film-forming composition layer, and (3) heating the film-forming composition layer to form a film-forming composition layer on the surface of the metal material. Step 3 of forming a composite oxide film having a zinc-based composite plating film, a chemical conversion film, and a siliceous film in this order from the metal material side on the surface,
The zinc-based composite plating solution contains (A) zinc chloride, and (B) at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides, and has a pH of 1 to 5.5,
The film-forming composition contains (a) an alkoxysilane oligomer and (b) a solvent, and the solvent is water and/or a water-soluble organic solvent.
本発明の複合酸化物皮膜の形成方法により形成される複合酸化物皮膜は、上述の本発明の亜鉛系複合めっき皮膜の形成方法により形成される亜鉛系複合めっき皮膜の表面に、化成皮膜及びシリカ質皮膜がこの順に形成された皮膜である。すなわち、本発明の複合酸化物皮膜によれば、金属材料の表面に、当該金属材料側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜を形成することができる。金属材料の表面に、上記複合酸化物皮膜を形成することにより、金属材料に、更に優れた耐食性を付与することができる。 The complex oxide film formed by the method for forming a complex oxide film of the present invention has a chemical conversion film and a silica film formed on the surface of the zinc-based composite plating film formed by the method for forming a zinc-based composite plating film of the present invention described above. The quality film is a film formed in this order. That is, according to the composite oxide film of the present invention, a composite oxide film having a zinc-based composite plating film, a chemical conversion film, and a siliceous film in this order from the metal material side can be formed on the surface of a metal material. . By forming the above composite oxide film on the surface of the metal material, even better corrosion resistance can be imparted to the metal material.
（工程１）
工程１は、金属材料を亜鉛系複合めっき液に浸漬して亜鉛系複合めっき皮膜を形成する工程である。工程１は、上記本発明の亜鉛系複合めっき皮膜の形成方法の工程１と同一であり、工程１により、上記本発明の亜鉛系複合めっき皮膜の形成方法と同様に、金属材料の表面に亜鉛系複合めっき皮膜が形成される。
(Step 1)
Step 1 is a step in which a metal material is immersed in a zinc-based composite plating solution to form a zinc-based composite plating film. Step 1 is the same as step 1 of the method for forming a zinc-based composite plating film of the present invention, and in step 1, zinc is applied to the surface of the metal material similarly to the method for forming a zinc-based composite plating film of the present invention. A composite plating film is formed.
（工程２）
工程２は、亜鉛系複合めっき皮膜の表面に皮膜形成組成物を塗布して皮膜形成組成物層を形成する工程である。
(Step 2)
Step 2 is a step of applying a film-forming composition to the surface of the zinc-based composite plating film to form a film-forming composition layer.
工程２において、皮膜形成組成物は、（ａ）アルコキシシランオリゴマー、及び（ｂ）溶媒を含有し、溶媒は、水及び／又は水溶性有機溶媒である。 In Step 2, the film-forming composition contains (a) an alkoxysilane oligomer and (b) a solvent, and the solvent is water and/or a water-soluble organic solvent.
（ａ）アルコキシシランオリゴマー
アルコキシシランオリゴマーとしては特に限定されず、例えば、アルコキシシランを水、アルコール、グリコール又はグリコールエーテル中に添加し、酸、塩基、有機金属化合物等の触媒を混合して加水分解、縮合反応を行うことにより調製されたものを用いることができる。
(a) Alkoxysilane oligomer The alkoxysilane oligomer is not particularly limited. For example, alkoxysilane is added to water, alcohol, glycol, or glycol ether, and hydrolyzed by mixing with a catalyst such as an acid, a base, or an organometallic compound. , those prepared by performing a condensation reaction can be used.
皮膜形成組成物では、アルコキシシランオリゴマーは、予めアルコキシシランを加水分解し、縮合させたアルコキシシラン縮合物を溶媒に添加し、触媒を混合したアルコキシシランオリゴマー溶液として用いることができる。 In the film-forming composition, the alkoxysilane oligomer can be used as an alkoxysilane oligomer solution in which an alkoxysilane condensate obtained by previously hydrolyzing and condensing an alkoxysilane is added to a solvent and a catalyst is mixed therein.
皮膜形成組成物では、また、アルコキシランオリゴマーは、アルコキシシラン、又は、アルコキシシラン及びアルコキシシランの低縮合物を溶媒に添加し、水及び触媒を混合したアルコキシシランオリゴマー溶液として用いることができる。この場合、アルコキシシランオリゴマー溶液中でアルコキシシランの加水分解及び縮合反応が進行する、いわゆるゾル－ゲル法によりアルコキシシランオリゴマーが形成される。 In the film-forming composition, the alkoxysilane oligomer can be used as an alkoxysilane oligomer solution in which an alkoxysilane or an alkoxysilane and a low condensate of alkoxysilane are added to a solvent, and water and a catalyst are mixed. In this case, an alkoxysilane oligomer is formed by a so-called sol-gel method in which hydrolysis and condensation reactions of alkoxysilane proceed in an alkoxysilane oligomer solution.
上記アルコシキシランは、例えば、式：（Ｒ１）ｍＳｉ（ＯＲ２）４－ｍ（式中、Ｒ１は官能基、Ｒ２は低級アルキル基である。ｍは０～３の整数である）で表され、上記化学式において、官能基としては、ビニル、３－グリシドキシプロピル、３－グリシドキシプロピルメチル、２－（３、４－エポキシシクロヘキシル）エチル、ｐ－スチリル、３－メタクリロキシプロピル、３－メタクリロキシプロピルメチル、３－アクリロキシプロピル、３－アミノプロピル、Ｎ－２－（アミノエチル）－３－アミノプロピル、Ｎ－２－（アミノエチル）－３－アミノプロピルメチル、３－トリエトキシシリル－Ｎ－（１、３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピル、Ｎ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピル、トリス－（トリメトキシシリルプロピル）イソシアヌレート、３－ウレイドプロピル、３－メルカプトプロピル、３－メルカプトプロピルメチル、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピル、３－プロピルコハク酸無水物等が挙げられる。 The above alkoxyxylan has the formula: (R 1 ) m Si(OR 2 ) 4-m (wherein R 1 is a functional group and R 2 is a lower alkyl group. m is an integer of 0 to 3). In the above chemical formula, the functional groups include vinyl, 3-glycidoxypropyl, 3-glycidoxypropylmethyl, 2-(3,4-epoxycyclohexyl)ethyl, p-styryl, and 3-glycidoxypropylmethyl. Methacryloxypropyl, 3-methacryloxypropylmethyl, 3-acryloxypropyl, 3-aminopropyl, N-2-(aminoethyl)-3-aminopropyl, N-2-(aminoethyl)-3-aminopropylmethyl , 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyl, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl, Tris-( Examples include trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl, 3-mercaptopropyl, 3-mercaptopropylmethyl, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyl, 3-propylsuccinic anhydride, etc. .
低級アルキル基としては、具体的には、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔｅｒｔ－ブチル、ｓｅｃ－ブチル、ｎ－ペンチル、１－エチルプロピル、イソペンチル、ネオペンチル等の炭素数１～６程度の直鎖状又は分岐鎖状のアルキル基等が挙げられる。 Specifically, lower alkyl groups include carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, 1-ethylpropyl, isopentyl, and neopentyl. Examples include linear or branched alkyl groups of about 1 to 6 numbers.
上記化学式で表されるアルコキシシランの具体例としては、Ｓｉ（ＯＣＨ３）４、Ｓｉ（ＯＣ２Ｈ５）４、ＣＨ３Ｓｉ（ＯＣＨ３）３、ＣＨ３Ｓｉ（ＯＣ２Ｈ５）３、Ｃ２Ｈ５Ｓｉ（ＯＣＨ３）３、Ｃ２Ｈ５Ｓｉ（ＯＣ２Ｈ５）４、ＣＨＣＨ２Ｓｉ（ＯＣＨ３）３、ＣＨ２ＣＨＯＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３Ｏ）３、ＣＨ２Ｃ（ＣＨ３）ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＣＨ２ＣＨＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＮＨ２（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、ＳＨ（ＣＨ２）３Ｓｉ（ＣＨ３）３、ＮＣＯ（ＣＨ２）３Ｓｉ（Ｃ２Ｈ５Ｏ）３等が挙げられる。 Specific examples of alkoxysilanes represented by the above chemical formula include Si(OCH 3 ) 4 , Si(OC 2 H 5 ) 4 , CH 3 Si(OCH 3 ) 3 , CH 3 Si(OC 2 H 5 ) 3 , C2H5Si ( OCH3 ) 3 , C2H5Si ( OC2H5 ) 4 , CHCH2Si ( OCH3 ) 3 , CH2CHOCH2O ( CH2 ) 3Si ( CH3O ) 3 , CH2C ( CH3 )COO( CH2 ) 3Si ( OCH3 ) 3 , CH2CHCOO ( CH2 ) 3Si ( OCH3 ) 3 , NH2 ( CH2 ) 3Si ( OCH3 ) 3 , Examples include SH(CH 2 ) 3 Si(CH 3 ) 3 and NCO(CH 2 ) 3 Si(C 2 H 5 O) 3.
触媒としては、酸、塩基、有機金属化合物等を用いることができる。 As the catalyst, acids, bases, organometallic compounds, etc. can be used.
酸としては、例えば、塩酸、硝酸、硫酸、リン酸、ホウ酸等の無機酸；ギ酸、酢酸、クエン酸、シュウ酸等の有機酸が挙げられる。 Examples of acids include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and boric acid; and organic acids such as formic acid, acetic acid, citric acid, and oxalic acid.
塩基としては、例えば、水酸化カリウム、水酸化ナトリウム等のアルカリ金属又はアルカリ土類金属の水酸化物；モノエチルアミン等の第一級アミン、ジエチルアミン等の第二級アミン、トリエチルアミン等の第三級アミン、アンモニア等のアミン化合物が挙げられる。 Examples of bases include alkali metal or alkaline earth metal hydroxides such as potassium hydroxide and sodium hydroxide; primary amines such as monoethylamine, secondary amines such as diethylamine, and tertiary amines such as triethylamine. Examples include amine compounds such as amines and ammonia.
有機金属化合物としては、例えば、チタン、ジルコニウム、アルミニウム、錫などの金属成分を含む水溶性の有機金属キレート化合物や金属アルコキシド等が挙げられる。 Examples of the organometallic compound include water-soluble organometallic chelate compounds and metal alkoxides containing metal components such as titanium, zirconium, aluminum, and tin.
有機金属キレート化合物としては、例えば、チタンジイソプロポキシビスアセチルアセトネート、チタンテトラアセチルアセトネート、チタンジオクチロキシビスエチルアセトアセトネート、チタンオクチレングリコレート、チタンジイソプロポキシビスエチルアセチルアセトネート、チタンラクテート、チタンラクテートアンモニウム塩、チタンジイソプロポキシビストリエタノールアミネート等のチタンキレート化合物；ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムジブトキシビスエチルアセトアセテート、ジルコニウムトリブトキシモノステアレート等のジルコニウムキレート化合物；エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリスエチルアセテート、アルキルアセトアセテートアルミニウムジイソプロピレート、アルミニウムモノアセチルアセトネートビスエチルアセトアセテート等のアルミニウムキレート化合物等が挙げられる。 Examples of organometallic chelate compounds include titanium diisopropoxybisacetylacetonate, titanium tetraacetylacetonate, titanium dioctyloxybisethylacetoacetonate, titanium octylene glycolate, titanium diisopropoxybisethylacetylacetonate, Titanium chelate compounds such as titanium lactate, titanium lactate ammonium salt, titanium diisopropoxy bistriethanolaminate; zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium dibutoxy bisethylacetoacetate, zirconium tributoxy monostearate Zirconium chelate compounds such as ethylacetoacetate aluminum diisopropylate, aluminum trisethyl acetate, alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bisethylacetoacetate, and the like.
金属アルコキシドとしては、例えば、テトライソプロピルチタネート、テトラノルマルブチルチタネート、ブチルチタネートダイマー、テトラターシャリーブチルチタネート、テトラオクチルチタネート等のチタンアルコキシド化合物；ノルマルプロピルジルコネート、ノルマルブチルジルコネート等のジルコニウムアルコキシド化合物；アルミニウムイソプロピレート、モノブトキシアルミニウムジイソプロピレート、アルミニウムブチレート等のアルミニウムアルコキシド化合物等が挙げられる。 Examples of metal alkoxides include titanium alkoxide compounds such as tetraisopropyl titanate, tetra-normal butyl titanate, butyl titanate dimer, tetra-tertiary butyl titanate, and tetraoctyl titanate; zirconium alkoxide compounds such as normal propyl zirconate and normal butyl zirconate; Examples include aluminum alkoxide compounds such as aluminum isopropylate, monobutoxyaluminum diisopropylate, and aluminum butyrate.
上記触媒は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 The above catalysts may be used alone or in combination of two or more.
触媒の配合量は特に限定されず、皮膜形成用組成物を１００質量％として、０．０１～２０質量％が好ましく、０．１～１０質量％がより好ましい。 The amount of the catalyst blended is not particularly limited, and is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on 100% by weight of the film-forming composition.
アルコキシシランオリゴマーの重合度は特に限定的されず、１０００～１００００が好ましい。皮膜形成用組成物中では、アルコキシシランの加水分解、縮合反応が進行するが、金属材料の表面に塗布する際に、円滑な塗布作業を阻害しないことが好ましい。アルコキシシランオリゴマーの重合度が上記範囲であることにより、皮膜形成用組成物を、金属材料の表面に容易に塗布することができる。 The degree of polymerization of the alkoxysilane oligomer is not particularly limited, and is preferably from 1,000 to 10,000. Although hydrolysis and condensation reactions of the alkoxysilane proceed in the film-forming composition, it is preferable not to impede smooth application work when applying it to the surface of a metal material. When the degree of polymerization of the alkoxysilane oligomer is within the above range, the film-forming composition can be easily applied to the surface of the metal material.
上記アルコキシシランオリゴマー溶液中のアルコキシシランオリゴマーの含有量は、アルコキシシランオリゴマー溶液を１００質量％として１～５０質量％が好ましく、１０～４０質量％がより好ましい。アルコキシシランオリゴマー溶液中のアルコキシシランオリゴマーの含有量が上記範囲であると、シリカ質皮膜を十分に形成することができる。 The content of the alkoxysilane oligomer in the alkoxysilane oligomer solution is preferably 1 to 50% by weight, more preferably 10 to 40% by weight, based on 100% by weight of the alkoxysilane oligomer solution. When the content of the alkoxysilane oligomer in the alkoxysilane oligomer solution is within the above range, a siliceous film can be sufficiently formed.
皮膜形成組成物中のアルコキシシランオリゴマーの含有量は、皮膜形成組成物を１００質量％として０．５～４５質量％が好ましく、１０～３５質量％がより好ましい。皮膜形成組成物中のアルコキシシランオリゴマーの含有量が上記範囲であると、シリカ質皮膜を十分に形成することができる。 The content of the alkoxysilane oligomer in the film-forming composition is preferably 0.5-45% by mass, more preferably 10-35% by mass, based on 100% by mass of the film-forming composition. When the content of the alkoxysilane oligomer in the film-forming composition is within the above range, a siliceous film can be sufficiently formed.
（ｂ）溶媒
皮膜形成組成物は、溶媒として、水及び／又は水溶性有機溶媒を含有する。溶媒として水を単独で用いる場合、本発明の皮膜形成用組成物のｐＨは、１～５が好ましく、２～４がより好ましい。ｐＨが上記範囲であると、溶媒として水を用いた際に、皮膜形成用組成物が、優れた安定性を示すことができる。
(b) Solvent The film-forming composition contains water and/or a water-soluble organic solvent as a solvent. When water is used alone as a solvent, the pH of the film-forming composition of the present invention is preferably 1 to 5, more preferably 2 to 4. When the pH is within the above range, the film-forming composition can exhibit excellent stability when water is used as a solvent.
水溶性有機溶媒としては、特に限定されず、従来公知の水溶性有機溶媒を用いることができる。このような水溶性有機溶媒としては、アルコール系溶媒、グリコール系溶媒、グリコールエーテル系溶媒、エーテルアルコール系溶媒等が挙げられ、これらの中でも、水との親和性に優れる点で、プロピレングリコール、プロピレングリコールモノメチルエーテルが好ましい。 The water-soluble organic solvent is not particularly limited, and conventionally known water-soluble organic solvents can be used. Examples of such water-soluble organic solvents include alcohol solvents, glycol solvents, glycol ether solvents, and ether alcohol solvents. Among these, propylene glycol and propylene Glycol monomethyl ether is preferred.
上記水及び水溶性有機溶媒は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 The above water and water-soluble organic solvents may be used alone or in combination of two or more.
皮膜形成組成物中の溶媒の含有量は、皮膜形成組成物を１００質量％として５０～９５質量％が好ましく、６０～８５質量％がより好ましい。皮膜形成組成物中の溶媒の含有量が上記範囲であると、成膜性がより一層向上する。 The content of the solvent in the film-forming composition is preferably 50 to 95% by mass, more preferably 60 to 85% by mass, based on 100% by mass of the film-forming composition. When the content of the solvent in the film-forming composition is within the above range, film-forming properties are further improved.
（有機金属化合物）
皮膜形成組成物は、有機金属化合物を含有していてもよい。有機金属化合物としては、金属成分と有機成分を含む化合物であれば特に限定されず、例えば、縮合反応の触媒として機能し得るものが好適に用いられる。
(organometallic compound)
The film-forming composition may contain an organometallic compound. The organometallic compound is not particularly limited as long as it contains a metal component and an organic component, and for example, a compound that can function as a catalyst for a condensation reaction is preferably used.
有機金属化合物を構成する金属としては、チタン、ジルコニウム、アルミニウム、及び錫からなる群より選択される少なくとも１種を用いることが好ましい。 As the metal constituting the organometallic compound, it is preferable to use at least one selected from the group consisting of titanium, zirconium, aluminum, and tin.
有機金属化合物としては、有機金属キレート化合物及び金属アルコキシドからなる群より選択される少なくとも１種を用いることが好ましい。 As the organometallic compound, it is preferable to use at least one selected from the group consisting of organometallic chelate compounds and metal alkoxides.
有機金属化合物としては、具体的には、有機チタン化合物、有機ジルコニウム化合物、有機アルミニウム化合物等が挙げられる。 Specific examples of the organic metal compound include organic titanium compounds, organic zirconium compounds, and organic aluminum compounds.
有機チタン化合物としては、テトライソプロピルチタネート、テトラノルマルブチルチタネート、ブチルチタネートダイマー、テトラターシャリーブチルチタネート、テトラオクチルチタネート等のチタンアルコキシド化合物；チタンジイソプロポキシビスアセチルアセトネート、チタンテトラアセチルアセトネート、チタンジオクチロキシビスエチルアセトアセトネート、チタンオクチレングリコレート、チタンジイソプロポキシビスエチルアセチルアセトネート、チタンラクテート、チタンラクテートアンモニウム塩、チタンジイソプロポキシビストリエタノールアミネート等のチタンキレート化合物等が挙げられる。 Examples of organic titanium compounds include titanium alkoxide compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, tetra-tertiary butyl titanate, and tetraoctyl titanate; titanium diisopropoxy bisacetylacetonate, titanium tetraacetylacetonate, and titanium. Titanium chelate compounds such as dioctyloxybisethylacetoacetonate, titanium octylene glycolate, titanium diisopropoxybisethylacetylacetonate, titanium lactate, titanium lactate ammonium salt, titanium diisopropoxybistriethanolaminate, etc. .
有機ジルコニウム化合物としては、ノルマルプロピルジルコネート、ノルマルブチルジルコネート等のジルコニウムアルコキシド化合物；ジルコニウムテトラアセチルアセトネート、ジルコニウムトリブトキシモノアセチルアセトネート、ジルコニウムジブトキシビスエチルアセトアセテート、ジルコニウムトリブトキシモノステアレート等のジルコニウムキレート化合物が挙げられる。 Examples of organic zirconium compounds include zirconium alkoxide compounds such as normal propyl zirconate and normal butyl zirconate; zirconium tetraacetylacetonate, zirconium tributoxy monoacetylacetonate, zirconium dibutoxy bisethylacetoacetate, zirconium tributoxy monostearate, etc. Examples include zirconium chelate compounds.
有機アルミニウム化合物としては、アルミニウムイソプロピレート、モノブトキシアルミニウムジイソプロピレート、アルミニウムブチレート等のアルミニウムアルコキシド化合物；エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリスエチルアセテート、アルキルアセトアセテートアルミニウムジイソプロピレート、アルミニウムモノアセチルアセトネートビスエチルアセトアセテート等のアルミニウムキレート化合物等が挙げられる。 Examples of organoaluminum compounds include aluminum alkoxide compounds such as aluminum isopropylate, monobutoxyaluminum diisopropylate, and aluminum butyrate; ethyl acetoacetate aluminum diisopropylate, aluminum trisethyl acetate, alkyl acetoacetate aluminum diisopropylate, and aluminum monoacetyl. Examples include aluminum chelate compounds such as acetonate bisethyl acetoacetate.
上記有機金属化合物は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 The above organometallic compounds may be used alone or in combination of two or more.
有機金属化合物の含有量は特に限定されず、ケイ素化合物１００質量部に対して０．０１～５０質量部程度とすればよく、０．１～３０質量部が好ましく、１～３０質量部がより好ましく、５～３０質量部が更に好ましく、１０～２５質量部が特に好ましく、１５～２５質量部が最も好ましい。有機金属化合物の含有量の下限が上記範囲であることにより、粒子用皮膜形成処理液の製膜性がより一層向上する。また、有機金属化合物の含有量の上限が上記範囲であることにより、製膜性がより一層向上する。 The content of the organometallic compound is not particularly limited, and may be about 0.01 to 50 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 1 to 30 parts by mass, based on 100 parts by mass of the silicon compound. It is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, and most preferably 15 to 25 parts by weight. When the lower limit of the content of the organometallic compound is within the above range, the film formability of the particle film forming treatment liquid is further improved. Further, by setting the upper limit of the content of the organometallic compound within the above range, film formability is further improved.
皮膜形成組成物は、有機金属化合物以外に、触媒を含有していてもよい。皮膜形成組成物は、製膜性がより一層優れる点で、有機金属化合物以外の触媒を含有しないことが好ましい。 The film-forming composition may contain a catalyst in addition to the organometallic compound. The film-forming composition preferably does not contain any catalyst other than the organometallic compound, since it has even better film-forming properties.
（金属塩）
皮膜形成組成物は、金属塩を含有していてもよい。金属塩としては特に限定されず、従来公知の金属塩を用いることができる。このような金属塩としては、例えば、Ｃｒ、Ｔｉ、Ｚｒ、Ｓｒ、Ｖ、Ｗ、Ｍｏ、Ｃｅの金属塩が挙げられる。
(metal salt)
The film-forming composition may also contain metal salts. The metal salt is not particularly limited, and conventionally known metal salts can be used. Examples of such metal salts include metal salts of Cr, Ti, Zr, Sr, V, W, Mo, and Ce.
Ｃｒ金属塩としては、硫酸クロム、硝酸クロム、酢酸クロム、二クロム酸塩等が挙げられる。Ｔｉ金属塩としては、塩化チタン、硫酸チタン等が挙げられる。Ｚｒ金属塩としては、硫酸ジルコニル、オキシ塩化ジルコニウム等のジルコニル塩；Ｚｒ（ＳＯ４）２、Ｚｒ（ＮＯ３）２等のジルコニウム塩が挙げられる。Ｓｒ金属塩としては、塩化ストロンチウム、過酸化ストロンチウム、硝酸ストロンチウム等が挙げられる。Ｖ金属塩としては、バナジン酸アンモン、バナジン酸ナトリウム等のバナジン酸塩；オキシ硝酸バナジウム等のオキシバナジン酸塩等が挙げられる。Ｗ金属塩としては、タングステン酸アンモン、タングステン酸ナトリウムなどのタングステン酸塩等が挙げられる。Ｍｏ金属塩としては、モリブデン酸アンモン、モリブデン酸ナトリウム等のモリブデン酸塩；リンモリブデン酸ナトリウム等のリンモリブデン酸塩等が挙げられる。Ｃｅ金属塩としては、塩化セリウム、硫酸セリウム、過塩素酸セリウム、リン酸セリウム、硝酸セリウム等が挙げられる。 Examples of the Cr metal salt include chromium sulfate, chromium nitrate, chromium acetate, dichromate, and the like. Examples of the Ti metal salt include titanium chloride and titanium sulfate. Examples of the Zr metal salt include zirconyl salts such as zirconyl sulfate and zirconium oxychloride; zirconium salts such as Zr(SO 4 ) 2 and Zr(NO 3 ) 2 . Examples of the Sr metal salt include strontium chloride, strontium peroxide, and strontium nitrate. Examples of the V metal salt include vanadate salts such as ammonium vanadate and sodium vanadate; and oxyvanadate salts such as vanadium oxynitrate. Examples of the W metal salt include tungstate salts such as ammonium tungstate and sodium tungstate. Examples of Mo metal salts include molybdates such as ammonium molybdate and sodium molybdate; phosphomolybdates such as sodium phosphomolybdate, and the like. Examples of the Ce metal salt include cerium chloride, cerium sulfate, cerium perchlorate, cerium phosphate, and cerium nitrate.
上記金属塩は、一種単独で用いてもよいし、二種以上を混合して用いてもよい。 The above metal salts may be used alone or in combination of two or more.
皮膜形成組成物中の金属塩の含有量は、上記アルコキシシランオリゴマーを１００質量部として、０．１～３０質量部が好ましく、１０～２５質量部がより好ましい。金属塩の含有量の下限が上記範囲であると、化成皮膜及びシリカ質皮膜がより一層十分に形成され、防錆性がより一層向上する。金属塩の含有量の上限が上記範囲であると、化成皮膜及びシリカ質皮膜のクラックの発生がより一層抑制され、防錆性がより一層向上する。 The content of the metal salt in the film-forming composition is preferably 0.1 to 30 parts by weight, more preferably 10 to 25 parts by weight, based on 100 parts by weight of the alkoxysilane oligomer. When the lower limit of the content of the metal salt is within the above range, the chemical conversion film and the siliceous film are formed even more sufficiently, and the rust prevention properties are further improved. When the upper limit of the content of the metal salt is within the above range, the occurrence of cracks in the chemical conversion coating and the siliceous coating is further suppressed, and the rust prevention properties are further improved.
（潤滑剤）
皮膜形成組成物は、潤滑剤を含有していてもよい。潤滑剤を含有することにより、ボルト、ナット等の摺動面に皮膜を形成した場合に、当該摺動面に適度な潤滑性を付与することができ、有用である。
(lubricant)
The film-forming composition may also contain a lubricant. By containing a lubricant, when a film is formed on the sliding surface of bolts, nuts, etc., it is possible to impart appropriate lubricity to the sliding surface, which is useful.
潤滑剤としては、アマイドワックス、パラフィンワックス、カルナバワックス、ラノリンワックス、ポリテトラフルオロエチレンワックス、ポリエチレンワックス、ポリプロピレンワックス等の微粉末ワックス；アミノ変性ジメチルシリコーンオイル、エポキシ変性ジメチルシリコーンオイル、カルビノール変性ジメチルシリコーンオイル、メルカプト変性ジメチルシリコーンオイル、カルボキシル変性ジメチルシリコーンオイル、メタクリル変性ジメチルシリコーンオイル、アクリル変性ジメチルシリコーンオイル、ポリエーテル変性ジメチルシリコーンオイル、フェノール変性ジメチルシリコーンオイル、シラノール変性ジメチルシリコーンオイル、カルボン酸無水物変性ジメチルシリコーンオイル、ジオール変性ジメチルシリコーンオイル、アラルキル変性ジメチルシリコーンオイル、フロロアルキル変性ジメチルシリコーンオイル、長鎖アルキル変性ジメチルシリコーンオイル、高級脂肪酸エステル変性ジメチルシリコーンオイル、高級脂肪酸変性ジメチルシリコーンオイル、フェニル変性ジメチルシリコーンオイル等のジメチルシリコーンオイルが挙げられる。 As lubricants, fine powder waxes such as amide wax, paraffin wax, carnauba wax, lanolin wax, polytetrafluoroethylene wax, polyethylene wax, and polypropylene wax; amino-modified dimethyl silicone oil, epoxy-modified dimethyl silicone oil, carbinol-modified dimethyl Silicone oil, mercapto-modified dimethyl silicone oil, carboxyl-modified dimethyl silicone oil, methacrylic-modified dimethyl silicone oil, acrylic-modified dimethyl silicone oil, polyether-modified dimethyl silicone oil, phenol-modified dimethyl silicone oil, silanol-modified dimethyl silicone oil, carboxylic acid anhydride Modified dimethyl silicone oil, diol modified dimethyl silicone oil, aralkyl modified dimethyl silicone oil, fluoroalkyl modified dimethyl silicone oil, long chain alkyl modified dimethyl silicone oil, higher fatty acid ester modified dimethyl silicone oil, higher fatty acid modified dimethyl silicone oil, phenyl modified dimethyl Examples include dimethyl silicone oil such as silicone oil.
皮膜形成組成物中の潤滑剤の含有量は、上記アルコキシシランオリゴマー溶液を１００質量部として、０．５～３０質量部が好ましく、１～２０質量部がより好ましい。潤滑剤の含有量が上記範囲であることにより、化成皮膜及びシリカ質皮膜の積層皮膜がより一層十分に形成され、当該皮膜に潤滑性をより一層十分に付与することができ、皮膜の摩擦係数をより一層低減することができる。 The content of the lubricant in the film-forming composition is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the alkoxysilane oligomer solution. When the content of the lubricant is within the above range, the laminated film of the chemical conversion film and the siliceous film can be formed even more sufficiently, and the film can be provided with even more sufficient lubricity, and the friction coefficient of the film can be improved. can be further reduced.
（コロイダルシリカ）
皮膜形成組成物は、コロイダルシリカを含有していてもよい。コロイダルシリカは造膜助剤として作用し、皮膜形成組成物により形成された積層皮膜の防錆性をより一層向上させることができ、且つ、当該積層皮膜の急激な収縮がより一層緩和される。
(colloidal silica)
The film-forming composition may contain colloidal silica. Colloidal silica acts as a film-forming auxiliary agent, and can further improve the rust prevention properties of the laminated film formed by the film-forming composition, and further alleviate rapid shrinkage of the laminated film.
コロイダルシリカは、粒子径約１００ｎｍ以下の球状又は球が鎖に繋がった形状のシリカナノ粒子が溶媒中に分散した分散体であり、水を溶媒とする水系コロイダルシリカ、各種の有機溶剤を溶媒とする溶剤系コロイダルシリカをいずれも用いることができる。水系コロイダルシリカにはアルカリ性タイプと酸性タイプを示すものがあり、いずれも使用可能であるが、液状組成物の安定性を保つことができる点で、酸性タイプのコロイダルシリカが好ましい。 Colloidal silica is a dispersion in which silica nanoparticles in the form of spheres or chains of spheres with a particle diameter of about 100 nm or less are dispersed in a solvent. Colloidal silica is a water-based colloidal silica that uses water as a solvent, and various organic solvents as a solvent. Any solvent-based colloidal silica can be used. Water-based colloidal silica includes alkaline and acidic types, both of which can be used, but acidic colloidal silica is preferred since it can maintain the stability of the liquid composition.
溶剤系コロイダルシリカの溶剤としては、例えば、メタノール、イソプロパノール、ジメチルアセトアミド、エチレングリコール、エチレングリコールモノｎ－プロピルエーテル、エチレングリコールモノエチルエーテル、酢酸エチル、プロピレングリコールモノエチルエーテルアセテート、メチルエチルケトン、メチルイソブチルケトン、トルエン、プロピレングリコール等を挙げることができる。コロイダルシリカにおけるシリカ含有量は特に限定されず、固形分濃度として５～４０質量％程度が好ましい。 Examples of solvents for solvent-based colloidal silica include methanol, isopropanol, dimethylacetamide, ethylene glycol, ethylene glycol mono-n-propyl ether, ethylene glycol monoethyl ether, ethyl acetate, propylene glycol monoethyl ether acetate, methyl ethyl ketone, and methyl isobutyl ketone. , toluene, propylene glycol and the like. The silica content in colloidal silica is not particularly limited, and is preferably about 5 to 40% by mass as a solid content concentration.
皮膜形成組成物におけるコロイダルシリカの配合量は、上記アルコキシシランオリゴマー溶液を１００質量部として、固形分量で２～６０質量部が好ましく、５～５０質量部がより好ましい。また、皮膜形成組成物を１００質量％として、固形分量で１～５０質量％が好ましく、２～４０質量％がより好ましい。 The amount of colloidal silica in the film-forming composition is preferably 2 to 60 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the alkoxysilane oligomer solution. Furthermore, the solid content is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the film-forming composition.
（水ガラス）
皮膜形成組成物は、水ガラスを含有していてもよい。皮膜形成組成物が水ガラスを含有することにより、皮膜の緻密性がより一層向上する。
(water glass)
The film-forming composition may contain water glass. When the film-forming composition contains water glass, the denseness of the film is further improved.
水ガラスとして特に限定されず、従来公知の水ガラスを用いることができる。このような水ガラスとしては、例えば、珪酸ソーダ、珪酸カリウム、珪酸リチウム等が挙げられる。 The water glass is not particularly limited, and conventionally known water glass can be used. Examples of such water glass include sodium silicate, potassium silicate, lithium silicate, and the like.
皮膜形成組成物における水ガラスの配合量は、皮膜形成組成物を１００質量％として、１～５０質量％が好ましく、２～４０質量％がより好ましい。 The amount of water glass in the film-forming composition is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the film-forming composition.
工程２では、皮膜形成組成物は、ゾル－ゲル法により調製されていることが好ましい。すなわち、アルコキシランオリゴマーは、アルコキシシラン、又は、アルコキシシラン及びアルコキシシランの低縮合物を溶媒に添加し、水及び触媒を混合したアルコキシシランオリゴマー溶液として用いることが好ましい。この場合、アルコキシシランオリゴマー溶液中でアルコキシシランの加水分解及び縮合反応が進行し、アルコキシシランオリゴマーが形成される。 In step 2, the film-forming composition is preferably prepared by a sol-gel method. That is, the alkoxysilane oligomer is preferably used as an alkoxysilane oligomer solution prepared by adding alkoxysilane or a low condensate of alkoxysilane and alkoxysilane to a solvent, and mixing water and a catalyst. In this case, hydrolysis and condensation reactions of alkoxysilane proceed in the alkoxysilane oligomer solution to form an alkoxysilane oligomer.
亜鉛系複合めっき皮膜の表面に皮膜形成組成物を塗布する塗布方法としては、従来公知の方法を用いることができ、例えば、ディップコート法、ディップスピンコート法、スプレーコート法、ロールコート法、スピンコート法、バーコート法等の公知の方法が挙げられる。これらの中でも、亜鉛系複合めっき皮膜の表面の形状にとらわれずに均一に塗布することができる点で、ディップスピンコート法、スプレーコート法が好ましい。 Conventionally known methods can be used to apply the film-forming composition to the surface of the zinc-based composite plating film, such as dip coating, dip spin coating, spray coating, roll coating, and spin coating. Known methods such as a coating method and a bar coating method can be used. Among these, the dip spin coating method and the spray coating method are preferred in that they can be applied uniformly regardless of the surface shape of the zinc-based composite plating film.
上記塗布方法により皮膜形成組成物を塗布することにより、金属材料の表面に形成された亜鉛系複合めっき皮膜の表面に、皮膜形成組成物層が形成される。皮膜形成組成物層の厚みは、１～５０μｍが好ましく、５～３０μｍがより好ましい。皮膜形成組成物層の厚みが上記範囲であることにより、後述する工程３により形成される積層皮膜の厚みを適切な範囲に調整することができ、金属材料の寸法精度を損なわず、金属材料の表面に優れた防錆性及び耐摩耗性を付与することができる。 By applying the film-forming composition using the above coating method, a film-forming composition layer is formed on the surface of the zinc-based composite plating film formed on the surface of the metal material. The thickness of the film-forming composition layer is preferably 1 to 50 μm, more preferably 5 to 30 μm. By setting the thickness of the film-forming composition layer within the above range, the thickness of the laminated film formed in step 3 described below can be adjusted to an appropriate range, without impairing the dimensional accuracy of the metal material. Excellent rust prevention and wear resistance can be imparted to the surface.
以上説明した工程２により、亜鉛系複合めっき皮膜の表面に皮膜形成組成物を塗布して皮膜形成組成物層を形成することができる。 According to Step 2 explained above, a film-forming composition layer can be formed by applying the film-forming composition to the surface of the zinc-based composite plating film.
（工程３）
工程３は、皮膜形成組成物層を加熱して、金属材料の表面に、当該金属材料側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜を形成する工程である。
(Step 3)
Step 3 is a step of heating the film-forming composition layer to form a composite oxide film having a zinc-based composite plating film, a chemical conversion film, and a siliceous film in this order from the metal material side on the surface of the metal material. be.
亜鉛系複合めっき皮膜の表面に形成された皮膜形成組成物層を加熱する加熱方法としては限定されず、従来公知の方法により加熱すればよい。例えば、亜鉛系複合めっき皮膜が表面に形成された金属材料ごと皮膜形成組成物層を乾燥機内に入れ、一定時間保持して加熱する加熱方法が挙げられる。 The heating method for heating the film-forming composition layer formed on the surface of the zinc-based composite plating film is not limited, and may be heated by a conventionally known method. For example, a heating method may be used in which the film-forming composition layer is placed in a dryer together with the metal material on which the zinc-based composite plating film is formed, and heated while being held for a certain period of time.
加熱温度は、通常、２０～２００℃が好ましく、４０～１８０℃がより好ましく、６０～１５０℃が更に好ましい。熱処理時間は、３０秒～３０分が好ましく、５～３０分がより好ましい。 The heating temperature is usually preferably 20 to 200°C, more preferably 40 to 180°C, even more preferably 60 to 150°C. The heat treatment time is preferably 30 seconds to 30 minutes, more preferably 5 to 30 minutes.
なお、常温が２０℃付近の場合、工程３における加熱は、特に乾燥機等を用いて加熱することを要せず、常温下で一定時間放置してもよい。 Note that when the room temperature is around 20° C., the heating in step 3 does not require the use of a dryer or the like, and may be left at room temperature for a certain period of time.
上記加熱により皮膜形成組成物層が加熱されて、亜鉛系複合めっき皮膜の表面に、当該亜鉛系複合めっき皮膜側から、化成皮膜及びシリカ質皮膜をこの順に有する積層皮膜が形成される。 The film-forming composition layer is heated by the above heating, and a laminated film having a chemical conversion film and a siliceous film in this order from the zinc-based composite plating film side is formed on the surface of the zinc-based composite plating film.
以上説明した工程３により、金属材料の表面に、金属材料側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜が形成される。 Through step 3 described above, a composite oxide film having a zinc-based composite plating film, a chemical conversion film, and a siliceous film in this order from the metal material side is formed on the surface of the metal material.
本発明の複合酸化物皮膜の形成方法によれば、金属材料の表面に形成された亜鉛系複合めっき皮膜の表面に皮膜形成組成物を塗布し、加熱するだけで、皮膜形成組成物層が、化成皮膜及びシリカ質皮膜が積層された積層皮膜となり、金属材料の表面側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜がこの順に積層された複合酸化物皮膜を形成することができ、金属材料の表面により一層優れた防錆性を容易に付与することができる。本発明の複合酸化物皮膜の形成方法によれば、金属材料上に、当該金属材料の表面側から亜鉛系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜が積層されている物品を得ることができる。 According to the method for forming a composite oxide film of the present invention, a film-forming composition layer can be formed by simply applying a film-forming composition to the surface of a zinc-based composite plating film formed on the surface of a metal material and heating it. A composite oxide film can be formed in which a chemical conversion film and a siliceous film are laminated in this order, and a zinc-based composite plating film, a chemical conversion film, and a siliceous film are laminated in this order from the surface side of the metal material. Even better rust prevention properties can be easily imparted to the surface of the material. According to the method for forming a composite oxide film of the present invention, a composite oxide film having a zinc-based composite plating film, a chemical conversion film, and a siliceous film in this order is laminated on a metal material from the surface side of the metal material. You can get the goods you want.
上記積層皮膜（化成皮膜及びシリカ質皮膜の積層体）の厚みは、０．１～１０μｍが好ましく、０．５～５μｍがより好ましい。積層皮膜の厚みが上記範囲であることにより、金属材料の寸法精度を損なわず、金属材料の表面に、より優れた防錆性及び耐摩耗性を付与することができる。 The thickness of the laminated film (laminated body of a chemical conversion film and a siliceous film) is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm. When the thickness of the laminated film is within the above range, it is possible to impart better rust prevention and wear resistance to the surface of the metal material without impairing the dimensional accuracy of the metal material.
上記積層皮膜において、化成皮膜の厚みは０．０１～１μｍが好ましく、０．１～１μｍがより好ましい。化成皮膜の厚みが上記範囲であることにより、より一層優れた防錆性を示すことができる。 In the above laminated film, the thickness of the chemical conversion film is preferably 0.01 to 1 μm, more preferably 0.1 to 1 μm. When the thickness of the chemical conversion film is within the above range, even more excellent rust prevention properties can be exhibited.
上記積層皮膜において、シリカ質皮膜の厚みは０．０９～９μｍが好ましく、０．４～４μｍがより好ましい。シリカ質皮膜の厚みが上記範囲であることにより、より一層優れた防錆性及び耐摩耗性を示すことができる。 In the above laminated film, the thickness of the siliceous film is preferably 0.09 to 9 μm, more preferably 0.4 to 4 μm. When the thickness of the siliceous film is within the above range, even better rust prevention and wear resistance can be exhibited.
本発明の亜鉛系複合めっき液、亜鉛系複合めっき皮膜の形成方法、及び、複合酸化物皮膜の形成方法によれば、金属材料に耐食性能を付与することができる。金属材料の耐食性能は、ＪＩＳ Ｚ２３７１に準拠した方法により塩水噴霧試験を行い、金属材料の表面積に対する赤錆の発生面積比率が１０％となるまでの時間を測定する測定方法により測定することができる。 According to the zinc-based composite plating solution, the method for forming a zinc-based composite plating film, and the method for forming a composite oxide film of the present invention, corrosion resistance can be imparted to metal materials. The corrosion resistance performance of a metal material can be measured by conducting a salt spray test according to JIS Z2371 and measuring the time until the ratio of the area where red rust occurs to the surface area of the metal material reaches 10%.
上記測定方法により測定される耐食性能は、１０時間以上が好ましく、２０時間以上がより好ましく、４０時間以上が更に好ましく、８０時間以上が特に好ましく、１００時間以上が最も好ましく、１５０時間以上がより最も好ましい。 The corrosion resistance measured by the above measuring method is preferably 10 hours or more, more preferably 20 hours or more, even more preferably 40 hours or more, particularly preferably 80 hours or more, most preferably 100 hours or more, and more preferably 150 hours or more. Most preferred.
以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。 EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.
（めっき皮膜の形成）
表１に示す原料を表１に示す配合で混合し、各実施例及び比較例のめっき液を１Ｌ調製した。次いで、電解めっきに用いる陽極として50ｍｍ×150ｍｍ、厚み2ｍｍのニッケル板を用意した。また、電解めっきに用いる陰極として、50ｍｍ×100ｍｍ、厚み0.2ｍｍの鉄板を用意し、陰極に用いた。
(Formation of plating film)
The raw materials shown in Table 1 were mixed in the formulation shown in Table 1 to prepare 1 L of plating solution for each example and comparative example. Next, a 50 mm x 150 mm, 2 mm thick nickel plate was prepared as an anode to be used for electrolytic plating. Furthermore, an iron plate measuring 50 mm x 100 mm and 0.2 mm in thickness was prepared and used as a cathode for electrolytic plating.
１Ｌのめっき液中に、金属材料を亜鉛系複合めっき液に浸漬して、表１に示す条件で電解めっきを行い、めっき皮膜を形成し、試験片１を調製した。 A metal material was immersed in a zinc-based composite plating solution in 1 L of a plating solution, and electrolytic plating was performed under the conditions shown in Table 1 to form a plating film, thereby preparing a test piece 1.
（複合酸化物皮膜の形成）
表２に示すように、実施例１、実施例２、比較例２又は比較例４で調製した試験片１のめっき皮膜の表面に、スプレー塗布により皮膜形成組成物Ａ又はＢを塗布して、皮膜形成組成物層を形成した。皮膜形成組成物層の厚みは1.0μｍであった。皮膜形成組成物Ａ及びＢの配合を以下に示す。
(Formation of composite oxide film)
As shown in Table 2, film-forming composition A or B was applied by spray coating to the surface of the plating film of test piece 1 prepared in Example 1, Example 2, Comparative Example 2, or Comparative Example 4. A film-forming composition layer was formed. The thickness of the film-forming composition layer was 1.0 μm. The formulations of film-forming compositions A and B are shown below.
＜皮膜形成組成物Ａ＞
（ａ）アルコキシシランオリゴマー：テトラメトキシシラン 15質量部
（ｂ) アルコキシシランオリゴマー：3-メルカプトプロピルシラン 15質量部
（ｃ）溶媒：水 70質量部
（ｄ）有機金属化合物：上記組成100質量部に対して 10質量部
<Film-forming composition A>
(a) Alkoxysilane oligomer: 15 parts by mass of tetramethoxysilane (b) Alkoxysilane oligomer: 15 parts by mass of 3-mercaptopropylsilane (c) Solvent: 70 parts by mass of water (d) Organometallic compound: 100 parts by mass of the above composition 10 parts by mass
＜皮膜形成組成物Ｂ＞
（ａ）アルコキシシランオリゴマー：テトラエトキシシラン 15質量部
（ｂ) アルコキシシランオリゴマー：3-メルカプトプロピルシラン 15質量部
（ｃ）溶媒：プロピレングリコールモノメチルエーテル 70質量部
（ｄ）有機金属化合物：上記組成100質量部に対して 10質量部
<Film-forming composition B>
(a) Alkoxysilane oligomer: 15 parts by mass of tetraethoxysilane (b) Alkoxysilane oligomer: 15 parts by mass of 3-mercaptopropylsilane (c) Solvent: 70 parts by mass of propylene glycol monomethyl ether (d) Organometallic compound: Above composition 100 10 parts by mass to parts by mass
乾燥機を用いて皮膜形成組成物層を１５０℃、１５分間の条件で加熱処理して、めっき皮膜の表面に、化成皮膜及びシリカ質皮膜をこの順に有する積層皮膜を形成し、試験片２を調製した。 The film-forming composition layer was heat-treated at 150° C. for 15 minutes using a dryer to form a laminated film having a chemical conversion film and a siliceous film in this order on the surface of the plating film, and test piece 2 was prepared. Prepared.
上記実施例及び比較例について、下記評価を行った。 The following evaluations were performed for the above Examples and Comparative Examples.
試験例１：耐食性試験
実施例及び比較例で調製された試験片を用いて、ＪＩＳ Ｚ２３７１に準拠した方法により塩水噴霧試験を行い、試験片の表面積に対する赤錆の発生面積比率が１０％となるまでの時間を測定した。結果を図１～図１０に示す。
Test Example 1: Using the test pieces prepared in Corrosion Resistance Test Examples and Comparative Examples, a salt spray test was conducted in accordance with JIS Z2371 until the area ratio of red rust to the surface area of the test piece reached 10%. The time was measured. The results are shown in FIGS. 1 to 10.
図１～４の結果から、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５の範囲内である実施例１及び２の亜鉛系複合めっき液を用いて形成された亜鉛系複合めっき皮膜は、亜鉛系複合めっき皮膜の厚みが２μｍ又は４μｍであり、薄くても赤錆の発生が抑制されており、優れた耐食性を示すことが分かった。また、実施例２では、亜鉛系複合めっき皮膜の厚みが４μｍであっても、コロイダルシリカを含有しないめっき液を用いて、厚みが８μｍのめっき皮膜を形成した比較例５と同等の耐食性を示すことが分かった。 From the results in FIGS. 1 to 4, it is clear that (A) zinc chloride and (B) at least one metal compound selected from the group consisting of metal oxide, metal carbide, and metal nitride are contained, and the pH is The zinc-based composite plating films formed using the zinc-based composite plating solutions of Examples 1 and 2 within the range of 1 to 5.5 have a thickness of 2 μm or 4 μm, and are thin. It was also found that the occurrence of red rust was suppressed and exhibited excellent corrosion resistance. In addition, in Example 2, even if the thickness of the zinc-based composite plating film was 4 μm, it showed the same corrosion resistance as Comparative Example 5, in which a plating film with a thickness of 8 μm was formed using a plating solution that did not contain colloidal silica. That's what I found out.
図５～１０の結果から、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５の範囲内である実施例１及び２の亜鉛系複合めっき液を用いて形成された亜鉛系複合めっき皮膜の表面に、化成皮膜及びシリカ質皮膜をこの順に有する積層皮膜が形成された実施例３～６では、白錆及び赤錆の発生迄の時間が更に長くなっており、耐食性が更に向上したことが分かった。 From the results shown in FIGS. 5 to 10, it was found that (A) zinc chloride, and (B) at least one metal compound selected from the group consisting of metal oxide, metal carbide, and metal nitride, and the pH was A laminated film having a chemical conversion film and a siliceous film in this order is formed on the surface of a zinc-based composite plating film formed using the zinc-based composite plating solution of Examples 1 and 2 within the range of 1 to 5.5. In Examples 3 to 6, the time required for white rust and red rust to occur was longer, indicating that the corrosion resistance was further improved.
試験例２：塗膜密着性試験
表２に記載した各実施例及び比較例の試験片２をそれぞれ複数用意した。次いで、試験片２を１００℃に維持した恒温槽内で、１００℃の水に浸漬した。各実施例及び比較例の試験片２を１時間毎に一つずつ恒温槽から取り出し、JIS K-5600-5-6に準拠した測定方法により、碁盤目の間隔が１ｍｍの条件で碁盤目クロスカットテープ剥離試験を行った。試験は、試験片２の積層皮膜が剥離するまで行い、塗膜密着性を比較した。結果を図１１に示す。
Test Example 2: Paint film adhesion test A plurality of test pieces 2 of each example and comparative example listed in Table 2 were prepared. Next, the test piece 2 was immersed in 100°C water in a constant temperature bath maintained at 100°C. Test pieces 2 of each Example and Comparative Example were taken out from the thermostatic chamber one by one every hour, and the cross-cut cross section was measured using a measurement method based on JIS K-5600-5-6 under the condition that the grid interval was 1 mm. A cut tape peel test was conducted. The test was conducted until the laminated film of Test Piece 2 was peeled off, and the adhesion of the paint film was compared. The results are shown in FIG.
図１１の結果から、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５の範囲内である実施例１及び２の亜鉛系複合めっき液を用いて形成された亜鉛系複合めっき皮膜の表面に、化成皮膜及びシリカ質皮膜をこの順に有する積層皮膜が形成された実施例３では、浸漬時間１００時間の条件で塗膜密着性試験を行っても塗膜の剥離が抑制されており、塗膜の密着性に優れることが分かった。これに対し、コロイダルシリカを含有しないめっき液を用いて形成されためっき皮膜の表面に、化成皮膜及びシリカ質皮膜をこの順に有する積層皮膜が形成された比較例６では、浸漬時間２４時間の条件で塗膜密着性試験を行うと、碁盤目以外での剥離が生じ、浸漬時間１００時間の条件では、全ての碁盤目で剥離が生じ、塗膜密着性に劣ることが分かった。 From the results shown in FIG. 11, it is clear that (A) zinc chloride and (B) at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides are contained, and the pH is 1 to 1. A laminated film having a chemical conversion film and a siliceous film in this order was formed on the surface of the zinc-based composite plating film formed using the zinc-based composite plating solutions of Examples 1 and 2 within the range of 5.5. In Example 3, peeling of the coating film was suppressed even when a coating film adhesion test was conducted under the condition of immersion time of 100 hours, and it was found that the coating film had excellent adhesiveness. On the other hand, in Comparative Example 6, in which a laminated film having a chemical conversion film and a siliceous film in this order was formed on the surface of a plating film formed using a plating solution that did not contain colloidal silica, the immersion time was 24 hours. When a coating film adhesion test was conducted, peeling occurred in areas other than the grid pattern, and under the condition of immersion time of 100 hours, peeling occurred in all the grid patterns, indicating that the coating film adhesion was poor.
試験例３：めっき皮膜均一性試験
実施例１及び比較例２の試験片１の表面を、金属顕微鏡により1000倍の条件で撮影し、目視で観察して比較した。また、後述する試験例４の付き廻り性試験を行い、試験片３の、図１３のａ～ｆに示す箇所のめっき皮膜についても同様に、表面を、金属顕微鏡により1000倍の条件で撮影し、目視で観察して比較し、下記評価基準に従って評価した。結果を図１２、１４、１５及び表４に示す。
○：めっき皮膜全体にピット発生なし
△：めっき皮膜に部分的にピットが発生
×：めっき皮膜全体にピットが発生
Test Example 3: Plating film uniformity test The surfaces of the test pieces 1 of Example 1 and Comparative Example 2 were photographed using a metallurgical microscope at 1000 times magnification, and visually observed and compared. In addition, the coverage test of Test Example 4, which will be described later, was conducted, and the surface of the plating film at the locations a to f in FIG. , visually observed and compared, and evaluated according to the following evaluation criteria. The results are shown in FIGS. 12, 14, 15 and Table 4.
○: No pits are formed on the entire plating film △: Pit is partially formed on the plating film ×: Pit is formed on the entire plating film
図１２の結果から、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５の範囲内である実施例１の亜鉛系複合めっき液を用いて形成された亜鉛系複合めっき皮膜は、ピットの発生が抑制されており、優れた均一性を示すことが分かった。これに対し、コロイダルシリカを含有しない比較例２のめっき液を用いて形成されためっき皮膜は、多数のピットが発生しており、均一性に劣ることが分かった。 From the results in FIG. 12, it is clear that (A) zinc chloride and (B) at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides are contained, and the pH is 1 to 1. It was found that the zinc-based composite plating film formed using the zinc-based composite plating solution of Example 1, which was within the range of 5.5, exhibited excellent uniformity with suppressed occurrence of pits. On the other hand, it was found that the plating film formed using the plating solution of Comparative Example 2 that did not contain colloidal silica had a large number of pits and was inferior in uniformity.
試験例４：付き廻り性試験
図１３に示す付き廻り性試験装置を用意した。付き廻り性試験装置では、電解めっきに用いる陽極として50ｍｍ×150ｍｍ、厚み2ｍｍのニッケル板を用意した。また、電解めっきに用いる陰極として、62ｍｍ×130ｍｍ、厚み0.3ｍｍの鉄板(ベントカソード板)を用意し、図１３及び図１４に示す形状に折り曲げて試験片３とした。付き廻り性試験装置の内部を満たすように、表３に示す配合のめっき液を充填してめっき浴を調製し、表３に示す条件でめっき皮膜を形成した。試験片３の、図１３のａ～ｆに示す箇所のめっき皮膜の状態を目視で観察し、付き廻り性を評価した。また、図１３のａ～ｆに示す箇所のめっき皮膜の膜厚、及び表層のＳｉ濃度（ａｔ％）を高周波グロー放電発光表面分析法にて測定した。結果を図１４、図１５、表４に示す。
○：めっき皮膜が全面に析出している。
×：めっき皮膜が部分的に析出している。
Test Example 4: Power-pulling test A power-pulling test device shown in FIG. 13 was prepared. In the coverage test device, a 50 mm x 150 mm, 2 mm thick nickel plate was prepared as an anode used for electrolytic plating. Further, as a cathode used for electrolytic plating, an iron plate (bent cathode plate) having a size of 62 mm x 130 mm and a thickness of 0.3 mm was prepared and bent into the shape shown in FIGS. 13 and 14 to obtain a test piece 3. A plating bath was prepared by filling a plating solution having the composition shown in Table 3 so as to fill the inside of the coverage test device, and a plating film was formed under the conditions shown in Table 3. The state of the plating film at the locations a to f in FIG. 13 of Test Piece 3 was visually observed, and the coverage was evaluated. In addition, the thickness of the plating film and the Si concentration (at%) of the surface layer at the locations a to f in FIG. 13 were measured using a high frequency glow discharge luminescence surface analysis method. The results are shown in FIGS. 14, 15, and Table 4.
○: A plating film is deposited on the entire surface.
×: The plating film is partially deposited.
試験例５：タクト（生産効率）試験
比較例１０の処理時間を基準として、下記評価基準に従ってタクト（生産効率）を評価した。結果を表４に示す。表４では、比較例１０の評価を×とした。
○：比較例１０の半分の処理時間（電解めっき時間）で比較例１０の膜厚と同等以上の膜厚が得られた。
×：比較例１０と同等の処理時間（電解めっき時間）で比較例１０の膜厚と同等の膜厚が得られた。
Test Example 5: Tact (Production Efficiency) Test Based on the processing time of Comparative Example 10, tact (production efficiency) was evaluated according to the following evaluation criteria. The results are shown in Table 4. In Table 4, Comparative Example 10 was evaluated as ×.
○: A film thickness equal to or greater than that of Comparative Example 10 was obtained with half the processing time (electrolytic plating time) of Comparative Example 10.
×: A film thickness equivalent to that of Comparative Example 10 was obtained with the same processing time (electrolytic plating time) as that of Comparative Example 10.
なお、表４中、「ｎ．ｄ．」は、検出限界以下であることを示す。 In addition, in Table 4, "n.d." indicates that it is below the detection limit.
表４の結果から、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５の範囲内である実施例７の亜鉛系複合めっき液は、試験片３のａ～ｆの全ての箇所で膜厚が厚くなっており、十分に亜鉛系複合めっき皮膜が形成されていることが分かった。また、表４の結果から、実施例７の亜鉛系複合めっき液は、比較例１０のジンケート浴により形成されためっき皮膜の厚みと同等の厚みの亜鉛系複合めっき皮膜が形成されていることが分かった。また、実施例７の亜鉛系複合めっき液を用いると、比較例１０のジンケート浴を用いた場合よりも、タクト（生産効率）が向上することが分かった。更に、図１４及び図１５の結果からも、実施例７の亜鉛系複合めっき液は、試験片３のａ～ｆの全ての箇所でめっき皮膜が十分に形成されていることが裏付けられている。以上より、実施例７の亜鉛系複合めっき液は、優れた付き廻り性を示すことが分かった。これに対し、コロイダルシリカを含有しない硫酸浴を用いた比較例１１、コロイダルシリカを含有する硫酸浴を用いた比較例１２、及び、コロイダルシリカを含有しない塩化浴を用いた比較例１３では、めっき皮膜の均一性に劣ることが分かった。 From the results in Table 4, it is clear that the zinc chloride contains (A) zinc chloride, and (B) at least one metal compound selected from the group consisting of metal oxides, metal carbides, and metal nitrides, and has a pH of 1 to 1. The zinc-based composite plating solution of Example 7, which was within the range of 5.5, had a thick film thickness at all locations a to f of test specimen 3, indicating that a zinc-based composite plating film was sufficiently formed. I found out that there is. Furthermore, from the results in Table 4, it was found that the zinc-based composite plating solution of Example 7 formed a zinc-based composite plating film with a thickness equivalent to that of the plating film formed by the zincate bath of Comparative Example 10. Do you get it. Furthermore, it was found that when the zinc-based composite plating solution of Example 7 was used, the tact (production efficiency) was improved compared to when the zincate bath of Comparative Example 10 was used. Furthermore, the results in FIGS. 14 and 15 confirm that the zinc-based composite plating solution of Example 7 sufficiently forms a plating film at all locations a to f of test piece 3. . From the above, it was found that the zinc-based composite plating solution of Example 7 exhibited excellent coverage. On the other hand, in Comparative Example 11 using a sulfuric acid bath containing no colloidal silica, Comparative Example 12 using a sulfuric acid bath containing colloidal silica, and Comparative Example 13 using a chloride bath containing no colloidal silica, plating It was found that the uniformity of the film was poor.
試験例６：耐水素脆化試験
電解めっきに用いる陰極として、4ｍｍ×70ｍｍ、厚み0.3ｍｍのSK-85鋼板を用意し、陰極に用いた。それ以外は実施例１、比較例１及び比較例２と同様の条件でめっき皮膜を形成し、それぞれ実施例８、比較例１４及び比較例１５の試験片１を調製した。次いで、得られた実施例８、比較例１４及び比較例１５の試験片１を室温で放置し、当該試験片１を用いて、７日毎に下記方法により押込み加重を測定し、めっき皮膜の破断応力とした。
Test Example 6: Hydrogen embrittlement test An SK-85 steel plate with a size of 4 mm x 70 mm and a thickness of 0.3 mm was prepared and used as a cathode for electrolytic plating. Other than that, plating films were formed under the same conditions as in Example 1, Comparative Example 1, and Comparative Example 2, and Test Pieces 1 of Example 8, Comparative Example 14, and Comparative Example 15 were prepared, respectively. Next, the obtained test pieces 1 of Example 8, Comparative Example 14, and Comparative Example 15 were left at room temperature, and the indentation load was measured using the test pieces 1 every 7 days by the method described below to determine the breakage of the plating film. It was defined as stress.
（押込み加重の測定方法）
Ｂｏｅｉｎｇ Ａｉｒｃｒａｆｔ Ｃｏｍｐａｎｙ規格ＢＡＣ ５７１８に準拠した測定方法により、島津製作所製３点曲げ試験機を用いて、押込み速度0.5ｍｍ／ｍｉｎ、押込み加重2.0ｋＮの条件で加重をかけて試験片１の中央を押込み、押込み加重を測定した。押込みは、試験片１の長手方向（70ｍｍの方向）において、支点を試験片１の中央から左右20ｍｍの２点（支点間隔40ｍｍ）として試験片１を設置し、試験片１の長手方向の中央で支点とは反対側の面（上面）から加重をかけることにより行った。
(Method of measuring indentation load)
According to a measurement method based on Boeing Aircraft Company standard BAC 5718, the center of test piece 1 was pushed in using a Shimadzu 3-point bending tester under conditions of a pushing speed of 0.5 mm/min and a pushing load of 2.0 kN. , the indentation load was measured. For indentation, in the longitudinal direction (70 mm direction) of the test piece 1, the test piece 1 is set up with two supporting points 20 mm left and right from the center of the test piece 1 (40 mm spacing between the support points). This was done by applying weight from the side opposite the fulcrum (top side).
結果を図１６に示す。 The results are shown in FIG.
図１６の結果から、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物、金属炭化物及び金属窒化物からなる群より選択される少なくとも１種の金属化合物を含有し、ｐＨが１～５．５の範囲内である亜鉛系複合めっき液を用いて形成された実施例８の亜鉛系複合めっき皮膜は、めっき皮膜を形成する際に発生した水素のめっき皮膜中からの水素透過性が向上しており、めっき皮膜が形成された被めっき物の水素脆化が抑制されることが分かった。これに対し、金属化合物であるコロイダルシリカを含有せず、ジンケート浴である亜鉛系複合めっき液を用いて形成された比較例１４のめっき皮膜は、めっき皮膜を形成する際に発生した水素がめっき皮膜中に吸蔵され、当該めっき皮膜の水素透過性に劣るため、めっき皮膜が形成された被めっき物が水素脆化することが分かった。また、金属化合物であるコロイダルシリカを含有しない亜鉛系複合めっき液を用いて形成された比較例１５のめっき皮膜は、酸性浴であるためある程度水素のめっき皮膜中からの水素透過性は向上するが、実施例８と比較して、めっき皮膜の水素透過性に劣るため、めっき皮膜が形成された被めっき物が水素脆化することが分かった。 From the results in FIG. 16, it is clear that (A) zinc chloride and (B) at least one metal compound selected from the group consisting of metal oxide, metal carbide, and metal nitride are contained, and the pH is 1 to 1. The zinc-based composite plating film of Example 8, which was formed using a zinc-based composite plating solution within the range of It was found that hydrogen embrittlement of the plated object on which a plating film was formed was suppressed. On the other hand, in the plating film of Comparative Example 14, which did not contain colloidal silica, which is a metal compound, and was formed using a zinc-based composite plating solution that is a zincate bath, the hydrogen generated when forming the plating film was It has been found that hydrogen is occluded in the film and the plating film has poor hydrogen permeability, resulting in hydrogen embrittlement of the plated object on which the plating film is formed. In addition, the plating film of Comparative Example 15, which was formed using a zinc-based composite plating solution that does not contain colloidal silica, which is a metal compound, is an acidic bath, so hydrogen permeability from within the plating film is improved to some extent. It was found that, compared to Example 8, the plating film was inferior in hydrogen permeability, so that the object to be plated on which the plating film was formed was subject to hydrogen embrittlement.
本発明の亜鉛系複合めっき液、亜鉛系複合めっき皮膜の形成方法、及び複合酸化物皮膜の形成方法は、自動車部品、航空機部品等のめっき皮膜の形成に好適に使用することができ、高い耐久性が要求される航空機部品のめっき皮膜の形成に特に好適に使用することができる。 The zinc-based composite plating solution, the method for forming a zinc-based composite plating film, and the method for forming a composite oxide film of the present invention can be suitably used for forming plating films for automobile parts, aircraft parts, etc., and have high durability. It can be particularly suitably used for forming plating films for aircraft parts that require high properties.
Claims (5)
（Ａ）亜鉛の塩化物、並びに、
（Ｂ）金属酸化物
を含有し、
前記（Ａ）亜鉛の塩化物の含有量が、３０ｇ／Ｌ以上１５０ｇ／Ｌ以下であり、
前記金属酸化物は、Ｓｉ、Ｔｉ、Ｐ、Ｃｅ、Ｃｏ、Ｃｒ、Ｖ、Ｗ、Ｚｒ、Ｆｅ、Ｂｉ及びＳｎからなる群より選択される少なくとも１種の金属の金属酸化物であり、
ｐＨが１～５．５である、
ことを特徴とするＺｎ－Ｎｉ系複合めっき液。 A Zn-Ni composite plating solution for forming a Zn-Ni composite plating film,
(A) Zinc chloride, and
(B) contains a metal oxide;
The content of zinc chloride (A) is 30 g/L or more and 150 g/L or less,
The metal oxide is a metal oxide of at least one metal selected from the group consisting of Si, Ti, P, Ce, Co, Cr, V, W, Zr, Fe, Bi, and Sn,
pH is 1 to 5.5,
A Zn-Ni composite plating solution characterized by the following.
金属材料をＺｎ－Ｎｉ系複合めっき液に浸漬する工程１を有し、
前記Ｚｎ－Ｎｉ系複合めっき液は、
（Ａ）亜鉛の塩化物、並びに、
（Ｂ）金属酸化物
を含有し、
前記（Ａ）亜鉛の塩化物の含有量が、３０ｇ／Ｌ以上１５０ｇ／Ｌ以下であり、
前記金属酸化物は、Ｓｉ、Ｔｉ、Ｐ、Ｃｅ、Ｃｏ、Ｃｒ、Ｖ、Ｗ、Ｚｒ、Ｆｅ、Ｂｉ及びＳｎからなる群より選択される少なくとも１種の金属の金属酸化物であり、
ｐＨが１～５．５である、
ことを特徴とするＺｎ－Ｎｉ系複合めっき皮膜の形成方法。 A method for forming a Zn-Ni composite plating film, the method comprising:
A step 1 of immersing a metal material in a Zn-Ni composite plating solution,
The Zn-Ni composite plating solution is
(A) Zinc chloride, and
(B) contains a metal oxide;
The content of zinc chloride (A) is 30 g/L or more and 150 g/L or less,
The metal oxide is a metal oxide of at least one metal selected from the group consisting of Si, Ti, P, Ce, Co, Cr, V, W, Zr, Fe, Bi, and Sn,
pH is 1 to 5.5,
A method for forming a Zn-Ni composite plating film, characterized by:
（１）金属材料をＺｎ－Ｎｉ系複合めっき液に浸漬してＺｎ－Ｎｉ系複合めっき皮膜を形成する工程１、
（２）前記Ｚｎ－Ｎｉ系複合めっき皮膜の表面に皮膜形成組成物を塗布して皮膜形成組成物層を形成する工程２、及び
（３）前記皮膜形成組成物層を加熱して、前記金属材料の表面に、当該金属材料側からＺｎ－Ｎｉ系複合めっき皮膜、化成皮膜及びシリカ質皮膜をこの順に有する複合酸化物皮膜を形成する工程３
を含み、
前記Ｚｎ－Ｎｉ系複合めっき液は、（Ａ）亜鉛の塩化物、並びに、（Ｂ）金属酸化物を含有し、
前記（Ａ）亜鉛の塩化物の含有量が、３０ｇ／Ｌ以上１５０ｇ／Ｌ以下であり、
ｐＨが１～５．５であり、
前記皮膜形成組成物は、（ａ）アルコキシシランオリゴマー、及び（ｂ）溶媒を含有し、前記溶媒は、水及び／又は水溶性有機溶媒である、
ことを特徴とする複合酸化物皮膜の形成方法。 A method for forming a composite oxide film, the method comprising:
(1) Step 1 of immersing a metal material in a Zn-Ni composite plating solution to form a Zn-Ni composite plating film;
(2) Step 2 of applying a film-forming composition to the surface of the Zn-Ni composite plating film to form a film-forming composition layer; and (3) heating the film-forming composition layer to form a film-forming composition layer to form a film-forming composition layer. Step 3 of forming a composite oxide film having a Zn-Ni composite plating film, a chemical conversion film, and a siliceous film in this order from the metal material side on the surface of the material.
including;
The Zn-Ni composite plating solution contains (A) zinc chloride and (B) metal oxide,
The content of zinc chloride (A) is 30 g/L or more and 150 g/L or less,
pH is 1 to 5.5,
The film-forming composition contains (a) an alkoxysilane oligomer and (b) a solvent, where the solvent is water and/or a water-soluble organic solvent.
A method for forming a composite oxide film, characterized by the following.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005264170A (en) | 2004-03-16 | 2005-09-29 | Hoden Seimitsu Kako Kenkyusho Ltd | Chromium-free surface treatment agent for galvanized product |
| CN1834307A (en) | 2006-03-15 | 2006-09-20 | 哈尔滨工业大学 | Zn-Ni-Al2O3 nano composite deposit and its prepn. process |
| JP2010037584A (en) | 2008-08-01 | 2010-02-18 | Sumitomo Metal Ind Ltd | Surface treatment liquid suitable for galvanized metal material, and galvanized metal material |
| JP2010215973A (en) | 2009-03-17 | 2010-09-30 | Sumitomo Metal Ind Ltd | Surface-treated galvanized metal material and surface treatment solution |
| CN102268673A (en) | 2011-06-07 | 2011-12-07 | 广东联塑科技实业有限公司 | Method for preparing selective absorption coating of plastic solar thermal collector |
| JP5156499B2 (en) | 2008-06-19 | 2013-03-06 | 矢崎総業株式会社 | Electrical junction box |
| WO2015011778A1 (en) | 2013-07-23 | 2015-01-29 | 株式会社日立製作所 | Anti-corrosion coating film structure, metallic member equipped with same, anti-corrosion treatment method, and surface-treating agent |
| JP2018044221A (en) | 2016-09-16 | 2018-03-22 | 本田技研工業株式会社 | Zinc-nickel composite plating bath, zinc-nickel composite plating film, die and plating method |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6050179A (en) * | 1983-08-31 | 1985-03-19 | Nippon Kokan Kk <Nkk> | Production of steel plate coated with highly corrosion- resistant film on one side |
| JPS60211095A (en) * | 1984-04-03 | 1985-10-23 | Kawasaki Steel Corp | Surface treated steel sheet having high corrosion resistance |
| JPS61194195A (en) * | 1985-02-21 | 1986-08-28 | Sumitomo Metal Ind Ltd | Highly-corrosion resistant two-layer plated steel plate |
| JPS63130796A (en) * | 1986-11-21 | 1988-06-02 | Kawasaki Steel Corp | Composite chemical conversion coating steel sheet having excellent corrosion resistance and paint adhesion and production thereof |
| JPS63143294A (en) * | 1986-12-06 | 1988-06-15 | Nisshin Steel Co Ltd | Double-layer electroplated steel sheet having excellent corrosion resistance |
| JPH0663119B2 (en) * | 1987-02-19 | 1994-08-17 | 新日本製鐵株式会社 | Double-layer plated steel sheet with excellent resistance weldability |
| JPS63203778A (en) * | 1987-02-19 | 1988-08-23 | Nippon Steel Corp | Highly corrosion-resistant double-layered dispersion plated steel sheet |
| JPH0280597A (en) * | 1988-09-19 | 1990-03-20 | Nippon Steel Corp | Composite electroplated steel sheet having high corrosion resistance |
| JP3068690B2 (en) * | 1991-12-02 | 2000-07-24 | 高砂鐵工株式会社 | Surface treatment method for metallic materials with excellent paint adhesion |
-
2019
- 2019-07-08 JP JP2019127225A patent/JP7417888B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005264170A (en) | 2004-03-16 | 2005-09-29 | Hoden Seimitsu Kako Kenkyusho Ltd | Chromium-free surface treatment agent for galvanized product |
| CN1834307A (en) | 2006-03-15 | 2006-09-20 | 哈尔滨工业大学 | Zn-Ni-Al2O3 nano composite deposit and its prepn. process |
| JP5156499B2 (en) | 2008-06-19 | 2013-03-06 | 矢崎総業株式会社 | Electrical junction box |
| JP2010037584A (en) | 2008-08-01 | 2010-02-18 | Sumitomo Metal Ind Ltd | Surface treatment liquid suitable for galvanized metal material, and galvanized metal material |
| JP2010215973A (en) | 2009-03-17 | 2010-09-30 | Sumitomo Metal Ind Ltd | Surface-treated galvanized metal material and surface treatment solution |
| CN102268673A (en) | 2011-06-07 | 2011-12-07 | 广东联塑科技实业有限公司 | Method for preparing selective absorption coating of plastic solar thermal collector |
| WO2015011778A1 (en) | 2013-07-23 | 2015-01-29 | 株式会社日立製作所 | Anti-corrosion coating film structure, metallic member equipped with same, anti-corrosion treatment method, and surface-treating agent |
| JP2018044221A (en) | 2016-09-16 | 2018-03-22 | 本田技研工業株式会社 | Zinc-nickel composite plating bath, zinc-nickel composite plating film, die and plating method |
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