JP3137535B2 - Zinc-containing metal-coated steel sheet composite excellent in coatability and method for producing the same - Google Patents
Zinc-containing metal-coated steel sheet composite excellent in coatability and method for producing the sameInfo
- Publication number
- JP3137535B2 JP3137535B2 JP06144735A JP14473594A JP3137535B2 JP 3137535 B2 JP3137535 B2 JP 3137535B2 JP 06144735 A JP06144735 A JP 06144735A JP 14473594 A JP14473594 A JP 14473594A JP 3137535 B2 JP3137535 B2 JP 3137535B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- steel sheet
- ions
- treatment
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims description 166
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 95
- 239000011701 zinc Substances 0.000 title claims description 95
- 229910052725 zinc Inorganic materials 0.000 title claims description 95
- 229910000831 Steel Inorganic materials 0.000 title claims description 83
- 239000010959 steel Substances 0.000 title claims description 83
- 229910052751 metal Inorganic materials 0.000 title claims description 34
- 239000002184 metal Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000011282 treatment Methods 0.000 claims description 180
- 239000011248 coating agent Substances 0.000 claims description 98
- 238000000576 coating method Methods 0.000 claims description 98
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 78
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 70
- 238000000034 method Methods 0.000 claims description 62
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 55
- 229910019142 PO4 Inorganic materials 0.000 claims description 50
- 239000010452 phosphate Substances 0.000 claims description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- -1 iron ion Chemical class 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 27
- 230000004913 activation Effects 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 20
- 238000005868 electrolysis reaction Methods 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 229910001453 nickel ion Inorganic materials 0.000 claims description 19
- 229910021645 metal ion Inorganic materials 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 15
- 238000007746 phosphate conversion coating Methods 0.000 claims description 14
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 13
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910001437 manganese ion Inorganic materials 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 229940085991 phosphate ion Drugs 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims 1
- 238000007739 conversion coating Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 44
- 239000000243 solution Substances 0.000 description 44
- 239000000203 mixture Substances 0.000 description 31
- 238000012545 processing Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- 239000002585 base Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 238000004070 electrodeposition Methods 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007602 hot air drying Methods 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 3
- 238000005246 galvanizing Methods 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229940005654 nitrite ion Drugs 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000005237 degreasing agent Methods 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 102220491117 Putative postmeiotic segregation increased 2-like protein 1_C23F_mutation Human genes 0.000 description 1
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- WJSSIRUDIALLQN-UHFFFAOYSA-K dizinc;phosphate Chemical compound [Zn+2].[Zn+2].[O-]P([O-])([O-])=O WJSSIRUDIALLQN-UHFFFAOYSA-K 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-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
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
Description
【０００１】[0001]
【産業上の利用分野】本発明は、塗装性、特に電着塗装
性における塗膜密着性にすぐれ、かつ塗装後にすぐれた
耐食性を示す亜鉛含有金属めっき鋼板複合体、およびそ
の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a zinc-containing metal-coated steel sheet composite exhibiting excellent paintability, in particular, electrodeposition coating property and excellent corrosion resistance after coating, and a method for producing the same. is there.
【０００２】[0002]
【従来の技術】従来から自動車車体用鋼板として、穴あ
き腐食や赤錆発生を抑制をするために亜鉛含有金属によ
りめっきを施した鋼板（以下、亜鉛含有金属めっき鋼板
と記す）が多く使用されている。特に最近は防錆力をさ
らに高めるために、亜鉛含有金属めっき層の厚さを、よ
り厚くする厚目付け化が進んでいる。2. Description of the Related Art Conventionally, as a steel sheet for an automobile body, a steel sheet plated with a zinc-containing metal (hereinafter referred to as a zinc-containing metal-plated steel sheet) to suppress perforation corrosion and red rust has been widely used. I have. In particular, in recent years, in order to further enhance the rust-preventive force, the thickness of the zinc-containing metal plating layer has been increased to be thicker.
【０００３】しかしながら、りん酸塩処理後に、塗装を
施した従来の亜鉛含有金属めっき鋼板は、ウェットな使
用環境下において塗膜が膨れ易いという欠点を有してい
る。従来よりこの問題点を解決する手段として、特公平
５−５９０５号公報に亜鉛含有合金材料又は、アルミニ
ウム含有合金のめっき皮膜の表面に、特定組成のニッケ
ル−鉄合金を陰極電解により特定量だけ析出させて得ら
れ、りん酸塩処理性等の化成処理性に優れためっき鋼板
が紹介されているが、この方法は電解法であるため、所
要設備が高価であり、又、製造に電気を使用するため、
製造コストが高くなるという欠点を有している。[0003] However, the conventional zinc-containing metal-plated steel sheet coated after the phosphate treatment has a drawback that the coating film easily swells in a wet use environment. As means for solving this problem, a nickel-iron alloy having a specific composition is deposited on a surface of a zinc-containing alloy material or an aluminum-containing alloy plating film in a specific amount by cathodic electrolysis as disclosed in Japanese Patent Publication No. 5-5905. Introduced plated steel sheet with excellent chemical conversion properties such as phosphatability, but this method is an electrolytic method, so the required equipment is expensive, and electricity is used for production. To do
There is a disadvantage that the manufacturing cost is high.
【０００４】一方、特開平２−２２８４８２号公報に
は、等電点３以下で、分散粒子径が０．１μｍ以下のコ
ロイド性粒子を含む酸性りん酸亜鉛処理水溶液で金属表
面を処理することにより、塗装性能のすぐれたりん酸亜
鉛皮膜を形成する方法が示されている。しかしながらこ
の方法では処理時間が長い為、製造コストが高くなり、
生産性が低下するという欠点を有している。On the other hand, JP-A-2-228482 discloses that a metal surface is treated with an aqueous zinc zinc phosphate treatment solution containing colloidal particles having an isoelectric point of 3 or less and a dispersed particle diameter of 0.1 μm or less. A method for forming a zinc phosphate film having excellent coating performance is disclosed. However, this method requires a long processing time, so that the production cost is high,
There is a disadvantage that productivity is reduced.
【０００５】上記のような従来技術の現状に鑑み、塗装
性に優れ、塗装後にすぐれた耐食性および塗膜密着性を
示す亜鉛含有金属めっき鋼板複合体、およびそれを低コ
ストでかつ高効率をもって製造する、塗装性に優れた亜
鉛含有金属めっき鋼板複合体の製造方法の開発が強く望
まれている。In view of the state of the prior art as described above, a zinc-containing metal-plated steel sheet composite exhibiting excellent paintability and exhibiting excellent corrosion resistance and coating film adhesion after coating, and its production at low cost and high efficiency It is strongly desired to develop a method for producing a zinc-containing metal-plated steel sheet composite having excellent paintability.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、塗装性に優
れ、かつ塗装後に優れた防食性および塗膜密着性を示す
亜鉛含有金属めっき鋼板複合体、およびそれを高効率、
低コストにより製造する方法を提供しようとするもので
ある。DISCLOSURE OF THE INVENTION The present invention provides a zinc-containing metal-plated steel sheet composite having excellent paintability and exhibiting excellent anticorrosion properties and coating film adhesion after coating, and a highly efficient zinc-containing metal-coated steel sheet composite.
It is intended to provide a method of manufacturing at low cost.
【０００７】[0007]
【課題を解決するための手段】本発明の塗装性に優れた
亜鉛含有金属めっき鋼板複合体は亜鉛含有金属めっき鋼
板からなる基体と、その表面に形成され、亜鉛とりんと
を重量比（亜鉛／りん）２．５０４：１〜３．１６６：
１で含み、且つ、鉄、コバルト、ニッケル、カルシウ
ム、マグネシウム及びマンガンから選ばれた１種以上の
金属を０．０６〜９．０重量％の含有率で含有するりん
酸亜鉛複合皮膜と、このりん酸亜鉛複合皮膜上に形成さ
れ、かつ微小な結晶サイズを有するりん酸塩化成皮膜を
有することを特徴とするものである。SUMMARY OF THE INVENTION The zinc-coated metal-coated steel sheet composite of the present invention, which is excellent in paintability, has a base made of a zinc-containing metal-plated steel sheet and a zinc / phosphorus formed on the surface thereof, having a weight ratio (zinc / phosphorous). Phosphorus) 2.504: 1 to 3.166:
1; and a zinc phosphate composite coating containing at least one metal selected from iron, cobalt, nickel, calcium, magnesium and manganese at a content of 0.06 to 9.0% by weight. It is characterized by having a phosphate conversion coating formed on a zinc phosphate composite coating and having a fine crystal size.
【０００８】本発明の亜鉛含有金属めっき鋼板複合体に
おいて、前記りん酸亜鉛複合皮膜が、ニッケル及びマン
ガンから選ばれた少なくとも１種の金属を１．０〜９．
０重量％の含有率で含有することが好ましい。In the zinc-containing metal-plated steel sheet composite according to the present invention, the zinc phosphate composite coating contains at least one metal selected from nickel and manganese in an amount of 1.0 to 9.
It is preferable to contain it at a content of 0% by weight.
【０００９】本発明の亜鉛含有金属めっき鋼板複合体に
おいて前記りん酸亜鉛複合皮膜の付着量が０．３〜３．
０ｇ／ｍ2 であることが好ましい。In the zinc-containing metal-plated steel sheet composite according to the present invention, the zinc phosphate composite coating has an adhesion amount of 0.3 to 3.0.
It is preferably 0 g / m 2 .
【００１０】本発明の亜鉛含有金属めっき鋼板複合体に
おいて、前記りん酸塩化成皮膜が、１〜１２μｍの微細
化された結晶サイズを有することが好ましい。[0010] In the zinc-containing metal-plated steel sheet composite of the present invention, the phosphate conversion coating preferably has a refined crystal size of 1 to 12 µm.
【００１１】本発明の塗装性に優れた亜鉛含有金属めっ
き鋼板複合体の製造方法は、前記本発明の亜鉛含有金属
めっき鋼板複合体を製造するために、亜鉛含有金属めっ
き鋼板の表面に、下記成分（１）〜（４）： （１）りん酸イオン ５〜３０ｇ／リットル （２）硝酸イオン １．０〜１５ｇ／リットル （３）亜鉛イオン ０．１〜８．０ｇ／リットル （４）鉄イオン、ニッケルイオン、マンガ ンイオン、コバルトイオン、カルシ ウムイオン、およびマグネシウムイ オンから選ばれた少なくとも１種の 金属イオン ０．１〜８．０ｇ／リットル を含有し、かつ前記亜鉛イオンの、前記他の全金属イオ
ンに対する重量比が１：１０〜１０：１である電解めっ
き液による陰極電解処理を施して、前記りん酸亜鉛複合
皮膜を形成し、このりん酸亜鉛複合皮膜上にりん酸塩化
成処理を施して前記微細な結晶サイズを有するりん酸塩
化成皮膜を形成することを特徴とするものである。[0011] The method for producing a zinc-containing metal-plated steel sheet composite having excellent coatability according to the present invention comprises the steps of: Components (1) to (4): (1) phosphate ion 5 to 30 g / liter (2) nitrate ion 1.0 to 15 g / liter (3) zinc ion 0.1 to 8.0 g / liter (4) iron Ion, nickel ion, manganese ion, cobalt ion, calcium ion, and at least one metal ion selected from the group consisting of magnesium ion and 0.1 to 8.0 g / liter, and the zinc ion, Cathodic electrolytic treatment with an electrolytic plating solution having a weight ratio to all metal ions of 1:10 to 10: 1 is performed to form the zinc phosphate composite film. The present invention is characterized in that a phosphate conversion coating having the fine crystal size is formed by performing a phosphate conversion treatment on the composite coating.
【００１２】前記本発明法において、前記陰極電解処理
が、０．２〜３０Ａ／dm2 の電流密度において施される
ことが好ましい。In the method of the present invention, it is preferable that the cathodic electrolysis is performed at a current density of 0.2 to 30 A / dm 2 .
【００１３】本発明の塗装性に優れた亜鉛含有金属めっ
き鋼板複合体の製造方法は、前記本発明の亜鉛含有金属
めっきの鋼板複合体を製造するために、亜鉛含有金属め
っき鋼板の表面に、下記成分（１）〜（４）： （１）りん酸イオン １０〜３０ｇ／リットル （２）硝酸イオン １．０〜１５ｇ／リットル （３）亜鉛イオン ０．１〜８．０ｇ／リットル （４）鉄イオン、ニッケルイオン、マンガ ンイオン、コバルトイオン、カルシ ウムイオン、およびマグネシウムイ オンから選ばれた少なくとも１種の 金属イオン ０．１〜８．０ｇ／リットル を含有し、前記亜鉛イオンの、前記他の全金属イオンに
対する重量比が１：１０〜１０：１であり、かつ、過酸
化物、フッ化物イオン、錯フッ化物イオン、および亜硝
酸イオンから選ばれた少なくとも１種からなる反応促進
剤を更に含む化成処理液を、接触させて前記りん酸亜鉛
複合皮膜を形成し、このりん酸亜鉛複合皮膜上に、りん
酸塩化成処理を施して前記微細な結晶サイズを有するり
ん酸塩化成皮膜を形成することを特徴とするものであ
る。[0013] The method for producing a zinc-containing metal-plated steel sheet composite having excellent coating properties according to the present invention comprises the steps of: The following components (1) to (4): (1) phosphate ion 10 to 30 g / liter (2) nitrate ion 1.0 to 15 g / liter (3) zinc ion 0.1 to 8.0 g / liter (4) At least one metal ion selected from iron ions, nickel ions, manganese ions, cobalt ions, calcium ions, and magnesium ions in an amount of 0.1 to 8.0 g / liter; The weight ratio to all metal ions is 1:10 to 10: 1, and a small amount selected from peroxide, fluoride ions, complex fluoride ions, and nitrite ions. A chemical conversion treatment solution further containing at least one reaction accelerator is contacted to form the zinc phosphate composite coating, and a phosphate chemical conversion treatment is performed on the zinc phosphate composite coating to form the finely divided zinc phosphate composite coating. A phosphate conversion coating having a crystal size is formed.
【００１４】上記本発明方法において、前記化成処理液
中に、前記反応促進剤が、０．０１〜８．０ｇ／リット
ル〔但し、フッ化物イオンおよび錯フッ化物イオンの場
合、フッ素イオン量に換算する〕の濃度で含まれること
が好ましい。In the method of the present invention, the chemical conversion treatment solution contains 0.01 to 8.0 g / liter of the reaction accelerator [however, when fluoride ions and complex fluoride ions are used, the amount is calculated as the amount of fluorine ions. Is preferably contained at a concentration of
【００１５】上記本発明方法において、前記りん酸塩化
成皮膜が１〜１２μｍの微細化された結晶サイズを有す
ることが好ましい。In the method of the present invention, it is preferable that the phosphate conversion coating has a refined crystal size of 1 to 12 μm.
【００１６】上記本発明方法において、前記亜鉛含有金
属めっき鋼板の表面に、予め、（イ）ニッケルイオンお
よびコバルトイオンから選ばれた少なくとも１種の金属
を含む処理液で処理して、前記表面上に、前記少なくと
も１種の金属を、０．２〜５０mg／ｍ2 の金属付着量で
付着させる活性化処理、（ロ）チタンコロイド水性液で
処理する活性化処理、又は（ハ）エッチング処理液で金
属酸化物を除去する活性化処理、を施すことが好まし
い。In the method of the present invention, the surface of the zinc-containing metal-plated steel sheet is previously treated with (a) a treatment solution containing at least one metal selected from nickel ions and cobalt ions. An activation treatment for depositing the at least one metal at a metal adhesion amount of 0.2 to 50 mg / m 2 , (b) an activation treatment for treating with an aqueous titanium colloid solution, or (c) an etching treatment solution It is preferable to carry out an activation treatment for removing the metal oxide by the above.
【００１７】[0017]
【作用】本発明の亜鉛含有金属めっき鋼板複合体におい
て、その基体として用いられる亜鉛含有金属めっき鋼板
は、亜鉛、又は亜鉛と他の元素、例えば、ニッケル、
鉄、アルミニウム、マンガン、クロム、鉛、およびアン
チモンなどから選ばれた１種以上との合金によりめっき
された鋼板である。そのめっき方法は特に制限はなく、
溶融亜鉛めっき法、合金化溶融亜鉛めっき法、電気亜鉛
めっき法、および電気亜鉛合金（Ｚｎ−Ｎｉ，Ｚｎ−Ｆ
ｅ、Ｚｎ−Ｍｎ又はＺｎ−Ｃｒ合金など）めっき法、溶
融Ｚｎ−Ａｌめっき法、および蒸着めっき法などを包含
する。In the zinc-containing metal-plated steel sheet composite of the present invention, the zinc-containing metal-plated steel sheet used as the substrate is made of zinc, or zinc and other elements, for example, nickel,
It is a steel plate plated with an alloy with at least one selected from iron, aluminum, manganese, chromium, lead, antimony and the like. The plating method is not particularly limited,
Hot-dip galvanizing method, alloyed hot-dip galvanizing method, electro-galvanizing method, and electro-zinc alloy (Zn-Ni, Zn-F
e, Zn—Mn or Zn—Cr alloy) plating method, hot-dip Zn—Al plating method, vapor deposition plating method, and the like.
【００１８】本発明におけるりん酸亜鉛複合皮膜につい
て詳細に説明すると、亜鉛とりんとは複合皮膜の主構成
成分であって、その重量比（亜鉛／りん）が２．５０
４：１〜３．１６６：１であり、且つこの皮膜中の鉄、
コバルト、ニッケル、カルシウム、マグネシウム及びマ
ンガンから選ばれた１種以上の金属が０．０６〜９．０
重量％の含有率で含有されている。The zinc phosphate composite coating of the present invention will be described in detail. Zinc and phosphorus are the main components of the composite coating, and the weight ratio (zinc / phosphorus) is 2.50.
4: 1 to 3.166: 1 and the iron in this coating,
At least one metal selected from cobalt, nickel, calcium, magnesium and manganese is 0.06 to 9.0;
It is contained at a content of weight%.
【００１９】上記複合皮膜中において、亜鉛の一部が他
の二価以上の金属と置換した形で存在していると考えら
れる。亜鉛とりんの重量比が３．１６６：１を超える場
合、および鉄、コバルト、ニッケル、カルシウム、マグ
ネシウム及びマンガンから選ばれる１種以上の金属の含
有率が０．０６重量％未満の場合には、その上にさらに
りん酸塩化成処理を施して得られる複合体の電着塗装
性、および上塗り塗装後の塗装性能が不十分になる。一
方、亜鉛とりんとの重量比が２．５０４：１未満の場
合、および鉄、コバルト、ニッケル、カルシウム、マグ
ネシウム及びマンガンから選ばれた１種以上の金属の含
有率が９．０重量％を超える場合には、その上にさらに
りん酸塩処理を施して得られる複合体の塗装性能は良好
であるが、その性能は飽和し、製造コストが高くなり経
済的に不利になる。It is considered that in the composite film, a part of zinc is present in a form substituted by another divalent or higher metal. When the weight ratio of zinc to phosphorus exceeds 3.166: 1, and when the content of one or more metals selected from iron, cobalt, nickel, calcium, magnesium and manganese is less than 0.06% by weight, In addition, the electrodeposition coatability of the composite obtained by further performing a phosphate chemical conversion treatment thereon and the coating performance after the top coat coating become insufficient. On the other hand, when the weight ratio of zinc to phosphorus is less than 2.504: 1, and the content of one or more metals selected from iron, cobalt, nickel, calcium, magnesium and manganese exceeds 9.0% by weight In such a case, the coating performance of the composite obtained by further performing a phosphate treatment thereon is good, but the performance is saturated, the production cost is increased, and it is economically disadvantageous.
【００２０】りん酸亜鉛複合皮膜中の亜鉛以外の金属は
鉄、コバルト、ニッケル、カルシウム、マグネシウム及
びマンガンから選ばれ、その含有率が０．０６〜９．０
重量％の範囲内にコントロールすると、その上に更にり
ん酸塩処理を施して得られる複合体の電着塗装後、ある
いは上塗り塗装後の塗装性能が良好である。上記の金属
群のうちでもニッケル及びマンガンから選ばれた少なく
とも１種を１．０〜９．０重量％含有させることが好ま
しく、特にニッケルを１．５〜８．０重量％含有させる
ことがより好ましい。The metal other than zinc in the zinc phosphate composite coating is selected from iron, cobalt, nickel, calcium, magnesium and manganese, and the content is 0.06 to 9.0.
When the content is controlled within the range of weight%, the composite obtained by further performing a phosphate treatment thereon has good coating performance after electrodeposition coating or after top coating. It is preferable that at least one selected from the group consisting of nickel and manganese is contained in an amount of 1.0 to 9.0% by weight, more preferably 1.5 to 8.0% by weight of nickel. preferable.
【００２１】前記複合皮膜の付着量には特に限定はない
が、この複合皮膜を０．３〜３．０ｇ／ｍ2 の付着量
で、前記亜鉛含有金属めっき鋼板からなる基材上に形成
させることが好ましい。その付着量（皮膜重量）が０．
３ｇ／ｍ2 未満では、得られる複合体のプレス成形時に
りん酸亜鉛複合皮膜が破壊され、更にその上にりん酸塩
処理が施された複合体の電着塗装性能、あるいは上塗り
塗装後の塗装性能が不十分になる。また複合皮膜の付着
量が３．０ｇ／ｍ2 を超えると、その上に施されるりん
酸塩処理時にエッチングが起こりにくくなり、充分なり
ん酸塩皮膜の析出が不可能となるので好ましくない。Although there is no particular limitation on the amount of the composite coating, the composite coating is formed on the substrate made of the zinc-containing metal-plated steel sheet with an adhesion of 0.3 to 3.0 g / m 2 . Is preferred. The amount of adhesion (film weight) is 0.
If it is less than 3 g / m 2 , the zinc phosphate composite film is destroyed during press molding of the obtained composite, and further, the electrodeposition coating performance of the composite which has been subjected to phosphate treatment, or the coating after top coating Insufficient performance. On the other hand, if the amount of the composite coating exceeds 3.0 g / m 2 , etching is unlikely to occur during the phosphate treatment applied thereon, and it becomes impossible to sufficiently deposit a phosphate coating, which is not preferable. .
【００２２】りん酸亜鉛複合皮膜上に、更にりん酸塩処
理が施されるが、このときに用いられるりん酸塩処理液
の組成には格別の制限はなく、鋼板の材質、めっき層、
および複合皮膜の組成、厚さ、製品の用途などに応じて
適宜に設定することができる。また処理温度、処理時
間、処理方式、皮膜重量等にも何の制限もない。The phosphating treatment is further performed on the zinc phosphate composite coating. There is no particular limitation on the composition of the phosphating solution used at this time.
It can be set appropriately according to the composition and thickness of the composite film, the use of the product, and the like. There are no restrictions on the processing temperature, processing time, processing method, film weight, and the like.
【００２３】本発明において、上記のような構成を有す
るりん酸亜鉛複合被覆上に、りん酸塩化成処理を施す
と、このような複合皮膜なしに亜鉛含有金属めっき鋼板
上に直接りん酸塩化成処理を施した場合にくらべて、得
られるりん酸塩化成皮膜の結晶サイズが、明瞭に微細化
し、このため、得られる複合体の電着塗装性能、および
上塗り塗装後の塗装性能が著しく向上するという特徴が
ある。このようなりん酸亜鉛複合皮膜の特殊性態および
その利用は、本発明において、初めて見出され、その利
用に成功したものである。本発明においてりん酸亜鉛複
合皮膜上に形成されるりん酸塩化成皮膜の結晶サイズは
１〜１２μｍであることが好ましく２〜７μｍであるこ
とがより好ましく、３〜６μｍであることがさらに好ま
しい。In the present invention, when a phosphate conversion treatment is performed on the zinc phosphate composite coating having the above-described structure, the phosphate conversion treatment is directly performed on the zinc-containing metal-plated steel sheet without such a composite coating. As compared with the case where the treatment is performed, the crystal size of the obtained phosphate conversion coating is distinctly finer, and therefore, the electrodeposition coating performance of the obtained composite and the coating performance after the topcoat coating are significantly improved. There is a feature. Such a special aspect of the zinc phosphate composite film and its use have been found for the first time in the present invention and have been successfully used. In the present invention, the crystal size of the phosphate conversion coating formed on the zinc phosphate composite coating is preferably from 1 to 12 μm, more preferably from 2 to 7 μm, even more preferably from 3 to 6 μm.
【００２４】本発明におけるりん酸亜鉛複合皮膜をでき
るだけ短時間で形成させることが好ましく、それによっ
て製造コストを低減することが重要である。具体的には
１〜２０秒間の短時間で効率的に、りん酸亜鉛複合皮膜
を形成させることが好ましい。It is preferable to form the zinc phosphate composite coating in the present invention in as short a time as possible, and it is important to reduce the production cost. Specifically, it is preferable to form the zinc phosphate composite film efficiently in a short time of 1 to 20 seconds.
【００２５】この様な短時間内に、上記りん酸亜鉛複合
皮膜を形成する方法には、特に制限はなく、清浄な亜鉛
含有金属めっき鋼板を基体として、その表面にりん酸亜
鉛、りん酸ニッケル、りん酸マンガン、りん酸カルシウ
ム、りん酸鉄、りん酸マグネシウム、りん酸コバルト等
のオルトりん酸塩を、プラズマ溶射法、真空蒸着法、ス
パッタリング法等により被覆する方法も利用できるが、
これらの方法には、設備装置に多大な費用を要し、この
ため経済的に不利であるという欠点がある。The method for forming the above-mentioned zinc phosphate composite film within such a short time is not particularly limited, and a clean zinc-containing metal-plated steel sheet is used as a substrate, and zinc phosphate, nickel phosphate is coated on the surface thereof. A method of coating orthophosphates such as manganese phosphate, calcium phosphate, iron phosphate, magnesium phosphate, and cobalt phosphate by a plasma spraying method, a vacuum evaporation method, a sputtering method, etc. can also be used.
These methods have the disadvantage that the equipment is very expensive and therefore economically disadvantageous.
【００２６】本発明におけるりん酸亜鉛複合皮膜を簡便
な装置で経済的に形成する好ましい方法として、少なく
ともりん酸イオンを５〜３０ｇ／リットル、硝酸イオン
を１０〜１５ｇ／リットル、亜鉛イオンを０．１〜８．
０ｇ／リットル含有し、さらに他の金属イオンとして鉄
イオン、コバルトイオン、ニッケルイオン、カルシウム
イオン、マグネシウムイオン、マンガンイオンから選ば
れた１種以上を合計量で０．１〜８ｇ／リットル含有
し、且つ、亜鉛イオンの他の全金属イオンに対する重量
比（亜鉛イオン／他の全金属イオン）が１：１０〜１
０：１である水溶液を用いた化成処理、または電解処理
により形成することができる。As a preferred method of economically forming the zinc phosphate composite coating in the present invention with a simple apparatus, at least 5 to 30 g / liter of phosphate ions, 10 to 15 g / liter of nitrate ions, and 0.1 to 0.1 g of zinc ions. 1-8.
0 g / liter, and further contains at least one selected from iron ions, cobalt ions, nickel ions, calcium ions, magnesium ions, and manganese ions as other metal ions in a total amount of 0.1 to 8 g / liter, In addition, the weight ratio of zinc ions to all other metal ions (zinc ions / all other metal ions) is 1:10 to 1
It can be formed by a chemical conversion treatment using an aqueous solution of 0: 1 or an electrolytic treatment.
【００２７】前記水溶液に含まれる金属イオンの供給源
としては、特に制限はないが、具体的に例を挙げると、
当該金属の酸化物、水酸化物、および炭酸塩など、例え
ば酸化亜鉛、酸化鉄、酸化コバルト、酸化ニッケル、酸
化カルシウム、酸化マグネシウム、酸化マンガン、水酸
化亜鉛、水酸化鉄、水酸化コバルト、水酸化ニッケル、
水酸化カルシウム、水酸化マグネシウム、水酸化マンガ
ン、炭酸亜鉛、炭酸コバルト、炭酸ニッケル、炭酸カル
シウム、炭酸マグネシウム、炭酸マンガン等を用いるこ
とができる。これらの金属化合物をりん酸、硝酸、硫
酸、塩酸、フッ酸、珪フッ酸等の無機酸類、ギ酸、酢
酸、クエン酸等の有機酸類に溶解して処理浴に供給する
事もできる。又、当該金属の硝酸塩、硫酸塩、塩化物、
フッ化物、珪フッ化物、酢酸塩、ギ酸塩、クエン酸塩等
の可溶性塩類を供給源として用いてもよい。The source of metal ions contained in the aqueous solution is not particularly limited, but specific examples include:
Oxides, hydroxides, and carbonates of the metal, such as zinc oxide, iron oxide, cobalt oxide, nickel oxide, calcium oxide, magnesium oxide, manganese oxide, zinc hydroxide, iron hydroxide, cobalt hydroxide, water Nickel oxide,
Calcium hydroxide, magnesium hydroxide, manganese hydroxide, zinc carbonate, cobalt carbonate, nickel carbonate, calcium carbonate, magnesium carbonate, manganese carbonate, and the like can be used. These metal compounds can be dissolved in inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and hydrofluoric acid, and organic acids such as formic acid, acetic acid, and citric acid, and supplied to the treatment bath. Also, nitrates, sulfates, chlorides,
Soluble salts such as fluoride, silicofluoride, acetate, formate, and citrate may be used as the source.
【００２８】本発明の亜鉛含有金属めっき鋼板複合体を
製造するための、前記りん酸亜鉛複合皮膜形成方法とし
て、前記処理水溶液を電解液として用い、かつ亜鉛含有
金属めっき鋼板基材を陰極とし電解反応により処理する
方法、および、上記処理水溶液に反応促進剤を添加し、
電解に因らず、化成反応により処理する方法とが用いら
れる。In the method for forming a zinc phosphate composite film for producing the zinc-containing metal-plated steel sheet composite of the present invention, the treatment aqueous solution is used as an electrolyte, and the zinc-containing metal-plated steel sheet base material is used as a cathode. A method of treating by a reaction, and adding a reaction accelerator to the treatment aqueous solution,
A method of performing treatment by a chemical reaction regardless of electrolysis is used.
【００２９】本発明方法において、りん酸亜鉛複合皮膜
の形成に電解反応法が用いられる場合、それに必要とす
る電流密度には特に制限はなく、電解に使用する処理液
中の各成分濃度、成分比率、電解処理温度等により適宜
選択できる。一般に目標とする短時間（１〜２０秒間）
に複合皮膜の形成を達成するには、電流密度を０．２〜
３０Ａ／dm2 の範囲内にコントロールすることが好まし
い。電流密度が０．２Ａ／dm2 未満では目標とする短時
間内に所望のりん酸亜鉛複合皮膜を形成することが困難
になることがあり、また、それが３０Ａ／dm2 を超える
と電流効率が低下し経済的に不利になることがある。In the method of the present invention, when an electrolytic reaction method is used to form a zinc phosphate composite film, the current density required for the electrolytic reaction method is not particularly limited, and the concentration of each component in the processing solution used for electrolysis, It can be appropriately selected depending on the ratio, the electrolytic treatment temperature, and the like. Generally, target short time (1 to 20 seconds)
In order to achieve the formation of a composite film, the current density must be between 0.2 and
It is preferable to control within the range of 30 A / dm 2 . If the current density is less than 0.2 A / dm 2 , it may be difficult to form a desired zinc phosphate composite film within a target short time, and if it exceeds 30 A / dm 2 , the current efficiency may be reduced. May be reduced and become economically disadvantageous.
【００３０】上記電解処理液が他に含有することができ
る成分として特に制限はないが、りん酸亜鉛複合皮膜形
成反応の経済性を高めるためにりん酸亜鉛複合皮膜形成
反応効率を向上させる手段を併用してもよい。このよう
な反応効率を高める手段には制限はないが、具体的に例
をあげると、電解処理液の全酸度／遊離酸度の比率を調
節し、電解処理液の亜鉛含有金属めっき鋼板基材に対す
るエッチング力をコントロールする方法がある。全酸度
／遊離酸度の調節は通常のりん酸、硝酸等の酸、あるい
は炭酸ナトリウム、水酸化ナトリウム等のアルカリで調
節することにより行うことができる。一般に全酸度／遊
離酸度比が８：１〜３０：１であることが好ましい。There are no particular restrictions on the other components that can be contained in the electrolytic treatment solution. However, in order to increase the economic efficiency of the zinc phosphate composite film forming reaction, a means for improving the zinc phosphate composite film forming reaction efficiency is used. You may use together. There is no limitation on the means for increasing the reaction efficiency, but specific examples include adjusting the ratio of the total acidity / free acidity of the electrolytic solution to the zinc-containing metal-plated steel sheet substrate of the electrolytic solution. There is a method of controlling the etching power. The adjustment of the total acidity / free acidity can be performed by adjusting with a normal acid such as phosphoric acid or nitric acid, or an alkali such as sodium carbonate or sodium hydroxide. Generally, the ratio of total acidity / free acidity is preferably from 8: 1 to 30: 1.
【００３１】本発明方法において化成処理反応によりり
ん酸亜鉛複合皮膜を形成する場合、目標とする短時間
（１〜２０秒間）処理を達成するための一つの手段とし
て処理液中に反応促進剤を添加することが有用である。
反応促進剤としては、通常知られる酸化剤、および／ま
たはエッチング剤が使用できる。特に好ましい反応促進
剤として具体的に例を挙げると、無機過酸化物、過酸化
水素、亜硝酸イオンなどの酸化剤、フッ化物イオン、お
よび錯フッ化物イオン等のエッチング剤を含有すること
ができる。これらの反応促進剤の添加量には特に制限は
なく、目標とする処理時間に応じて適宜に定めることが
できる。一般に化成処理液中の反応促進剤の濃度は、
０．０１〜８．０ｇ／リットルであることが好ましい。
但し、フッ化物イオン、又は錯フッ化物イオンが用いら
れる場合、その濃度は、フッ素イオン量に換算して算出
する。When a zinc phosphate composite film is formed by a chemical conversion reaction in the method of the present invention, as one means for achieving a target short-time treatment (1 to 20 seconds), a reaction accelerator is added to the treatment solution. It is useful to add.
As the reaction accelerator, a commonly known oxidizing agent and / or etching agent can be used. Specific examples of particularly preferred reaction accelerators include an oxidizing agent such as inorganic peroxide, hydrogen peroxide and nitrite ion, and an etching agent such as fluoride ion and complex fluoride ion. . The amount of these reaction accelerators is not particularly limited, and can be appropriately determined according to the target processing time. In general, the concentration of the reaction accelerator in the chemical conversion solution is
It is preferably 0.01 to 8.0 g / liter.
However, when a fluoride ion or a complex fluoride ion is used, the concentration is calculated by converting the concentration into a fluorine ion amount.
【００３２】上記陰極電解処理反応、化成処理反応等の
何れかを用いる本発明方法においても、上記処理液中の
りん酸イオンの濃度が５ｇ／リットル未満では、短時間
処理が困難となり、また、それが３０ｇ／リットルを超
えると、短時間処理は達成できるが無駄な薬剤を消費す
るので経済的に不利になる。又、硝酸イオン濃度が１．
０ｇ／リットル未満では、短時間処理を達成することが
困難となり、又それが１．５ｇ／リットルを超えると、
短時間処理の効果が飽和に達し、薬剤の消費も増大する
ので経済的に不利になる。In the method of the present invention using either the cathodic electrolysis reaction or the chemical conversion reaction, if the concentration of phosphate ions in the treatment solution is less than 5 g / liter, it is difficult to carry out the treatment in a short time. If it exceeds 30 g / l, a short-time treatment can be achieved, but it is economically disadvantageous because it consumes useless drug. The nitrate ion concentration is 1.
If it is less than 0 g / liter, it is difficult to achieve a short-time treatment, and if it exceeds 1.5 g / liter,
The effect of the short-time treatment reaches saturation and the consumption of the drug increases, which is economically disadvantageous.
【００３３】本発明方法に用いられる処理水溶液におい
て、前述のように、０．１〜８．０ｇ／リットルの亜鉛
イオンとともに、合計量０．１〜８．０ｇ／リットルの
２価以上の少なくとも１種の他の金属イオン、すなわち
鉄イオン、コバルトイオン、ニッケルイオン、カルシウ
ムイオン、マグネシウムイオン、およびマンガンイオン
から選ばれた１種以上を含む。また、亜鉛イオンと他の
全金属イオンの重量比は１：１０〜１０：１である。前
記他の金属イオンの合計濃度が０．１ｇ／リットル未満
では短時間処理が困難となり、またそれが８ｇ／リット
ルを超えると短時間処理には好ましいが無駄な薬剤を消
費するので経済的に不利になる。As described above, in the treatment aqueous solution used in the method of the present invention, zinc ions of 0.1 to 8.0 g / liter and at least one of divalent or more of 0.1 to 8.0 g / liter are used together with zinc ions. And at least one other metal ion selected from iron ions, cobalt ions, nickel ions, calcium ions, magnesium ions, and manganese ions. The weight ratio of zinc ions to all other metal ions is 1:10 to 10: 1. If the total concentration of the other metal ions is less than 0.1 g / l, it is difficult to perform the treatment in a short time, and if it exceeds 8 g / l, it is preferable for the treatment in a short time, but it consumes unnecessary chemicals and is economically disadvantageous. become.
【００３４】亜鉛と他の金属イオンの重量比が１：１０
未満では、この複合皮膜上に更にりん酸塩処理して得ら
れた複合体の電着塗装性能、あるいは上塗り塗装後の塗
装性能が飽和に達し、製造コストが増加するので経済的
に不利である。又、亜鉛と他の金属イオンの重量比が１
０：１を超えると、形成したりん酸亜鉛複合皮膜中に含
まれる鉄、コバルト、ニッケル、カルシウム、マグネシ
ウム及びマンガンから選ばれた１種または２種以上の金
属の含有量が過少となり、この複合皮膜上に更にりん酸
塩処理し得られた複合体の電着塗装性能あるいは上塗り
塗装後の塗装性能が低下し好ましくない。The weight ratio of zinc to other metal ions is 1:10
If it is less than this, the electrodeposition coating performance of the composite obtained by further phosphate treatment on this composite coating, or the coating performance after top coating reaches saturation, and the production cost increases, which is economically disadvantageous. . The weight ratio of zinc to other metal ions is 1
If it exceeds 0: 1, the content of one or more metals selected from iron, cobalt, nickel, calcium, magnesium and manganese contained in the formed zinc phosphate composite film becomes too small, and this composite The electrodeposition coating performance of the composite obtained by further phosphate treatment on the film or the coating performance after the top coating is unpreferably reduced.
【００３５】尚、本発明における目的の一つである複合
皮膜形成処理の短時間化を達成するため処理方法として
特に好ましい方法としては、清浄な亜鉛含有金属めっき
鋼板表面を予め活性化処理を施した後、上記組成を有す
る処理液を温度３０〜７０℃に保ち、この亜鉛含有金属
めっき鋼板表面を処理することが好ましい。処理水溶液
の温度が３０℃未満ではりん酸亜鉛複合皮膜の形成速度
が緩慢になり短時間処理が困難となる。一方、７０℃を
超える温度としても本発明以上の効果は得られず経済的
に無駄である。As a particularly preferable method for achieving a shortened composite film forming treatment which is one of the objects of the present invention, a clean zinc-containing metal-plated steel sheet surface is preliminarily activated. After that, it is preferable to maintain the temperature of the treatment liquid having the above composition at 30 to 70 ° C. to treat the surface of the zinc-containing metal-plated steel sheet. If the temperature of the treatment aqueous solution is lower than 30 ° C., the formation rate of the zinc phosphate composite film becomes slow, and it becomes difficult to carry out the treatment in a short time. On the other hand, even if the temperature exceeds 70 ° C., the effect more than that of the present invention cannot be obtained and it is economically useless.
【００３６】活性化処理の方法については特に制限はな
いが、具体的に例をあげると、（イ）ニッケルイオンま
たはコバルトイオンあるいはその両者を含有する処理液
で処理して、ニッケルまたはコバルトあるいはその両者
の金属換算で０．２〜５０mg／ｍ2 を付着させる処理、
（ニ）チタンコロイド水溶液に接触させる処理、もしく
は、（ハ）亜鉛含有金属めっき鋼板表面に形成されてい
る金属酸化物の上層をエッチングする処理、などがあ
る。The method of the activation treatment is not particularly limited, but specific examples thereof include (a) treatment with a treatment solution containing nickel ions or cobalt ions or both to obtain nickel or cobalt or a mixture thereof. A treatment for adhering 0.2 to 50 mg / m 2 in terms of both metals,
(D) a process of contacting with a titanium colloid aqueous solution, or (c) a process of etching an upper layer of a metal oxide formed on the surface of a zinc-containing metal-plated steel sheet.
【００３７】上記の活性化処理方法（イ）についてさら
に説明する。この処理方法（イ）は、亜鉛含有金属めっ
き鋼板からなる基体の表面を、ニッケルイオンまたはコ
バルトイオンあるいはその両者を含有する処理液で処理
して、ニッケルまたはコバルトあるいはその両者を、金
属換算で０．２〜５０mg／ｍ2 の付着量で付着させるも
のである。この付着量が金属換算で０．２mg／ｍ2 未満
では、前記めっき鋼板表面の活性化が不十分であり、処
理時間の短時間化が困難となる。又、その付着量が５０
mg／ｍ2 を超えても、得られる効果は飽和に達し経済的
でない。The activation processing method (a) will be further described. In this treatment method (a), the surface of a substrate made of a zinc-containing metal-plated steel sheet is treated with a treatment solution containing nickel ions or cobalt ions or both, so that nickel or cobalt or both are reduced to 0 in metal conversion. .2 to 50 mg / m 2 . If the amount of adhesion is less than 0.2 mg / m 2 in terms of metal, activation of the surface of the plated steel sheet is insufficient, and it is difficult to shorten the processing time. In addition, the amount of adhesion is 50
Even if it exceeds mg / m 2 , the obtained effect reaches saturation and is not economical.
【００３８】前記（イ）の活性化処理液に使用できるニ
ッケルイオンまたはコバルトイオンの供給源には特に制
限はないが、硫酸ニッケル、硝酸ニッケル、塩化ニッケ
ル、珪フッ化ニッケル等の水溶性ニッケル塩類、硫酸コ
バルト、硝酸コバルト、塩化コバルト、珪フッ化コバル
ト等の水溶性コバルト塩類を、各々単独に、又はその２
種以上を適宜に組み合わせて使用することができる。There are no particular restrictions on the source of nickel ions or cobalt ions that can be used in the activation treatment liquid (a), but water-soluble nickel salts such as nickel sulfate, nickel nitrate, nickel chloride, nickel silicofluoride, etc. Water-soluble cobalt salts, such as cobalt sulfate, cobalt nitrate, cobalt chloride, cobalt silicofluoride, alone or
More than one species can be used in appropriate combination.
【００３９】前記活性化処理方法（ロ）に使用できるチ
タンコロイド処理液において、その中のチタンイオンの
供給源に特に制限はないが、例えば硫酸チタン、硫酸チ
タニル、酸化チタン、およびりん酸チタン等を各々単独
に、又はその２種以上を適宜に組み合わせて使用するこ
とが好ましい。In the titanium colloid treating solution which can be used in the activation treatment method (b), there is no particular limitation on the source of titanium ions contained therein. For example, titanium sulfate, titanyl sulfate, titanium oxide, titanium phosphate, etc. Are preferably used alone or in combination of two or more.
【００４０】前記活性化処理方法（ハ）に使用できるエ
ッチング剤に特に制限はないが、硫酸、硝酸、りん酸、
フッ酸、珪フッ酸、ピロりん酸等の無機酸類、クエン
酸、酒石酸、酢酸、蓚酸、グルコン酸等の有機酸類、お
よびＥＤＴＡ、ＮＴＡ等のキレート性の化合物を使用
し、亜鉛含有金属めっき鋼板表面に形成されている金属
酸化物の上層をエッチングし除去することができる。Although there is no particular limitation on the etching agent that can be used in the activation treatment method (C), sulfuric acid, nitric acid, phosphoric acid,
Using inorganic acids such as hydrofluoric acid, silicic hydrofluoric acid, and pyrophosphoric acid, organic acids such as citric acid, tartaric acid, acetic acid, oxalic acid, and gluconic acid, and chelating compounds such as EDTA and NTA. The upper layer of the metal oxide formed on the surface can be removed by etching.
【００４１】清浄な亜鉛含有金属めっき鋼板表面に、前
記活性化処理方法（イ）、（ロ）又は（ハ）を施した
後、この表面を前記複合皮膜形成用の処理液で処理する
ことにより、０．３〜３．０ｇ／ｍ2 の付着量のりん酸
亜鉛複合皮膜を、より短時間内に効率よく形成すること
が可能となる。After the activation treatment method (a), (b) or (c) is applied to the surface of a clean zinc-containing metal-plated steel sheet, the surface is treated with the treatment solution for forming a composite film. , 0.3 to 3.0 g / m 2 can be efficiently formed in a shorter time.
【００４２】鋼材の各種表面処理において、りん酸亜鉛
化成処理は長い歴史を有する技術であり塗装のための下
地処理として、現在も広く使用されている。りん酸亜鉛
化成皮膜の塗装下地としての効果は、この複合皮膜の物
理的な形状に由来し、塗膜に対してすぐれたアンカー効
果を示し、かつ塗膜に対する密着力を向上させるものと
考えられている。また亜鉛以外の特定金属、すなわち、
鉄、コバルト、ニッケル、カルシウム、マグネシウム及
びマンガン等の２価以上の金属は、皮膜中の亜鉛の一部
と置換した形で存在することにより、複合皮膜の耐アル
カリ性が向上する。特に腐食環境下、すなわち、皮膜の
界面のＨ+ の消費によるpH上昇に対して、上記の２価以
上の金属が複合皮膜の耐食性向上にすぐれた効果を示
す。In various surface treatments of steel materials, chemical conversion treatment with zinc phosphate has a long history and is still widely used as a base treatment for painting. The effect of the zinc phosphate conversion coating as a coating base is thought to be due to the physical shape of the composite coating, exhibiting an excellent anchoring effect on the coating and improving the adhesion to the coating. ing. Specific metals other than zinc, namely,
Divalent or higher-valent metals such as iron, cobalt, nickel, calcium, magnesium and manganese are present in the form of being substituted for part of zinc in the coating, whereby the alkali resistance of the composite coating is improved. Particularly, in a corrosive environment, that is, the increase in pH due to consumption of H + at the interface of the film, the above-mentioned divalent or higher metal exhibits an excellent effect of improving the corrosion resistance of the composite film.
【００４３】本発明によるりん酸亜鉛複合皮膜の、亜鉛
含有金属めっき鋼板に対する作用効果も、基本的には上
記作用と同一であると考えられる。通常の亜鉛含有金属
めっき鋼板に、直接りん酸塩処理を施して得られる複合
体の塗装性能よりも、本発明により、りん酸亜鉛複合皮
膜上に更にりん酸塩処理を施して得られた複合体の電着
塗装性能あるいは上塗り塗装後の塗装性能がすぐれてい
ることの理由としては、析出したりん酸塩皮膜の結晶サ
イズが微細化される為、塗膜の密着性、塗装後の耐食性
等の塗装性能が向上すると考えられる。The effect of the zinc phosphate composite coating according to the present invention on the zinc-containing metal-plated steel sheet is also considered to be basically the same as the above effect. According to the present invention, the composite obtained by further performing a phosphate treatment on the zinc phosphate composite coating is less than the coating performance of a composite obtained by directly performing a phosphate treatment on a normal zinc-containing metal-plated steel sheet. The reason why the electrodeposition coating performance of the body or the coating performance after topcoating is excellent is that the crystal size of the deposited phosphate film is finer, so that the adhesion of the coating film, corrosion resistance after coating, etc. It is considered that the coating performance of the paint is improved.
【００４４】即ち、りん酸塩化成皮膜における結晶サイ
ズが微細化することにより、りん酸塩皮膜内の結晶粒子
の比表面積が増大し、塗膜に対するアンカー効果が向上
し、塗膜の密着力等の塗装性能が向上する。また結晶サ
イズが微細になることにより、りん酸塩皮膜結晶間のピ
ンホールが小さくなり、腐食環境下でもバリアー効果を
発揮するため塗装性能が一層向上するものと考えられ
る。That is, as the crystal size in the phosphate conversion coating is reduced, the specific surface area of the crystal particles in the phosphate coating is increased, the anchor effect on the coating is improved, and the adhesion of the coating is improved. The painting performance is improved. Further, it is considered that the finer crystal size reduces pinholes between the phosphate film crystals and exerts a barrier effect even in a corrosive environment, thereby further improving the coating performance.
【００４５】[0045]
【実施例】下記実施例により本発明を具体的に説明する
が、本発明の範囲はこれらの実施例により特に限定され
るものではない。EXAMPLES The present invention will be described in detail with reference to the following Examples, but the scope of the present invention is not particularly limited by these Examples.
【００４６】１．亜鉛含有金属めっき鋼板基体 （イ）市販の板厚０．８mmの両面合金化溶融亜鉛めっき
鋼板（ＧＡ材：目付け量６０ｇ／ｍ2 ）、（ロ）両面電
気亜鉛めっき鋼板（ＥＧ材：目付け量２０ｇ／ｍ2 ）、
を基体として使用した。1. Zinc-containing metal-coated steel sheet substrate (a) Commercially available double-sided galvannealed steel sheet with a thickness of 0.8 mm (GA material: basis weight 60 g / m 2 ), (b) Double-sided electrogalvanized steel sheet (EG material: basis weight) 20 g / m 2 ),
Was used as a substrate.
【００４７】２．りん酸亜鉛複合皮膜形成処理 ２．１．基体表面の清浄化 前記基体に対し、予めりん酸ナトリウム系のアルカリ脱
脂剤のファインクリーナーＬ４４８０（日本パーカライ
ジング株式会社製）を薬剤濃度１８ｇ／リットルで含む
処理液を、処理温度：４５℃、処理時間：１２０秒、の
条件下にスプレーして脱脂し、次に基体表面に残存する
アルカリ分を水道水により洗浄し基体表面を清浄化し
た。2. 2. Zinc phosphate composite film forming treatment 2.1. Cleaning of Substrate Surface The substrate was previously treated with a treatment solution containing a sodium phosphate-based alkaline degreasing agent Fine Cleaner L4480 (manufactured by Nippon Parkerizing Co., Ltd.) at a chemical concentration of 18 g / liter, at a treatment temperature of 45 ° C. and for a treatment time. : Degreasing by spraying under the conditions of 120 seconds, and then the alkali remaining on the substrate surface was washed with tap water to clean the substrate surface.
【００４８】２．２．活性化処理 〔活性化処理Ｉ〕基体に対し、チタンコロイドを含む、
市販品、プレパレンＺ（日本パーカライジング株式会社
製）を１．５ｇ／リットルの濃度で水に希釈して調製し
た処理液を、処理温度：室温、処理時間：２秒の条件下
にスプレー処理を施した。2.2. Activation treatment [Activation treatment I] The substrate contains a titanium colloid,
A commercially available product, Preparen Z (manufactured by Nippon Parkerizing Co., Ltd.), was diluted with water at a concentration of 1.5 g / liter, and was subjected to spray treatment under the conditions of treatment temperature: room temperature and treatment time: 2 seconds. did.
【００４９】〔活性化処理II〕基体に、硫酸ニッケル：
２０ｇ／リットルの水溶液を用いて、処理温度：６０
℃、処理時間：２秒の条件下にスプレー処理を施すこと
より、表面にニッケルを付着させ、次に水洗した。[Activation Treatment II] Nickel sulfate:
Using an aqueous solution of 20 g / liter, treatment temperature: 60
The nickel was adhered to the surface by spraying under the condition of 2 ° C., treatment time: 2 seconds, and then washed with water.
【００５０】〔活性化処理III 〕基体に、硝酸（６７．
５％）を２９．６ｇ／リットルの濃度に希釈した水溶液
を用いて、室温、処理時間：３秒の条件下に浸漬処理を
施して、表面の金属酸化物の上層をエッチングし、水洗
した。[Activation treatment III] Nitric acid (67.
(5%) was diluted to a concentration of 29.6 g / liter, and immersion treatment was performed at room temperature for 3 seconds to etch the upper layer of the metal oxide on the surface and wash with water.
【００５１】〔活性化処理IV〕基体に、硫酸コバルト：
３０ｇ／リットルを含む水溶液を用いて、処理温度：６
０℃、処理時間：２秒の条件下にスプレー処理を施すこ
とより、表面にコバルトを付着させ、次に水洗した。[Activation Treatment IV] Cobalt sulfate:
Using an aqueous solution containing 30 g / liter, treatment temperature: 6
Cobalt was adhered to the surface by spraying under the conditions of 0 ° C. and treatment time: 2 seconds, and then washed with water.
【００５２】２．３．りん酸亜鉛複合皮膜形成用処理液
例 〔処理液Ａ〕りん酸をＰＯ4 として２０ｇ／リットル、
硝酸をＮＯ3 として３ｇ／リットル、フッ化水素酸をフ
ッ素イオンとして１．５ｇ／リットル含有する水溶液
に、酸化亜鉛を亜鉛イオン供給源として用い、亜鉛イオ
ンとして１．３ｇ／リットル、塩基性炭酸ニッケルをニ
ッケルイオン供給源として用い、ニッケルイオンとして
０．５ｇ／リットル、炭酸マンガンをマンガンイオン供
給源として用い、マンガンイオンとして０．５ｇ／リッ
トルの濃度で添加し、炭酸ナトリウムで全酸度／遊離酸
度の比率を２１：１に調整し、更に亜硝酸ナトリウムを
供給源として用い、亜硝酸イオンとして０．３ｇ／リッ
トル含有する化成処理液を調製した。2.3. Example of treatment solution for forming zinc phosphate composite film [Treatment solution A] Phosphoric acid as PO 4 at 20 g / liter,
An aqueous solution containing 3 g / l of nitric acid as NO 3 and 1.5 g / l of hydrofluoric acid as fluorine ions, using zinc oxide as a source of zinc ions, 1.3 g / l as zinc ions, and basic nickel carbonate Was used as a source of nickel ions, 0.5 g / liter of nickel ions were used as a source of manganese carbonate, and manganese ions were added at a concentration of 0.5 g / liter of manganese ions. The ratio was adjusted to 21: 1, and a chemical conversion treatment solution containing 0.3 g / l as nitrite ions was prepared using sodium nitrite as a supply source.
【００５３】〔処理液Ｂ〕りん酸をＰＯ4 として２０ｇ
／リットル、硝酸をＮＯ3 として３ｇ／リットル、フッ
化水素酸をフッ素イオンとして１．５ｇ／リットル含有
する水溶液に、酸化亜鉛を亜鉛イオン供給源として用
い、亜鉛イオンとして２．０ｇ／リットル、塩基性炭酸
ニッケルをニッケルイオン供給源として用い、ニッケル
イオンとして２．５ｇ／リットルの濃度で添加し、炭酸
ナトリウムにより全酸度／遊離酸度の比率を１７：１に
調整し、更に亜硝酸ナトリウムを供給源として用い、亜
硝酸イオンとして０．３ｇ／リットル含有する化成処理
液を調製した。[Treatment solution B] 20 g of phosphoric acid as PO 4
Per liter, an aqueous solution containing 3 g / liter of nitric acid as NO 3 and 1.5 g / liter of hydrofluoric acid as fluorine ions, using zinc oxide as a zinc ion supply source, 2.0 g / liter as zinc ions, and a base. Nickel carbonate is used as a source of nickel ions, nickel ions are added at a concentration of 2.5 g / l, the ratio of total acidity / free acidity is adjusted to 17: 1 with sodium carbonate, and sodium nitrite is further supplied. And a chemical conversion treatment solution containing 0.3 g / liter as nitrite ion was prepared.
【００５４】〔処理液Ｃ〕りん酸をＰＯ4 として６ｇ／
リットル、硝酸をＮＯ3 として１ｇ／リットル含有する
水溶液に、酸化亜鉛を亜鉛イオン供給源として用い、亜
鉛イオンとして２．０ｇ／リットルの濃度で添加し、ま
た、硝酸ニッケルをニッケルイオン供給源として用い、
ニッケルイオンとして０．５ｇ／リットルの濃度で添加
し、陰極電解処理液を調製した。[0054] [treatment liquid C] 6g of phosphoric acid as PO 4 /
Using zinc oxide as a source of zinc ions and adding 2.0 g / liter of zinc ions to an aqueous solution containing 1 g / liter of nitric acid as NO 3 and using nickel nitrate as a source of nickel ions. ,
Nickel ions were added at a concentration of 0.5 g / liter to prepare a cathodic electrolysis solution.
【００５５】〔処理液Ｄ〕りん酸をＰＯ4 として３０ｇ
／リットル、硝酸をＮＯ3 として８ｇ／リットル、珪フ
ッ化水素酸をフッ素イオンとして２．５ｇ／リットル含
有する水溶液に、酸化亜鉛を亜鉛イオン供給源として用
い、亜鉛イオンとして１．３ｇ／リットル、硝酸マンガ
ンをマンガンイオン供給源として用いマンガンイオンと
して０．５ｇ／リットル、炭酸カルシウムをカルシウム
イオン供給源として用い、カルシウムイオンとして０．
４ｇ／リットルの濃度で添加し、炭酸ナトリウムにより
全酸度／遊離酸度の比率を９：１に調整し、更に亜硝酸
ナトリウムを供給源として用い、亜硝酸イオンとして
０．７ｇ／リットル含有する化成処理液を調製した。[Treatment solution D] 30 g of phosphoric acid as PO 4
Aqueous solution containing 8 g / l of nitric acid as NO 3 and 2.5 g / l of hydrosilicofluoric acid as fluorine ions, using zinc oxide as a source of zinc ions, 1.3 g / l as zinc ions, Manganese nitrate was used as a source of manganese ions, 0.5 g / liter of manganese ions, calcium carbonate was used as a source of calcium ions, and 0.1 g of calcium ions.
A chemical conversion treatment was carried out at a concentration of 4 g / l, adjusting the ratio of total acidity / free acidity to 9: 1 with sodium carbonate, and further using sodium nitrite as a supply source and containing 0.7 g / l as nitrite ions. A liquid was prepared.
【００５６】〔処理液Ｅ〕りん酸をＰＯ4 として５ｇ／
リットル、硝酸をＮＯ3 として２ｇ／リットル含有する
水溶液に、酸化亜鉛を亜鉛イオン供給源として用い、亜
鉛イオンとして１．０ｇ／リットル、硝酸コバルトをコ
バルトイオン供給源として用い、コバルトイオンとして
０．５ｇ／リットル、硫酸第一鉄を供給源として用い、
鉄イオンとして０．１ｇ／リットルの濃度で添加し、陰
極電解処理液を調製した。[0056] The [treatment liquid E] phosphate as PO 4 5 g /
In an aqueous solution containing 2 g / liter of nitric acid as NO 3 , zinc oxide was used as a source of zinc ions, 1.0 g / liter of zinc ions, cobalt nitrate was used as a source of cobalt ions, and 0.5 g of cobalt ions was used. Per liter, using ferrous sulfate as a source,
Iron ion was added at a concentration of 0.1 g / liter to prepare a cathodic electrolysis solution.
【００５７】〔比較液Ｆ〕りん酸をＰＯ4 として２０ｇ
／リットル、硝酸をＮＯ3 として３ｇ／リットル、フッ
化水素酸をフッ素イオンとして１．５ｇ／リットル含有
する水溶液に、酸化亜鉛を亜鉛イオン供給源として用
い、亜鉛イオンとして１．３ｇ／リットルの濃度で添加
し、炭酸ナトリウムにより全酸度／遊離酸度の比率を２
１：１に調整し、更に亜硝酸ナトリウムを供給源として
用い亜硝酸イオンとして０．３ｇ／リットル含有する化
成処理液を調製した。[Comparative solution F] 20 g of phosphoric acid as PO 4
In an aqueous solution containing 3 g / l of nitric acid as NO 3 and 1.5 g / l of hydrofluoric acid as fluoride ions, zinc oxide is used as a zinc ion supply source, and a concentration of 1.3 g / l as zinc ions. And the ratio of total acidity / free acidity to 2 with sodium carbonate.
The ratio was adjusted to 1: 1, and a chemical conversion treatment solution containing 0.3 g / l as nitrite ion was prepared using sodium nitrite as a supply source.
【００５８】〔比較液Ｇ〕りん酸をＰＯ4 として５ｇ／
リットル、硝酸をＮＯ3 として２ｇ／リットル含有する
水溶液に、酸化亜鉛を亜鉛イオン供給源として用い、亜
鉛イオンとして１．０ｇ／リットルの濃度で添加し、陰
極電解処理液を調製した。[0058] The Comparative solution G] phosphate as PO 4 5 g /
Zinc oxide was used as a zinc ion supply source at a concentration of 1.0 g / liter as a zinc ion to an aqueous solution containing 2 g / liter of nitric acid as NO 3 to prepare a cathodic electrolysis solution.
【００５９】〔比較液Ｈ〕りん酸をＰＯ4 として４ｇ／
リットル、硝酸をＮＯ3 として１６ｇ／リットル、フッ
化水素酸をフッ素イオンとして１．５ｇ／リットル含有
する水溶液に、酸化亜鉛を亜鉛イオン供給源として用
い、亜鉛イオンとして１．３ｇ／リットル、硝酸ニッケ
ルをニッケルイオン供給源として用いニッケルイオンと
して０．０４ｇ／リットルの濃度で添加し、炭酸ナトリ
ウムにより全酸度／遊離酸度の比率を２１：１に調整
し、更に亜硝酸ナトリウムを供給源として用い、亜硝酸
イオンとして０．３ｇ／リットル含有する化成処理液を
調製した。[Comparative liquid H] 4 g /
An aqueous solution containing 16 g / l of nitric acid as NO 3 and 1.5 g / l of hydrofluoric acid as fluoride ions using zinc oxide as a zinc ion supply source, 1.3 g / l as zinc ions, and nickel nitrate Was added as a nickel ion supply source at a concentration of 0.04 g / liter as nickel ions, the ratio of total acidity / free acidity was adjusted to 21: 1 with sodium carbonate, and sodium nitrite was used as a supply source. A chemical conversion treatment solution containing 0.3 g / liter as nitrate ion was prepared.
【００６０】実施例１ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材を基体として用い、これに〔活性化処理Ｉ〕を施
し、次いでこれを、温度４５℃に加温した〔処理液Ａ〕
中に１秒間浸漬し、水洗、乾燥を順次行って、表１に示
した組成、付着量のりん酸亜鉛複合皮膜を形成した。更
にこのりん酸亜鉛複合皮膜上に、下記に示す工程〜
からなるりん酸塩化成処理を施して、亜鉛含有金属めっ
き鋼板複合体を作製した。 Embodiment 1 As described in 2.1. Using the GA material purified by the method described in the section as a substrate, the substrate was subjected to [activation treatment I], and then heated to a temperature of 45 ° C. [treatment liquid A].
The coating was immersed for 1 second, washed with water and dried in this order to form a zinc phosphate composite film having the composition and the amount of adhesion shown in Table 1. Further, on this zinc phosphate composite coating,
Was applied to produce a zinc-containing metal-plated steel sheet composite.
【００６１】りん酸塩化成処理 脱脂工程 りん酸ナトリウム含有アルカリ脱脂剤（商標：ファイン
クリーナーＬ４４８０、日本パーカライジング株式会社
製）を使用し下記条件下に複合体表面を脱脂した。 ＜条件＞ 薬剤濃度：１８ｇ／リットル、処理温度：４５℃、処理
時間：１２０秒、 スプレー処理[0061] phosphate chemical conversion treatment degreasing sodium phosphate containing an alkaline degreasing agent (trademark: Fine Cleaner L4480, manufactured by Nihon Parkerizing Co., Ltd.) was degreased complex surface under the following conditions using. <Conditions> Drug concentration: 18 g / liter, treatment temperature: 45 ° C, treatment time: 120 seconds, spray treatment
【００６２】 水洗工程 脱脂処理により複合体表面に残存するアルカリ分を水道
水に洗浄し表面を清浄化した。 ＜条件＞ 処理温度：常温、処理時間：２０秒、 スプレー処理Water Washing Step The alkali remaining on the surface of the complex due to the degreasing treatment was washed with tap water to clean the surface. <Conditions> Processing temperature: normal temperature, processing time: 20 seconds, spray processing
【００６３】 表面調整工程 微アルカリ性のチタンコロイドを含有する表面調整剤
（商標：プレパレン−ＺＴＨ、日本パーカライジング株
式会社製）を用いた。 ＜条件＞ 薬剤濃度：１．５ｇ／リットル、処理温度：常温、処理
時間：２０秒、 スプレー処理Surface Conditioning Step A surface conditioner (trade name: Preparen-ZTH, manufactured by Nippon Parkerizing Co., Ltd.) containing slightly alkaline titanium colloid was used. <Conditions> Drug concentration: 1.5 g / liter, treatment temperature: normal temperature, treatment time: 20 seconds, spray treatment
【００６４】 化成処理 りん酸塩処理剤（商標：パルボンド−Ｌ３０８０、日本
パーカライジング（株）製）を用いた。 ＜条件＞ 薬剤濃度：４８ｇ／リットル、処理温度：４３℃、処理
時間：１２０秒、 ディップ処理 遊離酸度：１ポイント（処理液１０mlをサンプリング
し、指示薬ブロムフェノールブルーを用い、０．１Ｎ
ＮａＯＨにより滴定したときの値（ml）） 全酸度：２３ポイント（処理液１０mlをサンプリング
し、指示薬フェノールフタレインを用い、０．１Ｎ Ｎ
ａＯＨにより滴定した値（ml）） 反応促進剤濃度：３ポイント（サッカロメーター法）Chemical conversion treatment A phosphating agent (trade name: Palbond-L3080, manufactured by Nippon Parkerizing Co., Ltd.) was used. <Conditions> Drug concentration: 48 g / liter, treatment temperature: 43 ° C., treatment time: 120 seconds, dip treatment Free acidity: 1 point (sample 10 ml of treatment solution, use indicator bromophenol blue, 0.1N
Value when titrated with NaOH (ml)) Total acidity: 23 points (sample of 10 ml of treatment solution, 0.1N N
Value titrated with aOH (ml)) Reaction accelerator concentration: 3 points (saccharometer method)
【００６５】 水洗工程 上記化成処理により複合体表面に残存する化成処理液を
水道水にて洗浄し表面を清浄化した。 ＜条件＞ 処理温度：常温、処理時間：２０秒、 スプレー処理Water Washing Step The chemical conversion treatment solution remaining on the surface of the composite due to the above chemical conversion treatment was washed with tap water to clean the surface. <Conditions> Processing temperature: normal temperature, processing time: 20 seconds, spray processing
【００６６】 脱イオン水洗 脱イオン水により複合体表面に残存する水分中の夾雑イ
オンを洗浄した。 ＜条件＞ 処理温度：常温、処理時間：２０秒、 スプレー処理Deionized Water Washing Contaminant ions in water remaining on the surface of the composite were washed with deionized water. <Conditions> Processing temperature: normal temperature, processing time: 20 seconds, spray processing
【００６７】 乾燥 表面の水分を除去するために熱風乾燥を実施した。 ＜条件＞ 処理温度：１００℃、処理時間：１２０秒、Drying Hot air drying was performed to remove moisture on the surface. <Conditions> Processing temperature: 100 ° C., processing time: 120 seconds,
【００６８】実施例２ 実施例１において、ＧＡ材の代わりにＥＧ材を用いたこ
とを除き、実施例１と同一の処理を行ない、表１に示し
た組成、および付着量のりん酸亜鉛複合皮膜を形成し
た。次にこの複合皮膜上に実施例１と同一のりん酸塩処
理を施して、亜鉛含有金属めっき鋼板複合体を作製し
た。 Example 2 The same treatment as in Example 1 was performed except that EG material was used instead of GA material, and the zinc phosphate composite having the composition and the adhesion amount shown in Table 1 was used. A film was formed. Next, the same phosphate treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００６９】実施例３ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材を基体として用い、これに活性化処理IIを施し、
次に、この基材を温度４５℃に加温された処理液Ｂに６
秒間浸漬し、水洗、乾燥を順次行って、表１に示した組
成、および付着量のりん酸亜鉛複合皮膜を形成した。次
に、この複合皮膜上に実施例１と同一のりん酸塩化成処
理を施して、亜鉛含有金属めっき鋼板複合体を作製し
た。 Embodiment 3 As described in 2.1. Using the GA material cleaned by the method described in the section as a substrate, and performing an activation treatment II on the substrate,
Next, the base material was added to the processing solution B heated to a temperature of 45 ° C. for 6 hours.
After immersion for 2 seconds, washing with water and drying were successively performed to form a zinc phosphate composite film having the composition and the adhesion amount shown in Table 1. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００７０】実施例４ 実施例３におけるＧＡ材の代わりに基体としてＥＧ材を
用いたことを除き、実施例３と同一の処理を行ない、表
１に示した組成、および付着量のりん酸亜鉛複合皮膜を
形成した。次に、この複合皮膜上に実施例１と同一のり
ん酸塩化成処理を施し、亜鉛含有金属めっき鋼板複合体
を作製した。 Example 4 The same treatment as in Example 3 was carried out except that the EG material was used as the base in place of the GA material in Example 3, and the zinc phosphate having the composition and the adhesion amount shown in Table 1 was used. A composite coating was formed. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００７１】実施例５ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材を基体として用い、かつこれを陰極として用い、
炭素板を陽極として用いて、温度４０℃に加温された処
理液Ｃ中において、電流密度９Ａ／dm2 の条件下に２秒
間陰極電解処理を施し、これを水洗、乾燥を順次行な
い、表１に示した組成、および付着量のりん酸亜鉛複合
皮膜を形成した。次に、この複合皮膜上に実施例１と同
一のりん酸塩化成処理を施して、亜鉛含有金属めっき鋼
板複合体を作製した。 Embodiment 5 The procedure described in 2.1. Using the GA material cleaned by the method described in section as a base, and using this as a cathode,
Using a carbon plate as an anode, in a treatment solution C heated to a temperature of 40 ° C., a cathodic electrolysis treatment is performed for 2 seconds under a condition of a current density of 9 A / dm 2 , and this is sequentially washed with water and dried. A zinc phosphate composite film having the composition and the amount of adhesion shown in No. 1 was formed. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００７２】実施例６ 実施例５において、ＧＡ材の代わりに、基体としてＥＧ
材を用いたことを除き、実施例５と同一の陰極電解処理
を施して表１に示した組成、および付着量のりん酸亜鉛
複合皮膜を形成した。次にこの複合皮膜上に実施例１と
同一のりん酸塩化成処理を施して、亜鉛含有金属めっき
鋼板複合体を作製した。 Example 6 In Example 5, EG was used as the base instead of the GA material.
Except that the material was used, the same cathodic electrolysis treatment as in Example 5 was performed to form a zinc phosphate composite film having the composition and the adhesion amount shown in Table 1. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００７３】実施例７ 予め前記２．１．項に記載された方法により清浄化され
たＧＡ材を基体として用い、これに活性化処理III を施
し、次に、これに、温度５０℃に加温された処理液Ｄに
１秒間浸漬し、水洗、乾燥して、表１に示した組成、お
よび付着量のりん酸亜鉛複合皮膜を形成した。次に、こ
の複合皮膜上に実施例１と同一のりん酸塩化成処理を施
して、亜鉛含有金属めっき鋼板複合体を作製した。 Embodiment 7 As described in 2.1. Using the GA material cleaned by the method described in the section as a substrate, performing an activation treatment III thereon, and then immersing the GA material in a treatment liquid D heated to a temperature of 50 ° C. for 1 second, After washing with water and drying, a zinc phosphate composite film having the composition and the adhesion amount shown in Table 1 was formed. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００７４】実施例８ 実施例７に記載のＧＡ材に替えて、基体としてＥＧ材を
用いたことを除き、実施例７と同一の処理を施し、表１
に示した組成、および付着量のりん酸亜鉛複合皮膜を形
成した。次に、この複合皮膜上に実施例１と同一のりん
酸塩化成処理を施して、亜鉛含有金属めっき鋼板複合体
を作製した。 Example 8 The same treatment as in Example 7 was performed except that an EG material was used as the base instead of the GA material described in Example 7, and Table 1 was used.
A zinc phosphate composite film having the composition and the amount of adhesion shown in Table 2 was formed. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００７５】実施例９ 予め前記２．１．項に記載した方法により清浄されたＧ
Ａ材を基体としてかつこれを陰極として用い、炭素板を
陽極に用い、温度５０℃に加温された処理液Ｅ中で、電
流密度６Ａ／dm2 、６秒間の陰極電解処理を行ない、水
洗、乾燥して、表１に示した組成、および付着量のりん
酸亜鉛複合皮膜を形成した。次に、これに実施例１と同
一のりん酸塩化成処理を施して、亜鉛含有金属めっき鋼
板複合体を作製した。 Embodiment 9 As described in 2.1. G purified by the method described in the paragraph
A material was used as a base and this was used as a cathode, a carbon plate was used as an anode, and a cathodic electrolysis treatment was performed at a current density of 6 A / dm 2 for 6 seconds in a treatment solution E heated to a temperature of 50 ° C. After drying, a zinc phosphate composite film having the composition and the adhesion amount shown in Table 1 was formed. Next, this was subjected to the same phosphate chemical conversion treatment as in Example 1 to produce a zinc-containing metal-plated steel sheet composite.
【００７６】実施例１０ 実施例９に記載のＧＡ材に替えて、基体としてＥＧ材を
用い、その他は実施例９と同一の陰極電解処理を施し、
表１に示した組成、および付着量のりん酸亜鉛複合皮膜
を形成した。この複合皮膜に実施例１と同一のりん酸塩
化成処理を施して、亜鉛含有金属めっき鋼板複合体を作
製した。 Example 10 Instead of the GA material described in Example 9, an EG material was used as a base, and the same cathodic electrolysis treatment as in Example 9 was performed, except that
A zinc phosphate composite film having the composition and the amount shown in Table 1 was formed. This composite coating was subjected to the same phosphate chemical conversion treatment as in Example 1 to produce a zinc-containing metal-plated steel sheet composite.
【００７７】実施例１１ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材を基体として用い、この基材を、温度５０℃に加
温された処理液Ａ中に３秒間浸漬し、水洗、乾燥して、
表１に示した組成、および付着量のりん酸亜鉛複合皮膜
を形成した。次に、この複合皮膜上に実施例１と同一の
りん酸塩化成処理を施して、亜鉛含有金属めっき鋼板複
合体を作製した。 Embodiment 11 As described in 2.1. Using the GA material cleaned by the method described in the section as a substrate, the substrate was immersed in a treatment liquid A heated to a temperature of 50 ° C. for 3 seconds, washed with water, and dried.
A zinc phosphate composite film having the composition and the amount shown in Table 1 was formed. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００７８】実施例１２ 実施例１１におけるＧＡ材に替えて、基体としてＥＧ材
を用いたことを除き、他は実施例１１と同一の処理を施
して、表１に示した組成、および付着量のりん酸亜鉛複
合皮膜を形成した。この複合皮膜上に実施例１と同一の
りん酸塩化成処理を施して、亜鉛含有金属めっき鋼板複
合体を作製した。 Example 12 Except that the EG material was used as the substrate in place of the GA material in Example 11, the same treatment as in Example 11 was performed except that the composition and the adhesion amount shown in Table 1 were used. A zinc phosphate composite film was formed. The same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００７９】実施例１３ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材を基体としてかつ陰極として用い、炭素板を陽極
に用い、温度３５℃に加温された処理液Ｃ中において、
電流密度３Ａ／dm2 、９秒間の陰極電解処理を施し、水
洗、乾燥を順次行って表１に示した組成、および付着量
のりん酸亜鉛複合皮膜を形成した。次に、この複合皮膜
上に実施例１と同一のりん酸塩化成処理を施して、亜鉛
含有金属めっき鋼板複合体を作製した。 Embodiment 13 As described in 2.1. In the treatment liquid C heated to a temperature of 35 ° C., using the GA material cleaned by the method described in the section as a base and a cathode, using a carbon plate as an anode,
A cathodic electrolysis treatment was performed at a current density of 3 A / dm 2 for 9 seconds, followed by washing with water and drying in that order to form a zinc phosphate composite film having the composition and the adhesion amount shown in Table 1. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００８０】実施例１４ 実施例１３におけるＧＡ材に替えて、基体としてＥＧ材
を用いたことを除き、実施例１３と同一の陰極電解処理
を施し、表１に示した組成、および付着量のりん酸亜鉛
複合皮膜を形成した。次にこの複合皮膜に実施例１と同
一のりん酸塩化成処理を施して、亜鉛含有金属めっき鋼
板複合体を作製した。 Example 14 The same cathodic electrolysis treatment as in Example 13 was performed, except that the EG material was used as the base instead of the GA material in Example 13, and the composition and the adhesion amount shown in Table 1 were measured. A zinc phosphate composite coating was formed. Next, the same phosphate conversion treatment as in Example 1 was applied to this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００８１】実施例１５ 予め前記２．１．項に記載した方法により清浄されたＧ
Ａ材を基体としてかつ陰極として用い、炭素板を陽極に
用い、温度４５℃に加温された処理液Ｅ中で、電流密度
１５Ａ／dm2 、２秒間の陰極電解処理を施し、水洗、乾
燥を順次行い表１に示した組成、および付着量のりん酸
亜鉛複合皮膜を形成した。次に、この複合皮膜上に実施
例１と同一のりん酸塩化成処理を施して、亜鉛含有金属
めっき鋼板複合体を作製した。 Embodiment 15 As described in 2.1. G purified by the method described in the paragraph
A material was used as a base and a cathode, and a carbon plate was used as an anode. In a treatment solution E heated to a temperature of 45 ° C., a current density of 15 A / dm 2 was subjected to cathodic electrolysis for 2 seconds, followed by washing with water and drying. Were successively performed to form a zinc phosphate composite film having the composition and the adhesion amount shown in Table 1. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００８２】実施例１６ 実施例１５に記載のＧＡ材に替えて、基体としてＥＧ材
を用いたことを除き、実施例１５と同一の陰極電解処理
を施し、表１に示した組成、および付着量のりん酸亜鉛
複合皮膜を形成した。次にこの複合皮膜上に実施例１と
同一のりん酸塩化成処理を施して、亜鉛含有金属めっき
鋼板複合体を作製した。 Example 16 The same cathodic electrolysis treatment as in Example 15 was performed, except that the EG material was used as the base instead of the GA material described in Example 15, and the composition and the adhesion shown in Table 1 were obtained. A quantity of zinc phosphate composite coating was formed. Next, the same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００８３】実施例１７ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材を基体として用い、これに活性化処理IVを施し、
次に、温度４５℃に加温された処理液Ａに１秒間浸漬
し、水洗、乾燥を順次行い、表１に示した組成、および
付着量のりん酸亜鉛複合皮膜を形成した。この複合皮膜
上に実施例１と同一のりん酸塩化成処理を施して、亜鉛
含有金属めっき鋼板複合体を作製した。 Embodiment 17 As described in 2.1. Using the GA material cleaned by the method described in section as a base, performing an activation treatment IV thereon,
Next, it was immersed in the treatment liquid A heated to a temperature of 45 ° C. for 1 second, washed with water, and dried in order to form a zinc phosphate composite film having the composition and the adhesion amount shown in Table 1. The same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００８４】実施例１８ 実施例１７に記載のＧＡ材に替えてＥＧ材を基材として
用いたことを除き、実施例１７と同一の化成処理を施
し、表１に示した組成、および付着量のりん酸亜鉛複合
皮膜を形成した。この複合皮膜上に実施例１と同一のり
ん酸塩化成処理を施して、亜鉛含有金属めっき鋼板複合
体を作製した。 Example 18 The same chemical conversion treatment as in Example 17 was carried out, except that the EG material was used as the base material instead of the GA material described in Example 17, and the composition and the adhesion amount shown in Table 1 were obtained. A zinc phosphate composite film was formed. The same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００８５】比較例１ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材を基体として用い、これに活性化処理Ｉを施し、
次に、温度５０℃に加温された比較液Ｆ中に３秒間浸漬
し、水洗、乾燥を順次行い、表１に示した組成、および
付着量のりん酸亜鉛皮膜を形成した。この皮膜上に実施
例１と同一のりん酸塩化成処理を施して、亜鉛含有金属
めっき鋼板複合体を作製した。 Comparative Example 1 As described in 2.1. Using a GA material cleaned by the method described in the section as a substrate, and performing an activation treatment I,
Next, it was immersed in a comparative solution F heated to a temperature of 50 ° C. for 3 seconds, washed with water, and dried in order to form a zinc phosphate film having the composition and the amount of adhesion shown in Table 1. The same phosphate conversion treatment as in Example 1 was performed on this film to produce a zinc-containing metal-plated steel sheet composite.
【００８６】比較例２ 予め前記２．１．項に記載された方法により清浄化され
たＧＡ材を基体としてかつ陰極として用い、炭素板を陽
極に用い、これを温度４５℃に加温された比較液Ｇ中
で、電流密度１５Ａ／dm2 、２秒間の陰極電解処理を施
し、水洗、乾燥を順次行い、表１に示した組成、および
付着量のりん酸亜鉛皮膜を形成した。この皮膜上に実施
例１と同一のりん酸塩化成処理を施して、亜鉛含有金属
めっき鋼板複合体を作製した。 Comparative Example 2 As described in 2.1. The GA material cleaned according to the method described in the above section was used as a base and as a cathode, and a carbon plate was used as an anode, and this was subjected to a current density of 15 A / dm 2 in a comparative solution G heated to a temperature of 45 ° C. After performing a cathodic electrolysis treatment for 2 seconds, washing with water and drying were sequentially performed to form a zinc phosphate film having the composition and the adhesion amount shown in Table 1. The same phosphate conversion treatment as in Example 1 was performed on this film to produce a zinc-containing metal-plated steel sheet composite.
【００８７】比較例３ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材を基体として用い、これに活性化処理III を施
し、次に温度４５℃に加温された比較液Ｈ中に６秒間浸
漬し、水洗、乾燥を順次行い、表１に示した組成、およ
び付着量のりん酸亜鉛複合皮膜を形成した。この複合皮
膜上に実施例１と同一のりん酸塩化成処理を施して、亜
鉛含有金属めっき鋼板複合体を作製した。 Comparative Example 3 As described in 2.1. Using a GA material cleaned by the method described in the section as a substrate, the substrate was subjected to an activation treatment III, and then immersed in a comparative solution H heated to a temperature of 45 ° C. for 6 seconds, washed with water, and dried. This was performed in order to form a zinc phosphate composite film having the composition and the adhesion amount shown in Table 1. The same phosphate conversion treatment as in Example 1 was performed on this composite film to produce a zinc-containing metal-plated steel sheet composite.
【００８８】比較例４ 比較例１に記載のＧＡ材に替えて、基体としてＥＧ材を
用いたことを除き、比較例１と同一の化成処理を施し、
表１に示した組成、および付着量のりん酸亜鉛皮膜を形
成した。次にこの皮膜上に実施例１と同一のりん酸塩化
成処理を施して、亜鉛含有金属めっき鋼板複合体を作製
した。 Comparative Example 4 The same chemical conversion treatment as in Comparative Example 1 was performed, except that the EG material was used as the base instead of the GA material described in Comparative Example 1.
A zinc phosphate film having the composition and the adhesion amount shown in Table 1 was formed. Next, the same phosphate conversion treatment as in Example 1 was performed on this film to produce a zinc-containing metal-plated steel sheet composite.
【００８９】比較例５ 比較例２に記載のＧＡ材に替えて、基体としてＥＧ材を
用いた。このＥＧ材に比較例２と同一の電解処理を施
し、表１に示した組成、および付着量のりん酸亜鉛皮膜
を形成した。次にこの皮膜上に実施例１と同一のりん酸
塩化成処理を施して、亜鉛含有金属めっき鋼板複合体を
作製した。 Comparative Example 5 Instead of the GA material described in Comparative Example 2, an EG material was used as a base. This EG material was subjected to the same electrolytic treatment as in Comparative Example 2 to form a zinc phosphate film having the composition and the adhesion amount shown in Table 1. Next, the same phosphate conversion treatment as in Example 1 was performed on this film to produce a zinc-containing metal-plated steel sheet composite.
【００９０】比較例６ 予め前記２．１．項に記載した方法により清浄化された
ＧＡ材に、直接に実施例１と同一のりん酸塩化成処理を
施した。 Comparative Example 6 The above 2.1. The same phosphate conversion treatment as in Example 1 was directly applied to the GA material cleaned by the method described in the section.
【００９１】比較例７ 予め前記２．１．項に記載した方法により清浄化された
ＥＧ材に、直接に実施例１と同一のりん酸塩化成処理を
施した。 Comparative Example 7 As described in 2.1. The same phosphate conversion treatment as in Example 1 was directly applied to the EG material cleaned by the method described in the section.
【００９２】前記実施例、および比較例により作成され
た亜鉛含有金属めっき鋼板複合体を、下記の特性試験に
供した。The zinc-containing metal-coated steel sheet composites prepared in the above Examples and Comparative Examples were subjected to the following characteristic tests.
【００９３】３．１．皮膜特性 ３．１．１．りん酸亜鉛複合皮膜重量 りん酸亜鉛複合皮膜の重量は、下記に示す方法により測
定した。 （１）予め、精密天秤により試験片の重量（Ｗ１：ｇ）
を測定しておき、この試験片を重クロム酸アンモニウム
２０ｇ／リットル、２５％アンモニア水４９０ｇ／リッ
トルを含む脱イオン水溶液中に、常温で１５分間浸漬を
して、りん酸亜鉛複合皮膜を除去した。 （２）試験片に水洗を施してこれに残存している重クロ
ム酸アンモニウム水溶液を除去し、乾燥した。 （３）再度、精密天秤により試験片の重量（Ｗ２：ｇ）
を測定し、その重量差（Ｗ１−Ｗ２）より単位面積当り
の皮膜重量を算出した。 （４）更に皮膜重量測定に使用した重クロム酸アンモニ
ウム水溶液中に溶解した亜鉛イオン及び鉄イオンを原子
吸光分析法により定量し、複合皮膜の単位面積当りに含
まれる亜鉛量及び鉄量を算出した。3.1. Film properties 3.1.1. Weight of zinc phosphate composite coating The weight of the zinc phosphate composite coating was measured by the following method. (1) Weight of test piece (W1: g) previously measured by a precision balance
Was measured, and this test piece was immersed in a deionized aqueous solution containing 20 g / l of ammonium bichromate and 490 g / l of 25% aqueous ammonia at room temperature for 15 minutes to remove the zinc phosphate composite film. . (2) The test piece was washed with water to remove the remaining aqueous solution of ammonium bichromate and dried. (3) Weight of the test piece again using a precision balance (W2: g)
Was measured, and the film weight per unit area was calculated from the weight difference (W1-W2). (4) Further, zinc ions and iron ions dissolved in the aqueous solution of ammonium bichromate used for the film weight measurement were quantified by atomic absorption spectrometry, and the amounts of zinc and iron contained per unit area of the composite film were calculated. .
【００９４】３．１．２．りん酸亜鉛複合皮膜組成比 りん酸亜鉛複合皮膜中の亜鉛、鉄以外の成分を蛍光Ｘ線
法により各々を測定し（mg／ｍ2 ）、その時の皮膜重量
中の含有率を算出した。3.1.2. Composition Ratio of Zinc Phosphate Composite Film Components other than zinc and iron in the zinc phosphate composite film were each measured by a fluorescent X-ray method (mg / m 2 ), and the content in the film weight at that time was calculated.
【００９５】３．１．３．りん酸塩処理後の皮膜の結晶
サイズ 二次電子線像を観察し、皮膜の結晶サイズの観察を行っ
た。3.1.3. Crystal size of film after phosphate treatment A secondary electron beam image was observed to observe the crystal size of the film.
【００９６】３．２．塗装性能試験 ３．２．１．試験片作製 実施例１〜１８、比較例１〜７において作成された亜鉛
含有金属めっき鋼板複合体に下記工程により塗装を施
し、試験片を作製した。3.2. Painting performance test 3.2.1. Preparation of Test Pieces The zinc-containing metal-plated steel sheet composites prepared in Examples 1 to 18 and Comparative Examples 1 to 7 were coated by the following steps to prepare test pieces.
【００９７】ａ）電着塗装 関西ペイント社製の自動車用カチオン電着塗料（商標：
ＥＬ−２０００）を用いて実施した。 ＜条件＞ 処理温度：３０℃、設定電圧：２００Ｖ、通常時間：３
分、膜厚：２０μｍA) Electrodeposition coating Cationic electrodeposition coating for automobiles (trade name: manufactured by Kansai Paint Co., Ltd.)
EL-2000). <Conditions> Processing temperature: 30 ° C., set voltage: 200 V, normal time: 3
Min, film thickness: 20 μm
【００９８】ｂ）焼付け 熱風乾燥により焼付けを実施した。 ＜条件＞ 処理温度：１７０℃、処理時間：２０分B) Baking Baking was performed by hot air drying. <Conditions> Processing temperature: 170 ° C, processing time: 20 minutes
【００９９】ｃ）中塗り塗装 関西ペイント社製の自動車用中塗り塗料（商標：ＴＰ−
３７）を用いて実施した。 ＜条件＞ 処理温度：常温、スプレー処理、膜厚：４０μｍC) Intermediate coating An intermediate coating for automobiles manufactured by Kansai Paint Co., Ltd. (trademark: TP-
37). <Conditions> Treatment temperature: normal temperature, spray treatment, film thickness: 40 μm
【０１００】ｄ）焼付け 熱風乾燥により焼付けを実施した。 ＜条件＞ 処理温度：１４０℃、処理時間：３０分D) Baking Baking was performed by hot air drying. <Conditions> Processing temperature: 140 ° C, processing time: 30 minutes
【０１０１】ｅ）上塗り塗装 関西ペイント社製の自動車用上塗り塗料（商標：ネオ６
０００）を用いて実施した。 ＜条件＞ 処理温度：常温、スプレー処理、膜厚：４０μｍE) Topcoat Paint for automobiles manufactured by Kansai Paint Co., Ltd. (trademark: Neo-6)
000). <Conditions> Treatment temperature: normal temperature, spray treatment, film thickness: 40 μm
【０１０２】ｆ）焼付け 熱風乾燥により焼付けを行った。 ＜条件＞ 処理温度：１４０℃、処理時間：３０分F) Baking Baking was performed by hot air drying. <Conditions> Processing temperature: 140 ° C, processing time: 30 minutes
【０１０３】３．２．２．電着塗装後耐食性試験 電着塗装後の試験片にＮＴカッターによりクロスカット
を入れ、この試験片を５％ＮａＣｌ溶液中に５５℃にお
いて１０日間浸漬した。クロスカット部に発生した膨れ
部をセロハンテープにより剥離し、その片側最大膨れ幅
（mm）を測定した。3.2.2. Corrosion resistance test after electrodeposition coating A test piece after electrodeposition coating was cross-cut with an NT cutter, and the test piece was immersed in a 5% NaCl solution at 55 ° C. for 10 days. The swollen portion generated at the cross cut portion was peeled off with a cellophane tape, and the maximum swollen width (mm) on one side was measured.
【０１０４】３．２．３．上塗り塗装後耐水二次密着性
試験 上塗り塗装後、脱イオン水中に４０℃において１０日間
浸漬後、この試験片にＮＴカッターにより１mm角の碁盤
目を切り、これにセロハンテープによる剥離処理を施
し、剥離個数を測定した。3.2.3. After top coating, water resistance secondary adhesion test After top coating, after immersing in deionized water at 40 ° C. for 10 days, the test piece was cut into a 1 mm square grid with an NT cutter, and subjected to a peeling treatment with cellophane tape. The peeled number was measured.
【０１０５】表１に、上記実施例および比較例において
用いられた活性化処理、およびりん酸亜鉛複合皮膜形成
用処理に用いられた処理液組成、濃度、および処理条件
を示す。Table 1 shows the compositions, concentrations, and processing conditions of the processing solutions used in the activation processing and the processing for forming the zinc phosphate composite film used in the above Examples and Comparative Examples.
【表１】 [Table 1]
【０１０６】表２に、上記実施例、および比較例におけ
る供試鋼材の種類、活性化処理の種類、りん酸亜鉛複合
皮膜形成用処理液の種類、温度、処理方法、処理時間を
示す。Table 2 shows the types of test specimens, the types of activation treatments, the types of treatment solutions for forming a zinc phosphate composite film, the temperatures, the treatment methods, and the treatment times in the above Examples and Comparative Examples.
【表２】 [Table 2]
【０１０７】表３に、上記実施例および比較例により得
られたりん酸亜鉛複合皮膜の組成、りん酸亜鉛化成皮膜
の結晶サイズおよび塗装性能試験結果を示す。Table 3 shows the composition of the zinc phosphate composite coating obtained in the above Examples and Comparative Examples, the crystal size of the zinc phosphate conversion coating, and the results of coating performance tests.
【表３】 [Table 3]
【０１０８】表３に示された結果から明らかなように、
本発明の実施例１〜１８により得られためっき鋼板複合
体は、電着塗装後の耐食性試験、上塗り塗装後の耐水二
次密着性試験においてともに良好な結果を示した。しか
し比較例１〜７においては、全ての試験が良好なもの
は、一つもなく、上塗り塗装後の耐水二次密着性試験の
結果は、実施例の結果よりもかなり不良であった。As is clear from the results shown in Table 3,
The plated steel sheet composites obtained in Examples 1 to 18 of the present invention showed good results in both a corrosion resistance test after electrodeposition coating and a water resistance secondary adhesion test after top coating. However, in Comparative Examples 1 to 7, none of the tests were good, and the result of the water-resistant secondary adhesion test after the top coat was considerably poorer than the result of the example.
【０１０９】[0109]
【発明の効果】本発明は、従来より問題のあった亜鉛含
有金属めっき鋼板のウェットな環境下における塗装後の
耐食性、塗膜の密着性等の塗膜性能の低下を、りん酸亜
鉛複合皮膜を形成し、更にその上にりん酸塩化成処理に
より形成された微細化成皮膜を形成することにより、り
ん酸塩処理単独では不十分であった塗装性能を補強する
ことが可能となり、高品質の亜鉛含有金属めっき鋼板複
合体を、低コストで効率よく製造することが可能となっ
た。りん酸亜鉛複合皮膜は、汎用性も高く、リサイクル
性を考慮しても広範囲の工業分野に適応可能な有用なも
のである。According to the present invention, a zinc phosphate composite coating is used to reduce the deterioration of coating performance such as corrosion resistance and coating adhesion in a wet environment of a zinc-containing metal-plated steel sheet which has been a problem. By forming a fine chemical conversion film formed by a phosphate conversion treatment thereon, it is possible to reinforce the coating performance that was insufficient with the phosphate treatment alone, and to obtain a high quality It has become possible to efficiently manufacture a zinc-containing metal-plated steel sheet composite at low cost. The zinc phosphate composite coating has high versatility and is useful in a wide range of industrial fields even in consideration of recyclability.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ２５Ｄ 11/36 Ｃ２５Ｄ 11/36 Ｃ (72)発明者 田中 淳夫 愛知県豊田市トヨタ町１番地 トヨタ自 動車株式会社内 (72)発明者 近田 滋 愛知県豊田市トヨタ町１番地 トヨタ自 動車株式会社内 (72)発明者 川口 博史 愛知県豊田市トヨタ町１番地 トヨタ自 動車株式会社内 (56)参考文献 特開 昭60−211080（ＪＰ，Ａ) 特表 平６−506263（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 22/00 - 22/86 C23C 2/28 C23C 28/00 C23F 15/00 C25D 11/36 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI C25D 11/36 C25D 11/36 C (72) Inventor Atsushi Tanaka 1st Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72 ) Inventor Shigeru Chikada 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (72) Inventor Hiroshi Kawaguchi 1 Toyota Town Toyota City, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (56) References JP-A 60-1985 211080 (JP, A) Special table Hei 6-506263 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C23C 22/00-22/86 C23C 2/28 C23C 28/00 C23F 15/00 C25D 11/36
Claims (10)
と、その表面に形成され、亜鉛とりんとを重量比（亜鉛
／りん）２．５０４：１〜３．１６６：１で含み、且
つ、鉄、コバルト、ニッケル、カルシウム、マグネシウ
ム及びマンガンから選ばれた１種以上の金属を０．０６
〜９．０重量％の含有率で含有するりん酸亜鉛複合皮膜
と、このりん酸亜鉛複合皮膜上に形成され、かつ微小な
結晶サイズを有するりん酸塩化成皮膜を有することを特
徴とする塗装性に優れた亜鉛含有金属めっき鋼板複合
体。1. A substrate made of a zinc-containing metal-plated steel sheet, and formed on the surface thereof, containing zinc and phosphorus in a weight ratio (zinc / phosphorus) of 2.504: 1 to 3.166: 1, and containing iron, One or more metals selected from cobalt, nickel, calcium, magnesium and manganese are added at 0.06
A zinc phosphate composite coating having a content of about 9.0% by weight and a phosphate conversion coating formed on the zinc phosphate composite coating and having a fine crystal size. A zinc-containing metal-plated steel sheet composite with excellent resistance.
びマンガンから選ばれた少なくとも１種の金属を１．０
〜９．０重量％の含有率で含有する、請求項１に記載の
亜鉛含有金属めっき鋼板複合体。2. The method according to claim 1, wherein the zinc phosphate composite coating contains at least one metal selected from nickel and manganese in an amount of 1.0%.
The zinc-containing metal-plated steel sheet composite according to claim 1, which is contained at a content of about 9.0% by weight.
３〜３．０ｇ／ｍ2である、請求項１に記載の亜鉛含有
金属めっき鋼板複合体。3. The method according to claim 1, wherein the zinc phosphate composite film has an adhesion amount of 0.5.
The zinc-containing metal-plated steel sheet composite according to claim 1, which has a weight of 3 to 3.0 g / m 2 .
微細化された結晶サイズを有する請求項１に記載の亜鉛
含有金属めっき鋼板複合体。4. The zinc-containing metal-coated steel sheet composite according to claim 1, wherein said phosphate conversion coating has a refined crystal size of 1 to 12 μm.
板複合体を製造するために、亜鉛含有金属めっき鋼板の
表面に、下記成分（１）〜（４）： （１）りん酸イオン ５〜３０ｇ／リットル （２）硝酸イオン １．０〜１５ｇ／リットル （３）亜鉛イオン ０．１〜８．０ｇ／リットル （４）鉄イオン、ニッケルイオン、マンガ ンイオン、コバルトイオン、カルシ ウムイオン、およびマグネシウムイ オンから選ばれた少なくとも１種の 金属イオン ０．１〜８．０ｇ／リットル を含有し、かつ前記亜鉛イオンの、前記他の全金属イオ
ンに対する重量比が０．１：１〜１０：１である電解め
っき液による陰極電解処理を施して、前記りん酸亜鉛複
合皮膜を形成し、このりん酸亜鉛複合皮膜上にりん酸塩
化成処理を施して前記微細な結晶サイズを有するりん酸
塩化成皮膜を形成することを特徴とする、塗装性に優れ
た亜鉛含有金属めっき鋼板複合体の製造方法。5. In order to produce the zinc-containing metal-plated steel sheet composite according to claim 1, the following components (1) to (4) are added to the surface of the zinc-containing metal-plated steel sheet: (1) phosphate ion 5 Up to 30 g / l (2) nitrate ion 1.0-15 g / l (3) zinc ion 0.1-8.0 g / l (4) iron ion, nickel ion, manganese ion, cobalt ion, calcium ion, and magnesium At least one metal ion selected from the group consisting of ions and 0.1 to 8.0 g / liter, and the weight ratio of the zinc ions to the total other metal ions is 0.1: 1 to 10: 1. Is subjected to a cathodic electrolysis treatment with an electrolytic plating solution which is the same as above, to form the zinc phosphate composite film, and a phosphate conversion treatment is performed on the zinc phosphate composite film to form the fine crystal size. Phosphorus and forming an acid chloride conversion coating method excellent zinc-containing metal-plated steel sheet complex paintability with.
dm2 の電流密度において施される、請求項５に記載の亜
鉛含有金属めっき鋼板複合体の製造方法。6. The method according to claim 1, wherein the cathodic electrolysis treatment is performed at 0.2 to 30 A /
applied at a current density of dm 2, the manufacturing method of the zinc-containing metal-plated steel sheet composite according to claim 5.
板複合体を製造するために、亜鉛含有金属めっき鋼板の
表面に、下記成分（１）〜（４）： （１）りん酸イオン １０〜３０ｇ／リットル （２）硝酸イオン １．０〜１５ｇ／リットル （３）亜鉛イオン ０．１〜８．０ｇ／リットル （４）鉄イオン、ニッケルイオン、マンガ ンイオン、コバルトイオン、カルシ ウムイオン、およびマグネシウムイ オンから選ばれた少なくとも１種の 金属イオン ０．１〜８．０ｇ／リットル を含有し、かつ前記亜鉛イオンの、前記他の全金属イオ
ンに対する重量比が１：１０〜１０：１であり、かつ、
過酸化物、フッ化物イオン、錯フッ化物イオン、および
亜硝酸イオンから選ばれた少なくとも１種からなる反応
促進剤を更に含む化成処理液を、接触させて、前記りん
酸亜鉛複合皮膜を形成し、このりん酸亜鉛複合皮膜上
に、りん酸塩化成処理を施して前記微細な結晶サイズを
有するりん酸塩化成皮膜を形成することを特徴とする、
塗装性に優れた亜鉛含有金属めっき鋼板複合体の製造方
法。7. In order to produce the zinc-containing metal-plated steel sheet composite according to claim 1, the following components (1) to (4) are added to the surface of the zinc-containing metal-plated steel sheet: Up to 30 g / l (2) nitrate ion 1.0-15 g / l (3) zinc ion 0.1-8.0 g / l (4) iron ion, nickel ion, manganese ion, cobalt ion, calcium ion, and magnesium At least one metal ion selected from the group consisting of ions and 0.1 to 8.0 g / liter, and the weight ratio of the zinc ions to the total other metal ions is 1:10 to 10: 1. ,And,
A chemical conversion treatment solution further containing a reaction accelerator comprising at least one selected from peroxides, fluoride ions, complex fluoride ions, and nitrite ions is contacted to form the zinc phosphate composite film. Forming a phosphate conversion coating having the fine crystal size by subjecting the zinc phosphate composite coating to a phosphate conversion treatment.
A method for producing a zinc-containing metal-plated steel sheet composite having excellent paintability.
が、０．０１〜８．０ｇ／リットル〔但し、フッ化物イ
オンおよび錯フッ化物イオンの場合、フッ素イオン量に
換算する〕の濃度で含まれる、請求項７に記載の亜鉛含
有金属めっき鋼板複合体の製造方法。8. The concentration of the reaction accelerator in the chemical conversion treatment solution of 0.01 to 8.0 g / liter (however, in the case of fluoride ions and complex fluoride ions, the concentration is converted to the amount of fluorine ions). The method for producing a zinc-containing metal-plated steel sheet composite according to claim 7, which is included in:
微細化された結晶サイズを有する、請求項５、又は７に
記載の亜鉛含有金属めっき鋼板複合体。9. The zinc-containing metal-coated steel sheet composite according to claim 5, wherein the phosphate conversion coating has a refined crystal size of 1 to 12 μm.
に、予め、 （イ）ニッケルイオンおよびコバルトイオンから選ばれ
た少なくとも１種の金属を含む処理液で処理して、前記
表面上に、前記少なくとも１種の金属を０．２〜５０mg
／ｍ2 の金属付着量で付着させる活性化処理、 （ロ）チタンコロイド水性液で処理する活性化処理、又
は （ニ）エッチング処理液で金属酸化物を除去する活性処
理、を施す、請求項５又は７に記載の方法。10. The surface of the zinc-containing metal-plated steel sheet is previously treated with (a) a treatment solution containing at least one metal selected from nickel ions and cobalt ions, and 0.2 to 50 mg of one metal
An activation treatment for depositing with a metal adhesion amount of / m 2 , (b) an activation treatment for treating with an aqueous titanium colloid solution, or (d) an activation treatment for removing metal oxides with an etching treatment solution. 8. The method according to 5 or 7.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06144735A JP3137535B2 (en) | 1994-06-27 | 1994-06-27 | Zinc-containing metal-coated steel sheet composite excellent in coatability and method for producing the same |
| EP94308277A EP0653502A3 (en) | 1993-11-11 | 1994-11-10 | Zinc-containing metal-plated composite steel article and method of producing the same. |
| KR1019940029625A KR100215263B1 (en) | 1993-11-11 | 1994-11-11 | Zinc containing metal plated composite steel article and method of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06144735A JP3137535B2 (en) | 1994-06-27 | 1994-06-27 | Zinc-containing metal-coated steel sheet composite excellent in coatability and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0813154A JPH0813154A (en) | 1996-01-16 |
| JP3137535B2 true JP3137535B2 (en) | 2001-02-26 |
Family
ID=15369133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06144735A Expired - Fee Related JP3137535B2 (en) | 1993-11-11 | 1994-06-27 | Zinc-containing metal-coated steel sheet composite excellent in coatability and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3137535B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144577A (en) * | 2019-06-24 | 2019-08-20 | 浙江日星标准件有限公司 | A kind of medium carbon alloy steel bolt metal non-phosphate film processing method |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3677000A (en) * | 1999-04-12 | 2000-11-14 | Toyo Kohan Co. Ltd. | Method for production of surface treated steel sheet, surface treated steel sheet, and surface treated steel sheet coated with resin comprising surface treated steel sheet and organic resin coating the steel sheet |
| JP4720830B2 (en) * | 1999-07-08 | 2011-07-13 | Ｊｆｅスチール株式会社 | Method for producing galvanized steel sheet with excellent perforation resistance and press workability |
| JP2001131763A (en) * | 1999-11-09 | 2001-05-15 | Nippon Steel Corp | Organic composite galvanized steel sheet |
| JP2003056645A (en) * | 2001-08-10 | 2003-02-26 | Tokai Rubber Ind Ltd | Rubber press-fitted torsional damper and method of manufacturing the torsional damper |
| JP4635638B2 (en) * | 2005-02-18 | 2011-02-23 | Ｊｆｅスチール株式会社 | Phosphate-treated electrogalvanized steel sheet with excellent corrosion resistance and blackening resistance |
| JP4868748B2 (en) * | 2005-03-01 | 2012-02-01 | 日新製鋼株式会社 | Phosphated steel sheet |
| KR100797289B1 (en) * | 2005-07-29 | 2008-01-23 | 주식회사 포스코 | Galvannealed steel sheet having excellent formability and method for producing the same |
| JP4571895B2 (en) * | 2005-08-12 | 2010-10-27 | 新日本製鐵株式会社 | Surface-treated steel sheet for environment-friendly electronic parts with excellent solder wettability, whisker resistance, and appearance stability over time, and method for producing the same |
| WO2011104868A1 (en) * | 2010-02-26 | 2011-09-01 | 株式会社サンベスト | Surface-modified metallic material, and complex of surface-modified metallic material, resin, elastomer and coating film, and process for production thereof |
| WO2016178210A1 (en) * | 2015-05-07 | 2016-11-10 | Phosfan Ltd | Method for applying ultrafine phosphate conversion crystal coatings |
| JP6927146B2 (en) * | 2018-05-25 | 2021-08-25 | Ｊｆｅスチール株式会社 | Manufacturing method of chemical conversion plated steel sheet |
| JP7332943B2 (en) * | 2019-08-29 | 2023-08-24 | 日本製鉄株式会社 | hot stamped body |
| CN114635141B (en) * | 2022-02-28 | 2023-10-27 | 武汉材保表面新材料有限公司 | Chemical film stripping liquid for non-phosphate conversion film on steel surface, preparation method and application |
| CN114875395A (en) * | 2022-03-31 | 2022-08-09 | 潍坊国一铝材有限公司 | Electrophoretic galvanized iron product and surface treatment method thereof |
-
1994
- 1994-06-27 JP JP06144735A patent/JP3137535B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110144577A (en) * | 2019-06-24 | 2019-08-20 | 浙江日星标准件有限公司 | A kind of medium carbon alloy steel bolt metal non-phosphate film processing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0813154A (en) | 1996-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1433875B1 (en) | Chemical conversion coating agent and surface-treated metal | |
| JP3063920B2 (en) | How to treat metal surfaces with phosphate | |
| JP3137535B2 (en) | Zinc-containing metal-coated steel sheet composite excellent in coatability and method for producing the same | |
| JP5462467B2 (en) | Chemical treatment solution for metal material and treatment method | |
| KR100215263B1 (en) | Zinc containing metal plated composite steel article and method of same | |
| WO2004055237A1 (en) | Treating fluid for surface treatment of metal and method for surface treatment | |
| EP0544650B1 (en) | A process for phosphate-coating metal surfaces | |
| JPH11335865A (en) | Processing agent for forming protective coating film on metal and its formation | |
| EP0125658B1 (en) | Corrosion resistant surface-treated steel strip and process for making | |
| WO1995012010A1 (en) | Composition and process for treating magnesium-containing metals and product therefrom | |
| JPH06506263A (en) | Phosphate treatment method for metal surfaces | |
| JP3088623B2 (en) | Method for forming zinc phosphate film on metal surface | |
| JPH10204649A (en) | Aqueous phosphate treating solution for metallic surface and its treatment | |
| JP3737168B2 (en) | Manufacturing method of electrogalvanized steel sheet with high whiteness and excellent paintability | |
| KR20040038635A (en) | Surface treating composition, surface treating solution, surface treating method and product with metallic material | |
| JPH07278891A (en) | Pretreatment for coating of metal material | |
| JP4393349B2 (en) | Cold-rolled steel sheet with excellent phosphatability and post-coating salt hot water resistance | |
| US5888315A (en) | Composition and process for forming an underpaint coating on metals | |
| EP1340839A1 (en) | Whiskerless galvanized product having multi-layer rust prevention film, composition for forming multi-layer rust prevention film and manufacturing method of whiskerless galvanized product having multi-layer rust prevention film | |
| JP3190188B2 (en) | Zinc-containing metal-coated steel sheet composite with excellent high-speed press formability | |
| US9309602B2 (en) | Electrolytic iron metallizing of zinc surfaces | |
| JP3417653B2 (en) | Pretreatment method for painting aluminum material | |
| WO2008054016A1 (en) | Phosphate-treated galvanized steel sheet and method for producing the same | |
| JP4635638B2 (en) | Phosphate-treated electrogalvanized steel sheet with excellent corrosion resistance and blackening resistance | |
| JP2781844B2 (en) | Undercoating agent for painting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |