JP2009068115A - Production method of surface-treated steel sheet, surface-treated steel sheet and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin - Google Patents
Production method of surface-treated steel sheet, surface-treated steel sheet and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin Download PDFInfo
- Publication number
- JP2009068115A JP2009068115A JP2008283766A JP2008283766A JP2009068115A JP 2009068115 A JP2009068115 A JP 2009068115A JP 2008283766 A JP2008283766 A JP 2008283766A JP 2008283766 A JP2008283766 A JP 2008283766A JP 2009068115 A JP2009068115 A JP 2009068115A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- treated steel
- resin
- phosphorus oxyacid
- treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 146
- 239000010959 steel Substances 0.000 title claims abstract description 146
- 229920005989 resin Polymers 0.000 title claims abstract description 75
- 239000011347 resin Substances 0.000 title claims abstract description 75
- 238000000576 coating method Methods 0.000 title claims abstract description 21
- 239000011248 coating agent Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical group O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims abstract description 13
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 30
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 28
- 239000011574 phosphorus Substances 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 238000004381 surface treatment Methods 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- KZNFRTXTQCISLO-UHFFFAOYSA-N oxovanadium;sulfuric acid Chemical compound [V]=O.OS(O)(=O)=O KZNFRTXTQCISLO-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 7
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 7
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 229920001225 polyester resin Polymers 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 5
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 5
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 claims description 5
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 5
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 claims description 5
- 235000019785 monomagnesium phosphate Nutrition 0.000 claims description 5
- 239000004431 polycarbonate resin Substances 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical group OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- 235000010210 aluminium Nutrition 0.000 claims description 4
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 21
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 5
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- IDDRQDSRIZZVSG-UHFFFAOYSA-N azanium;2-iodylbenzoate Chemical compound [NH4+].[O-]C(=O)C1=CC=CC=C1I(=O)=O IDDRQDSRIZZVSG-UHFFFAOYSA-N 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 27
- 229910052750 molybdenum Inorganic materials 0.000 description 16
- 239000011651 chromium Substances 0.000 description 14
- 238000007747 plating Methods 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- -1 vanadate ion Chemical class 0.000 description 13
- 229910052720 vanadium Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 11
- 239000011777 magnesium Chemical class 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229910052726 zirconium Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000002265 prevention Effects 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 5
- 229940041260 vanadyl sulfate Drugs 0.000 description 5
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 229910007567 Zn-Ni Inorganic materials 0.000 description 4
- 229910007614 Zn—Ni Inorganic materials 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Chemical group 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Chemical group CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000728 polyester Chemical group 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 229910052791 calcium Chemical class 0.000 description 1
- 239000011575 calcium Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000007610 electrostatic coating method Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/22—Orthophosphates containing alkaline earth metal cations
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/42—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also phosphates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
本発明は、Ｚｎめっき鋼板などに防錆性、および皮膜密着性に優れた保護皮膜を被覆してなる表面処理鋼板の製造方法、表面処理鋼板、およびその表面処理鋼板に有機樹脂を被覆してなる樹脂被覆表面処理鋼板に関する。 The present invention relates to a method for producing a surface-treated steel sheet obtained by coating a Zn-plated steel sheet or the like with a protective film excellent in rust prevention and film adhesion, a surface-treated steel sheet, and an organic resin on the surface-treated steel sheet. It relates to a resin-coated surface-treated steel sheet.
従来、鋼板、特にＺｎめっき鋼板の分野においては、防錆性およびその上に形成される塗膜や樹脂層などとの密着性を向上させるために、鋼板をリン酸塩やクロム酸塩を含む溶液中で表面処理し、リン酸塩皮膜やクロメート皮膜などの保護皮膜を形成させている。しかし、リン酸塩皮膜を形成させた鋼板は耐食性に乏しく、塗膜や有機樹脂を被覆しない場合に錆を生じやすい。また、塗膜や有機樹脂を被覆した場合、密着性、特に加工時の密着性が不十分である。
クロメート皮膜は電解を伴わない浸漬処理や塗布処理、電解処理などの方法を用いて鋼板上に形成され、リン酸塩皮膜よりも塗膜や有機樹脂を被覆しない場合の防錆性や、塗膜や有機樹脂を被覆した場合の密着性、および加工時密着性に優れている。しかし、電解を伴わない浸漬処理や塗布処理で形成されるクロメート皮膜中には有害な６価クロムが含有されており、人体や環境に対して好ましくない影響を与え得る。また電解処理による電解クロメート皮膜は有害な６価クロムを含む溶液を用いて行われ、さらに電解中に発生するクロム酸ミストは作業環境に好ましくない影響を与え得る。
このように、クロメート皮膜を施した鋼板は防錆性や加工密着性に優れ、そのため多方面で重用されているが、人体や環境に対して好ましくない影響を与える可能性を有しているため、優れた防錆性や加工密着性を有するクロメート皮膜に替わる処理皮膜が求められている。
その一例として、特公昭６２−３０２６５号公報は、リン酸と、酸可溶性亜鉛化合物として酸化亜鉛と、重金属促進剤および／または結晶リファイナーと、ホスホナート腐食防止剤としてアミノトリス（メチレン−ホスホン酸）、および水からなる組成物および、その組成物で金属部品をコーティングすることを開示しており、耐腐食性、および塗料密着性が向上することが記載されている。
上記の特公昭６２−３０２６５号公報において、重金属促進剤としてバナジウム、チタニウム、ジルコニウム、タングステンおよびモリブデン化合物があげられ、具体的にはモリブデン酸アンモニウム、またはメタバナジウム酸アンモニウムを用いることが記載されている。また結晶リファイナーとしてニッケル、コバルト、マグネシウムまたはカルシウムの酸可溶性塩があげられ、具体的には硝酸ニッケル、硝酸カルシウム、または硝酸コバルトを用いることが記載されている。
しかし、上記の特公昭６２−３０２６５号公報に記載された組成物を用いて亜鉛めっき鋼板などの金属板に処理皮膜を形成させても、得られた表面処理金属板の特性、特に表面処理金属板に有機樹脂皮膜を被覆した有機樹脂被覆金属板における皮膜の密着性、とりわけ加工密着性は、従来のクロメート処理皮膜を形成させた表面処理金属板に及ばない。また亜鉛めっき鋼板に適用した場合は耐白錆性に乏しい。
本発明は、クロメート処理を施した表面処理鋼板に替わる、耐食性、および有機樹脂皮膜の加工密着性に優れた表面処理鋼板の製造方法、表面処理鋼板、および表面処理鋼板に有機樹脂を被覆してなる樹脂被覆表面処理鋼板を提供することを目的とする。
The chromate film is formed on the steel plate using methods such as dipping, coating, and electrolytic processes that do not involve electrolysis. It has excellent adhesion when coated with organic resin, and adhesion during processing. However, harmful hexavalent chromium is contained in the chromate film formed by dipping or coating without electrolysis, which may have an undesirable effect on the human body and the environment. Moreover, the electrolytic chromate film by the electrolytic treatment is performed using a solution containing harmful hexavalent chromium, and chromic acid mist generated during electrolysis can adversely affect the working environment.
In this way, steel plates with a chromate film are excellent in rust prevention and work adhesion, so they are used in many ways, but they may have an undesirable effect on the human body and the environment. Accordingly, there is a need for a treatment film that replaces a chromate film having excellent rust prevention and processing adhesion.
As an example, Japanese Patent Publication No. 62-30265 discloses phosphoric acid, zinc oxide as an acid-soluble zinc compound, heavy metal promoter and / or crystal refiner, aminotris (methylene-phosphonic acid) as a phosphonate corrosion inhibitor, And a composition comprising water and coating a metal part with the composition are disclosed, and it is described that corrosion resistance and paint adhesion are improved.
In the above Japanese Patent Publication No. 62-30265, vanadium, titanium, zirconium, tungsten and molybdenum compounds are mentioned as heavy metal promoters, and specifically, it is described that ammonium molybdate or ammonium metavanadate is used. . Examples of the crystal refiner include acid-soluble salts of nickel, cobalt, magnesium, or calcium. Specifically, the use of nickel nitrate, calcium nitrate, or cobalt nitrate is described.
However, even when a treatment film is formed on a metal plate such as a galvanized steel plate using the composition described in the above Japanese Patent Publication No. 62-30265, the characteristics of the surface-treated metal plate, particularly the surface-treated metal, are obtained. The adhesion of the organic resin-coated metal plate with the organic resin film coated on the plate, particularly the processing adhesion, is not as good as that of the conventional surface-treated metal plate on which the chromate-treated film is formed. Moreover, when applied to a galvanized steel sheet, the white rust resistance is poor.
The present invention provides a method for producing a surface-treated steel sheet excellent in corrosion resistance and processing adhesion of an organic resin film, a surface-treated steel sheet, and a surface-treated steel sheet coated with an organic resin instead of a surface-treated steel sheet subjected to chromate treatment. An object of the present invention is to provide a resin-coated surface-treated steel sheet.
（１）本発明の表面処理鋼板の製造方法は、鋼板を、Ｖのオキシ硫酸塩の一種以上と、リンの酸素酸又はリンの酸素酸塩と、Ｚｎ化合物とを含有し、且つＣｒを含有しない水溶液中で浸漬処理あるいは電解処理することを特徴とする。
（２）本発明の表面処理鋼板の製造方法は、鋼板を、Ｖのオキシ硫酸塩の一種以上と、リンの酸素酸又はリンの酸素酸塩と、Ｚｎ化合物と、ホスホン酸塩とを含有し、且つＣｒを含有しない水溶液中で浸漬処理あるいは電解処理することを特徴とする。
（３）本発明の表面処理鋼板の製造方法は、前記（１）又は（２）において、前記鋼板が、Ｚｎめっき鋼板又はＺｎを含む合金めっき鋼板であることを特徴とする。
（４）本発明の表面処理鋼板の製造方法は、前記（１）〜（３）のいずれかにおいて、
前記リンの酸素酸又はリンの酸素酸塩が、リン酸、重リン酸アンモニウム、重リン酸ナトリウム、重リン酸カルシウム、重リン酸マグネシウム、重リン酸アルミニウムの一種以上からなることを特徴とする。
（５）本発明の表面処理鋼板の製造方法は、前記（２）〜（４）のいずれかにおいて、前記ホスホン酸塩が、アミノトリ（メチレン−ホスホン酸）であることを特徴とする。
（６）本発明の表面処理鋼板は、鋼板を、Ｖのオキシ硫酸塩の一種以上と、リンの酸素酸又はリンの酸素酸塩と、Ｚｎ化合物とを含有し、且つＣｒを含有しない水溶液中で浸漬処理あるいは電解処理して、Ｖのオキシ硫酸塩から形成された物質と、リンの酸素酸又はリンの酸素酸塩から形成された物質と、Ｚｎ化合物から形成された物質と、を含有する保護被膜を鋼板上に被覆してなることを特徴とする。
（７）本発明の表面処理鋼板は、鋼板を、Ｖのオキシ硫酸塩の一種以上と、リンの酸素酸又はリンの酸素酸塩と、Ｚｎ化合物と、ホスホン酸塩とを含有し、且つＣｒを含有しない水溶液中で浸漬処理あるいは電解処理して、Ｖのオキシ硫酸塩から形成された物質と、リンの酸素酸又はリンの酸素酸塩から形成された物質と、Ｚｎ化合物から形成された物質と、を含有する保護被膜を鋼板上に被覆してなることを特徴とする。
（８）本発明の表面処理鋼板は、前記（６）又は（７）において、前記鋼板が、Ｚｎめっき鋼板又はＺｎを含む合金めっき鋼板であることを特徴とする。
（９）本発明の樹脂被覆表面処理鋼板は、前記（６）〜（８）のいずれかに記載の表面処理鋼板に有機樹脂を被覆してなることを特徴とする。
（１０）本発明の樹脂被覆表面処理鋼板は、前記（９）において、前記有機樹脂が、ポリエステル系樹脂、ウレタン系樹脂、アクリル系樹脂、ポリオレフィン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、またはポリ塩化ビニル系樹脂のいずれかであることを特徴とする。
(1) The method for producing a surface-treated steel sheet according to the present invention comprises a steel sheet containing at least one of V oxysulfate, phosphorus oxyacid or phosphorus oxyacid salt, and Zn compound, and also containing Cr. It is characterized by immersing or electrolytic treatment in an aqueous solution that does not.
(2) The method for producing a surface-treated steel sheet according to the present invention comprises a steel sheet containing at least one of V oxysulfate, phosphorus oxyacid or phosphorus oxyacid salt, Zn compound, and phosphonate. In addition, it is characterized in that it is immersed or electrolyzed in an aqueous solution not containing Cr.
(3) The method for producing a surface-treated steel sheet according to the present invention is characterized in that, in the above (1) or (2), the steel sheet is a Zn-plated steel sheet or an alloy-plated steel sheet containing Zn.
(4) The method for producing a surface-treated steel sheet according to the present invention is any one of the above (1) to (3).
The phosphorus oxyacid or phosphorus oxyacid salt is composed of one or more of phosphoric acid, ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, and aluminum biphosphate.
(5) The method for producing a surface-treated steel sheet according to the present invention is characterized in that in any one of the above (2) to (4), the phosphonate is aminotri (methylene-phosphonic acid).
(6) The surface-treated steel sheet of the present invention comprises a steel sheet in an aqueous solution containing at least one type of oxysulfate of V, phosphorus oxyacid or phosphorus oxyacid salt, and Zn compound, and not containing Cr. A substance formed from V oxysulfate, a substance formed from phosphorus oxyacid or phosphorus oxyacid salt, and a substance formed from Zn compound. It is characterized by coating a protective film on a steel plate.
(7) The surface-treated steel sheet of the present invention comprises one or more of V oxysulfate, phosphorus oxyacid or phosphorus oxyacid salt, Zn compound and phosphonate, and Cr. A substance formed from V oxysulfate, a substance formed from phosphorus oxyacid or phosphorus oxyacid salt, and a substance formed from Zn compound by immersion treatment or electrolytic treatment in an aqueous solution containing no oxygen And a protective coating containing
(8) The surface-treated steel sheet of the present invention is characterized in that, in the above (6) or (7), the steel sheet is a Zn-plated steel sheet or an alloy-plated steel sheet containing Zn.
(9) The resin-coated surface-treated steel sheet of the present invention is characterized in that the surface-treated steel sheet according to any one of (6) to (8) is coated with an organic resin.
(10) In the resin-coated surface-treated steel sheet of the present invention, in (9), the organic resin is a polyester resin, a urethane resin, an acrylic resin, a polyolefin resin, a polycarbonate resin, a polyamide resin, or a poly resin. It is one of vinyl chloride resins.
本発明の表面処理浴においては、皮膜を形成させる主要成分としてＭｏ、Ｔｉ、Ｖ、Ｚｒのオキシ硫酸塩と、Ｐ化合物と、Ｚｎ化合物を用いている。さらに、Ｍｇ、Ａｌの硫酸塩の一種以上、および／またはホスホン酸塩を積極的に加えた表面処理浴を用いている。さらにまた、オキシ硫酸塩がオキシ硫酸モリブデンまたは硫酸バナジルであることを特徴とし、そして、Ｐ化合物が、リン酸、重リン酸アンモニウム、重リン酸ナトリウム、重リン酸カルシウム、重リン酸マグネシウム、重リン酸アルミニウムの一種以上からなることを特徴とする。
耐食性を向上させることを目的として、Ｃｒなどの金属をリン酸皮膜中に取り込むことが従来より実施され、とりわけＣｒは耐食性および塗料などの皮膜密着性に優れており、これまで多用されてきたが、上記示したように環境に有害となる恐れがあり、Ｃｒに替わる金属としてＭｏ、Ｗ、Ｖなどを用いることが試みられている。これらの金属はいずれもモリブデン酸イオン、タングステン酸イオン、バナジウム酸イオンなど、金属酸イオンの形で処理浴中に添加されて使用されているが、得られた表面処理皮膜はいずれもＣｒを用いた表面処理皮膜の特性を示すには至らなかった。
本発明においては、Ｃｒに替わる金属としてＭｏ、Ｔｉ、Ｖ、Ｚｒの一種以上をオキシ硫酸塩の形でＰ化合物およびＺｎ化合物とともに処理液中に含有させ、この処理浴を用いて形成させた処理皮膜中に、Ｍｏ、Ｔｉ、Ｖ、Ｚｒのオキシ硫酸塩とＰ化合物およびＺｎ化合物に由来する物質を取り込むことにより、従来のモリブデン酸アンモニウム、バナジウム酸アンモニウム、タングステン酸アンモニウム、チタン酸アンモニウムなどの化合物を含む処理浴を用いて形成させた処理皮膜よりも優れた皮膜特性が得られ、さらにＣｒを用いた表面処理皮膜と同等以上の皮膜特性が得られることが判明した。この理由についてはよく分からないが、上記のＭｏ、Ｔｉ、Ｖ、Ｚｒを処理浴中にオキシ硫酸塩の形で含有させることにより、Ｍｏについては３価、５価および６価のモリブデンが酸素イオン（Ｏ２−）と硫酸イオン（ＳＯ４ ２−）と結びついた化合物、そして、Ｔｉ、Ｖ、Ｚｒについては４価のＴｉ、Ｖ、Ｚｒが酸素イオン（Ｏ２−）と硫酸イオン（ＳＯ４ ２−）と結びついた化合物から由来する物質が、ＰおよびＺｎとともに鋼板上に形成させた皮膜の骨格をなす成分となり、この皮膜が優れた防錆性を有していると考えられる。特に、前記鋼板がＺｎめっき鋼板あるいはＺｎ系合金めっき鋼板である場合は、めっき皮膜中のＺｎや合金元素とも結びついて、Ｍｏ、Ｔｉ、Ｖ、Ｚｒの一種以上とＰとＺｎが主に皮膜の骨格をなす成分となり、この皮膜が優れた防錆性を有していると考えられる。また、上記皮膜中にさらにＭｇ、Ａｌの一種以上、および／またはホスホン酸塩を積極的に含ませることにより、より防錆性は向上すると考えられる。
さらに、これらの皮膜中には原子価の高い状態のＭｏ、Ｔｉ、Ｖ、Ｚｒが好ましい形で含まれており、他の物質を酸化させ酸化皮膜形成を促進し、自らは還元されて原子価の低い状態に移ると考えられる。この反応はクロム酸イオンが有している酸化機能と同じようなものと考えられ、皮膜の自己修復性があるために優れた防錆性を示すと考えられる。
以下に本発明についてその内容を説明する。
In the surface treatment bath of the present invention, Mo, Ti, V, and Zr oxysulfates, P compounds, and Zn compounds are used as main components for forming a film. Further, a surface treatment bath to which one or more of Mg and Al sulfates and / or phosphonates are positively added is used. Furthermore, the oxysulfate is characterized by molybdenum oxysulfate or vanadyl sulfate, and the P compound is phosphoric acid, ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, deuterated phosphoric acid It is characterized by comprising at least one kind of aluminum.
For the purpose of improving the corrosion resistance, it has been practiced to incorporate a metal such as Cr into the phosphoric acid film, and in particular, Cr is excellent in corrosion resistance and film adhesion such as paint, and has been widely used so far. As described above, there is a risk of being harmful to the environment, and attempts have been made to use Mo, W, V, or the like as a metal instead of Cr. All of these metals are used in the form of metal acid ions such as molybdate ion, tungstate ion, vanadate ion, etc., which are used in the treatment bath. The properties of the surface-treated film were not shown.
In the present invention, at least one of Mo, Ti, V, and Zr as a metal replacing Cr is contained in a treatment liquid together with a P compound and a Zn compound in the form of an oxysulfate, and a treatment formed using this treatment bath. Conventional compounds such as ammonium molybdate, ammonium vanadate, ammonium tungstate, ammonium titanate by incorporating substances derived from Mo, Ti, V, Zr oxysulfates and P compounds and Zn compounds into the film It has been found that film properties superior to those of a treatment film formed using a treatment bath containing, and film properties equivalent to or better than those of a surface treatment film using Cr can be obtained. The reason for this is not well understood, but when Mo, Ti, V, and Zr are contained in the treatment bath in the form of oxysulfate, trivalent, pentavalent, and hexavalent molybdenum are oxygen ions. A compound in which (O 2− ) and sulfate ion (SO 4 2− ) are combined, and for Ti, V, and Zr, tetravalent Ti, V, and Zr are oxygen ions (O 2− ) and sulfate ions (SO 4). 2- ) The substance derived from the compound combined with) becomes a component that forms the skeleton of the film formed on the steel plate together with P and Zn, and this film is considered to have excellent rust prevention properties. In particular, when the steel sheet is a Zn-plated steel sheet or a Zn-based alloy-plated steel sheet, it is combined with Zn or an alloy element in the plating film, so that one or more of Mo, Ti, V, and Zr and P and Zn are mainly formed of the film. It becomes a skeleton component, and this film is considered to have excellent antirust properties. Moreover, it is thought that rust prevention property improves more by containing Mg, Al 1 or more types, and / or a phosphonate more actively in the said film | membrane.
Furthermore, these films contain Mo, Ti, V, Zr in a high valence state in a preferable form, and oxidize other substances to promote the formation of an oxide film. It is thought that it will move to a low state. This reaction is considered to be similar to the oxidation function possessed by chromate ions, and is considered to exhibit excellent rust prevention due to the self-repairing property of the film.
The contents of the present invention will be described below.
まず処理浴について説明する。本発明の処理浴は、オキシ硫酸モリブデン、硫酸チタニル、硫酸バナジル、硫酸ジルコニルであるＭｏ、Ｔｉ、Ｖ、Ｚｒのオキシ硫酸塩の一種以上と、リン酸、重リン酸アンモニウム（リン酸二水素アンモニウム）、重リン酸ナトリウム（リン酸二水素ナトリウム）などのＰ化合物、および酸化亜鉛などのＺｎ化合物を含有する水溶液からなり、それに、耐錆性を向上させる硫酸マグネシウムや硫酸アルミニウムなど、ＭｇまたはＡｌの硫酸塩の一種以上、および／またはアミノトリ（メチレン−ホスホン酸）などのホスホン酸塩を加えても良い。さらにまた、電導度を向上させ処理浴を安定させるために、例えば硫酸ナトリウムや硫酸アンモニウムなどの塩類を添加してもよい。
オキシ硫酸モリブデン、硫酸チタニル、硫酸バナジル、硫酸ジルコニルなどの含有量の総量は３〜１５０ｇ／ｌ、好ましくは５〜５０ｇ／ｌである。３ｇ／ｌ未満の場合は皮膜の生成量が少なく、良好な皮膜特性が得られない。１５０ｇ／ｌを超えると、皮膜の色調が変化し、また皮膜の加工密着性が低下する。さらに薬品が高価であることに加えて、処理時に鋼板に付着して持ち出される量が増加し、経済的でなくなる。
上記の金属のオキシ硫酸塩はいずれも本発明に適用可能であるが、オキシ硫酸モリブデン
および硫酸バナジルを用いた場合は安定した処理浴が得られ、好ましい。
Ｐ化合物の含有量は３〜１５０ｇ／ｌ、好ましくは５〜５０ｇ／ｌである。３ｇ／ｌ未満の場合は皮膜の生成量が少なく、良好な皮膜特性が得られない。１５０ｇ／ｌを超えると皮膜の加工密着性が低下する。さらに処理時に鋼板に付着して持ち出される量が増加し、経済的でなくなる。
上記のＰ化合物は、正リン酸、縮合リン酸、亜リン酸、次亜リン酸を始めとしたＰを含有するＰの酸素酸、酸素酸塩類などの化合物の一種以上が適用可能であるが、重リン酸化合物である重リン酸アンモニウム、重リン酸ナトリウム、重リン酸カルシウム、重リン酸マグネシウム、重リン酸アルミニウムを用いた場合は安定した処理浴が得られ、好ましい。
Ｚｎ化合物の含有量は１〜１０ｇ／ｌ、好ましくは２〜８ｇ／ｌである。１ｇ／ｌ未満の場合は皮膜の生成量が少なく、良好な耐白錆性が得られない。１０ｇ／ｌを超えると皮膜の加工密着性が低下する。さらに処理時に鋼板に付着して持ち出される量が増加し、経済的でなくなる。
上記のＺｎ化合物は、酸に可溶なものであればよいが、酸化亜鉛を用いた場合は安定した処理浴が得られ、好ましい。
本発明において、上記の金属のオキシ硫酸塩の一種類以上、Ｐ化合物、およびＺｎ化合物を含有させた処理浴を用いて表面処理鋼板を作成し、それに有機樹脂を被覆した場合、良好な耐食性および皮膜密着性を示す樹脂被覆表面処理鋼板が得られる。しかし、この処理浴を亜鉛めっき鋼板に適用して有機樹脂を被覆せずに裸で用いた場合、白錆の発生を完全に抑制することはかなり困難である。そのため、処理浴にさらに硫酸マグネシウムや硫酸アルミニウムなどのＭｇまたはＡｌの硫酸塩の一種以上、および／またはホスホン酸塩を含有させる。ＭｇまたはＡｌの硫酸塩の含有量は総量で３〜５０ｇ／ｌが好ましい。３ｇ／ｌ未満では効果が得られず、５０ｇ／ｌを超えて含有させても十分な効果が得られ、それ以上含有させる必要はない。ホスホン酸塩の含有量は総量で１〜８０ｇ／ｌが好ましい。
なお、Ｐ化合物としてＭｇまたはＡｌを含む、重リン酸マグネシウムまたは重リン酸アルミニウムを用いた場合は、ＭｇまたはＡｌの硫酸塩を含有させた場合と同様の効果が得られる。
さらにまた、電導度を向上させ処理浴を安定させるために、例えば硫酸ナトリウムや硫酸アンモニウムなどの塩類を５０ｇ／ｌ以下含有させてもよい。
処理浴のｐＨは１〜５が好ましく、より好ましくは２〜４である。ｐＨが１未満の場合は不均一な皮膜となり、ｐＨが５を超えると処理浴が不安定になるとともに、皮膜の耐食性が低下する。
ｐＨ調整はアンモニア、苛性ソーダなどのアルカリ、および硫酸、リン酸などの酸の添加により行う。処理浴の温度は２０〜５０℃の範囲が好ましい。
上記のようにして作成した処理浴を用い、鋼板に処理皮膜を生成させる。処理方法としては浸漬処理、電解処理のいずれも可能である。浸漬処理の場合、１〜６０秒、好ましくは２〜１０秒で十分な厚さの処理皮膜が得られる。６０秒以上浸漬しても皮膜の厚さはそれ程増加しなくなる。
電解処理の場合は短時間で厚い皮膜が得られ、陰極処理、陽極処理のいずれも適用可能である。いずれの場合も０．５〜３０Ａ／ｄｍ２、好ましくは１〜１０Ａ／ｄｍ２の電流密度で０．１〜１０秒間通電することが好ましい。０．５Ａ／ｄｍ２未満では皮膜の成長に時間がかかり過ぎ、短時間で厚い皮膜を得ることができない。３０Ａ／ｄｍ２を超えるとヤケを生じ、均一な皮膜が得られない。１０秒間を超えて通電すると皮膜が厚くなり過ぎて、処理皮膜の上に有機樹脂フィルムなどの樹脂皮膜を被覆した場合、樹脂皮膜の加工密着性が低下する。
First, the treatment bath will be described. The treatment bath of the present invention comprises one or more of Mo, Ti, V, Zr oxysulfates which are molybdenum oxysulfate, titanyl sulfate, vanadyl sulfate, zirconyl sulfate, phosphoric acid, ammonium biphosphate (ammonium dihydrogen phosphate). ), An aqueous solution containing a P compound such as sodium biphosphate (sodium dihydrogen phosphate), and a Zn compound such as zinc oxide, and magnesium or aluminum sulfate such as magnesium sulfate or aluminum sulfate for improving rust resistance. One or more of the sulfates and / or phosphonates such as aminotri (methylene-phosphonic acid) may be added. Furthermore, in order to improve electrical conductivity and stabilize the treatment bath, for example, salts such as sodium sulfate and ammonium sulfate may be added.
The total content of molybdenum oxysulfate, titanyl sulfate, vanadyl sulfate, zirconyl sulfate and the like is 3 to 150 g / l, preferably 5 to 50 g / l. If it is less than 3 g / l, the amount of film produced is small, and good film properties cannot be obtained. If it exceeds 150 g / l, the color tone of the film changes, and the work adhesion of the film decreases. Furthermore, in addition to the high price of chemicals, the amount of chemicals attached to the steel sheet during processing increases, which is not economical.
Any of the above metal oxysulfates can be applied to the present invention, but when molybdenum oxysulfate and vanadyl sulfate are used, a stable treatment bath is obtained, which is preferable.
The content of the P compound is 3 to 150 g / l, preferably 5 to 50 g / l. If it is less than 3 g / l, the amount of film produced is small, and good film properties cannot be obtained. If it exceeds 150 g / l, the work adhesion of the coating will be reduced. Furthermore, the amount taken out by adhering to the steel sheet during processing increases, which is not economical.
As the above-mentioned P compound, one or more compounds such as orthophosphoric acid, condensed phosphoric acid, phosphorous acid, hypophosphorous acid and other P-containing oxygen acids and oxyacid salts are applicable. In the case of using ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, and aluminum biphosphate which are biphosphate compounds, a stable treatment bath is obtained, which is preferable.
The content of the Zn compound is 1 to 10 g / l, preferably 2 to 8 g / l. When the amount is less than 1 g / l, the amount of film formed is small and good white rust resistance cannot be obtained. If it exceeds 10 g / l, the work adhesion of the coating will be reduced. Furthermore, the amount taken out by adhering to the steel sheet during processing increases, which is not economical.
The Zn compound is not particularly limited as long as it is soluble in an acid. However, when zinc oxide is used, a stable treatment bath is obtained, which is preferable.
In the present invention, when a surface-treated steel sheet is prepared using a treatment bath containing one or more of the above metal oxysulfates, a P compound, and a Zn compound, and coated with an organic resin, good corrosion resistance and A resin-coated surface-treated steel sheet exhibiting film adhesion is obtained. However, when this treatment bath is applied to a galvanized steel sheet and used without being coated with an organic resin, it is quite difficult to completely suppress the occurrence of white rust. Therefore, the treatment bath further contains at least one of Mg or Al sulfates such as magnesium sulfate and aluminum sulfate and / or phosphonates. The total amount of Mg or Al sulfate is preferably 3 to 50 g / l. If it is less than 3 g / l, no effect is obtained, and even if it is contained in excess of 50 g / l, a sufficient effect is obtained, and it is not necessary to contain any more. The total amount of phosphonate is preferably 1 to 80 g / l.
When magnesium deuterium phosphate or aluminum deuterate containing Mg or Al as the P compound is used, the same effect as that obtained when Mg or Al sulfate is contained is obtained.
Furthermore, in order to improve the electrical conductivity and stabilize the treatment bath, for example, a salt such as sodium sulfate or ammonium sulfate may be contained in an amount of 50 g / l or less.
The pH of the treatment bath is preferably 1 to 5, more preferably 2 to 4. When the pH is less than 1, the film becomes uneven. When the pH exceeds 5, the treatment bath becomes unstable and the corrosion resistance of the film decreases.
The pH is adjusted by adding an alkali such as ammonia or caustic soda, and an acid such as sulfuric acid or phosphoric acid. The temperature of the treatment bath is preferably in the range of 20 to 50 ° C.
Using the treatment bath prepared as described above, a treatment film is formed on the steel plate. As the treatment method, either immersion treatment or electrolytic treatment is possible. In the case of immersion treatment, a treatment film having a sufficient thickness can be obtained in 1 to 60 seconds, preferably 2 to 10 seconds. Even if immersed for 60 seconds or more, the thickness of the film does not increase so much.
In the case of electrolytic treatment, a thick film can be obtained in a short time, and both cathodic treatment and anodic treatment can be applied. In any case, it is preferable to energize for 0.1 to 10 seconds at a current density of 0.5 to 30 A / dm 2 , preferably 1 to 10 A / dm 2 . If it is less than 0.5 A / dm 2 , it takes too much time to grow the film, and a thick film cannot be obtained in a short time. If it exceeds 30 A / dm 2 , burns occur and a uniform film cannot be obtained. When the current is applied for more than 10 seconds, the film becomes too thick, and when a resin film such as an organic resin film is coated on the treated film, the work adhesion of the resin film is lowered.
次に、上記の表面処理皮膜を被覆する下地となる鋼板について説明する。鋼板としては、通常のアルミキルド連続鋳造鋼を熱間圧延し表面に生じたスケールを除去した熱延鋼板、熱延鋼板を冷間圧延し焼鈍を施した冷延鋼板や、これらの鋼板にＳｎ、Ｎｉ、Ｃｏ、Ｍｏ、Ｚｎのいずれか一種からなる単層めっき、または二種以上からなる複層めっきや合金めっきを施しためっき鋼板を用いることができる。その中で汎用性の高いＺｎめっき鋼板としては、溶融Ｚｎめっき鋼板、ＡｌやＭｇを含んだ溶融Ｚｎ系合金めっき鋼板、電気Ｚｎめっき鋼板、またはＺｎ−Ｎｉ、Ｚｎ−Ｆｅ、Ｚｎ−Ｃｏ等の電気Ｚｎ系合金めっき鋼板、特に電気Ｚｎ−Ｃｏ−Ｍｏめっき鋼板があるが、いずれも本発明に使用することができる。
本発明の表面処理は以下のようにして行う。すなわち、上記の熱延鋼板や冷延鋼板に定法を用いて酸洗処理および脱脂処理を施す。または、酸洗処理および脱脂処理を施した後、上記のいずれかのめっきを施し、めっき鋼板とする。次いでこの鋼板またはめっき鋼板を、上記の処理浴中で上記の条件下で浸漬処理または電解処理し、表面処理皮膜を形成させる。
以上のようにして、本発明の表面処理鋼板を得ることができる。
Next, the steel plate which becomes the foundation | substrate which coat | covers said surface treatment film is demonstrated. As the steel sheet, a hot rolled steel sheet obtained by removing the scale produced on the surface by hot rolling normal aluminum killed continuous cast steel, a cold rolled steel sheet obtained by cold rolling and annealing the hot rolled steel sheet, and Sn, A single-layer plating made of any one of Ni, Co, Mo, and Zn, or a plated steel sheet that has been subjected to multiple-layer plating or alloy plating made of two or more types can be used. Among them, as a highly versatile Zn-plated steel sheet, a hot-dip Zn-plated steel sheet, a molten Zn-based alloy-plated steel sheet containing Al or Mg, an electric Zn-plated steel sheet, or Zn-Ni, Zn-Fe, Zn-Co, etc. There are electrical Zn-based alloy-plated steel plates, particularly electrical Zn-Co-Mo plated steel plates, any of which can be used in the present invention.
The surface treatment of the present invention is performed as follows. That is, the hot-rolled steel sheet and the cold-rolled steel sheet are subjected to pickling treatment and degreasing treatment using a conventional method. Or after performing a pickling process and a degreasing process, any one of said plating is given and it is set as a plated steel plate. Next, this steel plate or plated steel plate is subjected to immersion treatment or electrolytic treatment in the above treatment bath under the above conditions to form a surface treatment film.
As described above, the surface-treated steel sheet of the present invention can be obtained.
次いで本発明の樹脂被覆表面処理鋼板について説明する。本発明の樹脂被覆表面処理鋼板は、上記のようにして作成した表面処理鋼板に、有機樹脂を被覆したものである。有機樹脂としては、表面処理鋼板に被覆可能であれば如何なる樹脂も適用できるが、ポリエステル系樹脂、ポリオレフィン系樹脂、ポリ塩化ビニル系樹脂、ポリカーボネート系樹脂、ウレタン系樹脂、アクリル系樹脂、のいずれかを用いることが好ましい。さらに、前記有機樹脂に、コロイダルシリカ、ポリテトラフルオロエチレン、ポリエチレンワックス、シランカップリング剤又はクロム非含有防錆剤の一種以上を含ませることにより、潤滑性、密着性および耐食性をより向上させることができる。
ポリエステル樹脂としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、これらの樹脂の多価酸成分および／または多価アルコール成分の一部を他の成分と置き換えた共重合ポリエステル樹脂、ブチレンテレフタレート単位を主体とする共重合ポリエステル樹脂、これらのポリエステル樹脂をブレンドした樹脂を挙げることができる。
ポリオレフィン樹脂としては、ポリエチレン、ポリプロピレン、ポリブテン、ポリメチルペンテン、などのホモポリマー、エチレン・プロピレン共重合体、エチレン・プロピレン・ジエン共重合体、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸エチル共重合体、オレフィン重合体などの共重合ポリマーを挙げることができる。
ポリ塩化ビニル樹脂としては、ポリ塩化ビニル樹脂に、ジ−（２−エチルヘキシル）フタレート、ジブチルフタレート、ジオクチルアジペートなどの可塑剤を１０〜５０重量部含有させたものを用いることが好ましい。
ポリカーボネート樹脂としては、ビスフェノールＡ−ポリカーボネート樹脂が好ましい。
またポリアミド樹脂としては、６−ナイロン、６，６−ナイロン、６，１０−ナイロン、１２−ナイロンを挙げることができる。
ウレタン系樹脂としては、環境保全の観点からは有機溶媒系樹脂よりも水に溶解または分散可能な水性樹脂が好ましく、ウレタン樹脂以外にアクリル、オレフィン、ポリエステルあるいはフッ素等で変性したウレタン樹脂が適当である。
アクリル系樹脂としては、水性樹脂が好ましく、アクリル樹脂以外にウレタン、オレフィン、ポリエステルあるいはフッ素等で変性したアクリル樹脂が適当である。
なお、上記有機樹脂中に樹脂層全体の硬さを高め、耐疵付き性、および耐摩耗性、さらには耐食性向上を目的としてコロイダルシリカを含有させても良い。また、潤滑性向上を目的としてポリテトラフルオロエチレンおよびポリエチレンワックス等の潤滑剤粉末を含有させても良い。
さらに、クロム非含有防錆剤を含有させることにより、より耐食性を向上させる。また、シランカップリング剤を含有させた有機樹脂層を設けることが、より耐食性および密着性を向上させる。
Next, the resin-coated surface-treated steel sheet of the present invention will be described. The resin-coated surface-treated steel sheet of the present invention is obtained by coating the surface-treated steel sheet prepared as described above with an organic resin. As the organic resin, any resin can be applied as long as it can be coated on the surface-treated steel sheet, but any one of a polyester resin, a polyolefin resin, a polyvinyl chloride resin, a polycarbonate resin, a urethane resin, and an acrylic resin. Is preferably used. Furthermore, by including at least one of colloidal silica, polytetrafluoroethylene, polyethylene wax, silane coupling agent or chromium-free rust preventive agent in the organic resin, lubricity, adhesion and corrosion resistance are further improved. Can do.
Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, copolymer polyester resin in which a part of the polyhydric acid component and / or polyhydric alcohol component of these resins is replaced with other components, and a copolymer mainly composed of butylene terephthalate units. Examples thereof include polymerized polyester resins and resins obtained by blending these polyester resins.
Polyolefin resins include polyethylene, polypropylene, polybutene, polymethylpentene, and other homopolymers, ethylene / propylene copolymers, ethylene / propylene / diene copolymers, ethylene / vinyl acetate copolymers, and ethylene / ethyl acrylate copolymers. Examples thereof include copolymer polymers such as polymers and olefin polymers.
As the polyvinyl chloride resin, it is preferable to use a polyvinyl chloride resin containing 10 to 50 parts by weight of a plasticizer such as di- (2-ethylhexyl) phthalate, dibutyl phthalate, or dioctyl adipate.
As the polycarbonate resin, bisphenol A-polycarbonate resin is preferable.
Examples of the polyamide resin include 6-nylon, 6,6-nylon, 6,10-nylon, and 12-nylon.
As the urethane-based resin, an aqueous resin that can be dissolved or dispersed in water is more preferable than an organic solvent-based resin from the viewpoint of environmental conservation. In addition to the urethane resin, a urethane resin modified with acrylic, olefin, polyester, fluorine, or the like is suitable. is there.
As the acrylic resin, an aqueous resin is preferable, and in addition to the acrylic resin, an acrylic resin modified with urethane, olefin, polyester, fluorine, or the like is suitable.
The organic resin may contain colloidal silica for the purpose of increasing the hardness of the entire resin layer and improving scratch resistance, wear resistance, and corrosion resistance. Further, lubricant powder such as polytetrafluoroethylene and polyethylene wax may be contained for the purpose of improving lubricity.
Furthermore, corrosion resistance is improved more by containing a chromium non-containing rust preventive agent. Moreover, providing an organic resin layer containing a silane coupling agent further improves the corrosion resistance and adhesion.
有機樹脂を本発明の表面処理鋼板上に形成させる方法としては、フィルムラミネート、押し出しラミネートなどのラミネート法、粉体塗装法、ロールコート法、スプレー法、静電塗装法等、公知の塗装方法が適用可能である。ラミネート法の場合、これらの樹脂を延伸フィルム、または未延伸フィルムとして製膜し、その樹脂フィルムを本発明の表面処理鋼板に熱接着法を用いて積層してもよいし、ポリエステル系、アクリル系、ウレタン系、エポキシ系、メラミン系などの接着剤を用いて表面処理鋼板に接着してもよい。さらに樹脂を加熱溶融し、直接表面処理鋼板上に押し出して積層してもよい。
さらに、ポリ塩化ビニル樹脂のように、ポリマーと可塑剤を溶媒に溶解させてゾル状にしたものを表面処理鋼板に塗布し、その後加熱してゲル化させてもよい。
中でも、環境保全の観点から有機溶媒系樹脂よりも水に溶解または分散可能な水性樹脂を用い、有機樹脂層の厚さが比較的薄くてよいこと、塗装作業の簡便さ、および経済性の観点から、樹脂を溶解した水溶液中に本発明の表面処理鋼板を浸漬し、絞りロール等を用いて余分の樹脂溶液を除去した後、乾燥させる方法を採用することが好ましい。乾燥方法は熱風乾燥、ガスオーブン、電気オーブン、誘導加熱炉等、いずれの手段を用いてもよく、処理量と経済性の観点から最も有利な方法を採用すればよい。また、塗装被膜が生成した後、ＵＶ照射や電子線照射を併用してもよい。
以上のようにして、本発明の本発明の樹脂被覆表面処理鋼板を得ることができる。
以下、実施例にて本発明をさらに詳細に説明する。
As a method for forming the organic resin on the surface-treated steel sheet of the present invention, a known coating method such as a laminating method such as film laminating or extrusion laminating, a powder coating method, a roll coating method, a spray method, an electrostatic coating method, or the like can be used. Applicable. In the case of the laminating method, these resins may be formed as a stretched film or an unstretched film, and the resin film may be laminated on the surface-treated steel sheet of the present invention using a thermal bonding method. Alternatively, it may be bonded to the surface-treated steel sheet using an adhesive such as urethane, epoxy, or melamine. Further, the resin may be melted by heating and extruded and laminated directly on the surface-treated steel sheet.
Further, a polymer and a plasticizer dissolved in a solvent and made into a sol like a polyvinyl chloride resin may be applied to the surface-treated steel sheet and then heated to be gelled.
Among these, from the viewpoint of environmental conservation, an aqueous resin that can be dissolved or dispersed in water rather than an organic solvent-based resin is used, and the organic resin layer may have a relatively thin thickness, ease of painting work, and economical viewpoint Therefore, it is preferable to employ a method of immersing the surface-treated steel sheet of the present invention in an aqueous solution in which the resin is dissolved, removing the excess resin solution using a squeeze roll or the like, and then drying. As a drying method, any means such as hot air drying, gas oven, electric oven, induction heating furnace, etc. may be used, and the most advantageous method may be adopted from the viewpoint of throughput and economy. Further, after the coating film is formed, UV irradiation or electron beam irradiation may be used in combination.
As described above, the resin-coated surface-treated steel sheet according to the present invention can be obtained.
Hereinafter, the present invention will be described in more detail with reference to examples.
（実施例）
表面処理鋼板の作成 厚さ０．３ｍｍの冷延鋼板に、定法を用いてアルカリ電解脱脂処理及び硫酸酸洗処理を施した後、下記の条件でＺｎめっき、Ｚｎ−Ｃｏ−Ｍｏめっき、またはＺｎ−Ｎｉ合金めっきを施し、Ｚｎめっき鋼板、Ｚｎ−Ｃｏ−Ｍｏめっき鋼板、またはＺｎ−Ｎｉ合金めっき鋼板を作成した。
［Ｚｎめっき条件］
浴組成
ＺｎＳＯ４・７Ｈ２Ｏ：２５０ｇ／ｌ
（ＮＨ４）２ＳＯ４：３０ｇ／ｌ
浴温 ：４０ ℃
電流密度 ：２０ Ａ／ｄｍ２
めっき付着量 ： ５ ｇ／ｍ２
［Ｚｎ−Ｃｏ−Ｍｏめっき条件］
浴組成
ＺｎＳＯ４・７Ｈ２Ｏ：２５０ｇ／ｌ
ＣｏＳＯ４・７Ｈ２Ｏ：５０ｇ／ｌ
（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏ：０．２ｇ／ｌ
（ＮＨ４）２ＳＯ４：３０ｇ／ｌ
光沢剤（ジシアンジアミドホルムアルデヒド縮合物の塩酸塩）：４ｍｌ／ｌ
浴温 ：４０ ℃
電流密度 ：２０Ａ／ｄｍ２
めっき付着量 ： ５ ｇ／ｍ２
［Ｚｎ−Ｎｉ合金めっき条件］
浴組成
ＺｎＳＯ４・７Ｈ２Ｏ：２５０ｇ／ｌ
ＮｉＳＯ４・７Ｈ２Ｏ：５０ｇ／ｌ
（ＮＨ４）２ＳＯ４：１５ｇ／ｌ
ポリビニールアルコール：２ｇ／ｌ
浴温：５０ ℃
電流密度：２５ Ａ／ｄｍ２
めっき付着量：５ ｇ／ｍ２
上記のようにして作成したＺｎめっき鋼板、Ｚｎ−Ｃｏ−Ｍｏめっき鋼板、またはＺｎ−Ｎｉ合金めっき鋼板に、表１から表４に示す浴組成の表面処理浴、条件で表面処理を施し、表面処理鋼板を作成した。
(Example)
Preparation of surface-treated steel sheet Cold-rolled steel sheet having a thickness of 0.3 mm was subjected to alkaline electrolytic degreasing treatment and sulfuric acid pickling treatment using a conventional method, and then subjected to Zn plating, Zn-Co-Mo plating, or Zn under the following conditions: -Ni alloy plating was performed, and a Zn plated steel plate, a Zn-Co-Mo plated steel plate, or a Zn-Ni alloy plated steel plate was prepared.
[Zn plating conditions]
Bath composition ZnSO 4 · 7H 2 O: 250 g / l
(NH 4 ) 2 SO 4 : 30 g / l
Bath temperature: 40 ° C
Current density: 20 A / dm 2
Plating adhesion amount: 5 g / m 2
[Zn-Co-Mo plating conditions]
Bath composition ZnSO 4 · 7H 2 O: 250 g / l
CoSO 4 · 7H 2 O: 50g / l
(NH 4) 6 Mo 7 O 24 · 4H 2 O: 0.2g / l
(NH 4 ) 2 SO 4 : 30 g / l
Brightening agent (hydrochloride of dicyandiamide formaldehyde condensate): 4 ml / l
Bath temperature: 40 ° C
Current density: 20 A / dm 2
Plating adhesion amount: 5 g / m 2
[Zn-Ni alloy plating conditions]
Bath composition ZnSO 4 · 7H 2 O: 250 g / l
NiSO 4 · 7H 2 O: 50g / l
(NH 4 ) 2 SO 4 : 15 g / l
Polyvinyl alcohol: 2g / l
Bath temperature: 50 ° C
Current density: 25 A / dm 2
Plating adhesion amount: 5 g / m 2
Surface treatment was performed on the Zn-plated steel sheet, Zn-Co-Mo-plated steel sheet, or Zn-Ni alloy-plated steel sheet prepared as described above under the surface treatment baths and conditions of the bath compositions shown in Tables 1 to 4, and the surface A treated steel plate was created.
このようにして作成した表面処理鋼板の耐食性を、下記に示す要領で評価した。比較材１として、無水クロム酸：２５ｇ／ｌ、硫酸：０．１ｇ／ｌを処理浴として電解クロメート処理し、電気Ｚｎ−Ｃｏ−Ｍｏめっき鋼板上に全クロム量として３０ｍｇ／ｍ２のクロム水和酸化物皮膜を形成させた電気Ｚｎ−Ｃｏ−Ｍｏめっき鋼板を使用した。また、クロメート処理なしの電気Ｚｎ−Ｃｏ−Ｍｏめっき鋼板も比較材２として使用した。
The corrosion resistance of the surface-treated steel sheet thus prepared was evaluated in the following manner. As comparative material 1, chromic anhydride: 25 g / l, sulfuric acid: 0.1 g / l was used as an electrolytic chromate treatment as a treatment bath, and the total amount of chromium was 30 mg / m 2 of chromium water on the electric Zn—Co—Mo plated steel sheet. An electric Zn—Co—Mo plated steel sheet on which a sum oxide film was formed was used. In addition, an electric Zn—Co—Mo plated steel sheet without chromate treatment was also used as the comparative material 2.
表面処理鋼板の耐食性の評価
耐食性
表１から表４に示す本発明の表面処理鋼板、および比較材１、２について、９０度折り曲げを行った試験片を用いて、ＪＩＳ−Ｚ２３７１に基づいた塩水噴霧試験を２４時間実施した後、表面を目視観察し、平板部分と９０度折り曲げ加工部分とを次に示す５段階の評点で評価した。
評点５：表面に変化が認められない。
評点４：表面に実用上問題とならない程度のわずかな白錆が認められる。
評点３：表面に実用上問題となる程度の白錆が認められる。
評点２：表面にかなりの白錆が認められる。
評点１：表面全体に白錆が認められる。
結果を表５に示す。
Evaluation of Corrosion Resistance of Surface Treated Steel Sheet Corrosion Resistance Salt water spray based on JIS-Z2371, using the surface treated steel sheets of the present invention shown in Tables 1 to 4 and Comparative Samples 1 and 2, using specimens bent 90 degrees After the test was conducted for 24 hours, the surface was visually observed, and the flat plate portion and the 90-degree bent portion were evaluated with the following five grades.
Score 5: No change is observed on the surface.
Score 4: Slight white rust is observed on the surface to the extent that does not cause any practical problems.
Score 3: White rust of a practically problematic level is observed on the surface.
Score 2: A considerable amount of white rust is observed on the surface.
Score 1: White rust is observed on the entire surface.
The results are shown in Table 5.
次に、上記の表１から表４の中から選んだ表面処理鋼板に、表６及び表７に示す樹脂をそれぞれの条件で積層し、樹脂被覆表面処理鋼板を作成した。さらに、クロメート処理なしの電気Ｚｎ−Ｃｏ−Ｍｏめっき鋼板（比較材２）の上に有機樹脂を被覆した比較材４を作成した。また、従来の電解クロメート処理を行い、電気Ｚｎ−Ｃｏ−Ｍｏめっき鋼板上に全クロム量として３０ｍｇ／ｍ２のクロム水和酸化物皮膜を形成させた電気Ｚｎ−Ｃｏ−Ｍｏめっき鋼板（比較材１）の上に有機樹脂を被覆した比較材３を作成した。
Next, the resin shown in Table 6 and Table 7 was laminated on the surface-treated steel sheet selected from Table 1 to Table 4 above to create a resin-coated surface-treated steel sheet. Furthermore, the comparative material 4 which coat | covered the organic resin on the electric Zn-Co-Mo plated steel plate (comparative material 2) without chromate treatment was created. In addition, an electric Zn-Co-Mo plated steel sheet (comparative material) in which a conventional electrolytic chromate treatment was performed and a chromium hydrated oxide film having a total chromium content of 30 mg / m 2 was formed on the electric Zn-Co-Mo plated steel sheet. The comparative material 3 which coat | covered the organic resin on 1) was created.
このようにして得られた樹脂被覆表面処理鋼板の皮膜密着性を、先に示した耐食性とともに下記に示す要領で評価した。
The film adhesion of the thus obtained resin-coated surface-treated steel sheet was evaluated in the following manner together with the corrosion resistance shown above.
皮膜密着性
樹脂被覆表面処理鋼板を絞り比２．２で円筒カップ状に絞り加工し、カップ側面の皮膜を粘着テープで強制剥離し、皮膜の剥離程度を目視観察し、次に示す５段階の評点で評価した。
評点５：剥離が認められない。
評点４：実用上問題とならない程度のわずかな剥離が認められる。
評点３：実用上問題となる程度の剥離が認められる。
評点２：かなりの剥離が認められる。
評点１：側面全体に剥離が認められる。
以上の特性評価結果を表８に示す。
Film adhesion resin-coated surface-treated steel sheet is drawn into a cylindrical cup shape with a drawing ratio of 2.2, the film on the side of the cup is forcibly peeled with an adhesive tape, and the degree of film peeling is visually observed. Evaluated by rating.
Rating 5: No peeling is observed.
Score 4: Slight peeling that is not a practical problem is observed.
Score 3: Peeling that is a problem in practical use is recognized.
Score 2: Considerable peeling is observed.
Score 1: Peeling is observed on the entire side surface.
The above characteristic evaluation results are shown in Table 8.
表５に示すように、本発明の表面処理鋼板は、比較材２と比較して、優れた特性を示し、従来の電解クロメートを施した比較材１と比べても、同等以上の耐食性を有している。
また、本発明の表面処理鋼板に有機樹脂を被覆した樹脂被覆表面処理鋼板は、表８に示すように、電解クロメート無しのＺｎ−Ｃｏ−Ｍｏめっき鋼板の上に有機樹脂を被覆した比較材４よりも優れた特性を有し、従来の電解クロメートの上に有機樹脂を被覆した比較材３と比べても、同等以上の優れた耐食性、皮膜密着性を有している。
As shown in Table 5, the surface-treated steel sheet of the present invention exhibits superior characteristics compared to the comparative material 2, and has a corrosion resistance equal to or higher than that of the comparative material 1 subjected to conventional electrolytic chromate. is doing.
Moreover, as shown in Table 8, the resin-coated surface-treated steel sheet in which the surface-treated steel sheet of the present invention is coated with an organic resin is a comparative material 4 in which an organic resin is coated on a Zn—Co—Mo plated steel sheet without electrolytic chromate. Compared with the comparative material 3 which coat | covered the organic resin on the conventional electrolytic chromate, it has the same or more excellent corrosion resistance and film | membrane adhesiveness.
本発明は、Ｍｏ、Ｔｉ、Ｖ、Ｚｒのオキシ硫酸塩の一種以上と、Ｐ化合物と、Ｚｎ化合物とを含有する水溶液中で鋼板を浸漬処理、または電解処理することを特徴とする表面処理鋼板の製造方法であり、さらに、Ｍｇ、Ａｌの硫酸塩の一種以上、およびまたはホスホン酸塩を積極的に加えた水溶液中での、鋼板の浸漬処理または電解処理を特徴とする。さらにまた、前記オキシ硫酸塩がオキシ硫酸モリブデンまたは硫酸バナジルであることを特徴とする。そして、前記Ｐ化合物が、リン酸、重リン酸アンモニウム、重リン酸ナトリウム、重リン酸カルシウム、重リン酸マグネシウム、重リン酸アルミニウムの一種以上からなることを特徴とする表面処理鋼板の製造方法である。
また、その製造方法を用いてなる表面処理鋼板、およびその表面処理鋼板に有機樹脂を被覆した樹脂被覆表面処理鋼板である。本発明の表面処理鋼板の製造方法は作業環境の保全性に優れ、その製造方法を用いてなる表面処理鋼板は耐食性に優れており、さらにその表面処理鋼板に有機樹脂を被覆した樹脂被覆表面処理鋼板は耐食性に加えて皮膜の密着性に優れている。
The present invention relates to a surface-treated steel sheet characterized by dipping or electrolytically treating a steel sheet in an aqueous solution containing one or more oxysulfate salts of Mo, Ti, V, and Zr, a P compound, and a Zn compound. Further, the method is characterized in that the steel sheet is immersed or electrolyzed in an aqueous solution to which one or more of Mg and Al sulfates and / or phosphonates are positively added. Furthermore, the oxysulfate is characterized by being molybdenum oxysulfate or vanadyl sulfate. And the said P compound consists of 1 or more types of phosphoric acid, ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, and aluminum biphosphate, It is a manufacturing method of the surface treatment steel plate characterized by the above-mentioned. .
Moreover, it is the surface treatment steel plate which uses the manufacturing method, and the resin coating surface treatment steel plate which coat | covered the organic resin to the surface treatment steel plate. The manufacturing method of the surface-treated steel sheet of the present invention is excellent in work environment maintenance, the surface-treated steel sheet using the manufacturing method is excellent in corrosion resistance, and the surface-treated steel sheet is coated with an organic resin. In addition to corrosion resistance, the steel sheet has excellent film adhesion.
Claims (10)
Ｖのオキシ硫酸塩の一種以上と、リンの酸素酸又はリンの酸素酸塩と、Ｚｎ化合物とを含有し、且つＣｒを含有しない水溶液中で浸漬処理あるいは電解処理することを特徴とする、表面処理鋼板の製造方法。 Steel plate,
A surface characterized by immersion treatment or electrolytic treatment in an aqueous solution containing one or more oxysulfate salts of V, phosphorus oxyacid or phosphorus oxyacid salt, and Zn compound, and not containing Cr A method for producing a treated steel sheet.
Ｖのオキシ硫酸塩から形成された物質と、リンの酸素酸又はリンの酸素酸塩から形成された物質と、Ｚｎ化合物から形成された物質と、
を含有する保護被膜を鋼板上に被覆してなることを特徴とする、表面処理鋼板。 The steel sheet is immersed or electrolyzed in an aqueous solution containing one or more oxysulfates of V, phosphorus oxyacid or phosphorus oxyacid salt, and Zn compound, and not containing Cr,
A substance formed from V oxysulfate, a substance formed from phosphorus oxyacid or phosphorus oxyacid salt, a substance formed from Zn compound,
A surface-treated steel sheet obtained by coating a steel sheet with a protective film containing
Ｖのオキシ硫酸塩から形成された物質と、リンの酸素酸又はリンの酸素酸塩から形成された物質と、Ｚｎ化合物から形成された物質と、
を含有する保護被膜を鋼板上に被覆してなることを特徴とする、表面処理鋼板。 Immersion treatment or electrolytic treatment of a steel sheet in an aqueous solution containing one or more of V oxysulfate, phosphorus oxyacid or phosphorus oxyacid salt, Zn compound, and phosphonate and not containing Cr do it,
A substance formed from V oxysulfate, a substance formed from phosphorus oxyacid or phosphorus oxyacid salt, a substance formed from Zn compound,
A surface-treated steel sheet obtained by coating a steel sheet with a protective film containing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008283766A JP4845951B2 (en) | 1999-04-12 | 2008-11-04 | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1999104592 | 1999-04-12 | ||
| JP10459299 | 1999-04-12 | ||
| JP2008283766A JP4845951B2 (en) | 1999-04-12 | 2008-11-04 | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000610880A Division JP4312391B2 (en) | 1999-04-12 | 2000-04-11 | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009068115A true JP2009068115A (en) | 2009-04-02 |
| JP4845951B2 JP4845951B2 (en) | 2011-12-28 |
Family
ID=14384711
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000610880A Expired - Lifetime JP4312391B2 (en) | 1999-04-12 | 2000-04-11 | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin |
| JP2008283766A Expired - Fee Related JP4845951B2 (en) | 1999-04-12 | 2008-11-04 | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000610880A Expired - Lifetime JP4312391B2 (en) | 1999-04-12 | 2000-04-11 | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin |
Country Status (3)
| Country | Link |
|---|---|
| JP (2) | JP4312391B2 (en) |
| AU (1) | AU3677000A (en) |
| WO (1) | WO2000061835A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101490564B1 (en) * | 2012-12-21 | 2015-02-05 | 주식회사 포스코 | Hot press formed products having excellent corrosion resistance and method for manufacturing the same |
| JP2018028115A (en) * | 2016-08-15 | 2018-02-22 | 国立大学法人広島大学 | Agent and method for repairing plating base material, and plating base material |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3935664B2 (en) * | 2000-08-01 | 2007-06-27 | 住友金属工業株式会社 | Treatment liquid for insulating film formation of electrical steel sheet and method |
| TWI268965B (en) | 2001-06-15 | 2006-12-21 | Nihon Parkerizing | Treating solution for surface treatment of metal and surface treatment method |
| JP2004076024A (en) * | 2002-08-09 | 2004-03-11 | Nippon Paint Co Ltd | Aluminum base material processing method and product |
| EP1650327A4 (en) | 2003-07-29 | 2009-11-25 | Jfe Steel Corp | Surface-treated steel sheet and method for producing same |
| JP5093797B2 (en) * | 2006-03-24 | 2012-12-12 | 新日本製鐵株式会社 | Steel plate for containers with excellent can processability |
| ES2719740T3 (en) * | 2006-09-08 | 2019-07-12 | Nippon Steel Corp | Steel plate for container, and method for its production |
| JP7077121B2 (en) * | 2018-04-27 | 2022-05-30 | Ｎｏｆメタルコーティングス株式会社 | Repairable plating base material |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6210292A (en) * | 1985-07-09 | 1987-01-19 | Nippon Steel Corp | Manufacturing method of colored galvanized steel sheet |
| JPS6365086A (en) * | 1986-09-06 | 1988-03-23 | Nippon Steel Corp | Black surface treated steel sheet and its manufacturing method |
| JPS63195296A (en) * | 1987-02-09 | 1988-08-12 | Nippon Steel Corp | Manufacturing method of colored surface-treated steel sheet |
| JPH01246370A (en) * | 1988-03-25 | 1989-10-02 | Nippon Paint Co Ltd | Chemical conversion treatment for aluminum |
| JPH04128384A (en) * | 1990-09-17 | 1992-04-28 | Nippon Paint Co Ltd | Treatment of metallic surface, treating bath and treating agent |
| JPH07286285A (en) * | 1994-04-20 | 1995-10-31 | Nippon Paint Co Ltd | Chemical conversion treatment solution for metal surfaces |
| JPH0813154A (en) * | 1994-06-27 | 1996-01-16 | Nippon Parkerizing Co Ltd | Zinc-containing metal-plated steel sheet composite having excellent paintability, and method for producing the same |
| JPH08302477A (en) * | 1994-12-06 | 1996-11-19 | Nippon Parkerizing Co Ltd | Zinc phosphate chemical conversion treatment liquid for metal materials and treatment method |
| JPH09137278A (en) * | 1995-09-06 | 1997-05-27 | Nippon Parkerizing Co Ltd | Method for treating metal surface and aqueous composition used therefor |
| JPH10183364A (en) * | 1996-10-30 | 1998-07-14 | Nippon Hyomen Kagaku Kk | Protective film forming agent for metal and treatment thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861441A (en) * | 1986-08-18 | 1989-08-29 | Nippon Steel Corporation | Method of making a black surface treated steel sheet |
| JP3319831B2 (en) * | 1993-09-22 | 2002-09-03 | 日本パーカライジング株式会社 | Autodeposition type surface treatment agent for metal material and surface treatment method |
-
2000
- 2000-04-11 AU AU36770/00A patent/AU3677000A/en not_active Abandoned
- 2000-04-11 JP JP2000610880A patent/JP4312391B2/en not_active Expired - Lifetime
- 2000-04-11 WO PCT/JP2000/002356 patent/WO2000061835A1/en not_active Ceased
-
2008
- 2008-11-04 JP JP2008283766A patent/JP4845951B2/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6210292A (en) * | 1985-07-09 | 1987-01-19 | Nippon Steel Corp | Manufacturing method of colored galvanized steel sheet |
| JPS6365086A (en) * | 1986-09-06 | 1988-03-23 | Nippon Steel Corp | Black surface treated steel sheet and its manufacturing method |
| JPS63195296A (en) * | 1987-02-09 | 1988-08-12 | Nippon Steel Corp | Manufacturing method of colored surface-treated steel sheet |
| JPH01246370A (en) * | 1988-03-25 | 1989-10-02 | Nippon Paint Co Ltd | Chemical conversion treatment for aluminum |
| JPH04128384A (en) * | 1990-09-17 | 1992-04-28 | Nippon Paint Co Ltd | Treatment of metallic surface, treating bath and treating agent |
| JPH07286285A (en) * | 1994-04-20 | 1995-10-31 | Nippon Paint Co Ltd | Chemical conversion treatment solution for metal surfaces |
| JPH0813154A (en) * | 1994-06-27 | 1996-01-16 | Nippon Parkerizing Co Ltd | Zinc-containing metal-plated steel sheet composite having excellent paintability, and method for producing the same |
| JPH08302477A (en) * | 1994-12-06 | 1996-11-19 | Nippon Parkerizing Co Ltd | Zinc phosphate chemical conversion treatment liquid for metal materials and treatment method |
| JPH09137278A (en) * | 1995-09-06 | 1997-05-27 | Nippon Parkerizing Co Ltd | Method for treating metal surface and aqueous composition used therefor |
| JPH10183364A (en) * | 1996-10-30 | 1998-07-14 | Nippon Hyomen Kagaku Kk | Protective film forming agent for metal and treatment thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101490564B1 (en) * | 2012-12-21 | 2015-02-05 | 주식회사 포스코 | Hot press formed products having excellent corrosion resistance and method for manufacturing the same |
| JP2018028115A (en) * | 2016-08-15 | 2018-02-22 | 国立大学法人広島大学 | Agent and method for repairing plating base material, and plating base material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4312391B2 (en) | 2009-08-12 |
| AU3677000A (en) | 2000-11-14 |
| JP4845951B2 (en) | 2011-12-28 |
| WO2000061835A1 (en) | 2000-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4845951B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin | |
| WO2011118588A1 (en) | Steel sheet for container and method for producing same | |
| JP3967519B2 (en) | Zn-Mg electroplated metal plate and method for producing the same | |
| JP3987633B2 (en) | Metal protective film forming treatment agent and forming method | |
| JP4615807B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet | |
| JP3305703B2 (en) | Chemical treated steel sheet with excellent corrosion resistance | |
| JPWO2001042530A1 (en) | Surface-treated steel sheet manufacturing method, surface-treated steel sheet, and resin-coated surface-treated steel sheet | |
| JPWO2000061835A1 (en) | Surface-treated steel sheet manufacturing method, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating a surface-treated steel sheet with an organic resin | |
| CA2600996C (en) | Surface treated metal material | |
| JP4179527B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin | |
| JP2005105321A (en) | Method for manufacturing surface treated steel sheet of excellent appearance, surface treated steel sheet, film-covered surface-treated steel sheet | |
| JP3302676B2 (en) | Chemical treated steel sheet with excellent corrosion resistance | |
| JPWO2000055390A1 (en) | Surface-treated steel sheet manufacturing method, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating a surface-treated steel sheet with an organic resin | |
| JPS6213590A (en) | Surface-treated steel sheet having excellent coating property, adhesion after coating and corrosion resistance and its production | |
| JP3302679B2 (en) | Steel structure with excellent corrosion resistance | |
| JPH01108396A (en) | Manufacturing method of galvanized steel sheet for cationic electrodeposition coating | |
| JPH04333576A (en) | Production of surface-treated steel sheet having excellent adhesive property | |
| JP2003105587A (en) | Surface treated steel sheet for electronic part, and production method therefor | |
| JPH06340998A (en) | Surface treatment of metal with resin and chromate by cathode electrolysis | |
| KR920010778B1 (en) | Double layer alloy plated steel sheet with excellent plating adhesion, phosphate treatment and water resistance, and manufacturing method | |
| JP2954417B2 (en) | Black surface-treated steel sheet with excellent corrosion resistance and method for producing the same | |
| JP2569993B2 (en) | Method for producing chromate-treated galvanized steel sheet with excellent corrosion resistance, fingerprint resistance and paintability | |
| JPH04268096A (en) | Formation of chemical conversion film | |
| JPH0456798A (en) | Method for producing chromate-treated galvanized steel sheet with excellent corrosion resistance, fingerprint resistance, paintability, and surface color | |
| JPH06256971A (en) | Electrogalvanized steel sheet excellent in image clarity of coating and having high corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110622 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110817 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110902 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20110902 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111004 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111011 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141021 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4845951 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| 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 |