JP4179527B2 - 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 - Google Patents
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 Download PDFInfo
- Publication number
- JP4179527B2 JP4179527B2 JP2000605805A JP2000605805A JP4179527B2 JP 4179527 B2 JP4179527 B2 JP 4179527B2 JP 2000605805 A JP2000605805 A JP 2000605805A JP 2000605805 A JP2000605805 A JP 2000605805A JP 4179527 B2 JP4179527 B2 JP 4179527B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- treated steel
- resin
- treated
- film
- 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 - Lifetime
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 142
- 239000010959 steel Substances 0.000 title claims description 142
- 229920005989 resin Polymers 0.000 title claims description 73
- 239000011347 resin Substances 0.000 title claims description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000000576 coating method Methods 0.000 title claims description 13
- 239000011248 coating agent Substances 0.000 title claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 23
- 229910052750 molybdenum Inorganic materials 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 239000011574 phosphorus Substances 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 16
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052720 vanadium Inorganic materials 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000004645 polyester resin Substances 0.000 claims description 7
- 229920001225 polyester resin Polymers 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical group [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 6
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 6
- 229910000352 vanadyl sulfate Inorganic materials 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
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000010210 aluminium Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 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 4
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 4
- 239000008119 colloidal silica Substances 0.000 claims description 4
- 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 4
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 4
- 229910000401 monomagnesium phosphate Inorganic materials 0.000 claims description 4
- 235000019785 monomagnesium phosphate Nutrition 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 20
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 12
- 239000011651 chromium Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 7
- 230000002265 prevention Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 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
- 229910007567 Zn-Ni Inorganic materials 0.000 description 4
- 229910007614 Zn—Ni Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000008397 galvanized steel Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000003449 preventive effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-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
- 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
- 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 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
- 230000015572 biosynthetic process Effects 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
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052805 deuterium Inorganic materials 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 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
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 229920000728 polyester Chemical group 0.000 description 2
- 239000000843 powder Substances 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
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 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 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-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
- 229910001208 Crucible steel Inorganic materials 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 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
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 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
- 229910052793 cadmium Inorganic materials 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
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 239000012528 membrane Substances 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
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920006122 polyamide resin Polymers 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
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates 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
- 229910052715 tantalum Inorganic materials 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 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
-
- 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
- C23C22/20—Orthophosphates containing aluminium cations
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Description
【技術分野】
【０００１】
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。
【背景技術】
【０００２】
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、特開平１０−１８３３６４号公報は、Ｍｏ、Ｗ、Ｖ、Ｎｂ、Ｔａ、Ｔｉ、Ｚｒ、Ｃｅ、Ｓｒ、３価のクロムの１種以上の金属元素と、リンの酸素酸、酸素酸塩あるいはこれらの無水物に由来する物質を主成分とする皮膜、またはさらに酸化性物質に由来する物質、アルカリ土類金属、珪素、無機コロイドに由来する少なくとも１種類の物質を含有する皮膜を、Ｚｎ、Ｎｉ、Ｃｕ、Ａｇ、Ｆｅ、Ｃｄ、Ａｌ、Ｍｇまたはこれらの合金に被覆したものを開示しており、均一で良好な外観と耐食性を兼ね備えた皮膜を生成することが可能であることが記載されている。
上記の特開平１０−１８３３６４号公報において、上記金属の供給源としてモリブデン酸イオン、タングステン酸イオン、バナジン酸イオン、ニオブ酸イオン、タンタル酸イオン、三価のクロムイオンなどがあげられ、さらにこれらのイオンの供給源として、それぞれモリブデン酸ソーダ、モリブデン酸アンモン、タングステン酸アンモン、バナジン酸アンモン、酢酸クロム、硝酸クロムなどを用いることが記載されている。
さらに、リンの酸素酸、酸素酸塩あるいはこれらの無水物に由来する物質として、正リン酸、亜リン酸、次亜リン酸、ピロリン酸、トリポリリン酸、過リン酸などを用いることが記載されている。そして、上記の金属供給源と上記のリンの酸素酸、酸素酸塩あるいはこれらの無水物が皮膜の骨格をなす成分であり、酸化性が溶液の安定性を確保し、金属をエッチングしてスムーズな皮膜生成に寄与している、としている。
しかし、上記の特開平１０−１８３３６４号公報に記載された処理浴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と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。
【発明の開示】
【０００３】
（１）本発明の表面処理鋼板の製造方法は、鋼板を、Ｍｏ、Ｔｉ、Ｖ又はＺｒのオキシ硫酸塩の一種以上と、リンの酸素酸又は酸素酸塩と、Ｍｇ又はＡｌの硫酸塩の一種以上と、を含有する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、前記（１）において、前記オキシ硫酸塩がオキシ硫酸モリブデンであ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）において、前記オキシ硫酸塩が硫酸バナジル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）のいずかにおいて、
前記リンの酸素酸又は酸素酸塩が、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又は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（１）〜（４）のいずかにおいて、
前記鋼板が、Ｚｎめっき鋼板あるいはＺｎを含む合金めっき鋼板であることを特徴とする。
（６）本発明の表面処理鋼板の製造方法は、前記（５）において、
前記Ｚｎを含む合金めっき鋼板が、Ｚｎ−Ｃｏ−Ｍｏめっき鋼板であることを特徴とする。
（７）本発明の表面処理鋼板は、Ｍｏ、Ｔｉ、Ｖ又はＺｒの一種以上と、リンの酸素酸又は酸素酸塩から形成された物質と、Ｍｇ又はＡｌの一種以上の物質と、を含有する保護皮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（７）において、前記鋼板が、Ｚｎめっき鋼板あるいはＺｎを含む合金めっき鋼板であることを特徴とする。
（９）本発明の表面処理鋼板は、前記（８）において、前記Ｚｎめっき鋼板あるいはＺｎを含む合金めっき鋼板が、電解処理で形成されたものであることを特徴とする。
（１０）本発明の表面処理鋼板は、前記（９）において、前記Ｚｎを含む合金めっき鋼板が、Ｚｎ−Ｃｏ−Ｍｏめっき鋼板であることを特徴とする。
（１１）本発明の樹脂被覆表面処理鋼板は、前記（７）〜（１０）のいずれか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。
（１２）本発明の樹脂被覆表面処理鋼板は、前記（１１）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又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。
（１３）本発明の樹脂被覆表面処理鋼板は、前記（１１）又は（１２）において、
前記有機樹脂が、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むことを特徴とする。
【発明を実施するための最良の形態】
【０００４】
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、リン化合物を用いている。さらに、Ｍｇ、Ａｌの硫酸塩の一種以上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、リン化合物が、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又は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。リン酸またはリン酸塩は単独でも皮膜を形成するが、その皮膜は多孔質であり、鋼板上に皮膜を形成させた場合、耐食性に乏しい。耐食性を向上させることを目的として、クロム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、とりわけクロム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、クロム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、バナジン酸イオンなど、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クロム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、クロムに替わる金属としてＭｏ、Ｔｉ、Ｖ又はＺｒの一種以上をオキシ硫酸塩の形でリン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又はＺｒのオキシ硫酸塩とリン化合物に由来する物質を取り込むことにより、クロム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又は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又はＺｒについては４価のＴｉ、Ｖ又は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や合金元素と結びついて、Ｍｏ、Ｔｉ、Ｖ又は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Ｍｇ又はＡｌの一種以上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又は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。
【０００５】
以下に本発明についてその内容を説明する。
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、重リン酸アンモニウム（リン酸二水素アンモニウム）や重リン酸ナトリウム（リン酸二水素ナトリウム）などのリン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。
リン化合物の含有量は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。
上記のリン化合物は、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を含有するリンの酸素酸、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。
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とリン化合物のみ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は、白錆が発生しやすい。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を含有させる。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。なお、リン化合物として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。
【０００６】
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。
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。
【０００７】
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出来る。
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又は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又は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−ナイロン又は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又は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。
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。
【実施例】
【０００８】
以下、実施例にて本発明をさらに詳細に説明する。
＜表面処理鋼板の作成＞ 厚さ０．３ｍｍの冷延鋼板に、定法を用いて硫酸酸洗処理およびアルカリ電解脱脂処理を施した後、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 ： ２５０ ｇ／ｌ
（ＮＨ４）２ＳＯ４ ： ３０ ｇ／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 ： ２５０ ｇ／ｌ
ＣｏＳＯ４・７Ｈ２Ｏ ： ５０ ｇ／ｌ
（ＮＨ４）６Ｍｏ７Ｏ２４・４Ｈ２Ｏ： ０．２ ｇ／ｌ
（ＮＨ４）２ＳＯ４ ： ３０ ｇ／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）：４ ｍｌ／ｌ
浴温 ： ４０ ℃
電流密度 ： ２０ Ａ／ｄｍ２
めっき付着量 ： ５ ｇ／ｍ２
［Ｚｎ−Ｎｉ合金めっき条件］
浴組成 ＺｎＳＯ４・７Ｈ２Ｏ ： ２５０ ｇ／ｌ
ＮｉＳＯ４・７Ｈ２Ｏ ： ５０ ｇ／ｌ
（ＮＨ４）２ＳＯ４ ： １５ ｇ／ｌ
ポリビニールアルコール ： ２ ｇ／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。
【０００９】
【表１】
【表２】
【表３】
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。
（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。
【００１３】
【表４】
【００１４】
【表５】
【表６】
【表７】
【表８】
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。
（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。
【産業上の利用可能性】
【００１９】
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、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。
また、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。【Technical field】
[0001]
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.
[Background]
[0002]
Conventionally, in the field of steel sheets, particularly Zn-plated steel sheets, the steel sheets contain phosphates or chromates in order to improve rust prevention and adhesion to the coating film or resin layer formed thereon. Surface treatment is performed in a solution to form a protective film such as a phosphate film or a chromate film. However, the steel sheet on which the phosphate film is formed has poor corrosion resistance, and rust is likely to occur when the paint film or organic resin is not coated. Further, when a coating film or an organic resin is coated, the adhesiveness, particularly the adhesiveness during processing is insufficient.
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 Laid-Open No. 10-183364 discloses one or more metal elements such as Mo, W, V, Nb, Ta, Ti, Zr, Ce, Sr, and trivalent chromium, phosphorus oxygen acid, oxygen A film containing as a main component a substance derived from an acid salt or an anhydride thereof, or a film containing at least one substance derived from a substance derived from an oxidizing substance, an alkaline earth metal, silicon, or an inorganic colloid , Zn, Ni, Cu, Ag, Fe, Cd, Al, Mg, or an alloy thereof is disclosed, and it is possible to produce a film having a uniform and good appearance and corrosion resistance. Is described.
In the above-mentioned JP-A-10-183364, examples of the metal source include molybdate ion, tungstate ion, vanadate ion, niobate ion, tantalate ion, trivalent chromium ion, and the like. It is described that sodium molybdate, ammonium molybdate, ammonium tungstate, ammonium vanadate, chromium acetate, chromium nitrate, etc. are used as the ion source.
Furthermore, it is described that orthophosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, superphosphoric acid, etc. are used as substances derived from phosphorus oxyacids, oxyacid salts, or anhydrides thereof. ing. The above-mentioned metal supply source and the above-mentioned phosphorus oxyacid, oxyacid salt or anhydride thereof are the components that form the skeleton of the film, and the oxidization property ensures the stability of the solution, and the metal is etched and smooth. It is said that it contributes to the formation of a proper film.
However, even when a treatment film is formed on a metal plate such as a galvanized steel plate using the treatment bath described in JP-A-10-183364, 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 to an organic resin film, the surface-treated steel sheet, and the surface-treated steel sheet coated with an organic resin, instead of the surface-treated steel sheet subjected to the chromate treatment. An object of the present invention is to provide a resin-coated surface-treated steel sheet.
DISCLOSURE OF THE INVENTION
[0003]
(1) In the method for producing a surface-treated steel sheet according to the present invention, the steel sheet is made of one or more of Mo, Ti, V or Zr oxysulfate, phosphorus oxyacid or oxyacid salt, and Mg or Al sulfate. It is characterized by immersing or electrolytically treating in an aqueous solution containing one or more.
(2) The method for producing a surface-treated steel sheet according to the present invention is characterized in that in (1), the oxysulfate is molybdenum oxysulfate.
(3) The method for producing a surface-treated steel sheet according to the present invention is characterized in that in (1), the oxysulfate is vanadyl sulfate.
(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 oxygen acid or oxyacid salt of phosphorus is composed of one or more of ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate or aluminum biphosphate.
(5) The method for producing a surface-treated steel sheet according to the present invention is any one of the above (1) to (4).
The steel plate is a Zn-plated steel plate or an alloy-plated steel plate containing Zn.
(6) In the manufacturing method of the surface-treated steel sheet of the present invention,
The alloy-plated steel sheet containing Zn is a Zn-Co-Mo plated steel sheet.
(7) The surface-treated steel sheet of the present invention contains one or more of Mo, Ti, V or Zr, a substance formed from phosphorus oxyacid or oxyacid salt, and one or more substances of Mg or Al. It is characterized in that a protective film is coated on a steel plate.
(8) The surface-treated steel sheet of the present invention is characterized in that, in the above (7), the steel sheet is a Zn-plated steel sheet or an alloy-plated steel sheet containing Zn.
(9) The surface-treated steel sheet of the present invention is characterized in that, in the above (8), the Zn-plated steel sheet or the alloy-plated steel sheet containing Zn is formed by electrolytic treatment.
(10) The surface-treated steel sheet according to the present invention is characterized in that in (9), the alloy-plated steel sheet containing Zn is a Zn-Co-Mo plated steel sheet.
(11) 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 (7) to (10) is coated with an organic resin.
(12) In the resin-coated surface-treated steel sheet of the present invention, in (11), the organic resin is any one of a polyester resin, a urethane resin, an acrylic resin, a polyolefin resin, or a polyvinyl chloride resin. It is characterized by that.
(13) The resin-coated surface-treated steel sheet of the present invention is the above (11) or (12),
The organic resin contains one or more of colloidal silica, polytetrafluoroethylene, polyethylene wax, silane coupling agent, or chromium-free rust preventive agent.
BEST MODE FOR CARRYING OUT THE INVENTION
[0004]
In the surface treatment bath of the present invention, Mo, Ti, V, Zr oxysulfates and phosphorus 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 are positively added is used. Furthermore, the oxysulfate is characterized by being molybdenum oxysulfate or vanadyl sulfate, and the phosphorus compound is one of ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate or aluminum biphosphate It is characterized by the above. Phosphoric acid or phosphate alone forms a film, but the film is porous and has poor corrosion resistance when the film is formed on a steel sheet. For the purpose of improving the corrosion resistance, it has been practiced to incorporate a metal such as chromium into a phosphoric acid film. In particular, chromium 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 chromium. All of these metals are added to the treatment bath in the form of metal acid ions such as molybdate, tungstate, vanadate, etc., but the surface treatment film obtained uses chromium. The properties of the surface-treated film were not shown.
In the present invention, one or more of Mo, Ti, V or Zr as a metal instead of chromium is contained in a treatment liquid together with a phosphorus compound in the form of an oxysulfate, and in the treatment film formed using this treatment bath. It has been found that by incorporating a substance derived from Mo, Ti, V or Zr oxysulfate and a phosphorus compound, film properties equivalent to or better than those of a surface treatment film using chromium can be obtained. The reason for this is not well understood, but when Mo, Ti, V, or Zr is contained in the form of oxysulfate in the treatment bath, trivalent, pentavalent, and hexavalent molybdenum becomes oxygen ions. A compound in which (O 2− ) and sulfate ion (SO 4 2− ) are combined, and for Ti, V or Zr, tetravalent Ti, V or Zr is oxygen ion (O 2− ) and sulfate ion (SO 4). 2- ) The substance derived from the compound combined with) becomes a component that forms a skeleton of the film formed on the steel plate together with P, and this film is considered to have excellent rust prevention properties. In particular, when the steel plate is a Zn-plated steel plate or a Zn-based alloy-plated steel plate, it is combined with Zn or an alloy element in the plating film, and one or more of Mo, Ti, V or 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 including one or more of Mg or Al actively in the said film | membrane.
Furthermore, these films contain Mo, Ti, V or 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.
[0005]
The contents of the present invention will be described below.
First, the treatment bath will be described. The treatment bath of the present invention comprises one or more of Mo, Ti, V, and Zr oxysulfates that are molybdenum oxysulfate, titanyl sulfate, vanadyl sulfate, and zirconyl sulfate, ammonium biphosphate (ammonium dihydrogen phosphate), It consists of an aqueous solution containing a phosphorus compound such as sodium phosphate (sodium dihydrogen phosphate), and it can be added with one or more of Mg or Al sulfate such as magnesium sulfate and aluminum sulfate to improve rust resistance. good. 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 phosphorus 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 phosphorus compound, one or more compounds such as phosphoric oxyacids and oxyacid salts containing P including orthophosphoric acid, condensed phosphoric acid, phosphorous acid and hypophosphorous acid 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.
In the present invention, when a surface-treated steel sheet is prepared using a treatment bath containing only one or more of the above metal oxysulfates and a phosphorus compound, and coated with an organic resin, good corrosion resistance and film adhesion A resin-coated surface-treated steel sheet is obtained.
However, when this treatment bath is applied to a galvanized steel sheet and used without being coated with an organic resin, white rust is likely to occur. Therefore, the treatment bath further contains one or more of Mg or Al sulfates such as magnesium sulfate and aluminum sulfate. The total content 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 more. In addition, when magnesium deuterium phosphate or aluminum deuterium phosphate containing Mg or Al as the phosphorus compound is used, the same effect as 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 sulfuric acid or phosphoric acid. The temperature of the treatment bath is preferably in the range of 20 to 50 ° C.
[0006]
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 are applicable. 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.
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 plate, a hot-dip Zn-plated steel plate, a hot-dip Zn-based alloy-plated steel plate containing Al or Mg, an electric Zn-plated steel plate, or an electric Zn-based alloy-plated steel plate, particularly an electric Zn-Co- There are Mo-plated steel sheets, 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.
[0007]
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 polyester resin, polyolefin resin, polyvinyl chloride resin, polycarbonate resin, urethane resin, and acrylic resin can be used. It is preferable to use it. 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. I can do it.
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. Mention may be made of copolymer polymers such as polymers or 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, a lubricant powder such as polytetrafluoroethylene or 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.
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.
【Example】
[0008]
Hereinafter, the present invention will be described in more detail with reference to examples.
<Creation of surface-treated steel sheet> After subjecting a cold-rolled steel sheet having a thickness of 0.3 mm to a sulfuric acid pickling treatment and an alkaline electrolytic degreasing treatment using a conventional method, Zn plating, Zn-Co-Mo plating, Alternatively, Zn-Ni alloy plating was performed to prepare a Zn-plated steel plate, a Zn-Co-Mo plated steel plate, or a Zn-Ni alloy-plated steel plate.
[Zn plating conditions]
Bath composition ZnSO 4 · 7H 2 O: 250 g / l
(NH4) 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: 50 g / l
(NH 4) 6Mo 7 O 24 · 4H 2 O: 0.2 g / l
(NH 4 ) 2 SO 4 : 30 g / l
Brightener (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: 50 g / l
(NH 4 ) 2 SO 4 : 15 g / l
Polyvinyl alcohol: 2 g / 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.
[0009]
[Table 1]
[Table 2]
[Table 3]
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.
(Evaluation of corrosion resistance of surface-treated steel sheet)
(Corrosion resistance)
After performing the salt spray test based on JIS-Z2371, for the surface-treated steel sheets of the present invention shown in Table 1 to Table 4 and Comparative Materials 1 and 2, using a test piece bent 90 degrees, 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.
[0013]
[Table 4]
[0014]
[Table 5]
[Table 6]
[Table 7]
[Table 8]
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.
(Film adhesion)
The 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 off with an adhesive tape, the degree of peeling of the film is visually observed, and evaluated by the following five grades. did.
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.
[Industrial applicability]
[0019]
The surface-treated steel sheet of the present invention exhibits excellent characteristics as compared with the comparative material 2 and has corrosion resistance equal to or higher than that of the comparative material 1 subjected to conventional electrolytic chromate.
In addition, the resin-coated surface-treated steel sheet in which the surface-treated steel sheet of the present invention is coated with an organic resin has characteristics superior to those of the comparative material 4 in which an organic resin is coated on a Zn-Co-Mo plated steel sheet without electrolytic chromate. Even compared with the comparative material 3 in which an organic resin is coated on a conventional electrolytic chromate, it has equivalent or better corrosion resistance and film adhesion.
Moreover, the manufacturing method of the surface-treated steel sheet according to the present invention is excellent in work environment maintenance, the surface-treated steel sheet using the manufacturing method is excellent in corrosion resistance, and is further coated with an organic resin on the surface-treated steel sheet. The surface-treated steel sheet is excellent in the adhesion of the film in addition to the corrosion resistance.
Claims (13)
Ｍｇ又はＡｌの硫酸塩の一種以上と、
を含有する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。A steel plate, one or more of Mo, Ti, V or Zr oxysulfate, and an oxygen acid or oxyacid salt of phosphorus;
One or more of Mg or Al sulfate,
A method for producing a surface-treated steel sheet, which comprises dipping treatment or electrolytic treatment in an aqueous solution containing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6599799 | 1999-03-12 | ||
| PCT/JP2000/001403 WO2000055390A1 (en) | 1999-03-12 | 2000-03-08 | Method for producing surface treated steel sheet, surface treated steel sheet and surface treated steel sheet coated with resin comprising surface treated steel sheet and organic resin coated thereon |
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| Publication Number | Publication Date |
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| JP4179527B2 true JP4179527B2 (en) | 2008-11-12 |
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| JP2000605805A Expired - Lifetime JP4179527B2 (en) | 1999-03-12 | 2000-03-08 | 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 |
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| JP (1) | JP4179527B2 (en) |
| AU (1) | AU2938900A (en) |
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| JP4500132B2 (en) * | 2003-08-20 | 2010-07-14 | Ｊｆｅスチール株式会社 | Chromate-free surface-treated Al-Zn alloy-plated steel sheet with excellent corrosion resistance, workability and appearance quality and method for producing the same |
| JP4517737B2 (en) * | 2004-06-15 | 2010-08-04 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet with excellent corrosion resistance, conductivity, and coating appearance |
| JP4998707B2 (en) * | 2007-01-29 | 2012-08-15 | Ｊｆｅスチール株式会社 | Surface-treated metal plate and manufacturing method thereof, resin-coated metal plate, metal can and can lid |
| JP4521010B2 (en) * | 2007-04-09 | 2010-08-11 | 日本パーカライジング株式会社 | Metal surface treatment agent, metal surface treatment method and surface treatment metal material |
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| JP3392008B2 (en) * | 1996-10-30 | 2003-03-31 | 日本表面化学株式会社 | Metal protective film forming treatment agent and treatment method |
| JPH1161429A (en) * | 1997-08-28 | 1999-03-05 | Nippon Steel Corp | Surface treated metal material |
| JP3987633B2 (en) * | 1998-05-21 | 2007-10-10 | 日本表面化学株式会社 | Metal protective film forming treatment agent and forming method |
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