WO2022044195A1 - Coated steel sheet and coated steel sheet manufacturing method - Google Patents
Coated steel sheet and coated steel sheet manufacturing method Download PDFInfo
- Publication number
- WO2022044195A1 WO2022044195A1 PCT/JP2020/032350 JP2020032350W WO2022044195A1 WO 2022044195 A1 WO2022044195 A1 WO 2022044195A1 JP 2020032350 W JP2020032350 W JP 2020032350W WO 2022044195 A1 WO2022044195 A1 WO 2022044195A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- steel sheet
- coated steel
- phosphate
- less
- group
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 227
- 239000010959 steel Substances 0.000 title claims abstract description 227
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 131
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 129
- 239000010452 phosphate Substances 0.000 claims abstract description 129
- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
- 239000002184 metal Substances 0.000 claims abstract description 82
- 238000007747 plating Methods 0.000 claims abstract description 59
- 238000007789 sealing Methods 0.000 claims abstract description 58
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 40
- 239000011701 zinc Substances 0.000 claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000000126 substance Substances 0.000 claims description 50
- 150000002739 metals Chemical class 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000004566 building material Substances 0.000 claims description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 4
- 102000004316 Oxidoreductases Human genes 0.000 claims description 4
- 108090000854 Oxidoreductases Proteins 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 34
- 238000005260 corrosion Methods 0.000 abstract description 34
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 11
- 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
- 230000008021 deposition Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 23
- 239000013078 crystal Substances 0.000 description 20
- -1 phosphate anion Chemical class 0.000 description 14
- 125000004429 atom Chemical group 0.000 description 13
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 10
- 229910001335 Galvanized steel Inorganic materials 0.000 description 10
- 230000002708 enhancing effect Effects 0.000 description 10
- 239000008397 galvanized steel Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 5
- 229910000165 zinc phosphate Inorganic materials 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OXAUNDBQHKIUSD-UHFFFAOYSA-N azanium;titanium;fluoride Chemical compound [NH4+].[F-].[Ti] OXAUNDBQHKIUSD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 2
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 2
- 239000004137 magnesium phosphate Substances 0.000 description 2
- 229960002261 magnesium phosphate Drugs 0.000 description 2
- 235000010994 magnesium phosphates Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000002926 oxygen Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- OSKILZSXDKESQH-UHFFFAOYSA-K zinc;iron(2+);phosphate Chemical compound [Fe+2].[Zn+2].[O-]P([O-])([O-])=O OSKILZSXDKESQH-UHFFFAOYSA-K 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- 229940122361 Bisphosphonate Drugs 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910000954 Medium-carbon steel Inorganic materials 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910001327 Rimmed steel Inorganic materials 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- SDXDHLDNCJPIJZ-UHFFFAOYSA-N [Zr].[Zr] Chemical compound [Zr].[Zr] SDXDHLDNCJPIJZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Definitions
- the present invention relates to a coated steel sheet and a method for manufacturing a coated steel sheet.
- Steel sheets used for the exterior and roof of buildings may be required to have a black appearance in order to enhance their design.
- a coated steel sheet in which a coating film (coating) is formed on the surface of a galvanized steel sheet, some methods have been proposed in which the appearance of the galvanized steel sheet is blackened by blackening the coating film.
- Patent Document 1 contains a predetermined amount of a compound having two nickel ions or cobalt ions, an ammonium ion or a primary amino group, a nitrate ion, and a fluoride on the surface of a zinc-based plating material. It is described that the zinc-based plating material can be blackened by contacting with a treatment liquid having a pH of 2.0 to 4.8.
- a hot-dip galvanized steel sheet or a hot-dip galvanized steel sheet is treated with zinc phosphate in a zinc phosphate-treated bath containing a predetermined amount of Fe 2+ , Mn 2- and Ni 2+ . It is stated that the lightness index can be 20-40.
- the appearance of the galvanized steel sheet can be blackened by surface-treating the galvanized steel sheet with a predetermined treatment liquid.
- the coated steel sheet used for the exterior and roof of a building is also required to have corrosion resistance that suppresses the generation of white rust for a long period of time. Not high enough. Therefore, conventionally, in order to improve the corrosion resistance of a galvanized steel sheet, a chrome sealing film and an organic film have been formed on the surface of a phosphate-treated layer formed by zinc phosphate treatment or the like.
- the chrome sealing film has an effect of enhancing the adhesion of the organic film while enhancing the corrosion resistance of the coated steel sheet (for example, the organic film is sufficiently adhered even after being processed).
- the present invention has been made in view of the above points, and the appearance of the coated steel sheet having a chromium-free sealing film and an organic film that does not substantially contain chromium (Cr) is sufficiently blackened and is further blackened. It is an object of the present invention to provide a coated steel sheet having sufficiently improved corrosion resistance and adhesion of a processed portion, and a method for manufacturing such a coated steel sheet.
- the coated steel sheet according to the embodiment of the present invention for solving the above problems has a steel sheet, a zinc-based plating layer, and a total adhesion amount of Ni and Co of 20 mg / m 2 or more and 100 mg / m 2 or less, and is a treated layer.
- the surface brightness (L *) of the coated steel sheet is 55 or less.
- the method for manufacturing a coated steel plate according to an embodiment of the present invention for solving the above problems includes a step of preparing a plated steel plate having a zinc-based plating layer and contacting the zinc-based plating layer with Ni and Co.
- a chemical conversion treatment solution containing a group 4 metal oxidase, a group 1 metal or a salt thereof, and an ammonium ion and having a pH of 7.0 or more and 9.0 or less is applied in contact with the phosphate treatment layer. It has a step of forming a chrome-free sealing film and a step of contacting with the chrome-free sealing film to form an organic film.
- a coated steel sheet having a chromium-free sealing film and an organic film that substantially does not contain chromium (Cr) the appearance is sufficiently blackened, and the corrosion resistance and the adhesion of the processed portion are sufficient.
- Enhanced coated steel sheets, and methods for manufacturing such coated steel sheets are provided.
- An embodiment of the present invention relates to a painted steel sheet in which a coating film is formed on the surface of the steel sheet.
- a coating film is formed on the surface of the steel sheet.
- a steel sheet, a zinc-based plating layer, a phosphate-treated layer, a chrome-free sealing film, and an organic-based film are laminated in this order, and the surface brightness (L *) is 55 or less. Is.
- the steel sheet may be any steel sheet that can form a zinc-based plating layer, may be carbon steel containing low carbon steel, medium carbon steel, high carbon steel, or the like, or may be an alloy steel containing Mn, Cr, Si, Ni, or the like. But it may be.
- the steel plate may be a killed steel containing Al killed steel or the like, or may be a rimmed steel. When good press formability is required, a steel sheet for deep drawing containing low-carbon Ti-added steel, low-carbon Nb-added steel, or the like is preferable as the steel sheet. Further, a high-strength steel plate in which the amounts of P, Si, Mn and the like are adjusted to specific values may be used.
- the zinc-based plating layer is a plating layer containing zinc as a main component.
- the plating constituting the zinc-based plating layer is described from Zn plating (pure zinc plating), Zn—Al alloy plating, Zn—Mg alloy plating, Zn—Ni alloy plating, Zn—Al—Mg alloy plating, and the like. It can be selected according to the application of the surface-treated zinc-based plated steel plate.
- the zinc-based plating layer may be a plating layer formed by any known method such as an electroplating method, a hot-dip plating method, and a vapor deposition plating method.
- the zinc-based plating layer is preferably a plating layer formed by a hot-dip plating method because a zinc-based plating layer having a larger amount of adhesion can be easily produced.
- the zinc-based plating layer preferably contains Al of 0.1% by mass or more and 22.0% by mass or less in order to enhance the corrosion resistance of the coated steel sheet.
- the zinc-based plating layer preferably has an adhesion amount of 100 g / m 2 or more in order to enhance the durability of the zinc-based plating layer when the coated steel sheet is used as an exterior building material in a relatively harsh environment such as a beach area. ..
- Phosphate-treated layer is a layer containing phosphate crystals formed on the surface of the zinc-based plating layer.
- the phosphate-treated layer is a film having a phosphate anion and having a plurality of phosphate crystals composed of compounds capable of forming sparingly water-soluble crystals arranged on the surface of the zinc-based plating layer.
- phosphate crystals include magnesium phosphate, manganese phosphate, zinc phosphate, iron phosphate, zinc iron phosphate, zinc phosphate calcium and the like.
- the phosphate treatment layer contains Ni and Co. Both Ni and Co give the coated steel sheet a black appearance, presumably by substituting and precipitating fine particles on the surface of the zinc-based plating layer to produce a light scattering effect. From the viewpoint of better blackening the appearance of the coated steel sheet, the total amount of Ni and Co adhered to the phosphate-treated layer is 20 mg / m 2 or more. On the other hand, from the viewpoint of suppressing the deterioration of the corrosion resistance of the coated steel sheet due to the above-mentioned substitution precipitation inhibiting the precipitation of phosphate crystals, the total adhesion amount of Ni and Co in the phosphate-treated layer is 100 mg / m. 2 or less.
- the total amount of Ni and Co adhered to the phosphate-treated layer is preferably 30 mg / m 2 or more and 80 mg / m 2 or less, and 40 mg / m 2 or more and 70 mg / m 2 or less. More preferred.
- the phosphate-treated layer may contain metal elements such as Mn, Mg, Ca, and Fe, or an aliphatic amine as other components.
- the amount of the phosphate-treated layer adhered is such that the amount of the phosphate crystals adhered is increased and the thickness of the precipitation layer due to Ni and Co deposited at the position where the phosphate crystals are not adhered is increased to increase the thickness of the coated steel plate.
- the temperature should be 2.0 g / m 2 or more.
- the phosphate-treated layer is used.
- the amount of adhesion shall be 7.0 g / m 2 or less.
- the amount of the phosphate-treated layer adhered is preferably 2.5 g / m 2 or more and 7.0 g / m 2 or less, and 3.0 g / m 2 or more and 6.0 g / m 2 or less. It is more preferable to have.
- the brightness (L *) of the surface of the coated steel sheet is 55 by appropriately controlling the total amount of Ni and Co adhered to the phosphate-treated layer and the amount of adhesion of the phosphate-treated layer.
- it can be preferably 50 or less, more preferably 40 or more and 50 or less.
- the brightness (L *) is a value measured by a spectral reflection measurement method based on JIS K 5600-4-5 (1999) using a spectroscopic color difference meter.
- the 60 ° gloss value of the surface of the coated steel sheet is obtained by appropriately controlling the total amount of Ni and Co adhered to the phosphate-treated layer and the amount of adhesion of the phosphate-treated layer. It can be 10 or less, preferably 8 or less, and more preferably 5 or less.
- the 60 ° gloss value is a value measured in accordance with JIS K 5600-4-5 (1999).
- Chromium-free sealing film is a film containing an oxygenate of a Group 4 metal and a Group 1 metal or a salt thereof formed on the surface of the phosphate-treated layer.
- the chromium-free sealing film is a chemical conversion treatment formed by a chemical conversion treatment liquid containing an oxidase of a group 4 metal, a salt of the group 1 metal or a salt thereof, and an ammonium ion and having a pH of 7.0 or more and 9.0 or less. It is a film.
- the above-mentioned group 4 metal oxygen salt improves the corrosion resistance (flat portion corrosion resistance and processed portion corrosion resistance) of the coated steel sheet by forming a dense chemical conversion treatment film (chromium-free sealing film).
- the Group 4 metals include Ti, Zr and Hf.
- the above-mentioned group 4 metal oxyate salt is a salt of an inorganic acid containing a group 4 metal atom and an oxygen atom.
- the above salts include hydrides, ammonium salts, alkali metal salts, alkaline earth metal salts and the like.
- the oxygen salt of the Group 4 metal is preferably an ammonium salt of an inorganic acid containing a Group 4 metal atom and an oxygen atom, and is zirconium ammonium carbonate. Is preferable.
- the amount of the oxygen acid salt of the Group 4 metal adhered to the chromium-free sealing film is 2 mg / m 2 or more and 80 mg / m 2 or less in terms of Group 4 metal atom. It is preferable that it is 5 mg / m 2 or more and 30 mg / m 2 or less.
- the Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid to provide adhesion between the chromium-free sealing film and the phosphate-treated layer, and between the chromium-free sealing film and the organic film. Improves adhesion. Further, the Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid, suppresses the bond between the Group 4 metal and phosphorus in the chemical conversion treatment, and gels the chemical conversion treatment liquid by these bonds. By suppressing the formation, the long-term storage stability (stability) of the chemical conversion treatment liquid is enhanced.
- the Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid, making it difficult for water to be removed when the chemical conversion treatment liquid is dried, and the chromium-free sealing film is excessively dried during production. It is possible to suppress the occurrence of cracks due to the cracking.
- the Group 1 metals include Li, Na, K and the like. Of these, the Group 1 metal is preferably Na from the viewpoint of further enhancing the adhesion to the phosphate-treated layer and the organic film and further suppressing the generation of cracks.
- the Group 1 metal may be a phosphate such as sodium diphosphate, potassium diphosphate and sodium tripolyphosphate, or 1-hydroxyethylidene-1,1-bisphosphonate disodium, and 1-hydroxyethylidene. It may be an organic phosphonic acid such as -1,1-diphosphonate pentasodium, or it may be another compound such as a hydroxide of a Group 1 metal.
- the Group 1 metals are sodium tripolyphosphate and 1-hydroxyethylidene. It is preferably -1,1-bisphosphonate disodium or 1-hydroxyethylidene-1,1-diphosphonate pentasodium.
- the amount of the Group 1 metal or its salt in the chromium-free sealing film is Group 4. It is preferable that the amount of the Group 1 metal atom is 0.5 parts by mass or more and 21 parts by mass or less with respect to 100 parts by mass of the metal atom. Similarly, the amount of the Group 1 metal or a salt thereof in the chrome-free sealing film is preferably an amount such that the molar ratio of the Group 1 metal atom to the Group 4 metal atom is 0.02 or more and 0.8 or less. ..
- the amount of the chrome-free sealing film adhered is not particularly limited, but can be 3 mg / m 2 or more and 1000 mg / m 2 or less, and 5 mg / m 2 or more and 500 mg / m 2 or less from the viewpoint of improving spot weldability. Is preferable.
- the chromium-free sealing film contains oxides, hydroxides or fluorides of V, Mo, P, Ti or Si in order to further enhance the corrosion resistance of the coated steel sheet in a situation where salt water such as seawater is applied. You may.
- the chromium-free sealing film contains substantially no hexavalent chromium. Specifically, four 50 mm ⁇ 50 mm test pieces were cut out from the coated steel sheet, immersed in 100 mL of boiling pure water for 10 minutes, and then the hexavalent chromium eluted in the pure water was added to JIS H8625 (JIS H8625). 1993) It is below the detection limit when quantified by the concentration analysis method based on the "diphenylcarbazide colorimetric method" of 2.4.1 of the annex.
- the chemical conversion treatment liquid containing each of the above components is usually acidic.
- the phosphate treatment layer or the zinc-based plating layer may be partially dissolved in the chemical conversion treatment liquid.
- these layers are partially dissolved in the chemical conversion treatment liquid, the brightness of the coated steel sheet becomes high, the appearance of the coated steel sheet becomes uneven, and the components of these layers are mixed in the chromium-free sealing film and each of them is used. The properties expected of the layer may not be fully exhibited.
- a chromium-free sealing film is formed by using a chemical conversion treatment liquid having a pH of 7.0 or more and 9.0 or less.
- the method for adjusting the pH is not particularly limited, it is preferable to adjust the pH to the above range with ammonium ions from the viewpoint of suppressing the influence on the characteristics of the chromium-free sealing film.
- an ammonium salt derived from ammonium ions contained in the chemical conversion treatment liquid may remain on the chromium-free sealing film.
- Organic film is a film formed on the surface of the chromium-free sealing film and containing an organic resin as a main component.
- the organic resin constituting the organic film may be any organic resin usually used for surface treatment of galvanized steel sheets, and may be appropriately selected from, for example, urethane resin, fluororesin, acrylic resin, polyester resin and the like. Can be done.
- the organic film containing these organic resins can enhance the corrosion resistance and processability of the coated steel sheet.
- the organic resin is preferably a urethane resin or a polyester resin, and more preferably a urethane resin.
- the urethane resin usually has a structural unit derived from an isocyanate compound and a structural unit derived from a polyol compound.
- Examples of the structural unit derived from the isocyanate compound include a structural unit derived from an aliphatic diisocyanate and a structural unit derived from an alicyclic diisocyanate.
- Examples of the aliphatic diisocyanate include phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate.
- Examples of the alicyclic diisocyanate include cyclohexane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate.
- Examples of the structural unit derived from the above-mentioned polyol compound include a structural unit derived from a polyolefin polyol.
- Examples of the polyolefin polyols include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols and polybutadiene polyols.
- the organic film is one or more compounds selected from the group consisting of an oxide of a valve metal, a hydroxide of a valve metal, or a fluoride of a valve metal (hereinafter, also simply referred to as "valve metal compound").
- valve metal compound a compound selected from the group consisting of an oxide of a valve metal, a hydroxide of a valve metal, or a fluoride of a valve metal (hereinafter, also simply referred to as "valve metal compound”).
- Etc. may be included.
- the valve metal compound can impart an excellent barrier action to the organic film while reducing the environmental load.
- the valve metal is a metal whose oxide exhibits high insulation resistance. Examples of the valve metal include one kind or two or more kinds of metals selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W. A known valve metal compound may be used.
- soluble fluoride of valve metal in the organic film, it is possible to impart a self-repairing action to the organic film.
- Fluoride of the valve metal dissolves in the moisture in the atmosphere and then reprecipitates as a sparingly soluble oxide or hydroxide on the surface of the plated steel sheet exposed from the film defect part, and the film defect part is formed. Can be filled.
- the organic film may further contain a soluble or sparingly soluble metal phosphate or a composite phosphate in addition to the soluble fluoride of the valve metal.
- Soluble phosphate elutes from the organic film into the film defect and reacts with the metal of the plated steel plate to form an insoluble phosphate, which can complement the self-healing action of the soluble fluoride of valve metal. can.
- the poorly soluble phosphate can be dispersed in the organic film to improve the film strength.
- the film thickness of the organic film is preferably 3.0 ⁇ m or more.
- the film thickness of the organic film is 3.0 ⁇ m or more, it becomes difficult for the corrosive factor permeating the organic film to reach the plating layer, and the corrosion resistance of the coated steel sheet can be sufficiently enhanced.
- the upper limit of the film thickness of the organic film is not particularly limited, it can be 15 ⁇ m.
- the organic film may be a colored film containing an organic pigment or the like, but from the viewpoint of further enhancing the visibility of the black appearance of the phosphate-treated layer and further enhancing the design of the coated steel sheet. , It is preferable that it is a clear film.
- coated steel sheet can be used for various purposes.
- the coated steel sheet has a sufficiently blackened appearance, and has sufficiently improved corrosion resistance and adhesion of the processed portion, so that it can be suitably used as an exterior building material such as a roof of a building. can.
- the coated steel sheet may be a flat plate or a processed product processed into various shapes.
- the above-mentioned coated steel sheet includes a step of preparing a plated steel sheet having a zinc-based plating layer, a step of forming the phosphate-treated layer, a step of forming the chrome-free sealing film, and the above-mentioned organic. It can be produced by a method including a step of forming a system film.
- Step of preparing a plated steel sheet In the step of preparing the above-mentioned plated steel sheet, the above-mentioned steel sheet is used as a base steel sheet, and the above-mentioned galvanized steel sheet is prepared. In this step, a plated steel sheet that has already been produced may be prepared, or the base steel sheet is subjected to zinc-based plating by a known method such as an electroplating method, a hot-dip plating method, or a vapor deposition plating method, and the plated steel sheet is subjected to zinc-based plating. May be produced.
- a known method such as an electroplating method, a hot-dip plating method, or a vapor deposition plating method
- Step of Forming Phosphate Treatment Layer In the step of forming the phosphate treatment layer, a phosphate treatment liquid is applied so as to be in contact with the zinc-based plating layer of the prepared plated steel plate, and the zinc-based plating is performed. Phosphate crystals are deposited on the surface of the layer.
- the phosphate treatment liquid is a treatment liquid containing Ni or Co and phosphate ions.
- the phosphate treatment solution can be prepared by dissolving phosphate or phosphoric acid and a metal salt capable of generating Ni or Co ions in an aqueous solvent.
- Examples of the above phosphate include magnesium phosphate, manganese phosphate, zinc phosphate, iron phosphate, zinc iron phosphate, zinc phosphate calcium and the like.
- the concentration of phosphate ions in the phosphate treatment solution is 0.03. It is preferably mol / L or more and 0.5 mol / L or less.
- the concentration of Ni or Co ions in the phosphate treatment solution is the total adhesion of Ni and Co when the adhesion amount of the phosphate treatment layer is 2.0 g / m 2 or more and 7.0 g / m 2 or less. The amount may be adjusted to be 20 mg / m 2 or more and 100 mg / m 2 or less.
- the phosphate treatment solution further contains a polyamine-based organic inhibitor containing an aliphatic polyamine containing polyethylamine, polyethyleneimine, polyetheramine, polyaminoacrylate and the like, and an aromatic polyamine containing polyaniline and the like. May be good.
- the polyamine-based organic inhibitor can precipitate the crystal particles of phosphate at appropriate intervals and can make the crystal particles of phosphate finer.
- the number average molecular weight of the polyamine-based organic inhibitor is preferably 200 or more and 30,000 or less. Further, from the viewpoint of appropriately adjusting the amount of precipitated phosphate crystals, the concentration of the polyamine-based organic inhibitor in the phosphate treatment liquid is preferably 0.01% by mass or more and 5% by mass or less.
- the phosphate treatment solution may further contain nitrate ions. Nitrate ions promote the precipitation of phosphate.
- the concentration of nitrate ions in the phosphate treatment solution is preferably 0.01 mol / L or more and 1.0 mol / L or less.
- the phosphate treatment solution may further contain fluoride.
- fluoride include sodium fluoride, potassium fluoride, sodium hydrogen fluoride and the like.
- concentration of fluoride in the phosphate treatment liquid is preferably 0.001 mol / L or more and 0.5 mol / L or less.
- the method for applying the phosphate treatment liquid is not particularly limited, and may be appropriately selected from known methods for applying the phosphate treatment liquid to the surface of the plating layer.
- Examples of the above-mentioned applying method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping pulling method, and the like.
- the phosphate treatment liquid may be applied so that the amount of the phosphate treatment layer applied is 2.0 g / m 2 or more and 7.0 g / m 2 or less.
- the temperature of the phosphate treatment liquid at the time of application is preferably 40 ° C. or higher and 80 ° C. or lower.
- a phosphate treatment solution heated to 40 ° C. or higher and 80 ° C. or lower is used, a large number of fine phosphate crystals can be stably precipitated in a short time.
- the surface of the galvanized steel sheet may be adjusted with a known surface conditioner before the phosphate treatment liquid is applied.
- Step of Forming Chrome-Free Sealing Film In the step of forming the chrome-free sealing film, an oxidase of Group 4 metal, a salt of Group 1 metal or its salt, and ammonium so as to be in contact with the formed phosphate-treated layer. A chemical conversion treatment solution containing ions and having a pH of 7.0 or more and 9.0 or less is applied and dried to form a chrome-free sealing film on the surface of the phosphate-treated layer.
- the above-mentioned chemical conversion treatment liquid is a chemical conversion treatment liquid containing the above-mentioned acid acid salt of the Group 4 metal and the Group 1 metal or a salt thereof, and the pH of which is adjusted to 7.0 or more and 9.0 or less by ammonium ions.
- the pH of the chemical conversion treatment liquid is preferably 7.2 or more and 8.5 or less, and more preferably 7.3 or more and 8.0 or less.
- the content of the above-mentioned Group 4 metal oxynate and Group 1 metal or a salt thereof is not particularly limited.
- the concentration of the Group 4 metal atom in the chemical conversion treatment liquid is preferably 5 g / L or more and 40 g / L or less, and more preferably 5 g / L or more and 35 g / L or less.
- the concentration of the Group 1 metal atom in the chemical conversion treatment liquid is preferably 0.2 g / L or more.
- the amount of the Group 1 metal or a salt thereof in the chemical conversion treatment liquid is such that the Group 1 metal atom is 0.5 parts by mass or more and 21 parts by mass or less with respect to 100 parts by mass of the Group 4 metal atom. It is also preferable that the molar ratio of the group 1 metal atom to the group 4 metal atom is 0.02 or more and 0.8 or less.
- the chemical conversion treatment liquid contains oxides, hydroxides or fluorides of V, Mo, P, Ti or Si in order to further enhance the corrosion resistance of the coated steel sheet in a situation where salt water such as seawater is applied. You may be.
- the method for applying the chemical conversion treatment liquid is not particularly limited, and may be appropriately selected from known methods such as a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dipping pulling method.
- Step of Forming Organic Film In the step of forming the organic film, the organic film treatment liquid containing the above-mentioned organic resin is applied and dried so as to be in contact with the formed chrome-free sealing film. An organic film is formed on the surface of the chrome-free sealing film.
- a molten Zn-0.1 mass% Al plating layer (plating adhesion amount 200 g / m 2 ) was formed on the surface of ordinary steel having a plate thickness of 0.6 mm to obtain a plated steel sheet 3.
- a molten Zn-6% by mass Al-3% by mass Mg plating layer (plating adhesion amount 140 g / m 2 ) was formed on the surface of ordinary steel having a plate thickness of 0.6 mm to obtain a plated steel sheet 4.
- chrome-free sealing film Zirconium zirconium in an amount that has a Zr concentration of 5 g / L as an oxidate of a Group 4 metal, and sodium diphosphate in an amount that has a Na concentration of 0.5 g / L as a salt of a Group 1 metal.
- a chemical conversion treatment liquid for forming a chrome-free sealing film containing (a salt of a group 1 metal) and ammonia in an amount such that the pH of the aqueous solution was 7.5 was prepared.
- the chemical conversion treatment liquid was applied to the surface of the plated steel sheet 1 on which the phosphate-treated layer was formed, and dried in an oven at 200 ° C. to form a chrome-free sealing film.
- the amount of the chemical conversion treatment liquid applied was adjusted so that the amount of the chromium-free sealing film adhered was 10 mg / m 2 .
- the coated steel sheet 4 and the coated steel sheet 5 were formed in the same manner as the coated steel sheet 3 except that the content of ammonia in the chemical conversion treatment solution was changed so that the pH of the chemical conversion treatment solution was 7.1 and 8.9, respectively. Obtained.
- a coated steel sheet 6 was obtained in the same manner as the coated steel sheet 3 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
- the type of Group 4 metal oxyate acid salt contained in the chemical conversion treatment liquid was changed to titanium ammonium fluoride (group 4 metal oxyate acid salt) having a Ti concentration of 2 g / L, and the pH of the chemical conversion treatment liquid was changed.
- a coated steel plate 7 was obtained in the same manner as the coated steel plate 3 except that the content of ammonia in the chemical conversion treatment liquid was adjusted so as to be 7.1.
- a coated steel sheet 8 was obtained in the same manner as the coated steel sheet 3 except that the type of the organic resin contained in the organic film treatment liquid was changed to an acrylic resin (Boncoat CG-8400 manufactured by DIC Corporation).
- the coated steel plate 11 was obtained in the same manner as the coated steel plate 3 except that the plated steel plate was changed to the plated steel plate 2.
- a coated steel sheet 12 was obtained in the same manner as the coated steel sheet 11 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
- the coated steel sheet 13 was obtained in the same manner as the coated steel sheet 3 except that the plated steel sheet was changed to the plated steel sheet 3.
- the type of organic resin contained in the organic film treatment liquid is changed to acrylic resin (Boncoat CG-8400 manufactured by DIC), and the organic film treatment liquid has a film thickness of 2.0 ⁇ m.
- a coated steel sheet 14 was obtained in the same manner as the coated steel sheet 13 except that the coating amount of was changed.
- the coated steel sheet 15 was obtained in the same manner as the coated steel sheet 3 except that the plated steel sheet was changed to the plated steel sheet 4 and the coating amount of the organic film treatment liquid was changed so that the film thickness of the organic film was 6.0 ⁇ m. rice field.
- the type of the oxychloride of the Group 4 metal contained in the chemical conversion treatment liquid was changed to titanium ammonium fluoride in an amount such that the Ti concentration was 2 g / L, and the pH of the chemical conversion treatment liquid was changed to 7.1.
- a coated steel sheet 16 was obtained in the same manner as the coated steel sheet 15 except that the content of ammonia in the treatment liquid was adjusted.
- a coated steel sheet 17 was obtained in the same manner as the coated steel sheet 15 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
- Ni and Ni in the phosphate treatment solution so that the total adhesion of Ni and Co in the phosphate treatment layer is 11 mg / m 2 , 18 mg / m 2 , 0 mg / m 2 and 110 mg / m 2 .
- the coated steel sheets 18 to 21 were obtained in the same manner as in the production of the coated steel sheet 1 except that the total content of Co was changed.
- the immersion time in the phosphate treatment solution was changed so that the adhesion amount of the phosphate treatment layer was 1.7 g / m 2 and 7.5 g / m 2 , and in either case, the phosphate treatment layer was used.
- the coated steel plate 22 was used in the same manner as the coated steel plate 1, except that the total content of Ni and Co in the phosphate treatment liquid was changed so that the total adhesion amount of Ni and Co was 62 mg / m 2 , the coated steel plate 22 was used. And a coated steel plate 23 was obtained.
- a coated steel sheet 24 was obtained in the same manner as the coated steel sheet 3 except that the chemical conversion treatment liquid did not contain a group 1 metal salt.
- the coated steel sheet 25 and the coated steel sheet 26 were formed in the same manner as the coated steel sheet 3 except that the content of ammonia in the chemical conversion treatment solution was changed so that the pH of the chemical conversion treatment solution was 6.5 and 10.6, respectively. Obtained.
- a coated steel sheet 27 was obtained in the same manner as the coated steel sheet 3 except that an organic film was not formed.
- a coated steel sheet 28 was obtained in the same manner as the coated steel sheet 3 except that the chemical conversion treatment liquid did not contain the oxygen acid salt of the Group 4 metal.
- a coated steel sheet 29 was obtained in the same manner as the coated steel sheet 3 except that the phosphate-treated layer and the chromium-free sealing were not formed.
- the plated steel sheet was changed to the plated steel sheet 4, and the coated steel sheet 30 was obtained in the same manner as the coated steel sheet 13 except that the phosphate-treated layer and the chrome-free sealing were not formed.
- Tables 1 and 2 show the adhered amounts of the plated steel plate and the phosphate-treated layer, the total adhered amount of Ni and Co in the phosphate-treated layer, and the chrome-free sealing of the coated steel plates 1 to 30.
- Types of Group 4 metals that make up Group 4 metal oxyphosphates types of Group 1 metals that form salts of Group 1 metals, pH of chemical conversion treatment solutions, types of organic resins that make up organic films, and their film thicknesses. Is shown.
- Evaluation Results Tables 3 and 4 show the evaluation results of corrosion resistance, brightness, and adhesion to the processed portion of the coated steel sheets 1 to 30.
- the total adhesion amount of the steel sheet, the zinc-based plating layer, and Ni and Co is 20 mg / m 2 or more and 100 mg / m 2 or less, and the adhesion amount of the treated layer is 2.
- a phosphate-treated layer having a pH of 0.0 g / m 2 or more and 7.0 g / m 2 or less, a chromium-free sealing film containing an oxidate of a Group 4 metal and a Group 1 metal or a salt thereof, and an organic film.
- the coated steel sheets 1 to 17 arranged in this order had a brightness (L *) of 55 or less, and had high corrosion resistance and adhesion to the processed portion.
- the total adhesion amount of Ni and Co in the phosphate-treated layer is 30 mg / m 2 or more and 80 mg / m 2 or less.
- the surface brightness of the painted steel sheet was lower, and the corrosion resistance was higher. This is because when the total amount of Ni and Co adhered to the phosphate-treated layer is 30 mg / m 2 or more, the surface brightness of the coated steel plate becomes lower because Ni and Co are sufficiently precipitated, and the phosphate treatment is performed.
- the total adhesion of Ni and Co in the layer was 80 mg / m 2 or less, it is considered that the corrosion resistance of the coated steel plate was higher because the precipitation of Ni and Co was difficult to inhibit the precipitation of phosphate crystals. ..
- the chrome-free sealing film contains Zr oxygenate as the oxygen acid salt of the Group 4 metal.
- the brightness of the surface of the coated steel sheet was lower than that when the chrome-free sealing film contained Ti oxidate as the oxidate of Group 4 metal. It is considered that this is because the pH of the chrome-free sealing treatment liquid is low, so that the phosphate film or Ni substitution layer on the surface is slightly removed, and the brightness of the surface of the coated steel sheet becomes lower.
- the adhesion amount of the phosphate-treated layer is 2.5 g / m 2 or more and 7.0 g / m 2 or less
- the surface of the coated steel sheet is surfaced.
- the brightness was lower. This is because when the amount of the phosphate-treated layer adhered is 2.5 g / m 2 or more and 7.0 g / m 2 or less, the amount of the phosphate film adhered is small and the surface brightness of the coated steel sheet becomes lower. It is thought that it was.
- the coated steel sheet 3 when the total adhesion amount of Ni and Co in the phosphate-treated layer is less than 20 mg / m 2 , the coated steel sheet The brightness of the surface was higher than 55. It is considered that this is because when the total adhesion amount of Ni and Co in the phosphate treatment layer was less than 20 mg / m 2 , the brightness of the surface of the coated steel sheet did not decrease because the precipitation amount of Ni or Co was small. Be done.
- the adhesion amount of the phosphate-treated layer is less than 2.0 g / m 2
- the brightness of the surface of the coated steel sheet is higher than 55. rice field. It is probable that when the adhesion amount of the phosphate-treated layer was less than 2.0 g / m 2 , the brightness of the surface of the coated steel sheet did not decrease because the adhesion amount of the phosphate film was small.
- the chromium-free sealing film does not contain the Group 1 metal or a salt thereof, the corrosion resistance of the coated steel sheet and the adhesion to the processed portion are deteriorated. This is because if the chromium-free sealing film does not contain a Group 1 metal or a salt thereof, the amount of hydroxyl groups in the chemical conversion treatment liquid is insufficient, so that the corrosion resistance of the coated steel sheet does not easily increase, and the organic film peels off, resulting in the processed portion of the coated steel sheet. It is probable that it was difficult to increase the adhesion.
- the coated steel sheet 3 does not have an organic film, the corrosion resistance and the corrosion resistance of the coated steel sheet are lowered.
- the corrosion resistance of the coated steel sheet is lowered.
- the coated steel sheet 3 and the coated steel sheet 29 and the comparison between the coated steel sheet 15 and the coated steel sheet 30 if the coated steel sheet does not have the phosphate-treated layer and the chrome-free sealing film, it is coated. Corrosion resistance, lightness and adhesion to the processed part of the steel sheet were not all desired.
- the coated steel sheet of the present invention is suitably used for, for example, various electronic devices, household electric appliances, medical devices, automobile bodies, vehicle-mounted products, building materials, and the like.
- the coated steel sheet of the present invention has excellent designability because of its low lightness, and also has excellent corrosion resistance and adhesion to the processed portion, so that it can be suitably used as a building material.
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Abstract
The purpose of the present invention is to provide: a coated steel sheet that has a chrome-free sealing coating and an organic coating, that has a sufficiently black appearance, and that has a sufficient high corrosion resistance and adhesion at a processed part; and a method for manufacturing such a coated steel sheet. The present invention, in order to achieve the purpose, pertains to a coated steel sheet having sequentially disposed therein: a steel sheet; a zinc plating layer; a phosphate treated layer which is deposited in an amount of 2.02-7.0 g/m2 and in which the total deposition amount of Ni and Co is 202-100 mg/m2; a chrome-free sealing coating containing an oxoate of a group 4 metal, and a group 1 metal or a salt thereof; and an organic coating. The luminosity (L*) of the surface of the coated steel sheet is 55 or less.
Description
本発明は、塗装鋼板および塗装鋼板の製造方法に関する。
The present invention relates to a coated steel sheet and a method for manufacturing a coated steel sheet.
建築物の外装や屋根などに用いる鋼板には、その意匠性を高めるため、黒色の外観を有することを求められることがある。亜鉛系めっき鋼板の表面に塗膜（皮膜）を形成した塗装鋼板において、上記塗膜を黒色化することにより、亜鉛系めっき鋼板の外観を黒色化する方法がいくつか提案されている。
Steel sheets used for the exterior and roof of buildings may be required to have a black appearance in order to enhance their design. In a coated steel sheet in which a coating film (coating) is formed on the surface of a galvanized steel sheet, some methods have been proposed in which the appearance of the galvanized steel sheet is blackened by blackening the coating film.
たとえば、特許文献１には、亜鉛系めっき材料の表面を、いずれも所定量の、ニッケルイオンまたはコバルトイオン、アンモニウムイオンまたは１級アミノ基を２個有する化合物、硝酸イオン、およびフッ化物を含有し、ｐＨが２．０～４．８である処理液に接触させることにより、上記亜鉛系めっき材料を黒色化することができると記載されている。
For example, Patent Document 1 contains a predetermined amount of a compound having two nickel ions or cobalt ions, an ammonium ion or a primary amino group, a nitrate ion, and a fluoride on the surface of a zinc-based plating material. It is described that the zinc-based plating material can be blackened by contacting with a treatment liquid having a pH of 2.0 to 4.8.
また、特許文献２には、所定量のＦｅ２＋、Ｍｎ２－およびＮｉ２＋を含むリン酸亜鉛処理浴中で、溶融亜鉛めっき鋼板または溶融亜鉛合金めっき鋼板にリン酸亜鉛処理を施すことにより、その明度指数を２０～４０にすることができると記載されている。
Further, in Patent Document 2, a hot-dip galvanized steel sheet or a hot-dip galvanized steel sheet is treated with zinc phosphate in a zinc phosphate-treated bath containing a predetermined amount of Fe 2+ , Mn 2- and Ni 2+ . It is stated that the lightness index can be 20-40.
特許文献１および特許文献２によれば、亜鉛系めっき鋼板を所定の処理液により表面処理することにより、上記亜鉛系めっき鋼板の外観を黒色化することができるとされている。
According to Patent Document 1 and Patent Document 2, the appearance of the galvanized steel sheet can be blackened by surface-treating the galvanized steel sheet with a predetermined treatment liquid.
しかし、建築物の外装や屋根などに用いる塗装鋼板には、白錆の発生を長期間にわたって抑制するという耐食性も求められるところ、特許文献１および特許文献２などに記載の構成のみでは、耐食性は十分には高まらない。そこで、従来は、亜鉛系めっき鋼板の耐食性を高めるために、クロムシーリング皮膜および有機系皮膜が、リン酸亜鉛処理などによって形成されるリン酸塩処理層の表面に形成されていた。上記クロムシーリング皮膜は、塗装鋼板の耐食性を高めつつ、上記有機系皮膜の密着性を高める（たとえば、加工された後にも有機系皮膜を十分に密着させる）という作用を有する。
However, the coated steel sheet used for the exterior and roof of a building is also required to have corrosion resistance that suppresses the generation of white rust for a long period of time. Not high enough. Therefore, conventionally, in order to improve the corrosion resistance of a galvanized steel sheet, a chrome sealing film and an organic film have been formed on the surface of a phosphate-treated layer formed by zinc phosphate treatment or the like. The chrome sealing film has an effect of enhancing the adhesion of the organic film while enhancing the corrosion resistance of the coated steel sheet (for example, the organic film is sufficiently adhered even after being processed).
これに対し、近年の規制強化により、塗装鋼板にはクロムフリー化が求められている。
On the other hand, due to the tightening of regulations in recent years, painted steel sheets are required to be chrome-free.
本発明は、かかる点に鑑みてなされたものであり、クロム（Ｃｒ）を実質的に含有しないクロムフリーシーリング皮膜および有機系皮膜を有する塗装鋼板において、外観が十分に黒色化されており、かつ耐食性および加工部の密着性が十分に高められた塗装鋼板、およびそのような塗装鋼板の製造方法を提供することをその目的とする。
The present invention has been made in view of the above points, and the appearance of the coated steel sheet having a chromium-free sealing film and an organic film that does not substantially contain chromium (Cr) is sufficiently blackened and is further blackened. It is an object of the present invention to provide a coated steel sheet having sufficiently improved corrosion resistance and adhesion of a processed portion, and a method for manufacturing such a coated steel sheet.
上記課題を解決するための本発明の一実施形態に関する塗装鋼板は、鋼板と、亜鉛系めっき層と、ＮｉおよびＣｏの合計付着量が２０ｍｇ／ｍ２以上１００ｍｇ／ｍ２以下であり、処理層の付着量が２．０ｇ／ｍ２以上７．０ｇ／ｍ２以下である、リン酸塩処理層と、４族金属の酸素酸塩および１族金属またはその塩を含有するクロムフリーシーリング皮膜と、有機系皮膜と、がこの順番に配置されている。上記塗装鋼板は、その表面の明度（Ｌ＊）が、５５以下である。
The coated steel sheet according to the embodiment of the present invention for solving the above problems has a steel sheet, a zinc-based plating layer, and a total adhesion amount of Ni and Co of 20 mg / m 2 or more and 100 mg / m 2 or less, and is a treated layer. A phosphate-treated layer having an adhesion amount of 2.0 g / m 2 or more and 7.0 g / m 2 or less, and a chrome-free sealing film containing an oxidate of a Group 4 metal and a Group 1 metal or a salt thereof. , And the organic film are arranged in this order. The surface brightness (L *) of the coated steel sheet is 55 or less.
また、上記課題を解決するための本発明の一実施形態に関する塗装鋼板の製造方法は、亜鉛系めっき層を有するめっき鋼板を用意する工程と、上記亜鉛系めっき層に接して、ＮｉおよびＣｏの合計付着量が２０ｍｇ／ｍ２以上１００ｍｇ／ｍ２以下であり、処理層の付着量が２．０ｇ／ｍ２以上７．０ｇ／ｍ２以下である、リン酸塩処理層を形成する工程と、上記リン酸塩処理層に接して、４族金属の酸素酸塩、１族金属またはその塩およびアンモニウムイオンを含有し、ｐＨが７．０以上９．０以下である化成処理液を付与して乾燥させ、クロムフリーシーリング皮膜を形成する工程と、上記クロムフリーシーリング皮膜に接して、有機系皮膜を形成する工程と、を有する。
Further, the method for manufacturing a coated steel plate according to an embodiment of the present invention for solving the above problems includes a step of preparing a plated steel plate having a zinc-based plating layer and contacting the zinc-based plating layer with Ni and Co. A step of forming a phosphate-treated layer in which the total adhesion amount is 20 mg / m 2 or more and 100 mg / m 2 or less, and the adhesion amount of the treatment layer is 2.0 g / m 2 or more and 7.0 g / m 2 or less. , A chemical conversion treatment solution containing a group 4 metal oxidase, a group 1 metal or a salt thereof, and an ammonium ion and having a pH of 7.0 or more and 9.0 or less is applied in contact with the phosphate treatment layer. It has a step of forming a chrome-free sealing film and a step of contacting with the chrome-free sealing film to form an organic film.
本発明によれば、クロム（Ｃｒ）を実質的に含有しないクロムフリーシーリング皮膜および有機系皮膜を有する塗装鋼板において、外観が十分に黒色化されており、かつ耐食性および加工部の密着性が十分に高められた塗装鋼板、およびそのような塗装鋼板の製造方法が提供される。
According to the present invention, in a coated steel sheet having a chromium-free sealing film and an organic film that substantially does not contain chromium (Cr), the appearance is sufficiently blackened, and the corrosion resistance and the adhesion of the processed portion are sufficient. Enhanced coated steel sheets, and methods for manufacturing such coated steel sheets are provided.
１．塗装鋼板
本発明の一実施形態は、鋼板の表面に塗膜（皮膜）が形成された塗装鋼板に関する。上記塗装鋼板は、鋼板と、亜鉛系めっき層と、リン酸塩処理層と、クロムフリーシーリング皮膜と、有機系皮膜とがこの順に積層されており、その表面の明度（Ｌ＊）が５５以下である。 1. 1. Painted Steel Sheet An embodiment of the present invention relates to a painted steel sheet in which a coating film is formed on the surface of the steel sheet. In the above-mentioned coated steel sheet, a steel sheet, a zinc-based plating layer, a phosphate-treated layer, a chrome-free sealing film, and an organic-based film are laminated in this order, and the surface brightness (L *) is 55 or less. Is.
本発明の一実施形態は、鋼板の表面に塗膜（皮膜）が形成された塗装鋼板に関する。上記塗装鋼板は、鋼板と、亜鉛系めっき層と、リン酸塩処理層と、クロムフリーシーリング皮膜と、有機系皮膜とがこの順に積層されており、その表面の明度（Ｌ＊）が５５以下である。 1. 1. Painted Steel Sheet An embodiment of the present invention relates to a painted steel sheet in which a coating film is formed on the surface of the steel sheet. In the above-mentioned coated steel sheet, a steel sheet, a zinc-based plating layer, a phosphate-treated layer, a chrome-free sealing film, and an organic-based film are laminated in this order, and the surface brightness (L *) is 55 or less. Is.
１－１．鋼板
鋼板は、亜鉛系めっき層を形成できる鋼板であればよく、低炭素鋼、中炭素鋼および高炭素鋼などを含む炭素鋼でもよいし、Ｍｎ、Ｃｒ、Ｓｉ、Ｎｉなどを含有する合金鋼でもよい。また、鋼板は、Ａｌキルド鋼などを含むキルド鋼でもよいし、リムド鋼でもよい。良好なプレス成形性が必要とされる場合は、低炭素Ｔｉ添加鋼および低炭素Ｎｂ添加鋼などを含む深絞り用鋼板が鋼板として好ましい。また、Ｐ、Ｓｉ、Ｍｎなどの量を特定の値に調整した高強度鋼板を用いてもよい。 1-1. Steel sheet The steel sheet may be any steel sheet that can form a zinc-based plating layer, may be carbon steel containing low carbon steel, medium carbon steel, high carbon steel, or the like, or may be an alloy steel containing Mn, Cr, Si, Ni, or the like. But it may be. Further, the steel plate may be a killed steel containing Al killed steel or the like, or may be a rimmed steel. When good press formability is required, a steel sheet for deep drawing containing low-carbon Ti-added steel, low-carbon Nb-added steel, or the like is preferable as the steel sheet. Further, a high-strength steel plate in which the amounts of P, Si, Mn and the like are adjusted to specific values may be used.
鋼板は、亜鉛系めっき層を形成できる鋼板であればよく、低炭素鋼、中炭素鋼および高炭素鋼などを含む炭素鋼でもよいし、Ｍｎ、Ｃｒ、Ｓｉ、Ｎｉなどを含有する合金鋼でもよい。また、鋼板は、Ａｌキルド鋼などを含むキルド鋼でもよいし、リムド鋼でもよい。良好なプレス成形性が必要とされる場合は、低炭素Ｔｉ添加鋼および低炭素Ｎｂ添加鋼などを含む深絞り用鋼板が鋼板として好ましい。また、Ｐ、Ｓｉ、Ｍｎなどの量を特定の値に調整した高強度鋼板を用いてもよい。 1-1. Steel sheet The steel sheet may be any steel sheet that can form a zinc-based plating layer, may be carbon steel containing low carbon steel, medium carbon steel, high carbon steel, or the like, or may be an alloy steel containing Mn, Cr, Si, Ni, or the like. But it may be. Further, the steel plate may be a killed steel containing Al killed steel or the like, or may be a rimmed steel. When good press formability is required, a steel sheet for deep drawing containing low-carbon Ti-added steel, low-carbon Nb-added steel, or the like is preferable as the steel sheet. Further, a high-strength steel plate in which the amounts of P, Si, Mn and the like are adjusted to specific values may be used.
１－２．亜鉛系めっき層
亜鉛系めっき層は、亜鉛を主成分とするめっき層である。亜鉛系めっき層を構成するめっきは、Ｚｎめっき（純亜鉛めっき）、Ｚｎ－Ａｌ系合金めっき、Ｚｎ－Ｍｇ合金めっき、Ｚｎ－Ｎｉ合金めっき、およびＺｎ－Ａｌ－Ｍｇ系合金めっきなどから、上記表面処理された亜鉛系めっき鋼板の用途などに応じて選択することができる。 1-2. Zinc-based plating layer The zinc-based plating layer is a plating layer containing zinc as a main component. The plating constituting the zinc-based plating layer is described from Zn plating (pure zinc plating), Zn—Al alloy plating, Zn—Mg alloy plating, Zn—Ni alloy plating, Zn—Al—Mg alloy plating, and the like. It can be selected according to the application of the surface-treated zinc-based plated steel plate.
亜鉛系めっき層は、亜鉛を主成分とするめっき層である。亜鉛系めっき層を構成するめっきは、Ｚｎめっき（純亜鉛めっき）、Ｚｎ－Ａｌ系合金めっき、Ｚｎ－Ｍｇ合金めっき、Ｚｎ－Ｎｉ合金めっき、およびＺｎ－Ａｌ－Ｍｇ系合金めっきなどから、上記表面処理された亜鉛系めっき鋼板の用途などに応じて選択することができる。 1-2. Zinc-based plating layer The zinc-based plating layer is a plating layer containing zinc as a main component. The plating constituting the zinc-based plating layer is described from Zn plating (pure zinc plating), Zn—Al alloy plating, Zn—Mg alloy plating, Zn—Ni alloy plating, Zn—Al—Mg alloy plating, and the like. It can be selected according to the application of the surface-treated zinc-based plated steel plate.
亜鉛系めっき層は、電気めっき法、溶融めっき法および蒸着めっき法などの公知のいずれの方法で形成されためっき層であってもよい。これらのうち、より付着量を多くした亜鉛系めっき層を容易に作製できることから、亜鉛系めっき層は、溶融めっき法で形成されためっき層であることが好ましい。
The zinc-based plating layer may be a plating layer formed by any known method such as an electroplating method, a hot-dip plating method, and a vapor deposition plating method. Of these, the zinc-based plating layer is preferably a plating layer formed by a hot-dip plating method because a zinc-based plating layer having a larger amount of adhesion can be easily produced.
亜鉛系めっき層は、塗装鋼板の耐食性を高めるため、０.１質量％以上かつ２２.０質量％以下のＡｌを含むことが好ましい。
The zinc-based plating layer preferably contains Al of 0.1% by mass or more and 22.0% by mass or less in order to enhance the corrosion resistance of the coated steel sheet.
亜鉛系めっき層は、海浜地帯などの比較的厳しい環境において上記塗装鋼板を外装建材として使用したときの亜鉛系めっき層の耐久性を高めるため、付着量が１００ｇ／ｍ２以上であることが好ましい。
The zinc-based plating layer preferably has an adhesion amount of 100 g / m 2 or more in order to enhance the durability of the zinc-based plating layer when the coated steel sheet is used as an exterior building material in a relatively harsh environment such as a beach area. ..
１－３．リン酸塩処理層
リン酸塩処理層は、上記亜鉛系めっき層の表面に形成された、リン酸塩結晶を含む層である。 1-3. Phosphate-treated layer The phosphate-treated layer is a layer containing phosphate crystals formed on the surface of the zinc-based plating layer.
リン酸塩処理層は、上記亜鉛系めっき層の表面に形成された、リン酸塩結晶を含む層である。 1-3. Phosphate-treated layer The phosphate-treated layer is a layer containing phosphate crystals formed on the surface of the zinc-based plating layer.
リン酸塩処理層は、リン酸アニオンを有する化合物であって、難水溶性の結晶を形成できる化合物からなる複数のリン酸塩結晶が、上記亜鉛系めっき層の表面に配置されてなる皮膜である。リン酸塩結晶の例には、リン酸マグネシウム、リン酸マンガン、リン酸亜鉛、リン酸鉄、リン酸亜鉛鉄、リン酸亜鉛カルシウムなどが含まれる。
The phosphate-treated layer is a film having a phosphate anion and having a plurality of phosphate crystals composed of compounds capable of forming sparingly water-soluble crystals arranged on the surface of the zinc-based plating layer. be. Examples of phosphate crystals include magnesium phosphate, manganese phosphate, zinc phosphate, iron phosphate, zinc iron phosphate, zinc phosphate calcium and the like.
リン酸塩処理層は、ＮｉおよびＣｏを含む。ＮｉおよびＣｏは、いずれも、おそらくは亜鉛系めっき層の表面で微細粒状に置換析出して光の散乱効果を生み出すことにより、塗装鋼板に黒色の外観を付与する。塗装鋼板の外観をより良好に黒色化する観点からは、リン酸塩処理層におけるＮｉおよびＣｏの合計付着量は、２０ｍｇ／ｍ２以上とする。一方で、上記置換析出がリン酸塩結晶の析出を阻害することによる、塗装鋼板の耐食性の低下を抑制する観点からは、リン酸塩処理層におけるＮｉおよびＣｏの合計付着量は、１００ｍｇ／ｍ２以下とする。上記観点からは、リン酸塩処理層におけるＮｉおよびＣｏの合計付着量は、３０ｍｇ／ｍ２以上８０ｍｇ／ｍ２以下であることが好ましく、４０ｍｇ／ｍ２以上７０ｍｇ／ｍ２以下であることがより好ましい。
The phosphate treatment layer contains Ni and Co. Both Ni and Co give the coated steel sheet a black appearance, presumably by substituting and precipitating fine particles on the surface of the zinc-based plating layer to produce a light scattering effect. From the viewpoint of better blackening the appearance of the coated steel sheet, the total amount of Ni and Co adhered to the phosphate-treated layer is 20 mg / m 2 or more. On the other hand, from the viewpoint of suppressing the deterioration of the corrosion resistance of the coated steel sheet due to the above-mentioned substitution precipitation inhibiting the precipitation of phosphate crystals, the total adhesion amount of Ni and Co in the phosphate-treated layer is 100 mg / m. 2 or less. From the above viewpoint, the total amount of Ni and Co adhered to the phosphate-treated layer is preferably 30 mg / m 2 or more and 80 mg / m 2 or less, and 40 mg / m 2 or more and 70 mg / m 2 or less. More preferred.
なお、リン酸塩処理層は、その他の成分としてＭｎ、Ｍｇ、Ｃａ、およびＦｅなどの金属元素または脂肪族アミンなどを含んでいてもよい。
The phosphate-treated layer may contain metal elements such as Mn, Mg, Ca, and Fe, or an aliphatic amine as other components.
リン酸塩処理層の付着量は、リン酸塩結晶の付着量を多くし、リン酸塩結晶が付着していない位置に析出するＮｉおよびＣｏによる析出層の厚みを大きくすることにより、塗装鋼板の外観をより良好に黒色化する観点からは、２．０ｇ／ｍ２以上とする。一方で、リン酸塩結晶のサイズが大きくなり、加工時に粉状に剥離しやすくなることによる、基材鋼板への塗膜の密着性の低下を抑制する観点からは、リン酸塩処理層の付着量は、７．０ｇ／ｍ２以下とする。上記観点からは、リン酸塩処理層の付着量は、２．５ｇ／ｍ２以上７．０ｇ／ｍ２以下であることが好ましく、３．０ｇ／ｍ２以上６．０ｇ／ｍ２以下であることがより好ましい。
The amount of the phosphate-treated layer adhered is such that the amount of the phosphate crystals adhered is increased and the thickness of the precipitation layer due to Ni and Co deposited at the position where the phosphate crystals are not adhered is increased to increase the thickness of the coated steel plate. From the viewpoint of better blackening the appearance of the above, the temperature should be 2.0 g / m 2 or more. On the other hand, from the viewpoint of suppressing the deterioration of the adhesion of the coating film to the base steel sheet due to the increase in the size of the phosphate crystals and the tendency to peel off into powder during processing, the phosphate-treated layer is used. The amount of adhesion shall be 7.0 g / m 2 or less. From the above viewpoint, the amount of the phosphate-treated layer adhered is preferably 2.5 g / m 2 or more and 7.0 g / m 2 or less, and 3.0 g / m 2 or more and 6.0 g / m 2 or less. It is more preferable to have.
本実施形態では、リン酸塩処理層におけるＮｉおよびＣｏの合計付着量と、リン酸塩処理層の付着量と、を適切に制御することにより、塗装鋼板の表面の明度（Ｌ＊）を５５以下、好ましくは５０以下、より好ましくは４０以上５０以下、とすることができる。なお、上記明度（Ｌ＊）は、分光型色差計を用いて、ＪＩＳ Ｋ ５６００－４－５（１９９９年）に準拠した分光反射測定法で測定された値とする。
In the present embodiment, the brightness (L *) of the surface of the coated steel sheet is 55 by appropriately controlling the total amount of Ni and Co adhered to the phosphate-treated layer and the amount of adhesion of the phosphate-treated layer. Hereinafter, it can be preferably 50 or less, more preferably 40 or more and 50 or less. The brightness (L *) is a value measured by a spectral reflection measurement method based on JIS K 5600-4-5 (1999) using a spectroscopic color difference meter.
また、本実施形態では、リン酸塩処理層におけるＮｉおよびＣｏの合計付着量と、リン酸塩処理層の付着量と、を適切に制御することにより、塗装鋼板の表面の６０°光沢値を１０以下、好ましくは８以下、より好ましくは５以下、とすることができる。なお、上記６０°光沢値は、ＪＩＳ Ｋ ５６００－４－５（１９９９年）に準拠して測定された値とする。
Further, in the present embodiment, the 60 ° gloss value of the surface of the coated steel sheet is obtained by appropriately controlling the total amount of Ni and Co adhered to the phosphate-treated layer and the amount of adhesion of the phosphate-treated layer. It can be 10 or less, preferably 8 or less, and more preferably 5 or less. The 60 ° gloss value is a value measured in accordance with JIS K 5600-4-5 (1999).
１－４．クロムフリーシーリング皮膜
クロムフリーシーリング皮膜は、上記リン酸塩処理層の表面に形成された、４族金属の酸素酸塩および１族金属またはその塩を含む皮膜である。 1-4. Chromium-free sealing film The chromium-free sealing film is a film containing an oxygenate of a Group 4 metal and a Group 1 metal or a salt thereof formed on the surface of the phosphate-treated layer.
クロムフリーシーリング皮膜は、上記リン酸塩処理層の表面に形成された、４族金属の酸素酸塩および１族金属またはその塩を含む皮膜である。 1-4. Chromium-free sealing film The chromium-free sealing film is a film containing an oxygenate of a Group 4 metal and a Group 1 metal or a salt thereof formed on the surface of the phosphate-treated layer.
クロムフリーシーリング皮膜は、４族金属の酸素酸塩、１族金属またはその塩、およびアンモニウムイオンを含有し、かつｐＨが７．０以上９．０以下である化成処理液により形成された化成処理皮膜である。
The chromium-free sealing film is a chemical conversion treatment formed by a chemical conversion treatment liquid containing an oxidase of a group 4 metal, a salt of the group 1 metal or a salt thereof, and an ammonium ion and having a pH of 7.0 or more and 9.0 or less. It is a film.
上記４族金属の酸素酸塩は、緻密な化成処理皮膜（クロムフリーシーリング皮膜）を形成することにより、塗装鋼板の耐食性（平坦部耐食性および加工部耐食性）を向上させる。
The above-mentioned group 4 metal oxygen salt improves the corrosion resistance (flat portion corrosion resistance and processed portion corrosion resistance) of the coated steel sheet by forming a dense chemical conversion treatment film (chromium-free sealing film).
上記４族金属には、Ｔｉ、ＺｒおよびＨｆが含まれる。上記４族金属の酸素酸塩は、４族金属原子および酸素原子を含む無機酸の塩である。上記塩の例には、水素酸塩、アンモニウム塩、アルカリ金属塩、およびアルカリ土類金属塩などが含まれる。これらのうち、塗装鋼板の耐食性をより高める観点からは、上記４族金属の酸素酸塩は、４族金属原子および酸素原子を含む無機酸のアンモニウム塩であることが好ましく、炭酸ジルコニウムアンモニウムであることが好ましい。
The Group 4 metals include Ti, Zr and Hf. The above-mentioned group 4 metal oxyate salt is a salt of an inorganic acid containing a group 4 metal atom and an oxygen atom. Examples of the above salts include hydrides, ammonium salts, alkali metal salts, alkaline earth metal salts and the like. Of these, from the viewpoint of further enhancing the corrosion resistance of the coated steel plate, the oxygen salt of the Group 4 metal is preferably an ammonium salt of an inorganic acid containing a Group 4 metal atom and an oxygen atom, and is zirconium ammonium carbonate. Is preferable.
塗装鋼板の耐食性をより高める観点からは、クロムフリーシーリング皮膜における上記４族金属の酸素酸塩の付着量は、４族金属原子換算で、２ｍｇ／ｍ２以上８０ｍｇ／ｍ２以下であることが好ましく、５ｍｇ／ｍ２以上３０ｍｇ／ｍ２以下であることがより好ましい。
From the viewpoint of further enhancing the corrosion resistance of the coated steel sheet, the amount of the oxygen acid salt of the Group 4 metal adhered to the chromium-free sealing film is 2 mg / m 2 or more and 80 mg / m 2 or less in terms of Group 4 metal atom. It is preferable that it is 5 mg / m 2 or more and 30 mg / m 2 or less.
上記１族金属またはその塩は、上記化成処理液中の水酸基量を高めて、クロムフリーシーリング皮膜とリン酸塩処理層との間の密着性、およびクロムフリーシーリング皮膜と有機系皮膜との間の密着性、を高める。また、上記１族金属またはその塩は、上記化成処理液中の水酸基量を高めて、化成処理中での４族金属とリンとの結合を抑制して、これらの結合による化成処理液のゲル化を抑制することにより、上記化成処理液の長期保存性（安定性）を高める。
The Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid to provide adhesion between the chromium-free sealing film and the phosphate-treated layer, and between the chromium-free sealing film and the organic film. Improves adhesion. Further, the Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid, suppresses the bond between the Group 4 metal and phosphorus in the chemical conversion treatment, and gels the chemical conversion treatment liquid by these bonds. By suppressing the formation, the long-term storage stability (stability) of the chemical conversion treatment liquid is enhanced.
また、上記１族金属またはその塩は、上記化成処理液中の水酸基量を高めて、化成処理液を乾燥させる際に水分を除去されにくくして、クロムフリーシーリング皮膜が作製中に過剰に乾燥されることによるクラックの発生を抑制することができる。
Further, the Group 1 metal or a salt thereof increases the amount of hydroxyl groups in the chemical conversion treatment liquid, making it difficult for water to be removed when the chemical conversion treatment liquid is dried, and the chromium-free sealing film is excessively dried during production. It is possible to suppress the occurrence of cracks due to the cracking.
上記１族金属には、Ｌｉ、Ｎａ、およびＫなどが含まれる。これらのうち、上記リン酸塩処理層および有機系皮膜との密着性をより高め、かつ、上記クラックの発生をより抑制する観点からは、上記１族金属は、Ｎａであることが好ましい。上記１族金属は、二リン酸ナトリウム、二リン酸カリウムおよびトリポリリン酸ナトリウムなどのリン酸塩であってもよいし、１－ヒドロキシエチリデン－１，１－ビスホスホン酸二ナトリウム、および１－ヒドロキシエチリデン－１，１－ジホスホン酸五ナトリウムなどの有機ホスホン酸であってもよいし、１族金属の水酸化物などの、その他の化合物であってもよい。これらのうち、上記リン酸塩処理層および有機系皮膜との密着性をより高め、かつ、上記クラックの発生をより抑制する観点からは、上記１族金属は、トリポリリン酸ナトリウム、１－ヒドロキシエチリデン－１，１－ビスホスホン酸二ナトリウム、または１－ヒドロキシエチリデン－１，１－ジホスホン酸五ナトリウムであることが好ましい。
The Group 1 metals include Li, Na, K and the like. Of these, the Group 1 metal is preferably Na from the viewpoint of further enhancing the adhesion to the phosphate-treated layer and the organic film and further suppressing the generation of cracks. The Group 1 metal may be a phosphate such as sodium diphosphate, potassium diphosphate and sodium tripolyphosphate, or 1-hydroxyethylidene-1,1-bisphosphonate disodium, and 1-hydroxyethylidene. It may be an organic phosphonic acid such as -1,1-diphosphonate pentasodium, or it may be another compound such as a hydroxide of a Group 1 metal. Of these, from the viewpoint of further enhancing the adhesion to the phosphate-treated layer and the organic film and further suppressing the generation of cracks, the Group 1 metals are sodium tripolyphosphate and 1-hydroxyethylidene. It is preferably -1,1-bisphosphonate disodium or 1-hydroxyethylidene-1,1-diphosphonate pentasodium.
上記リン酸塩処理層および有機系皮膜との密着性をより高め、かつ、上記クラックの発生をより抑制する観点からは、クロムフリーシーリング皮膜における上記１族金属またはその塩の量は、４族金属原子１００質量部に対して、１族金属原子が０．５質量部以上２１質量部以下となる量であることが好ましい。また、同様に、クロムフリーシーリング皮膜における上記１族金属またはその塩の量は、４族金属原子に対する１族金属原子のモル比が０．０２以上０．８以下となる量であることが好ましい。
From the viewpoint of further enhancing the adhesion to the phosphate-treated layer and the organic film and further suppressing the generation of cracks, the amount of the Group 1 metal or its salt in the chromium-free sealing film is Group 4. It is preferable that the amount of the Group 1 metal atom is 0.5 parts by mass or more and 21 parts by mass or less with respect to 100 parts by mass of the metal atom. Similarly, the amount of the Group 1 metal or a salt thereof in the chrome-free sealing film is preferably an amount such that the molar ratio of the Group 1 metal atom to the Group 4 metal atom is 0.02 or more and 0.8 or less. ..
クロムフリーシーリング皮膜の付着量は、特に限定されないものの、３ｍｇ／ｍ２以上１０００ｍｇ／ｍ２以下とすることができ、スポット溶接性を高める観点からは５ｍｇ／ｍ２以上５００ｍｇ／ｍ２以下とすることが好ましい。
The amount of the chrome-free sealing film adhered is not particularly limited, but can be 3 mg / m 2 or more and 1000 mg / m 2 or less, and 5 mg / m 2 or more and 500 mg / m 2 or less from the viewpoint of improving spot weldability. Is preferable.
クロムフリーシーリング皮膜は、海水などの塩水が付与されるような状況における上記塗装鋼板の耐食性をより高めるため、Ｖ、Ｍｏ、Ｐ、ＴｉまたはＳｉの酸化物、水酸化物またはフッ化物を含んでいてもよい。
The chromium-free sealing film contains oxides, hydroxides or fluorides of V, Mo, P, Ti or Si in order to further enhance the corrosion resistance of the coated steel sheet in a situation where salt water such as seawater is applied. You may.
クロムフリーシーリング皮膜は、６価クロムを実質的に含有しない。具体的には、上記塗装鋼板から５０ｍｍ×５０ｍｍの試験片４枚を切り出し、沸騰している純水１００ｍＬに１０分間浸漬した後、当該純水中に溶出した６価クロムを、ＪＩＳ Ｈ ８６２５（１９９３年）付属書の２．４．１の「ジフェニルカルバジッド比色法」に準拠する濃度の分析方法で定量したとき、検出限界以下である。
The chromium-free sealing film contains substantially no hexavalent chromium. Specifically, four 50 mm × 50 mm test pieces were cut out from the coated steel sheet, immersed in 100 mL of boiling pure water for 10 minutes, and then the hexavalent chromium eluted in the pure water was added to JIS H8625 (JIS H8625). 1993) It is below the detection limit when quantified by the concentration analysis method based on the "diphenylcarbazide colorimetric method" of 2.4.1 of the annex.
ところで、上記各成分を含有する化成処理液は、通常、酸性である。このような化成処理液を用いてクロムフリーシーリング皮膜を形成するとき、上記リン酸塩処理層または上記亜鉛系めっき層が部分的に化成処理液に溶解することがある。これらの層が部分的に化成処理液に溶解すると、塗装鋼板の明度が高くなったり、塗装鋼板の外観にムラが生じたり、またこれらの層の成分がクロムフリーシーリング皮膜に混入してそれぞれの層に期待する性質が十分には発揮されないことがある。
By the way, the chemical conversion treatment liquid containing each of the above components is usually acidic. When a chromium-free sealing film is formed using such a chemical conversion treatment liquid, the phosphate treatment layer or the zinc-based plating layer may be partially dissolved in the chemical conversion treatment liquid. When these layers are partially dissolved in the chemical conversion treatment liquid, the brightness of the coated steel sheet becomes high, the appearance of the coated steel sheet becomes uneven, and the components of these layers are mixed in the chromium-free sealing film and each of them is used. The properties expected of the layer may not be fully exhibited.
そのため、本実施形態では、上記層の溶解を抑制するため、ｐＨを７．０以上９．０以下にした化成処理液を用いて、クロムフリーシーリング皮膜を形成する。ｐＨの調整方法は特に限定されないものの、クロムフリーシーリング皮膜が有する特性への影響を抑制する観点からは、アンモニウムイオンによりｐＨを上記範囲に調整することが好ましい。このとき、クロムフリーシーリング皮膜には、化成処理液に含まれるアンモニウムイオンに由来するアンモニウム塩が残存することがある。
Therefore, in the present embodiment, in order to suppress the dissolution of the above layer, a chromium-free sealing film is formed by using a chemical conversion treatment liquid having a pH of 7.0 or more and 9.0 or less. Although the method for adjusting the pH is not particularly limited, it is preferable to adjust the pH to the above range with ammonium ions from the viewpoint of suppressing the influence on the characteristics of the chromium-free sealing film. At this time, an ammonium salt derived from ammonium ions contained in the chemical conversion treatment liquid may remain on the chromium-free sealing film.
１－５．有機系皮膜
有機系皮膜は、上記クロムフリーシーリング皮膜の表面に形成された、有機樹脂を主成分とする皮膜である。 1-5. Organic film The organic film is a film formed on the surface of the chromium-free sealing film and containing an organic resin as a main component.
有機系皮膜は、上記クロムフリーシーリング皮膜の表面に形成された、有機樹脂を主成分とする皮膜である。 1-5. Organic film The organic film is a film formed on the surface of the chromium-free sealing film and containing an organic resin as a main component.
有機系皮膜を構成する有機樹脂は、亜鉛系めっき鋼板の表面処理に通常使用される有機樹脂であればよく、たとえば、ウレタン樹脂、フッ素樹脂、アクリル樹脂、およびポリエステル樹脂などから、適宜選択することができる。これらの有機樹脂を含む有機系皮膜は、上記塗装鋼板の耐食性および加工性を高めることができる。
The organic resin constituting the organic film may be any organic resin usually used for surface treatment of galvanized steel sheets, and may be appropriately selected from, for example, urethane resin, fluororesin, acrylic resin, polyester resin and the like. Can be done. The organic film containing these organic resins can enhance the corrosion resistance and processability of the coated steel sheet.
これらのうち、耐食性および加工性をより高める観点からは、上記有機樹脂はウレタン樹脂またはポリエステル樹脂であることが好ましく、ウレタン樹脂であることがより好ましい。
Of these, from the viewpoint of further enhancing corrosion resistance and processability, the organic resin is preferably a urethane resin or a polyester resin, and more preferably a urethane resin.
上記ウレタン樹脂は、通常、イソシアネート化合物に由来する構成単位およびポリオール化合物に由来する構成単位を有する。
The urethane resin usually has a structural unit derived from an isocyanate compound and a structural unit derived from a polyol compound.
上記イソシアネート化合物に由来する構成単位の例には、脂肪族ジイソシアネートに由来する構成単位および脂環族ジイソシアネートに由来する構成単位が含まれる。上記脂肪族ジイソシアネートの例には、フェニレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネートおよびナフタレンジイソシアネートが含まれる。上記脂環族ジイソシアネートの例には、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ノルボルナンジイソシアネート、キシリレンジイソシアネートおよびテトラメチルキシリレンジイソシアネートが含まれる。
Examples of the structural unit derived from the isocyanate compound include a structural unit derived from an aliphatic diisocyanate and a structural unit derived from an alicyclic diisocyanate. Examples of the aliphatic diisocyanate include phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate. Examples of the alicyclic diisocyanate include cyclohexane diisocyanate, isophorone diisocyanate, norbornane diisocyanate, xylylene diisocyanate and tetramethylxylylene diisocyanate.
上記ポリオール化合物に由来する構成単位の例には、ポリオレフィンポリオールに由来する構成単位が含まれる。上記ポリオレフィンポリオールの例には、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリアセタールポリオール、ポリアクリレートポリオールおよびポリブタジエンポリオールが含まれる。
Examples of the structural unit derived from the above-mentioned polyol compound include a structural unit derived from a polyolefin polyol. Examples of the polyolefin polyols include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols and polybutadiene polyols.
上記有機系皮膜は、バルブメタルの酸化物、バルブメタルの水酸化物、またはバルブメタルのフッ化物からなる群から選ばれる１種類または２種類以上の化合物（以下、単に「バルブメタル化合物」ともいう）などを含んでもよい。バルブメタル化合物は、環境負荷を小さくしつつ、優れたバリア作用を有機系皮膜に付与することができる。バルブメタルとは、その酸化物が高い絶縁抵抗を示す金属をいう。バルブメタルとしては、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、ＭｏおよびＷからなる群から選ばれる１種類または２種類以上の金属が挙げられる。バルブメタル化合物としては公知のものを用いてよい。
The organic film is one or more compounds selected from the group consisting of an oxide of a valve metal, a hydroxide of a valve metal, or a fluoride of a valve metal (hereinafter, also simply referred to as "valve metal compound"). ) Etc. may be included. The valve metal compound can impart an excellent barrier action to the organic film while reducing the environmental load. The valve metal is a metal whose oxide exhibits high insulation resistance. Examples of the valve metal include one kind or two or more kinds of metals selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W. A known valve metal compound may be used.
また、バルブメタルの可溶性フッ化物を有機系皮膜に含ませることで、有機系皮膜に自己修復作用を付与することができる。バルブメタルのフッ化物は、雰囲気中の水分に溶け出した後、皮膜欠陥部から露出しているめっき鋼板の表面に難溶性の酸化物または水酸化物となって再析出し、皮膜欠陥部を埋めることができる。
Further, by including the soluble fluoride of valve metal in the organic film, it is possible to impart a self-repairing action to the organic film. Fluoride of the valve metal dissolves in the moisture in the atmosphere and then reprecipitates as a sparingly soluble oxide or hydroxide on the surface of the plated steel sheet exposed from the film defect part, and the film defect part is formed. Can be filled.
また、上記有機系皮膜は、上記バルブメタルの可溶性フッ化物に加えて、可溶性または難溶性の金属リン酸塩または複合リン酸塩をさらに含んでいてもよい。可溶性のリン酸塩は、有機系皮膜から皮膜欠陥部に溶出し、めっき鋼板の金属と反応して不溶性リン酸塩となることで、バルブメタルの可溶性フッ化物による自己修復作用を補完することができる。また、難溶性のリン酸塩は、有機系皮膜中に分散して皮膜強度を向上させることができる。
Further, the organic film may further contain a soluble or sparingly soluble metal phosphate or a composite phosphate in addition to the soluble fluoride of the valve metal. Soluble phosphate elutes from the organic film into the film defect and reacts with the metal of the plated steel plate to form an insoluble phosphate, which can complement the self-healing action of the soluble fluoride of valve metal. can. Further, the poorly soluble phosphate can be dispersed in the organic film to improve the film strength.
上記有機系皮膜の膜厚は、３．０μｍ以上であることが好ましい。上記有機系皮膜の膜厚が３．０μｍ以上であると、有機系皮膜を浸透した腐食因子がめっき層へ到達しにくくなり、塗装鋼板の耐食性を十分に高めることができる。上記有機系皮膜の膜厚の上限値は特に限定されないものの、１５μｍとすることができる。
The film thickness of the organic film is preferably 3.0 μm or more. When the film thickness of the organic film is 3.0 μm or more, it becomes difficult for the corrosive factor permeating the organic film to reach the plating layer, and the corrosion resistance of the coated steel sheet can be sufficiently enhanced. Although the upper limit of the film thickness of the organic film is not particularly limited, it can be 15 μm.
上記有機系皮膜は、有機顔料などを含む着色された皮膜であってもよいが、リン酸塩処理層による黒色の外観の視認性をより高めて、塗装鋼板の意匠性をより高める観点からは、クリア皮膜であることが好ましい。
The organic film may be a colored film containing an organic pigment or the like, but from the viewpoint of further enhancing the visibility of the black appearance of the phosphate-treated layer and further enhancing the design of the coated steel sheet. , It is preferable that it is a clear film.
１－６．用途
上記塗装鋼板は、各種用途に使用することができる。特に、上記塗装鋼板は、外観が十分に黒色化されており、かつ耐食性および加工部の密着性が十分に高められていることから、建築物の屋根などの外装建材として好適に使用することができる。 1-6. Applications The above-mentioned coated steel sheet can be used for various purposes. In particular, the coated steel sheet has a sufficiently blackened appearance, and has sufficiently improved corrosion resistance and adhesion of the processed portion, so that it can be suitably used as an exterior building material such as a roof of a building. can.
上記塗装鋼板は、各種用途に使用することができる。特に、上記塗装鋼板は、外観が十分に黒色化されており、かつ耐食性および加工部の密着性が十分に高められていることから、建築物の屋根などの外装建材として好適に使用することができる。 1-6. Applications The above-mentioned coated steel sheet can be used for various purposes. In particular, the coated steel sheet has a sufficiently blackened appearance, and has sufficiently improved corrosion resistance and adhesion of the processed portion, so that it can be suitably used as an exterior building material such as a roof of a building. can.
上記塗装鋼板は、平板であってもよいし、各種形状に加工された加工品であってもよい。
The coated steel sheet may be a flat plate or a processed product processed into various shapes.
２．塗装鋼板の製造方法
上述した塗装鋼板は、亜鉛系めっき層を有するめっき鋼板を用意する工程と、上記リン酸塩処理層を形成する工程と、上記クロムフリーシーリング皮膜を形成する工程と、上記有機系皮膜を形成する工程と、を含む方法により、製造することができる。 2. 2. Method for manufacturing coated steel sheet The above-mentioned coated steel sheet includes a step of preparing a plated steel sheet having a zinc-based plating layer, a step of forming the phosphate-treated layer, a step of forming the chrome-free sealing film, and the above-mentioned organic. It can be produced by a method including a step of forming a system film.
上述した塗装鋼板は、亜鉛系めっき層を有するめっき鋼板を用意する工程と、上記リン酸塩処理層を形成する工程と、上記クロムフリーシーリング皮膜を形成する工程と、上記有機系皮膜を形成する工程と、を含む方法により、製造することができる。 2. 2. Method for manufacturing coated steel sheet The above-mentioned coated steel sheet includes a step of preparing a plated steel sheet having a zinc-based plating layer, a step of forming the phosphate-treated layer, a step of forming the chrome-free sealing film, and the above-mentioned organic. It can be produced by a method including a step of forming a system film.
２－１．めっき鋼板を用意する工程
上記めっき鋼板を用意する工程では、上述した鋼板を基材鋼板とし、上述した亜鉛系めっきを施しためっき鋼板を用意する。本工程では、既に作製されためっき鋼板を用意してもよいし、上記基材鋼板に、電気めっき法、溶融めっき法および蒸着めっき法などの公知の方法で亜鉛系めっきを施して上記めっき鋼板を作製してもよい。 2-1. Step of preparing a plated steel sheet In the step of preparing the above-mentioned plated steel sheet, the above-mentioned steel sheet is used as a base steel sheet, and the above-mentioned galvanized steel sheet is prepared. In this step, a plated steel sheet that has already been produced may be prepared, or the base steel sheet is subjected to zinc-based plating by a known method such as an electroplating method, a hot-dip plating method, or a vapor deposition plating method, and the plated steel sheet is subjected to zinc-based plating. May be produced.
上記めっき鋼板を用意する工程では、上述した鋼板を基材鋼板とし、上述した亜鉛系めっきを施しためっき鋼板を用意する。本工程では、既に作製されためっき鋼板を用意してもよいし、上記基材鋼板に、電気めっき法、溶融めっき法および蒸着めっき法などの公知の方法で亜鉛系めっきを施して上記めっき鋼板を作製してもよい。 2-1. Step of preparing a plated steel sheet In the step of preparing the above-mentioned plated steel sheet, the above-mentioned steel sheet is used as a base steel sheet, and the above-mentioned galvanized steel sheet is prepared. In this step, a plated steel sheet that has already been produced may be prepared, or the base steel sheet is subjected to zinc-based plating by a known method such as an electroplating method, a hot-dip plating method, or a vapor deposition plating method, and the plated steel sheet is subjected to zinc-based plating. May be produced.
２－２．リン酸塩処理層を形成する工程
上記リン酸塩処理層を形成する工程では、上記用意されためっき鋼板の亜鉛系めっき層に接するように、リン酸塩処理液を付与し、上記亜鉛系めっき層の表面にリン酸塩の結晶を析出させる。 2-2. Step of Forming Phosphate Treatment Layer In the step of forming the phosphate treatment layer, a phosphate treatment liquid is applied so as to be in contact with the zinc-based plating layer of the prepared plated steel plate, and the zinc-based plating is performed. Phosphate crystals are deposited on the surface of the layer.
上記リン酸塩処理層を形成する工程では、上記用意されためっき鋼板の亜鉛系めっき層に接するように、リン酸塩処理液を付与し、上記亜鉛系めっき層の表面にリン酸塩の結晶を析出させる。 2-2. Step of Forming Phosphate Treatment Layer In the step of forming the phosphate treatment layer, a phosphate treatment liquid is applied so as to be in contact with the zinc-based plating layer of the prepared plated steel plate, and the zinc-based plating is performed. Phosphate crystals are deposited on the surface of the layer.
上記リン酸塩処理液は、ＮｉまたはＣｏと、リン酸イオンと、を含有する処理液である。上記リン酸塩処理液は、リン酸塩またはリン酸と、ＮｉまたはＣｏのイオンを生成可能な金属塩を水溶媒に溶解させることで調製されうる。上記リン酸塩の例には、リン酸マグネシウム、リン酸マンガン、リン酸亜鉛、リン酸鉄、リン酸亜鉛鉄、およびリン酸亜鉛カルシウムなどが含まれる。
The phosphate treatment liquid is a treatment liquid containing Ni or Co and phosphate ions. The phosphate treatment solution can be prepared by dissolving phosphate or phosphoric acid and a metal salt capable of generating Ni or Co ions in an aqueous solvent. Examples of the above phosphate include magnesium phosphate, manganese phosphate, zinc phosphate, iron phosphate, zinc iron phosphate, zinc phosphate calcium and the like.
十分な数のリン酸塩の結晶を析出させ、かつ、リン酸塩が凝集することによるスラッジの発生を抑制する観点からは、リン酸塩処理液中のリン酸イオンの濃度は、０.０３モル／Ｌ以上０.５モル／Ｌ以下であることが好ましい。リン酸塩処理液中のＮｉまたはＣｏのイオンの濃度は、リン酸塩処理層の付着量が２．０ｇ／ｍ２以上７．０ｇ／ｍ２以下であるときに、ＮｉおよびＣｏの合計付着量が２０ｍｇ／ｍ２以上１００ｍｇ／ｍ２以下となるように、調整すればよい。
From the viewpoint of precipitating a sufficient number of phosphate crystals and suppressing the generation of sludge due to the aggregation of phosphate, the concentration of phosphate ions in the phosphate treatment solution is 0.03. It is preferably mol / L or more and 0.5 mol / L or less. The concentration of Ni or Co ions in the phosphate treatment solution is the total adhesion of Ni and Co when the adhesion amount of the phosphate treatment layer is 2.0 g / m 2 or more and 7.0 g / m 2 or less. The amount may be adjusted to be 20 mg / m 2 or more and 100 mg / m 2 or less.
上記リン酸塩処理液は、さらに、ポリエチルアミン、ポリエチレンイミン、ポリエーテルアミンおよびポリアミノアクリレートなどを含む脂肪族ポリアミン、ならびにポリアニリンなどを含む芳香族ポリアミンなどを含む、ポリアミン系有機インヒビターを含有していてもよい。ポリアミン系有機インヒビターは、適度な間隔を空けてリン酸塩の結晶粒子を析出させ、かつ、リン酸塩の結晶粒子を微細化させることができる。
The phosphate treatment solution further contains a polyamine-based organic inhibitor containing an aliphatic polyamine containing polyethylamine, polyethyleneimine, polyetheramine, polyaminoacrylate and the like, and an aromatic polyamine containing polyaniline and the like. May be good. The polyamine-based organic inhibitor can precipitate the crystal particles of phosphate at appropriate intervals and can make the crystal particles of phosphate finer.
析出するリン酸塩結晶の量を適度に調整する観点からは、ポリアミン系有機インヒビターの数平均分子量は、２００以上３００００以下であることが好ましい。また、析出するリン酸塩結晶の量を適度に調整する観点からは、リン酸塩処理液中のポリアミン系有機インヒビターの濃度は、０.０１質量％以上５質量％以下であることが好ましい。
From the viewpoint of appropriately adjusting the amount of precipitated phosphate crystals, the number average molecular weight of the polyamine-based organic inhibitor is preferably 200 or more and 30,000 or less. Further, from the viewpoint of appropriately adjusting the amount of precipitated phosphate crystals, the concentration of the polyamine-based organic inhibitor in the phosphate treatment liquid is preferably 0.01% by mass or more and 5% by mass or less.
上記リン酸塩処理液は、さらに、硝酸イオンを含んでいてもよい。硝酸イオンは、リン酸塩の析出を促進させる。
The phosphate treatment solution may further contain nitrate ions. Nitrate ions promote the precipitation of phosphate.
析出するリン酸塩結晶の量を適度に調整する観点からは、リン酸塩処理液中の硝酸イオンの濃度は、０.０１モル／Ｌ以上１.０モル／Ｌ以下であることが好ましい。
From the viewpoint of appropriately adjusting the amount of precipitated phosphate crystals, the concentration of nitrate ions in the phosphate treatment solution is preferably 0.01 mol / L or more and 1.0 mol / L or less.
上記リン酸塩処理液は、さらに、フッ化物を含んでいてもよい。特にＡｌを含むめっき層の表面にリン酸塩皮膜を形成するとき、めっき層から溶出したＡｌがリン酸塩の析出を妨げることがあるが、リン酸塩処理液にフッ化物を添加することでこの溶出Ａｌの悪影響を抑制することができる。上記フッ化物の例には、フッ化ナトリウム、フッ化カリウム、フッ化水素ナトリウムなどが含まれる。析出するリン酸塩結晶の量を適度に調整する観点からは、リン酸塩処理液中のフッ化物の濃度は、０.００１モル／Ｌ以上０.５モル／Ｌ以下であることが好ましい。
The phosphate treatment solution may further contain fluoride. In particular, when a phosphate film is formed on the surface of a plating layer containing Al, Al eluted from the plating layer may prevent the precipitation of phosphate, but by adding fluoride to the phosphate treatment solution, The adverse effect of this eluted Al can be suppressed. Examples of the fluoride include sodium fluoride, potassium fluoride, sodium hydrogen fluoride and the like. From the viewpoint of appropriately adjusting the amount of precipitated phosphate crystals, the concentration of fluoride in the phosphate treatment liquid is preferably 0.001 mol / L or more and 0.5 mol / L or less.
上記リン酸塩処理液の付与方法は、特に限定されず、めっき層の表面にリン酸塩処理液を付与する公知の方法から適宜選択すればよい。上記付与方法の例には、ロールコート法、カーテンフロー法、スピンコート法、スプレー法、および浸漬引き上げ法などが含まれる。これらの方法により、リン酸塩処理層の付与量が２．０ｇ／ｍ２以上７．０ｇ／ｍ２以下となるように、リン酸塩処理液を付与すればよい。
The method for applying the phosphate treatment liquid is not particularly limited, and may be appropriately selected from known methods for applying the phosphate treatment liquid to the surface of the plating layer. Examples of the above-mentioned applying method include a roll coating method, a curtain flow method, a spin coating method, a spray method, a dipping pulling method, and the like. By these methods, the phosphate treatment liquid may be applied so that the amount of the phosphate treatment layer applied is 2.0 g / m 2 or more and 7.0 g / m 2 or less.
付与する際の上記リン酸塩処理液の温度は、４０℃以上８０℃以下であることが好ましい。４０℃以上８０℃以下に加温したリン酸塩処理液を使用すると、短時間で微細なリン酸塩結晶を安定して多数析出させることができる。
The temperature of the phosphate treatment liquid at the time of application is preferably 40 ° C. or higher and 80 ° C. or lower. When a phosphate treatment solution heated to 40 ° C. or higher and 80 ° C. or lower is used, a large number of fine phosphate crystals can be stably precipitated in a short time.
リン酸塩の析出を促進するため、リン酸塩処理液を付与する前に、亜鉛系めっき鋼板を公知の表面調整剤で表面調整してもよい。
In order to promote the precipitation of phosphate, the surface of the galvanized steel sheet may be adjusted with a known surface conditioner before the phosphate treatment liquid is applied.
２－３．クロムフリーシーリング皮膜を形成する工程
上記クロムフリーシーリング皮膜を形成する工程では、上記形成されたリン酸塩処理層に接するように、４族金属の酸素酸塩、１族金属またはその塩、およびアンモニウムイオンを含有し、かつｐＨが７．０以上９．０以下である化成処理液を付与し、乾燥させて、上記リン酸塩処理層の表面にクロムフリーシーリング皮膜を形成する。 2-3. Step of Forming Chrome-Free Sealing Film In the step of forming the chrome-free sealing film, an oxidase of Group 4 metal, a salt of Group 1 metal or its salt, and ammonium so as to be in contact with the formed phosphate-treated layer. A chemical conversion treatment solution containing ions and having a pH of 7.0 or more and 9.0 or less is applied and dried to form a chrome-free sealing film on the surface of the phosphate-treated layer.
上記クロムフリーシーリング皮膜を形成する工程では、上記形成されたリン酸塩処理層に接するように、４族金属の酸素酸塩、１族金属またはその塩、およびアンモニウムイオンを含有し、かつｐＨが７．０以上９．０以下である化成処理液を付与し、乾燥させて、上記リン酸塩処理層の表面にクロムフリーシーリング皮膜を形成する。 2-3. Step of Forming Chrome-Free Sealing Film In the step of forming the chrome-free sealing film, an oxidase of Group 4 metal, a salt of Group 1 metal or its salt, and ammonium so as to be in contact with the formed phosphate-treated layer. A chemical conversion treatment solution containing ions and having a pH of 7.0 or more and 9.0 or less is applied and dried to form a chrome-free sealing film on the surface of the phosphate-treated layer.
上記化成処理液は、上述した４族金属の酸素酸塩、および１族金属またはその塩を含有し、アンモニウムイオンによりｐＨを７．０以上９．０以下に調整された化成処理液である。
The above-mentioned chemical conversion treatment liquid is a chemical conversion treatment liquid containing the above-mentioned acid acid salt of the Group 4 metal and the Group 1 metal or a salt thereof, and the pH of which is adjusted to 7.0 or more and 9.0 or less by ammonium ions.
上記化成処理液は、ｐＨを７．０以上９．０以下に調整することで、酸や塩基によるリン酸塩処理層または亜鉛系めっき層の溶解を抑制して、塗装鋼板の外観へのムラの発生や、これらの層の成分がクロムフリーシーリング皮膜に混入することによるそれぞれの層の作用の阻害を、抑制する。上記観点からは、上記化成処理液のｐＨは７．２以上８．５以下であることが好ましく、７．３以上８．０以下であることがより好ましい。
By adjusting the pH of the chemical conversion treatment liquid to 7.0 or more and 9.0 or less, the dissolution of the phosphate-treated layer or the zinc-based plating layer by an acid or a base is suppressed, and the appearance of the coated steel sheet is uneven. And the inhibition of the action of each layer due to the inclusion of the components of these layers in the chrome-free sealing film is suppressed. From the above viewpoint, the pH of the chemical conversion treatment solution is preferably 7.2 or more and 8.5 or less, and more preferably 7.3 or more and 8.0 or less.
上記４族金属の酸素酸塩、および１族金属またはその塩の含有量は、特に限定されない。たとえば、上記化成処理液中の４族金属原子の濃度は、５ｇ／Ｌ以上４０ｇ／Ｌ以下であることが好ましく、５ｇ／Ｌ以上３５ｇ／Ｌ以下であることがより好ましい。また、上記化成処理液中の１族金属原子の濃度は、０．２ｇ／Ｌ以上であることが好ましい。また、上記化成処理液中の上記１族金属またはその塩の量は、４族金属原子１００質量部に対して、１族金属原子が０．５質量部以上２１質量部以下となる量であることが好ましく、また、同様に、４族金属原子に対する１族金属原子のモル比が０．０２以上０．８以下となる量であることが好ましい。
The content of the above-mentioned Group 4 metal oxynate and Group 1 metal or a salt thereof is not particularly limited. For example, the concentration of the Group 4 metal atom in the chemical conversion treatment liquid is preferably 5 g / L or more and 40 g / L or less, and more preferably 5 g / L or more and 35 g / L or less. Further, the concentration of the Group 1 metal atom in the chemical conversion treatment liquid is preferably 0.2 g / L or more. The amount of the Group 1 metal or a salt thereof in the chemical conversion treatment liquid is such that the Group 1 metal atom is 0.5 parts by mass or more and 21 parts by mass or less with respect to 100 parts by mass of the Group 4 metal atom. It is also preferable that the molar ratio of the group 1 metal atom to the group 4 metal atom is 0.02 or more and 0.8 or less.
また、上記化成処理液は、海水などの塩水が付与されるような状況における塗装鋼板の耐食性をより高めるため、Ｖ、Ｍｏ、Ｐ、ＴｉまたはＳｉの酸化物、水酸化物またはフッ化物を含んでいてもよい。
Further, the chemical conversion treatment liquid contains oxides, hydroxides or fluorides of V, Mo, P, Ti or Si in order to further enhance the corrosion resistance of the coated steel sheet in a situation where salt water such as seawater is applied. You may be.
上記化成処理液の付与方法は、特に限定されず、ロールコート法、カーテンフロー法、スピンコート法、スプレー法、および浸漬引き上げ法などの公知の方法から適宜選択すればよい。
The method for applying the chemical conversion treatment liquid is not particularly limited, and may be appropriately selected from known methods such as a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dipping pulling method.
２－４．有機系皮膜を形成する工程
上記有機系皮膜を形成する工程では、上記形成されたクロムフリーシーリング皮膜に接するように、上述した有機樹脂を含有する有機系皮膜処理液を付与し、乾燥させて、上記クロムフリーシーリング皮膜の表面に有機系皮膜を形成する。 2-4. Step of Forming Organic Film In the step of forming the organic film, the organic film treatment liquid containing the above-mentioned organic resin is applied and dried so as to be in contact with the formed chrome-free sealing film. An organic film is formed on the surface of the chrome-free sealing film.
上記有機系皮膜を形成する工程では、上記形成されたクロムフリーシーリング皮膜に接するように、上述した有機樹脂を含有する有機系皮膜処理液を付与し、乾燥させて、上記クロムフリーシーリング皮膜の表面に有機系皮膜を形成する。 2-4. Step of Forming Organic Film In the step of forming the organic film, the organic film treatment liquid containing the above-mentioned organic resin is applied and dried so as to be in contact with the formed chrome-free sealing film. An organic film is formed on the surface of the chrome-free sealing film.
以下、本発明について実施例を参照して詳細に説明するが、本発明はこれらの実施例により限定されない。
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
１．めっき鋼板（鋼板および亜鉛系めっき層）
厚み０．８ｍｍ、Ｎｏ．２Ｄ仕上げのＳＵＳ４３０の表面に溶融Ｚｎ－０．１質量％Ａｌめっき層（めっき付着量２００ｇ／ｍ２）を形成して、めっき鋼板１とした。 1. 1. Plated steel plate (steel plate and zinc-based plated layer)
Thickness 0.8 mm, No. A molten Zn-0.1% by mass Al plating layer (plating adhesion amount 200 g / m 2 ) was formed on the surface of the 2D-finished SUS430 to obtain a plated steel sheet 1.
厚み０．８ｍｍ、Ｎｏ．２Ｄ仕上げのＳＵＳ４３０の表面に溶融Ｚｎ－０．１質量％Ａｌめっき層（めっき付着量２００ｇ／ｍ２）を形成して、めっき鋼板１とした。 1. 1. Plated steel plate (steel plate and zinc-based plated layer)
Thickness 0.8 mm, No. A molten Zn-0.1% by mass Al plating layer (plating adhesion amount 200 g / m 2 ) was formed on the surface of the 2D-finished SUS430 to obtain a plated steel sheet 1.
厚み０．８ｍｍ、Ｎｏ．２Ｄ仕上げのＳＵＳ４３０の表面に溶融Ｚｎ－６質量％Ａｌ－３質量％Ｍｇめっき層（めっき付着量１４０ｇ／ｍ２）を形成して、めっき鋼板２とした。
Thickness 0.8 mm, No. A molten Zn-6% by mass Al-3% by mass Mg plating layer (plating adhesion amount 140 g / m 2 ) was formed on the surface of the 2D-finished SUS430 to obtain a plated steel sheet 2.
板厚０．６ｍｍの普通鋼の表面に溶融Ｚｎ－０．１質量％Ａｌめっき層（めっき付着量２００ｇ／ｍ２）を形成して、めっき鋼板３とした。
A molten Zn-0.1 mass% Al plating layer (plating adhesion amount 200 g / m 2 ) was formed on the surface of ordinary steel having a plate thickness of 0.6 mm to obtain a plated steel sheet 3.
板厚０．６ｍｍの普通鋼の表面に溶融Ｚｎ－６質量％Ａｌ－３質量％Ｍｇめっき層（めっき付着量１４０ｇ／ｍ２）を形成して、めっき鋼板４とした。
A molten Zn-6% by mass Al-3% by mass Mg plating layer (plating adhesion amount 140 g / m 2 ) was formed on the surface of ordinary steel having a plate thickness of 0.6 mm to obtain a plated steel sheet 4.
２．塗装鋼板の作製
２－１．リン酸塩処理層の形成
めっき鋼板１を、リン酸イオン濃度が３０ｇ／Ｌであり、かつＮｉおよびＣｏを含有するリン酸塩処理液に１０秒浸漬して、リン酸塩処理層を形成した。リン酸塩処理液の温度は、７０℃だった。このとき形成されるリン酸塩処理層の付着量は、３．３ｇ／ｍ２であり、リン酸塩処理層中のＮｉおよびＣｏの合計付着量は、２２ｍｇ／ｍ２である。 2. 2. Preparation of painted steel sheet 2-1. Formation of Phosphate Treatment Layer The plated steel plate 1 was immersed in a phosphate treatment solution having a phosphate ion concentration of 30 g / L and containing Ni and Co for 10 seconds to form a phosphate treatment layer. .. The temperature of the phosphate treatment solution was 70 ° C. The adhesion amount of the phosphate-treated layer formed at this time is 3.3 g / m 2 , and the total adhesion amount of Ni and Co in the phosphate-treated layer is 22 mg / m 2 .
２－１．リン酸塩処理層の形成
めっき鋼板１を、リン酸イオン濃度が３０ｇ／Ｌであり、かつＮｉおよびＣｏを含有するリン酸塩処理液に１０秒浸漬して、リン酸塩処理層を形成した。リン酸塩処理液の温度は、７０℃だった。このとき形成されるリン酸塩処理層の付着量は、３．３ｇ／ｍ２であり、リン酸塩処理層中のＮｉおよびＣｏの合計付着量は、２２ｍｇ／ｍ２である。 2. 2. Preparation of painted steel sheet 2-1. Formation of Phosphate Treatment Layer The plated steel plate 1 was immersed in a phosphate treatment solution having a phosphate ion concentration of 30 g / L and containing Ni and Co for 10 seconds to form a phosphate treatment layer. .. The temperature of the phosphate treatment solution was 70 ° C. The adhesion amount of the phosphate-treated layer formed at this time is 3.3 g / m 2 , and the total adhesion amount of Ni and Co in the phosphate-treated layer is 22 mg / m 2 .
２－２．クロムフリーシーリング皮膜の形成
４族金属の酸素酸塩としてＺｒ濃度が５ｇ／Ｌとなる量の炭酸ジルコニウムアンモニウム、１族金属の塩としてＮａ濃度が０．５ｇ／Ｌとなる量の二リン酸ナトリウム（１族金属の塩）、および水溶液のｐＨが７．５となる量のアンモニアを含有するクロムフリーシーリング皮膜形成用の化成処理液を用意した。リン酸塩処理層を形成しためっき鋼板１の表面に、上記化成処理液を塗布し、２００℃のオーブンで乾燥させて、クロムフリーシーリング皮膜を形成した。上記化成処理液の塗布量は、クロムフリーシーリング皮膜の付着量が１０ｍｇ／ｍ２となる量に調整した。 2-2. Formation of chrome-free sealing film Zirconium zirconium in an amount that has a Zr concentration of 5 g / L as an oxidate of a Group 4 metal, and sodium diphosphate in an amount that has a Na concentration of 0.5 g / L as a salt of a Group 1 metal. A chemical conversion treatment liquid for forming a chrome-free sealing film containing (a salt of a group 1 metal) and ammonia in an amount such that the pH of the aqueous solution was 7.5 was prepared. The chemical conversion treatment liquid was applied to the surface of the plated steel sheet 1 on which the phosphate-treated layer was formed, and dried in an oven at 200 ° C. to form a chrome-free sealing film. The amount of the chemical conversion treatment liquid applied was adjusted so that the amount of the chromium-free sealing film adhered was 10 mg / m 2 .
４族金属の酸素酸塩としてＺｒ濃度が５ｇ／Ｌとなる量の炭酸ジルコニウムアンモニウム、１族金属の塩としてＮａ濃度が０．５ｇ／Ｌとなる量の二リン酸ナトリウム（１族金属の塩）、および水溶液のｐＨが７．５となる量のアンモニアを含有するクロムフリーシーリング皮膜形成用の化成処理液を用意した。リン酸塩処理層を形成しためっき鋼板１の表面に、上記化成処理液を塗布し、２００℃のオーブンで乾燥させて、クロムフリーシーリング皮膜を形成した。上記化成処理液の塗布量は、クロムフリーシーリング皮膜の付着量が１０ｍｇ／ｍ２となる量に調整した。 2-2. Formation of chrome-free sealing film Zirconium zirconium in an amount that has a Zr concentration of 5 g / L as an oxidate of a Group 4 metal, and sodium diphosphate in an amount that has a Na concentration of 0.5 g / L as a salt of a Group 1 metal. A chemical conversion treatment liquid for forming a chrome-free sealing film containing (a salt of a group 1 metal) and ammonia in an amount such that the pH of the aqueous solution was 7.5 was prepared. The chemical conversion treatment liquid was applied to the surface of the plated steel sheet 1 on which the phosphate-treated layer was formed, and dried in an oven at 200 ° C. to form a chrome-free sealing film. The amount of the chemical conversion treatment liquid applied was adjusted so that the amount of the chromium-free sealing film adhered was 10 mg / m 2 .
２－３．有機系皮膜の形成
ポリエステル樹脂を含有する有機系皮膜処理液（東洋紡社製、バイロナールＭＤ－１１００）を用意した。リン酸塩処理層およびクロムフリーシーリング皮膜を形成しためっき鋼板１の表面に、上記有機系皮膜処理液を塗布して乾燥させ、膜厚が５．０μｍの有機系皮膜を形成した。このようにして形成された塗装鋼板を、塗装鋼板１とする。 2-3. Formation of Organic Film An organic film treatment solution containing a polyester resin (Byronal MD-1100, manufactured by Toyobo Co., Ltd.) was prepared. The organic film treatment liquid was applied to the surface of the plated steel sheet 1 on which the phosphate-treated layer and the chrome-free sealing film were formed and dried to form an organic film having a film thickness of 5.0 μm. The coated steel sheet thus formed is referred to as a coated steel sheet 1.
ポリエステル樹脂を含有する有機系皮膜処理液（東洋紡社製、バイロナールＭＤ－１１００）を用意した。リン酸塩処理層およびクロムフリーシーリング皮膜を形成しためっき鋼板１の表面に、上記有機系皮膜処理液を塗布して乾燥させ、膜厚が５．０μｍの有機系皮膜を形成した。このようにして形成された塗装鋼板を、塗装鋼板１とする。 2-3. Formation of Organic Film An organic film treatment solution containing a polyester resin (Byronal MD-1100, manufactured by Toyobo Co., Ltd.) was prepared. The organic film treatment liquid was applied to the surface of the plated steel sheet 1 on which the phosphate-treated layer and the chrome-free sealing film were formed and dried to form an organic film having a film thickness of 5.0 μm. The coated steel sheet thus formed is referred to as a coated steel sheet 1.
２－４．塗装鋼板２～塗装鋼板３０の作製
リン酸塩処理層中のＮｉおよびＣｏの合計付着量が９５ｍｇ／ｍ２および６２ｍｇ／ｍ２となるように、リン酸塩処理液中のＮｉおよびＣｏの合計含有量を変更した以外は塗装鋼板１の作製と同様にして、それぞれ、塗装鋼板２および塗装鋼板３を得た。 2-4. Preparation of Painted Steel Sheet 2 to Painted Steel Sheet 30 The total amount of Ni and Co in the phosphating solution so that the total amount of Ni and Co adhered in the phosphating layer is 95 mg / m 2 and 62 mg / m 2 . A coated steel sheet 2 and a coated steel sheet 3 were obtained in the same manner as in the production of the coated steel sheet 1 except that the content was changed.
リン酸塩処理層中のＮｉおよびＣｏの合計付着量が９５ｍｇ／ｍ２および６２ｍｇ／ｍ２となるように、リン酸塩処理液中のＮｉおよびＣｏの合計含有量を変更した以外は塗装鋼板１の作製と同様にして、それぞれ、塗装鋼板２および塗装鋼板３を得た。 2-4. Preparation of Painted Steel Sheet 2 to Painted Steel Sheet 30 The total amount of Ni and Co in the phosphating solution so that the total amount of Ni and Co adhered in the phosphating layer is 95 mg / m 2 and 62 mg / m 2 . A coated steel sheet 2 and a coated steel sheet 3 were obtained in the same manner as in the production of the coated steel sheet 1 except that the content was changed.
化成処理液のｐＨが７．１および８．９となるように、化成処理液中のアンモニアの含有量を変更した以外は塗装鋼板３と同様にして、それぞれ、塗装鋼板４および塗装鋼板５を得た。
The coated steel sheet 4 and the coated steel sheet 5 were formed in the same manner as the coated steel sheet 3 except that the content of ammonia in the chemical conversion treatment solution was changed so that the pH of the chemical conversion treatment solution was 7.1 and 8.9, respectively. Obtained.
有機系皮膜処理液が含有する有機系樹脂の種類を、ウレタン樹脂（ＤＩＣ社製、ハイドランＡＤＳ－１１０）に変更した以外は塗装鋼板３と同様にして、塗装鋼板６を得た。
A coated steel sheet 6 was obtained in the same manner as the coated steel sheet 3 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
化成処理液が含有する４族金属の酸素酸塩の種類を、Ｔｉ濃度が２ｇ／Ｌとなる量のフッ化チタンアンモニウム（４族金属の酸素酸塩）に変更し、化成処理液のｐＨが７．１となるように、化成処理液中のアンモニアの含有量を調整した以外は塗装鋼板３と同様にして、塗装鋼板７を得た。
The type of Group 4 metal oxyate acid salt contained in the chemical conversion treatment liquid was changed to titanium ammonium fluoride (group 4 metal oxyate acid salt) having a Ti concentration of 2 g / L, and the pH of the chemical conversion treatment liquid was changed. A coated steel plate 7 was obtained in the same manner as the coated steel plate 3 except that the content of ammonia in the chemical conversion treatment liquid was adjusted so as to be 7.1.
有機系皮膜処理液が含有する有機系樹脂の種類を、アクリル樹脂（ＤＩＣ社製、ボンコートＣＧ－８４００）に変更した以外は塗装鋼板３と同様にして、塗装鋼板８を得た。
A coated steel sheet 8 was obtained in the same manner as the coated steel sheet 3 except that the type of the organic resin contained in the organic film treatment liquid was changed to an acrylic resin (Boncoat CG-8400 manufactured by DIC Corporation).
リン酸塩処理層の付着量が２．１ｇ／ｍ２および６．８ｇ／ｍ２となるように、リン酸塩処理液への浸漬時間を変更した以外は塗装鋼板３と同様にして、それぞれ、塗装鋼板９および塗装鋼板１０を得た。
Similar to the coated steel sheet 3, except that the immersion time in the phosphate treatment liquid was changed so that the adhesion amount of the phosphate treatment layer was 2.1 g / m 2 and 6.8 g / m 2 , respectively. , A coated steel plate 9 and a coated steel plate 10 were obtained.
めっき鋼板をめっき鋼板２に変更した以外は塗装鋼板３と同様にして、塗装鋼板１１を得た。
The coated steel plate 11 was obtained in the same manner as the coated steel plate 3 except that the plated steel plate was changed to the plated steel plate 2.
有機系皮膜処理液が含有する有機系樹脂の種類を、ウレタン樹脂（ＤＩＣ社製、ハイドランＡＤＳ－１１０）に変更した以外は塗装鋼板１１と同様にして、塗装鋼板１２を得た。
A coated steel sheet 12 was obtained in the same manner as the coated steel sheet 11 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
めっき鋼板をめっき鋼板３に変更した以外は塗装鋼板３と同様にして、塗装鋼板１３を得た。
The coated steel sheet 13 was obtained in the same manner as the coated steel sheet 3 except that the plated steel sheet was changed to the plated steel sheet 3.
有機系皮膜処理液が含有する有機系樹脂の種類を、アクリル樹脂（ＤＩＣ社製、ボンコートＣＧ－８４００）に変更し、有機系皮膜の膜厚が２．０μｍとなるように有機系皮膜処理液の塗布量を変更した以外は塗装鋼板１３と同様にして、塗装鋼板１４を得た。
The type of organic resin contained in the organic film treatment liquid is changed to acrylic resin (Boncoat CG-8400 manufactured by DIC), and the organic film treatment liquid has a film thickness of 2.0 μm. A coated steel sheet 14 was obtained in the same manner as the coated steel sheet 13 except that the coating amount of was changed.
めっき鋼板をめっき鋼板４に変更し、有機系皮膜の膜厚が６．０μｍとなるように有機系皮膜処理液の塗布量を変更した以外は塗装鋼板３と同様にして、塗装鋼板１５を得た。
The coated steel sheet 15 was obtained in the same manner as the coated steel sheet 3 except that the plated steel sheet was changed to the plated steel sheet 4 and the coating amount of the organic film treatment liquid was changed so that the film thickness of the organic film was 6.0 μm. rice field.
化成処理液が含有する４族金属の酸素酸塩の種類を、Ｔｉ濃度が２ｇ／Ｌとなる量のフッ化チタンアンモニウムに変更し、化成処理液のｐＨが７．１となるように、化成処理液中のアンモニアの含有量を調整した以外は塗装鋼板１５と同様にして、塗装鋼板１６を得た。
The type of the oxychloride of the Group 4 metal contained in the chemical conversion treatment liquid was changed to titanium ammonium fluoride in an amount such that the Ti concentration was 2 g / L, and the pH of the chemical conversion treatment liquid was changed to 7.1. A coated steel sheet 16 was obtained in the same manner as the coated steel sheet 15 except that the content of ammonia in the treatment liquid was adjusted.
有機系皮膜処理液が含有する有機系樹脂の種類をウレタン樹脂（ＤＩＣ社製、ハイドランＡＤＳ－１１０）に変更した以外は塗装鋼板１５と同様にして、塗装鋼板１７を得た。
A coated steel sheet 17 was obtained in the same manner as the coated steel sheet 15 except that the type of the organic resin contained in the organic film treatment liquid was changed to urethane resin (Hydran ADS-110 manufactured by DIC Corporation).
リン酸塩処理層中のＮｉおよびＣｏの合計付着量が、１１ｍｇ／ｍ２、１８ｍｇ／ｍ２、０ｍｇ／ｍ２、および１１０ｍｇ／ｍ２となるように、リン酸塩処理液中のＮｉおよびＣｏの合計含有量を変更した以外は塗装鋼板１の作製と同様にして、それぞれ、塗装鋼板１８～塗装鋼板２１を得た。
Ni and Ni in the phosphate treatment solution so that the total adhesion of Ni and Co in the phosphate treatment layer is 11 mg / m 2 , 18 mg / m 2 , 0 mg / m 2 and 110 mg / m 2 . The coated steel sheets 18 to 21 were obtained in the same manner as in the production of the coated steel sheet 1 except that the total content of Co was changed.
リン酸塩処理層の付着量が１．７ｇ／ｍ２および７．５ｇ／ｍ２となるようにリン酸塩処理液への浸漬時間を変更し、いずれの場合においてもリン酸塩処理層中のＮｉおよびＣｏの合計付着量が６２ｍｇ／ｍ２となるように、リン酸塩処理液中のＮｉおよびＣｏの合計含有量を変更した以外は塗装鋼板１と同様にして、それぞれ、塗装鋼板２２および塗装鋼板２３を得た。
The immersion time in the phosphate treatment solution was changed so that the adhesion amount of the phosphate treatment layer was 1.7 g / m 2 and 7.5 g / m 2 , and in either case, the phosphate treatment layer was used. In the same manner as the coated steel plate 1, except that the total content of Ni and Co in the phosphate treatment liquid was changed so that the total adhesion amount of Ni and Co was 62 mg / m 2 , the coated steel plate 22 was used. And a coated steel plate 23 was obtained.
化成処理液に１族金属の塩を含有させなかった以外は塗装鋼板３と同様にして、塗装鋼板２４を得た。
A coated steel sheet 24 was obtained in the same manner as the coated steel sheet 3 except that the chemical conversion treatment liquid did not contain a group 1 metal salt.
化成処理液のｐＨが６．５および１０．６となるように、化成処理液中のアンモニアの含有量を変更した以外は塗装鋼板３と同様にして、それぞれ、塗装鋼板２５および塗装鋼板２６を得た。
The coated steel sheet 25 and the coated steel sheet 26 were formed in the same manner as the coated steel sheet 3 except that the content of ammonia in the chemical conversion treatment solution was changed so that the pH of the chemical conversion treatment solution was 6.5 and 10.6, respectively. Obtained.
有機系皮膜を形成しなかった以外は塗装鋼板３と同様にして、塗装鋼板２７を得た。
A coated steel sheet 27 was obtained in the same manner as the coated steel sheet 3 except that an organic film was not formed.
化成処理液に４族金属の酸素酸塩を含有させなかった以外は塗装鋼板３と同様にして、塗装鋼板２８を得た。
A coated steel sheet 28 was obtained in the same manner as the coated steel sheet 3 except that the chemical conversion treatment liquid did not contain the oxygen acid salt of the Group 4 metal.
リン酸塩処理層およびクロムフリーシーリングを形成しなかった以外は塗装鋼板３と同様にして、塗装鋼板２９を得た。
A coated steel sheet 29 was obtained in the same manner as the coated steel sheet 3 except that the phosphate-treated layer and the chromium-free sealing were not formed.
めっき鋼板をめっき鋼板４に変更し、リン酸塩処理層およびクロムフリーシーリングを形成しなかった以外は塗装鋼板１３と同様にして、塗装鋼板３０を得た。
The plated steel sheet was changed to the plated steel sheet 4, and the coated steel sheet 30 was obtained in the same manner as the coated steel sheet 13 except that the phosphate-treated layer and the chrome-free sealing were not formed.
表１および表２に、塗装鋼板１～塗装鋼板３０についての、めっき鋼板、リン酸塩処理層の付着量およびリン酸塩処理層中のＮｉおよびＣｏの合計付着量、クロムフリーシーリング中に含まれる４族金属酸素酸塩を構成する４族金属の種類、１族金属の塩を形成する１族金属の種類および化成処理液のｐＨ、有機系皮膜を構成する有機樹脂の種類およびその膜厚を、示す。
Tables 1 and 2 show the adhered amounts of the plated steel plate and the phosphate-treated layer, the total adhered amount of Ni and Co in the phosphate-treated layer, and the chrome-free sealing of the coated steel plates 1 to 30. Types of Group 4 metals that make up Group 4 metal oxyphosphates, types of Group 1 metals that form salts of Group 1 metals, pH of chemical conversion treatment solutions, types of organic resins that make up organic films, and their film thicknesses. Is shown.
３．塗装鋼板の評価
３－１．耐食性
塗装鋼板１～塗装鋼板３０を塩水噴霧試験機に投入し、２４０時間後の白錆発生面積率を求め、以下の基準により、当該白錆発生面積率から塗装鋼板１～塗装鋼板３０の耐食性を評価した。
◎： 白錆発生面積率は５％以下だった
○： 白錆発生面積率は５％より多く１０％以下だった
△： 白錆発生面積率は１０％より多く４０％以下だった
×： 白錆発生面積率は４０％より多かった 3. 3. Evaluation of painted steel sheet 3-1. Corrosion resistance The coated steel sheet 1 to 30 are put into a salt spray tester, and the white rust generation area ratio after 240 hours is obtained. Was evaluated.
⊚: White rust occurrence area ratio was 5% or less ○: White rust occurrence area ratio was more than 5% and 10% or less △: White rust occurrence area ratio was more than 10% and 40% or less ×: White Rust area ratio was more than 40%
３－１．耐食性
塗装鋼板１～塗装鋼板３０を塩水噴霧試験機に投入し、２４０時間後の白錆発生面積率を求め、以下の基準により、当該白錆発生面積率から塗装鋼板１～塗装鋼板３０の耐食性を評価した。
◎： 白錆発生面積率は５％以下だった
○： 白錆発生面積率は５％より多く１０％以下だった
△： 白錆発生面積率は１０％より多く４０％以下だった
×： 白錆発生面積率は４０％より多かった 3. 3. Evaluation of painted steel sheet 3-1. Corrosion resistance The coated steel sheet 1 to 30 are put into a salt spray tester, and the white rust generation area ratio after 240 hours is obtained. Was evaluated.
⊚: White rust occurrence area ratio was 5% or less ○: White rust occurrence area ratio was more than 5% and 10% or less △: White rust occurrence area ratio was more than 10% and 40% or less ×: White Rust area ratio was more than 40%
３－２．明度
塗装鋼板１～塗装鋼板３０の有機系皮膜の表面（塗装鋼板１についてはクロムフリーシーリングの表面）の明度（Ｌ＊）を、測色計（ＢＹＫ社製、スペクトロ－ガイド グロスＳ）で、光源：Ｄ６５、視野角：２°の条件で測定し、以下の基準により、測定された明度から塗装鋼板１～塗装鋼板３０の耐食性を評価した。
◎： 明度（Ｌ＊）は５０以下だった
○： 明度（Ｌ＊）は５０より大きく５５以下だった
△： 明度（Ｌ＊）は５５より大きく６５以下だった
×： 明度（Ｌ＊）は６５より大きかった 3-2. Brightness The brightness (L *) of the surface of the organic film of the painted steel sheet 1 to 30 (the surface of the chrome-free sealing for the painted steel sheet 1) is measured with a colorimeter (Spectro-Guide Gross S manufactured by BYK). Measurements were made under the conditions of a light source: D65 and a viewing angle of 2 °, and the corrosion resistance of the coated steel sheets 1 to 30 was evaluated from the measured brightness according to the following criteria.
⊚: Brightness (L *) was 50 or less ○: Brightness (L *) was greater than 50 and 55 or less Δ: Brightness (L *) was greater than 55 and 65 or less ×: Brightness (L *) was Was greater than 65
塗装鋼板１～塗装鋼板３０の有機系皮膜の表面（塗装鋼板１についてはクロムフリーシーリングの表面）の明度（Ｌ＊）を、測色計（ＢＹＫ社製、スペクトロ－ガイド グロスＳ）で、光源：Ｄ６５、視野角：２°の条件で測定し、以下の基準により、測定された明度から塗装鋼板１～塗装鋼板３０の耐食性を評価した。
◎： 明度（Ｌ＊）は５０以下だった
○： 明度（Ｌ＊）は５０より大きく５５以下だった
△： 明度（Ｌ＊）は５５より大きく６５以下だった
×： 明度（Ｌ＊）は６５より大きかった 3-2. Brightness The brightness (L *) of the surface of the organic film of the painted steel sheet 1 to 30 (the surface of the chrome-free sealing for the painted steel sheet 1) is measured with a colorimeter (Spectro-Guide Gross S manufactured by BYK). Measurements were made under the conditions of a light source: D65 and a viewing angle of 2 °, and the corrosion resistance of the coated steel sheets 1 to 30 was evaluated from the measured brightness according to the following criteria.
⊚: Brightness (L *) was 50 or less ○: Brightness (L *) was greater than 50 and 55 or less Δ: Brightness (L *) was greater than 55 and 65 or less ×: Brightness (L *) was Was greater than 65
３－３．加工部密着性
塗装鋼板１～塗装鋼板３０を沸騰させた水に２時間浸漬させた後、表面にカッターナイフで１ｍｍ角形の碁盤目状の切りきず（１００個）を形成し、切りきずを形成した部位をエリクセン試験機で５ｍｍ張出し加工した。張出し加工部に対して粘着テープで剥離テストを行い、以下の基準により、１００個の切りきずに対する剥離した切りきずの個数をもとに塗装鋼板１～塗装鋼板３０の加工部密着性を評価した。
◎： 皮膜の剥離はみられなかった
○： 剥離した切りきずの割合は、０％より多く５％以下だった
△： 剥離した切りきずの割合は、５％より多く３０％以下だった
×： 剥離した切りきずの割合は、３０％より多かった 3-3. Adhesion to the processed part After immersing the coated steel plate 1 to 30 in boiling water for 2 hours, a 1 mm square grid-shaped chip (100 pieces) was formed on the surface with a cutter knife, and the chip was formed. Was overhanged by 5 mm with an Ericssen testing machine. A peeling test was performed on the overhanging portion with an adhesive tape, and the adhesion to the processed portion of the coated steel sheet 1 to 30 was evaluated based on the number of peeled chips for 100 chips according to the following criteria.
⊚: No peeling of the film was observed. ○: The percentage of peeled chips was more than 0% and 5% or less. Δ: The percentage of peeled chips was more than 5% and 30% or less. ×: Peeled. The percentage of chips was more than 30%
塗装鋼板１～塗装鋼板３０を沸騰させた水に２時間浸漬させた後、表面にカッターナイフで１ｍｍ角形の碁盤目状の切りきず（１００個）を形成し、切りきずを形成した部位をエリクセン試験機で５ｍｍ張出し加工した。張出し加工部に対して粘着テープで剥離テストを行い、以下の基準により、１００個の切りきずに対する剥離した切りきずの個数をもとに塗装鋼板１～塗装鋼板３０の加工部密着性を評価した。
◎： 皮膜の剥離はみられなかった
○： 剥離した切りきずの割合は、０％より多く５％以下だった
△： 剥離した切りきずの割合は、５％より多く３０％以下だった
×： 剥離した切りきずの割合は、３０％より多かった 3-3. Adhesion to the processed part After immersing the coated steel plate 1 to 30 in boiling water for 2 hours, a 1 mm square grid-shaped chip (100 pieces) was formed on the surface with a cutter knife, and the chip was formed. Was overhanged by 5 mm with an Ericssen testing machine. A peeling test was performed on the overhanging portion with an adhesive tape, and the adhesion to the processed portion of the coated steel sheet 1 to 30 was evaluated based on the number of peeled chips for 100 chips according to the following criteria.
⊚: No peeling of the film was observed. ○: The percentage of peeled chips was more than 0% and 5% or less. Δ: The percentage of peeled chips was more than 5% and 30% or less. ×: Peeled. The percentage of chips was more than 30%
３－４．評価結果
塗装鋼板１～塗装鋼板３０に対する、耐食性、明度および加工部密着性の評価結果を、表３および表４に示す。 3-4. Evaluation Results Tables 3 and 4 show the evaluation results of corrosion resistance, brightness, and adhesion to the processed portion of the coated steel sheets 1 to 30.
塗装鋼板１～塗装鋼板３０に対する、耐食性、明度および加工部密着性の評価結果を、表３および表４に示す。 3-4. Evaluation Results Tables 3 and 4 show the evaluation results of corrosion resistance, brightness, and adhesion to the processed portion of the coated steel sheets 1 to 30.
表３および表４の結果から明らかなように、鋼板と、亜鉛系めっき層と、ＮｉおよびＣｏの合計付着量が２０ｍｇ／ｍ２以上１００ｍｇ／ｍ２以下であり、処理層の付着量が２．０ｇ／ｍ２以上７．０ｇ／ｍ２以下である、リン酸塩処理層と、４族金属の酸素酸塩および１族金属またはその塩を含有するクロムフリーシーリング皮膜と、有機系皮膜と、がこの順番に配置されている塗装鋼板１～塗装鋼板１７は、明度（Ｌ＊）が５５以下であり、かつ耐食性および加工部密着性が高かった。
As is clear from the results of Tables 3 and 4, the total adhesion amount of the steel sheet, the zinc-based plating layer, and Ni and Co is 20 mg / m 2 or more and 100 mg / m 2 or less, and the adhesion amount of the treated layer is 2. A phosphate-treated layer having a pH of 0.0 g / m 2 or more and 7.0 g / m 2 or less, a chromium-free sealing film containing an oxidate of a Group 4 metal and a Group 1 metal or a salt thereof, and an organic film. The coated steel sheets 1 to 17 arranged in this order had a brightness (L *) of 55 or less, and had high corrosion resistance and adhesion to the processed portion.
また、塗装鋼板１と塗装鋼板２および塗装鋼板３との比較から明らかなように、リン酸塩処理層中のＮｉおよびＣｏの合計付着量が３０ｍｇ／ｍ２以上８０ｍｇ／ｍ２以下であると、塗装鋼板の表面の明度がより低くなり、かつ耐食性がより高くなっていた。これは、リン酸塩処理層中のＮｉおよびＣｏの合計付着量が３０ｍｇ／ｍ２以上であると、ＮｉおよびＣｏが十分に析出したため塗装鋼板の表面の明度がより低くなり、リン酸塩処理層中のＮｉおよびＣｏの合計付着量が８０ｍｇ／ｍ２以下であると、ＮｉおよびＣｏの析出がリン酸塩結晶の析出を阻害しにくかったため塗装鋼板の耐食性がより高くなったものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 1 and the coated steel sheet 2 and the coated steel sheet 3, the total adhesion amount of Ni and Co in the phosphate-treated layer is 30 mg / m 2 or more and 80 mg / m 2 or less. , The surface brightness of the painted steel sheet was lower, and the corrosion resistance was higher. This is because when the total amount of Ni and Co adhered to the phosphate-treated layer is 30 mg / m 2 or more, the surface brightness of the coated steel plate becomes lower because Ni and Co are sufficiently precipitated, and the phosphate treatment is performed. When the total adhesion of Ni and Co in the layer was 80 mg / m 2 or less, it is considered that the corrosion resistance of the coated steel plate was higher because the precipitation of Ni and Co was difficult to inhibit the precipitation of phosphate crystals. ..
また、塗装鋼板３と塗装鋼板４および塗装鋼板５との比較から明らかなように、化成処理液のｐＨが７．２以上８．５以下であると、塗装鋼板の表面の明度がより低くなっていた。これは、化成処理液のｐＨが７．２以上８．５以下であると、化成処理液へのリン酸塩処理層の溶解が抑制されて、塗装鋼板の表面の明度をより低くできたものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 4 and the coated steel sheet 5, when the pH of the chemical conversion treatment liquid is 7.2 or more and 8.5 or less, the brightness of the surface of the coated steel sheet becomes lower. Was there. This is because when the pH of the chemical conversion treatment liquid is 7.2 or more and 8.5 or less, the dissolution of the phosphate-treated layer in the chemical conversion treatment liquid is suppressed, and the brightness of the surface of the coated steel sheet can be further lowered. it is conceivable that.
また、塗装鋼板３と塗装鋼板７との比較、および塗装鋼板１５と塗装鋼板１６との比較から明らかなように、クロムフリーシーリング皮膜が４族金属の酸素酸塩としてＺｒの酸素酸塩を含むと、クロムフリーシーリング皮膜が４族金属の酸素酸塩としてＴｉの酸素酸塩を含むときよりも、塗装鋼板の表面の明度がより低くなっていた。これは、クロムフリーシーリング処理液のｐＨが低いため、表面のリン酸塩皮膜またはＮｉ置換層が若干除去され、塗装鋼板の表面の明度がより低くなったものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 7, and the comparison between the coated steel sheet 15 and the coated steel sheet 16, the chrome-free sealing film contains Zr oxygenate as the oxygen acid salt of the Group 4 metal. The brightness of the surface of the coated steel sheet was lower than that when the chrome-free sealing film contained Ti oxidate as the oxidate of Group 4 metal. It is considered that this is because the pH of the chrome-free sealing treatment liquid is low, so that the phosphate film or Ni substitution layer on the surface is slightly removed, and the brightness of the surface of the coated steel sheet becomes lower.
また、塗装鋼板３と塗装鋼板９との比較から明らかなように、リン酸塩処理層の付着量が２．５ｇ／ｍ２以上７．０ｇ／ｍ２以下であると、塗装鋼板の表面の明度がより低くなっていた。これは、リン酸塩処理層の付着量が２．５ｇ／ｍ２以上７．０ｇ／ｍ２以下であると、リン酸塩皮膜の付着量が少ないため塗装鋼板の表面の明度がより低くなったものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 9, when the adhesion amount of the phosphate-treated layer is 2.5 g / m 2 or more and 7.0 g / m 2 or less, the surface of the coated steel sheet is surfaced. The brightness was lower. This is because when the amount of the phosphate-treated layer adhered is 2.5 g / m 2 or more and 7.0 g / m 2 or less, the amount of the phosphate film adhered is small and the surface brightness of the coated steel sheet becomes lower. It is thought that it was.
一方で、塗装鋼板３と塗装鋼板１８～塗装鋼板２０との比較から明らかなように、リン酸塩処理層中のＮｉおよびＣｏの合計付着量が２０ｍｇ／ｍ２未満であると、塗装鋼板の表面の明度が５５より高くなっていた。これは、リン酸塩処理層中のＮｉおよびＣｏの合計付着量が２０ｍｇ／ｍ２未満であると、ＮｉまたはＣｏの析出量が少ないため塗装鋼板の表面の明度が低くならなかったものと考えられる。
On the other hand, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheets 18 to 20, when the total adhesion amount of Ni and Co in the phosphate-treated layer is less than 20 mg / m 2 , the coated steel sheet The brightness of the surface was higher than 55. It is considered that this is because when the total adhesion amount of Ni and Co in the phosphate treatment layer was less than 20 mg / m 2 , the brightness of the surface of the coated steel sheet did not decrease because the precipitation amount of Ni or Co was small. Be done.
また、塗装鋼板３と塗装鋼板２１との比較から明らかなように、リン酸塩処理層中のＮｉおよびＣｏの合計付着量が１００ｍｇ／ｍ２より多いと、塗装鋼板の耐食性がより低くなっていた。これは、リン酸塩処理層中のＮｉおよびＣｏの合計付着量が１００ｍｇ／ｍ２より多いと、析出したＮｉまたはＣｏによりリン酸塩結晶の析出が阻害されたため、塗装鋼板の表面の耐食性が高まらなかったものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 21, when the total adhesion amount of Ni and Co in the phosphate-treated layer is more than 100 mg / m 2 , the corrosion resistance of the coated steel sheet is lower. rice field. This is because when the total amount of Ni and Co adhered to the phosphate-treated layer is more than 100 mg / m 2 , the precipitation of phosphate crystals is inhibited by the precipitated Ni or Co, so that the corrosion resistance of the surface of the coated steel plate is improved. It is probable that it did not rise.
また、塗装鋼板３と塗装鋼板２２との比較から明らかなように、リン酸塩処理層の付着量が２．０ｇ／ｍ２未満であると、塗装鋼板の表面の明度が５５より高くなっていた。これは、リン酸塩処理層の付着量が２．０ｇ／ｍ２未満であると、リン酸塩皮膜の付着量が少ないため塗装鋼板の表面の明度が低くならなかったものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 22, when the adhesion amount of the phosphate-treated layer is less than 2.0 g / m 2 , the brightness of the surface of the coated steel sheet is higher than 55. rice field. It is probable that when the adhesion amount of the phosphate-treated layer was less than 2.0 g / m 2 , the brightness of the surface of the coated steel sheet did not decrease because the adhesion amount of the phosphate film was small.
また、塗装鋼板３と塗装鋼板２３との比較から明らかなように、リン酸塩処理層の付着量が７．０ｇ／ｍ２より多いと、塗装鋼板の加工部密着性が低下していた。これは、リン酸塩処理層の付着量が７．０ｇ／ｍ２より多いと、リン酸塩結晶のサイズが大きくなり、加工時に粉状に剥離しやすくなったため、塗装鋼板の加工部密着性が高まりにくかったものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 23, when the adhesion amount of the phosphate-treated layer is more than 7.0 g / m 2 , the adhesion to the processed portion of the coated steel sheet is lowered. This is because when the amount of the phosphate-treated layer adhered is more than 7.0 g / m 2 , the size of the phosphate crystals becomes large and it becomes easy to peel off into powder during processing. It is probable that it was difficult to increase.
また、塗装鋼板３と塗装鋼板２４との比較から明らかなように、クロムフリーシーリング皮膜が１族金属またはその塩を含有しないと、塗装鋼板の耐食性および加工部密着性が低下していた。これは、クロムフリーシーリング皮膜が１族金属またはその塩を含有しないと、化成処理液中の水酸基量が不十分なため塗装鋼板の耐食性が高まりにくく、有機皮膜の剥離が生じ塗装鋼板の加工部密着性が高まりにくかったものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 24, if the chromium-free sealing film does not contain the Group 1 metal or a salt thereof, the corrosion resistance of the coated steel sheet and the adhesion to the processed portion are deteriorated. This is because if the chromium-free sealing film does not contain a Group 1 metal or a salt thereof, the amount of hydroxyl groups in the chemical conversion treatment liquid is insufficient, so that the corrosion resistance of the coated steel sheet does not easily increase, and the organic film peels off, resulting in the processed portion of the coated steel sheet. It is probable that it was difficult to increase the adhesion.
また、塗装鋼板３と塗装鋼板２５および塗装鋼板２６との比較から明らかなように、化成処理液のｐＨが７．０以上９．０以下の範囲から外れていると、塗装鋼板の表面の明度がより低くなっていた。これは、化成処理液のｐＨが７．０以上９．０以下でないと、リン酸塩処理層が化成処理液に溶解するため、塗装鋼板の表面の明度が低くなりにくかったものと考えられる。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 25 and the coated steel sheet 26, when the pH of the chemical conversion treatment liquid is out of the range of 7.0 or more and 9.0 or less, the surface brightness of the coated steel sheet is bright. Was lower. It is considered that this is because the phosphate-treated layer dissolves in the chemical conversion treatment liquid unless the pH of the chemical conversion treatment liquid is 7.0 or more and 9.0 or less, so that the brightness of the surface of the coated steel sheet is difficult to be lowered.
また、塗装鋼板３と塗装鋼板２７との比較から明らかなように、塗装鋼板が有機系皮膜を有さないと、塗装鋼板の耐食性および耐食性が低下していた。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 27, if the coated steel sheet does not have an organic film, the corrosion resistance and the corrosion resistance of the coated steel sheet are lowered.
また、塗装鋼板３と塗装鋼板２８との比較から明らかなように、クロムフリーシーリング皮膜が４族金属の酸素酸塩を含有しないと、塗装鋼板の耐食性が低下していた。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 28, if the chrome-free sealing film does not contain the oxygen acid salt of the Group 4 metal, the corrosion resistance of the coated steel sheet is lowered.
また、塗装鋼板３と塗装鋼板２９との比較、および塗装鋼板１５と塗装鋼板３０との比較から明らかなように、塗装鋼板がリン酸塩処理層およびクロムフリーシーリング皮膜を有さないと、塗装鋼板の耐食性、明度および加工部密着性のすべてが、所望の程度とはならなかった。
Further, as is clear from the comparison between the coated steel sheet 3 and the coated steel sheet 29 and the comparison between the coated steel sheet 15 and the coated steel sheet 30, if the coated steel sheet does not have the phosphate-treated layer and the chrome-free sealing film, it is coated. Corrosion resistance, lightness and adhesion to the processed part of the steel sheet were not all desired.
本発明の塗装鋼板は、たとえば各種電子機器、家庭用電化製品、医療機器、自動車車体、車両搭載用品、建築資材などに好適に用いられる。特に、本発明の塗装鋼板は、明度が低いため意匠性に優れており、かつ、耐食性および加工部密着性に優れているため、建築資材として好適に使用することができる。
The coated steel sheet of the present invention is suitably used for, for example, various electronic devices, household electric appliances, medical devices, automobile bodies, vehicle-mounted products, building materials, and the like. In particular, the coated steel sheet of the present invention has excellent designability because of its low lightness, and also has excellent corrosion resistance and adhesion to the processed portion, so that it can be suitably used as a building material.
Claims (7)
- 鋼板と、
亜鉛系めっき層と、
ＮｉおよびＣｏの合計付着量が２０ｍｇ／ｍ２以上１００ｍｇ／ｍ２以下であり、処理層の付着量が２．０ｇ／ｍ２以上７．０ｇ／ｍ２以下である、リン酸塩処理層と、
４族金属の酸素酸塩および１族金属またはその塩を含有するクロムフリーシーリング皮膜と、
有機系皮膜と、
がこの順番に配置されており、
その表面の明度（Ｌ＊）が５５以下である、
塗装鋼板。 Steel plate and
With a zinc-based plating layer,
With the phosphate-treated layer, the total adhesion amount of Ni and Co is 20 mg / m 2 or more and 100 mg / m 2 or less, and the adhesion amount of the treated layer is 2.0 g / m 2 or more and 7.0 g / m 2 or less. ,
Chromium-free sealing films containing group 4 metal oxidates and group 1 metals or salts thereof.
Organic film and
Are arranged in this order,
The brightness (L *) of the surface is 55 or less.
Painted steel plate. - 前記クロムフリーシーリング皮膜は、アンモニウム塩を含む、請求項１に記載の塗装鋼板。 The coated steel sheet according to claim 1, wherein the chromium-free sealing film contains an ammonium salt.
- 前記亜鉛系めっき層は、０．１質量％以上２０質量％以下のＡｌを含む、請求項１または２に記載の塗装鋼板。 The coated steel sheet according to claim 1 or 2, wherein the zinc-based plated layer contains Al of 0.1% by mass or more and 20% by mass or less.
- 前記亜鉛系めっき層は、付着量が１００ｇ／ｍ２以上である、請求項１～３のいずれか１項に記載の塗装鋼板。 The coated steel sheet according to any one of claims 1 to 3, wherein the zinc-based plating layer has an adhesion amount of 100 g / m 2 or more.
- 前記クロムフリーシーリング皮膜は、前記１族金属またはその塩として、トリポリリン酸ナトリウム、１－ヒドロキシエチリデン－１，１－ビスホスホン酸二ナトリウム、および１－ヒドロキシエチリデン－１，１－ジホスホン酸五ナトリウムからなる群から選択される塩を含有する、請求項１～４のいずれか１項に記載の塗装鋼板。 The chromium-free sealing film is composed of sodium tripolyphosphate, 1-hydroxyethylidene-1,1-bisphosphonate disodium, and 1-hydroxyethylidene-1,1-diphosphonate pentasodium as the group 1 metal or a salt thereof. The coated steel plate according to any one of claims 1 to 4, which contains a salt selected from the group.
- 外装建材である、請求項１～５のいずれか１項に記載の塗装鋼板。 The coated steel sheet according to any one of claims 1 to 5, which is an exterior building material.
- 亜鉛系めっき層を有するめっき鋼板を用意する工程と、
前記亜鉛系めっき層に接して、ＮｉおよびＣｏの合計付着量が２０ｍｇ／ｍ２以上１００ｍｇ／ｍ２以下であり、処理層の付着量が２．０ｇ／ｍ２以上７．０ｇ／ｍ２以下である、リン酸塩処理層を形成する工程と、
前記リン酸塩処理層に接して、４族金属の酸素酸塩、１族金属またはその塩およびアンモニウムイオンを含有し、ｐＨが７．０以上９．０以下である化成処理液を付与して乾燥させ、クロムフリーシーリング皮膜を形成する工程と、
前記クロムフリーシーリング皮膜に接して、有機系皮膜を形成する工程と、
を有する、
塗装鋼板の製造方法。
The process of preparing a plated steel sheet having a zinc-based plating layer and
In contact with the zinc-based plating layer, the total adhesion amount of Ni and Co is 20 mg / m 2 or more and 100 mg / m 2 or less, and the adhesion amount of the treated layer is 2.0 g / m 2 or more and 7.0 g / m 2 or less. The process of forming the phosphate-treated layer and
In contact with the phosphate treatment layer, a chemical conversion treatment solution containing an oxidase of a Group 4 metal or a salt thereof and an ammonium ion and having a pH of 7.0 or more and 9.0 or less is applied. The process of drying to form a chrome-free sealing film,
The step of forming an organic film in contact with the chrome-free sealing film and
Have,
Manufacturing method of painted steel sheet.
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|---|---|---|---|---|
| JP2005126811A (en) * | 2003-10-01 | 2005-05-19 | Nisshin Steel Co Ltd | Galvanized steel sheet excellent in corrosion resistance, coating characteristic and adhesive property |
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| WO2017002805A1 (en) * | 2015-07-02 | 2017-01-05 | 新日鐵住金株式会社 | Black coated steel sheet |
| WO2019187945A1 (en) * | 2018-03-26 | 2019-10-03 | 日新製鋼株式会社 | Chemical treatment liquid and chemically treated steel sheet |
| JP2020152986A (en) * | 2019-03-22 | 2020-09-24 | 日鉄日新製鋼株式会社 | Coated steel panel and method of manufacturing coated steel panel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005126811A (en) * | 2003-10-01 | 2005-05-19 | Nisshin Steel Co Ltd | Galvanized steel sheet excellent in corrosion resistance, coating characteristic and adhesive property |
| JP2014510837A (en) * | 2011-02-08 | 2014-05-01 | 日本パーカライジング株式会社 | Process and composition for improving the corrosion performance of zinc surfaces pretreated with zirconium oxide |
| WO2017002805A1 (en) * | 2015-07-02 | 2017-01-05 | 新日鐵住金株式会社 | Black coated steel sheet |
| WO2019187945A1 (en) * | 2018-03-26 | 2019-10-03 | 日新製鋼株式会社 | Chemical treatment liquid and chemically treated steel sheet |
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