JP2015158005A - Steel sheet for vessel and manufacturing method of the same - Google Patents
Steel sheet for vessel and manufacturing method of the same Download PDFInfo
- Publication number
- JP2015158005A JP2015158005A JP2014216848A JP2014216848A JP2015158005A JP 2015158005 A JP2015158005 A JP 2015158005A JP 2014216848 A JP2014216848 A JP 2014216848A JP 2014216848 A JP2014216848 A JP 2014216848A JP 2015158005 A JP2015158005 A JP 2015158005A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- steel plate
- film
- steel sheet
- tin oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 143
- 239000010959 steel Substances 0.000 title claims abstract description 143
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 54
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 22
- 229910017091 Fe-Sn Inorganic materials 0.000 claims abstract description 18
- 229910017142 Fe—Sn Inorganic materials 0.000 claims abstract description 18
- 230000005611 electricity Effects 0.000 claims abstract description 14
- 229910020938 Sn-Ni Inorganic materials 0.000 claims abstract description 13
- 229910008937 Sn—Ni Inorganic materials 0.000 claims abstract description 13
- 238000007747 plating Methods 0.000 claims description 80
- 239000007788 liquid Substances 0.000 claims description 45
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 150000004974 alkaline earth metal peroxides Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 156
- 239000011247 coating layer Substances 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 80
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 38
- 238000000034 method Methods 0.000 description 33
- 239000010936 titanium Substances 0.000 description 28
- 230000008569 process Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 13
- 239000012528 membrane Substances 0.000 description 11
- 238000004544 sputter deposition Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 238000011088 calibration curve Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000005211 surface analysis Methods 0.000 description 6
- 229910003271 Ni-Fe Inorganic materials 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- BFDQRLXGNLZULX-UHFFFAOYSA-N titanium hydrofluoride Chemical compound F.[Ti] BFDQRLXGNLZULX-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002335 surface treatment layer Substances 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- -1 titanium alkoxide Chemical class 0.000 description 2
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical class OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- GNRMKQMKBAJVLN-UHFFFAOYSA-J dipotassium;oxalate;oxygen(2-);titanium(4+);dihydrate Chemical compound O.O.[O-2].[K+].[K+].[Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GNRMKQMKBAJVLN-UHFFFAOYSA-J 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical class Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical class OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- AICMYQIGFPHNCY-UHFFFAOYSA-J methanesulfonate;tin(4+) Chemical compound [Sn+4].CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O.CS([O-])(=O)=O AICMYQIGFPHNCY-UHFFFAOYSA-J 0.000 description 1
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 1
- 229960002218 sodium chlorite Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000011697 sodium iodate Substances 0.000 description 1
- 235000015281 sodium iodate Nutrition 0.000 description 1
- 229940032753 sodium iodate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
-
- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/011—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of iron alloys or steels
-
- 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
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、容器用鋼板およびその製造方法に関する。 The present invention relates to a steel plate for containers and a method for producing the same.
缶等の容器に用いられる鋼板（容器用鋼板）として、例えば、特許文献１には、「金属板表面に無機成分を主体とする表面処理層…が形成されている…金属板であって、前記無機表面処理層が、…リン酸イオンを含有せずＦと水酸基を含むＴｉ或いはＴｉ及びＺｒの酸化物からなり、…Ｔｉの重量膜厚が５〜３００ｍｇ／ｍ2であることを特徴とする缶又は缶蓋用樹脂被覆表面処理金属板」が記載されている（［請求項１］）。 As a steel plate (container steel plate) used for a container such as a can, for example, in Patent Document 1, "a surface treatment layer mainly composed of an inorganic component is formed on a metal plate surface ... a metal plate, The inorganic surface treatment layer is composed of Ti or Ti and Zr oxide containing no phosphate ion and containing F and a hydroxyl group, and the weight film thickness of Ti is 5 to 300 mg / m 2. "Resin-coated surface-treated metal plate for cans or can lids" ([Claim 1]).
本発明者らは、特許文献１に記載された容器用鋼板の検討を行ったところ、塗料に対する密着性（以下、単に「密着性」ともいう）等については、比較的良好であることが分かった。 The present inventors have examined the steel plate for containers described in Patent Document 1 and found that the adhesiveness to the paint (hereinafter also simply referred to as “adhesiveness”) and the like is relatively good. It was.
そこで、これらの容器用鋼板について、さらに検討を行った。具体的には、Ｔｉを含有する皮膜（表面処理層）が配置される鋼板（金属板）として、Ｓｎ層やＦｅ−Ｓｎ合金層などのＳｎを含むめっき層で表面が覆われためっき鋼板を用いた場合について、検討を行った。
その結果、皮膜中のＴｉ量が多すぎる場合（例えば、皮膜のめっき鋼板の片面あたりのＴｉ換算の付着量が５ｍｇ／ｍ2以上である場合）には、皮膜が茶系色を呈したり、さらに、大気下での保管中に色調変化を起こして、より濃色の茶系色を呈したりすることが明らかとなった。このような色調の変化（茶系の呈色）は、容器用鋼板の外観を劣化させ、商品価値を著しく損なう。
Then, further examination was performed about these steel plates for containers. Specifically, as a steel plate (metal plate) on which a Ti-containing film (surface treatment layer) is disposed, a plated steel plate whose surface is covered with a plating layer containing Sn such as an Sn layer or an Fe—Sn alloy layer. The case where it was used was examined.
As a result, when the amount of Ti in the film is too large (for example, when the amount of Ti converted adhesion per side of the coated steel sheet is 5 mg / m 2 or more), the film exhibits a brown color, In addition, it was revealed that the color tone changed during storage in the atmosphere, resulting in a darker brown color. Such a change in color tone (brown coloration) deteriorates the appearance of the steel plate for containers and significantly impairs the commercial value.
本発明は、以上の点を鑑みてなされたものであり、外観に優れる容器用鋼板を提供することを目的とする。 This invention is made | formed in view of the above point, and it aims at providing the steel plate for containers excellent in an external appearance.
本発明者らは、上記目的を達成するために鋭意検討を行なった結果、Ｓｎ層などのめっき層とＴｉを含有する皮膜との間に、特定の錫酸化膜を設けることで、皮膜の着色や経時的な着色濃化を抑制できることを見出し、本発明を完成させた。 As a result of intensive studies to achieve the above object, the present inventors have provided a specific tin oxide film between a plating layer such as an Sn layer and a film containing Ti, thereby coloring the film. In addition, the present inventors have found that color concentration over time can be suppressed and the present invention has been completed.
すなわち、本発明は、以下の［１］〜［７］を提供する。
［１］鋼板の表面の少なくとも一部をＳｎ層、Ｆｅ−Ｓｎ−Ｎｉ合金層およびＦｅ−Ｓｎ合金層のうちから選ばれた少なくとも１層を含むめっき層が覆うめっき鋼板と、上記めっき鋼板の上記めっき層側の表面上に配置された皮膜とを有する容器用鋼板であって、上記めっき層と上記皮膜との間に、錫酸化物を含有する錫酸化膜を有し、上記錫酸化物の還元に要する電気量が２．０〜５．０ｍＣ／ｃｍ2であり、上記皮膜が、Ｔｉを含有し、上記めっき鋼板の片面あたりのＴｉ換算の付着量が２．５〜３０．０ｍｇ／ｍ2である、容器用鋼板。
［２］上記皮膜が、Ｎｉを含有し、上記めっき鋼板の片面あたりのＮｉ換算の付着量が０．１〜２０．０ｍｇ／ｍ2である、上記［１］に記載の容器用鋼板。
［３］上記皮膜の表面からの深さ方向の原子濃度分布において、０価Ｓｎの原子濃度が上記めっき層の０価Ｓｎの原子濃度の２５％と等しくなる深さＬ（単位：ｎｍ）と、上記皮膜の表面から深さＬまでの０価Ｓｎの平均原子濃度Ａ（単位：原子％）との積Ｘが、下記式（１）を満たす、上記［１］または［２］に記載の容器用鋼板。
０≦Ｘ（＝Ｌ×Ａ）≦６０・・・（１）
［４］上記［１］に記載の容器用鋼板を得る、容器用鋼板の製造方法であって、鋼板の表面の少なくとも一部をＳｎ層、Ｆｅ−Ｓｎ−Ｎｉ合金層およびＦｅ−Ｓｎ合金層のうちから選ばれた少なくとも１層を含むめっき層が覆うめっき鋼板を、酸化剤もしくは炭酸塩を含有する前処理液に浸漬する、または、上記前処理液中で陽極電解処理することにより、当該めっき鋼板のめっき層側の表面上に、上記錫酸化膜を形成する前処理工程と、Ｔｉ成分を含有する処理液中で、上記錫酸化膜を形成した上記めっき鋼板に陰極電解処理を施して、上記錫酸化膜の表面上に上記皮膜を形成する皮膜形成工程と、を備える容器用鋼板の製造方法。
［５］上記［２］に記載の容器用鋼板を得る、容器用鋼板の製造方法であって、鋼板の表面の少なくとも一部をＳｎ層、Ｆｅ−Ｓｎ−Ｎｉ合金層およびＦｅ−Ｓｎ合金層のうちから選ばれた少なくとも１層を含むめっき層が覆うめっき鋼板を、酸化剤もしくは炭酸塩を含有する前処理液に浸漬する、または、上記前処理液中で陽極電解処理することにより、当該めっき鋼板のめっき層側の表面上に、上記錫酸化膜を形成する前処理工程と、Ｔｉ成分およびＮｉ成分を含有する処理液中で、上記錫酸化膜を形成した上記めっき鋼板に陰極電解処理を施して、上記錫酸化膜の表面上に上記皮膜を形成する皮膜形成工程と、を備える容器用鋼板の製造方法。
［６］上記酸化剤が、過塩素酸塩類、アルカリ金属またはアルカリ土類金属の過酸化物、ならびに、過酸化水素またはその誘導体からなる群から選ばれる少なくとも１種であり、上記炭酸塩が、アルカリ金属の炭酸塩類である、上記［４］または［５］に記載の容器用鋼板の製造方法。
［７］上記めっき層中における上記鋼板片面当たりのＳｎ付着量が、０．１〜１５．０ｇ／ｍ2である、上記［４］〜［６］のいずれかに記載の容器用鋼板の製造方法。
That is, the present invention provides the following [1] to [7].
[1] A plated steel sheet in which at least a part of the surface of the steel sheet is covered with a plated layer including at least one layer selected from an Sn layer, an Fe—Sn—Ni alloy layer, and an Fe—Sn alloy layer; A steel plate for containers having a coating disposed on the surface on the plating layer side, having a tin oxide film containing tin oxide between the plating layer and the coating, and the tin oxide The amount of electricity required for the reduction is 2.0 to 5.0 mC / cm 2 , the film contains Ti, and the amount of Ti converted per one side of the plated steel sheet is 2.5 to 30.0 mg / A steel plate for containers which is m 2 .
[2] The steel plate for containers according to the above [1], wherein the coating contains Ni, and the adhesion amount in terms of Ni per one side of the plated steel plate is 0.1 to 20.0 mg / m 2 .
[3] In the atomic concentration distribution in the depth direction from the surface of the film, the depth L (unit: nm) at which the atomic concentration of zero-valent Sn is equal to 25% of the atomic concentration of zero-valent Sn of the plating layer The product X with the average atomic concentration A (unit: atomic%) of zero-valent Sn from the surface of the film to the depth L satisfies the following formula (1), according to the above [1] or [2] Steel plate for containers.
0 ≦ X (= L × A) ≦ 60 (1)
[4] A method for producing a container steel plate according to the above [1], wherein at least part of the surface of the steel sheet is an Sn layer, an Fe—Sn—Ni alloy layer, and an Fe—Sn alloy layer. By immersing a plated steel sheet covered with a plating layer including at least one layer selected from the above, in a pretreatment liquid containing an oxidizing agent or a carbonate, or by anodic electrolytic treatment in the pretreatment liquid, Cathodic electrolytic treatment is performed on the plated steel sheet on which the tin oxide film is formed in a pretreatment step for forming the tin oxide film on the surface on the plating layer side of the plated steel sheet and in a treatment liquid containing a Ti component. And a film forming step of forming the film on the surface of the tin oxide film.
[5] A method for producing a container steel plate according to the above [2], wherein at least a part of the surface of the steel plate is formed of a Sn layer, a Fe—Sn—Ni alloy layer, and a Fe—Sn alloy layer. By immersing a plated steel sheet covered with a plating layer including at least one layer selected from the above, in a pretreatment liquid containing an oxidizing agent or a carbonate, or by anodic electrolytic treatment in the pretreatment liquid, Cathodic electrolysis treatment on the plated steel sheet on which the tin oxide film is formed in a pretreatment step for forming the tin oxide film on the surface of the plated steel sheet on the plated layer side and in a treatment liquid containing a Ti component and a Ni component And a film forming step of forming the film on the surface of the tin oxide film.
[6] The oxidizing agent is at least one selected from the group consisting of perchlorates, alkali metal or alkaline earth metal peroxides, and hydrogen peroxide or a derivative thereof. The method for producing a steel plate for containers according to the above [4] or [5], which is an alkali metal carbonate.
[7] Production of steel plate for containers according to any of [4] to [6] above, wherein the Sn adhesion amount per one side of the steel plate in the plating layer is 0.1 to 15.0 g / m 2. Method.
本発明によれば、外観に優れる容器用鋼板を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the steel plate for containers excellent in an external appearance can be provided.
［容器用鋼板］
本発明の容器用鋼板は、Ｓｎ層やＦｅ−Ｓｎ合金層などのＳｎを含むめっき層（以下、「錫めっき層」ともいう）を有するめっき鋼板と、めっき鋼板の錫めっき層側の表面上に配置されたＴｉを含有する皮膜とを有し、さらに、錫めっき層と皮膜との間に、特定量の錫酸化膜を有する。これにより、皮膜が有する良好な密着性等の特性を維持しつつ、皮膜の着色や経時的な着色濃化を抑制でき、容器用鋼板の外観が優れる。
このメカニズム（理由）は明らかではないが、以下のように推測される。すなわち、錫酸化膜を形成することで、錫めっき層から皮膜中への不純物（主にＳｎ）ドープが抑制される。その結果、皮膜の主成分である酸化チタンのバンドギャップの縮小が抑制され、可視光吸収が低下する。これにより、茶系色の呈色が改善される。同様にして、大気放置時の経時的な着色濃化も改善される。
なお、上記メカニズムはいずれも推測であり、上記メカニズム以外であっても本発明の範囲内であるとする。
[Steel plate for containers]
The steel plate for containers of the present invention includes a plated steel plate having a Sn-containing plating layer (hereinafter also referred to as “tin-plated layer”) such as an Sn layer and an Fe—Sn alloy layer, and a surface of the plated steel plate on the tin plating layer side. And a coating film containing Ti, and a specific amount of tin oxide film between the tin plating layer and the coating film. Thereby, coloring of a film | membrane and coloring concentration with time can be suppressed, maintaining the characteristics, such as favorable adhesiveness which a film | membrane has, and the external appearance of the steel plate for containers is excellent.
The mechanism (reason) is not clear, but is presumed as follows. That is, by forming the tin oxide film, doping of impurities (mainly Sn) from the tin plating layer into the film is suppressed. As a result, the reduction of the band gap of titanium oxide, which is the main component of the film, is suppressed, and the visible light absorption is reduced. Thereby, the coloration of the brown color is improved. Similarly, the color concentration over time when left in the atmosphere is also improved.
In addition, all the said mechanisms are speculations, and it is assumed that it is within the scope of the present invention even if other than the above mechanisms.
以下に、めっき鋼板、皮膜および錫酸化膜の具体的な態様について詳述する。まず、めっき鋼板の態様について詳述する。 Below, the specific aspect of a plated steel plate, a membrane | film | coat, and a tin oxide film is explained in full detail. First, the aspect of a plated steel plate is explained in full detail.
〔めっき鋼板〕
めっき鋼板は、鋼板と、鋼板の表面の少なくとも一部を覆うＳｎ層、Ｆｅ−Ｓｎ−Ｎｉ合金層およびＦｅ−Ｓｎ合金層のうちから選ばれた少なくとも１層を含むめっき層とを有する。
素材の鋼板としては、一般的な缶用の鋼板を使用できる。めっき層は、連続層であってもよいし、不連続の島状であってもよい。また、めっき層は、鋼板の少なくとも片面に設けられていればよく、両面に設けられていてもよい。めっき層の形成は、含有される金属元素に応じた公知の方法で行える。
以下に、鋼板およびめっき層の好適態様について詳述する。
[Plated steel sheet]
The plated steel sheet has a steel sheet and a plating layer including at least one layer selected from an Sn layer, an Fe—Sn—Ni alloy layer, and an Fe—Sn alloy layer covering at least a part of the surface of the steel sheet.
As a raw steel plate, a general steel plate for cans can be used. The plating layer may be a continuous layer or a discontinuous island shape. Moreover, the plating layer should just be provided in the at least single side | surface of the steel plate, and may be provided in both surfaces. The plating layer can be formed by a known method according to the contained metal element.
Below, the suitable aspect of a steel plate and a plating layer is explained in full detail.
〈鋼板〉
鋼板の種類は特に限定されるものではない。通常、容器材料として使用される鋼板（例えば、低炭素鋼板、極低炭素鋼板）を用いることができる。この鋼板の製造方法、材質なども特に限定されるものではない。通常の鋼片製造工程から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造される。
<steel sheet>
The kind of steel plate is not particularly limited. Usually, a steel plate (for example, a low carbon steel plate or an ultra low carbon steel plate) used as a container material can be used. The manufacturing method and material of the steel plate are not particularly limited. It is manufactured through processes such as hot rolling, pickling, cold rolling, annealing, temper rolling and the like from a normal billet manufacturing process.
鋼板は、必要に応じて、その表面にニッケル含有層（Ｎｉ含有層）を形成したものを用い、このＮｉ含有層上に錫めっき層を形成してもよい。Ｎｉ含有層を有する鋼板を用いて錫めっきを施すことにより、島状Ｓｎを含む錫めっき層を形成できる。その結果、溶接性が向上する。
Ｎｉ含有層としてはニッケルが含まれていればよい。例えば、Ｎｉめっき層（Ｎｉ層）、Ｎｉ−Ｆｅ合金層などが挙げられる。
鋼板にＮｉ含有層を付与する方法は特に限定されない。例えば、公知の電気めっきなどの方法が挙げられる。また、Ｎｉ含有層としてＮｉ−Ｆｅ合金層を付与する場合、電気めっきなどにより鋼板表面上にＮｉ付与後、焼鈍することにより、鋼中にＮｉを拡散させ、Ｎｉ−Ｆｅ合金層を形成できる。
Ｎｉ含有層中のＮｉ付着量は特に限定されず、片面当たりのＮｉ換算量として５０〜２０００ｍｇ／ｍ2が好ましい。上記範囲内であれば、コスト面でも有利となる。
なお、Ｎｉ付着量は、蛍光Ｘ線により表面分析して測定できる。この場合、Ｎｉ付着量既知のＮｉ付着サンプルを用いて、Ｎｉ付着量に関する検量線をあらかじめ特定しておき、同検量線を用いて相対的にＮｉ付着量を特定する。ただし、後述する皮膜がＮｉを含む場合は、上記の蛍光Ｘ線による表面分析によりＮｉ含有層中のＮｉ付着量のみを測定することは困難である。その場合は、Ｎｉ含有層中のＮｉ付着量は、蛍光Ｘ線により求めたＮｉ付着量から後述する皮膜中に含まれるＮｉ付着量を差し引いて求めることができる。
If necessary, a steel plate having a nickel-containing layer (Ni-containing layer) formed on the surface thereof may be used, and a tin plating layer may be formed on the Ni-containing layer. By performing tin plating using a steel sheet having a Ni-containing layer, a tin plating layer containing island-shaped Sn can be formed. As a result, weldability is improved.
The Ni-containing layer only needs to contain nickel. For example, a Ni plating layer (Ni layer), a Ni—Fe alloy layer, and the like can be given.
The method for applying the Ni-containing layer to the steel plate is not particularly limited. For example, a known method such as electroplating can be used. Moreover, when providing a Ni-Fe alloy layer as a Ni-containing layer, Ni can be diffused in the steel by annealing after applying Ni on the steel sheet surface by electroplating or the like, thereby forming a Ni-Fe alloy layer.
The Ni adhesion amount in the Ni-containing layer is not particularly limited, and is preferably 50 to 2000 mg / m 2 as the Ni conversion amount per one side. If it is in the said range, it will become advantageous also in terms of cost.
The Ni adhesion amount can be measured by surface analysis with fluorescent X-rays. In this case, a calibration curve related to the Ni adhesion amount is specified in advance using a Ni adhesion sample with a known Ni adhesion amount, and the Ni adhesion amount is relatively specified using the calibration curve. However, when the film to be described later contains Ni, it is difficult to measure only the amount of Ni deposited in the Ni-containing layer by the surface analysis using the fluorescent X-ray. In that case, the Ni adhesion amount in the Ni-containing layer can be obtained by subtracting the Ni adhesion amount contained in the film described later from the Ni adhesion amount obtained by fluorescent X-rays.
〈めっき層（錫めっき層）〉
めっき鋼板は、鋼板表面上にＳｎを含有するめっき層（錫めっき層）を有する。この錫めっき層は、鋼板の少なくとも片面に設けられていればよく、両面に設けられていてもよい。
錫めっき層中における鋼板片面当たりのＳｎ付着量は、容器用鋼板の外観がより優れ、耐食性にも優れるという理由から、０．１〜１５．０ｇ／ｍ2が好ましく、０．２〜１５．０ｇ／ｍ2がより好ましく、加工性が優れる点で、１．０〜１５．０ｇ／ｍ2がさらに好ましい。
<Plating layer (tin plating layer)>
The plated steel sheet has a plating layer (tin plating layer) containing Sn on the steel sheet surface. The tin plating layer only needs to be provided on at least one side of the steel plate, and may be provided on both sides.
The Sn adhesion amount per one side of the steel plate in the tin plating layer is preferably 0.1 to 15.0 g / m 2 , because the appearance of the steel plate for containers is better and the corrosion resistance is better, and 0.2 to 15. more preferably 0 g / m 2, workability in view of excellent, more preferably 1.0~15.0g / m 2.
なお、Ｓｎ付着量は、蛍光Ｘ線により表面分析して測定できる。蛍光Ｘ線の場合、Ｓｎ付着量既知のＳｎ付着サンプルを用いて、Ｓｎ付着量に関する検量線をあらかじめ特定しておき、同検量線を用いて相対的にＳｎ付着量を特定する。 Note that the Sn adhesion amount can be measured by surface analysis using fluorescent X-rays. In the case of fluorescent X-rays, a calibration curve related to the Sn deposition amount is specified in advance using a Sn deposition sample with a known Sn deposition amount, and the Sn deposition amount is relatively identified using the calibration curve.
錫めっき層は、鋼板表面上の少なくとも一部を覆う層であり、連続層であってもよいし、不連続の島状であってもよい。 The tin plating layer is a layer covering at least a part on the surface of the steel plate, and may be a continuous layer or a discontinuous island shape.
錫めっき層としては、錫をめっきして得られる錫単体のめっき層であるＳｎ層からなる錫めっき層のほか、錫めっき後通電加熱などにより錫を加熱溶融させて得られる、Ｓｎ層の最下層（Ｓｎ層／鋼板界面）にＦｅ−Ｓｎ合金層が一部形成した錫めっき層、または、Ｓｎ層の全Ｓｎが合金化しＦｅ−Ｓｎ合金層を形成した錫めっき層も含む。
また、錫めっき層としては、Ｎｉ含有層を表面に有する鋼板に対して錫めっきを行い、さらに通電加熱などにより錫を加熱溶融させて得られる、Ｓｎ層の最下層（Ｓｎ層／鋼板界面）にＦｅ−Ｓｎ−Ｎｉ合金層、Ｆｅ−Ｓｎ合金層などが一部形成した錫めっき層、または、Ｓｎ層の全Ｓｎが合金化しＦｅ−Ｓｎ−Ｎｉ合金層、Ｆｅ−Ｓｎ合金層を形成した錫めっき層も含む。
As the tin plating layer, in addition to a tin plating layer composed of an Sn layer obtained by plating tin, the tin plating layer obtained by heating and melting tin by energization heating after tin plating, etc. It also includes a tin plating layer in which a Fe—Sn alloy layer is partially formed in the lower layer (Sn layer / steel plate interface) or a tin plating layer in which all Sn of the Sn layer is alloyed to form an Fe—Sn alloy layer.
In addition, as the tin plating layer, the lowermost layer of the Sn layer (Sn layer / steel plate interface) obtained by tin-plating a steel plate having a Ni-containing layer on the surface and further heating and melting tin by electric heating or the like A tin-plated layer in which a Fe-Sn-Ni alloy layer, a Fe-Sn alloy layer, etc. are partially formed, or all Sn in the Sn layer is alloyed to form a Fe-Sn-Ni alloy layer and a Fe-Sn alloy layer. Also includes a tin plating layer.
錫めっき層の製造方法としては、周知の方法（例えば、電気めっき法や溶融したＳｎに浸漬してめっきする方法）が挙げられる。
例えば、フェノールスルフォン酸錫めっき浴、メタンスルフォン酸錫めっき浴、またはハロゲン系錫めっき浴を用い、片面あたりの付着量が所定量となるように鋼板表面にＳｎを電気めっきする。その後、Ｓｎの融点（２３１．９℃）以上の温度で加熱溶融処理を行って、錫単体のめっき層（Ｓｎ層）の最下層またはＳｎ層の全Ｓｎを合金化しＦｅ−Ｓｎ合金層を形成した錫めっき層を製造できる。加熱溶融処理を省略した場合、錫単体のめっき層（Ｓｎ層）を製造できる。
As a manufacturing method of a tin plating layer, a known method (for example, an electroplating method or a method of plating by immersing in molten Sn) may be mentioned.
For example, a phenol sulfonate tin plating bath, a methane sulfonate tin plating bath, or a halogen-based tin plating bath is used, and Sn is electroplated on the surface of the steel sheet so that the adhesion amount per one surface becomes a predetermined amount. Then, heat melting treatment is performed at a temperature equal to or higher than the melting point of Sn (231.9 ° C.), and the lowermost layer of the tin simple substance plating layer (Sn layer) or all Sn in the Sn layer is alloyed to form an Fe—Sn alloy layer A tin-plated layer can be produced. When the heat melting treatment is omitted, a tin simple plating layer (Sn layer) can be produced.
また、鋼板がその表面上にＮｉ含有層を有する場合、Ｎｉ含有層上に錫めっきを施して錫単体のめっき層（Ｓｎ層）を形成させ、加熱溶融処理を行うと、Ｓｎ層の最下層（Ｓｎ層／鋼板界面）またはＳｎ層の全Ｓｎが合金化しＦｅ−Ｓｎ−Ｎｉ合金層、Ｆｅ−Ｓｎ合金層などが形成される。 Further, when the steel sheet has a Ni-containing layer on its surface, tin plating is performed on the Ni-containing layer to form a tin simple plating layer (Sn layer), and when the heat melting treatment is performed, the bottom layer of the Sn layer (Sn layer / steel plate interface) or all Sn in the Sn layer is alloyed to form an Fe—Sn—Ni alloy layer, an Fe—Sn alloy layer, or the like.
〔皮膜〕
次に、皮膜について説明する。皮膜は、概略的には、その成分として、Ｔｉ（チタニウム元素）を含有する皮膜であり、後述する処理液を用いて形成される。
[Coating]
Next, the film will be described. The film is generally a film containing Ti (titanium element) as its component, and is formed using a treatment liquid described later.
皮膜は、めっき鋼板の片面あたりのＴｉ換算の付着量（以下、「Ｔｉ付着量」ともいう）が２．５〜３０．０ｍｇ／ｍ2である。Ｔｉ付着量がこの範囲内であれば密着性が優れる。Ｔｉ付着量は、密着性がより優れるという理由から、３．０〜２０．０ｍｇ／ｍ2が好ましい。 The coating has a Ti equivalent adhesion amount (hereinafter also referred to as “Ti adhesion amount”) per side of the plated steel sheet of 2.5 to 30.0 mg / m 2 . If the amount of Ti adhesion is within this range, the adhesion is excellent. The Ti adhesion amount is preferably 3.0 to 20.0 mg / m 2 because the adhesion is more excellent.
また、皮膜は、密着性がより優れるという理由から、さらに、Ｎｉ（ニッケル元素）を含有するのが好ましい。この場合、めっき鋼板の片面あたりのＮｉ換算の付着量（以下、「Ｎｉ付着量」ともいう）は、０．１〜２０．０ｍｇ／ｍ2が好ましく、０．４〜１５．０ｍｇ／ｍ2がより好ましく、０．４〜６．０ｍｇ／ｍ2がさらに好ましい。
皮膜中のＴｉ、Ｎｉ等は、それぞれ、各種のチタン化合物、ニッケル化合物として含まれ、これら化合物の種類や態様は特に限定されない。
Moreover, it is preferable that the film further contains Ni (nickel element) for the reason that the adhesion is more excellent. In this case, the adhesion amount of Ni in terms of per side of the plated steel sheet (hereinafter, also referred to as "Ni deposition amount") is preferably 0.1~20.0mg / m 2, 0.4~15.0mg / m 2 Is more preferable, and 0.4 to 6.0 mg / m 2 is more preferable.
Ti, Ni, and the like in the film are included as various titanium compounds and nickel compounds, respectively, and the types and aspects of these compounds are not particularly limited.
なお、Ｔｉ付着量およびＮｉ付着量は、蛍光Ｘ線による表面分析により測定する。
蛍光Ｘ線分析は、例えば、下記条件により実施される。
・装置：リガク社製蛍光Ｘ線分析装置Ｓｙｓｔｅｍ３２７０
・測定径：３０ｍｍ
・測定雰囲気：真空
・スペクトル：Ｔｉ−Ｋα、Ｎｉ−Ｋα
・スリット：ＣＯＡＲＳＥ
・分光結晶：ＴＡＰ
上記条件により測定した皮膜の蛍光Ｘ線分析のＴｉ−Ｋα、Ｎｉ−Ｋαのピークカウント数を用いる。
The amount of Ti adhesion and the amount of Ni adhesion are measured by surface analysis using fluorescent X-rays.
The fluorescent X-ray analysis is performed, for example, under the following conditions.
Apparatus: X-ray fluorescence analyzer System 3270 manufactured by Rigaku Corporation
・ Measurement diameter: 30 mm
・ Measurement atmosphere: Vacuum ・ Spectrum: Ti-Kα, Ni-Kα
・ Slit: COARSE
-Spectral crystal: TAP
The peak count numbers of Ti-Kα and Ni-Kα in the fluorescent X-ray analysis of the film measured under the above conditions are used.
ただし、めっき層がＮｉを含む場合（めっき層がＮｉを含まずに、単に、Ｎｉ含有層を有する鋼板を用いた場合も含む。以下同様。）は、上記の蛍光Ｘ線による表面分析により皮膜中に含まれるＮｉ付着量のみを測定することは困難である。
その場合は、走査型電子顕微鏡（Scanning Electron Microscope：ＳＥＭ）や透過型電子顕微鏡（Transmission Electron Microscope：ＴＥＭ）による断面観察とグロー放電発光分析とを併用することで皮膜中に含まれるＮｉ付着量とめっき層中に含まれるＮｉ量とを区別できる。
具体的には、皮膜およびめっき層の断面を収束イオンビーム（Focused Ion Beam：ＦＩＢ）加工により露出させ、ＳＥＭまたはＴＥＭによる断面観察から皮膜の厚さを算出する。次いで、グロー放電発光分析によるスパッタリング深さとスパッタリング時間との関係を求める。その後、皮膜厚さに相当するスパッタリング時間までのグロー放電発光分析のＮｉ元素による発光カウント積算値を求める。このＮｉ元素による発光カウント積算値から、あらかじめ求めておいた検量線を用いて、Ｎｉ付着量を求めることができる。
ここで、検量線は以下の方法で作成する。
まず、Ｎｉを含まないめっき層上にＮｉを含む皮膜を有する、Ｎｉ付着量の異なる複数のサンプルについてグロー放電発光分析し、Ｎｉ元素による発光カウントが検出されなくなるスパッタリング時間までのカウント積算値を求める。次いでこれらのサンプルのＮｉ付着量を蛍光Ｘ線による表面分析により求める。このようにして、グロー放電発光分析によるＮｉカウント積算値とＮｉ付着量との検量線を作成する。
However, in the case where the plating layer contains Ni (including the case where the plating layer does not contain Ni, and simply uses a steel sheet having a Ni-containing layer; the same applies hereinafter), the film is analyzed by the surface analysis using the fluorescent X-ray. It is difficult to measure only the amount of deposited Ni contained therein.
In that case, the Ni adhesion amount contained in the film can be obtained by using both the cross-sectional observation by a scanning electron microscope (SEM) and a transmission electron microscope (TEM) and the glow discharge emission analysis. The amount of Ni contained in the plating layer can be distinguished.
Specifically, the cross section of the coating and the plating layer is exposed by focused ion beam (FIB) processing, and the thickness of the coating is calculated from cross-sectional observation by SEM or TEM. Next, the relationship between the sputtering depth and the sputtering time by glow discharge emission analysis is obtained. Thereafter, the integrated emission count value by Ni element of the glow discharge emission analysis up to the sputtering time corresponding to the film thickness is obtained. From the integrated emission count value of the Ni element, the Ni adhesion amount can be obtained using a calibration curve obtained in advance.
Here, the calibration curve is created by the following method.
First, glow discharge emission analysis is performed on a plurality of samples having a coating film containing Ni on a plating layer not containing Ni and having different Ni adhesion amounts, and a count integrated value up to a sputtering time at which no emission count due to Ni element is detected is obtained. . Next, the Ni adhesion amount of these samples is obtained by surface analysis using fluorescent X-rays. In this way, a calibration curve between the Ni count integrated value and the Ni adhesion amount by glow discharge emission analysis is created.
皮膜の厚さは、特に限定されないが、１０〜１２０ｎｍが好ましく、２０〜６０ｎｍがより好ましい。皮膜の厚さは、皮膜の断面を収束イオンビーム（ＦＩＢ）加工により露出させ、透過型電子顕微鏡（ＴＥＭ）観察による断面プロファイルから測定できる。 Although the thickness of a film is not specifically limited, 10-120 nm is preferable and 20-60 nm is more preferable. The thickness of the film can be measured from a cross-sectional profile obtained by observation with a transmission electron microscope (TEM) after exposing the cross section of the film by focused ion beam (FIB) processing.
また、本発明の容器用鋼板は、皮膜の表面からの深さ方向の原子濃度分布において、０価Ｓｎの原子濃度がめっき層の０価Ｓｎの原子濃度の２５％と等しくなる深さＬ（単位：ｎｍ）と、皮膜の表面から深さＬまでの０価Ｓｎの平均原子濃度Ａ（単位：原子％）との積Ｘが、下記式（１）を満たすことにより、外観がより優れる。
０≦Ｘ（＝Ｌ×Ａ）≦６０・・・（１）
The container steel plate of the present invention has a depth L (at which the atomic concentration of zero-valent Sn is equal to 25% of the atomic concentration of zero-valent Sn in the plating layer in the atomic concentration distribution in the depth direction from the surface of the coating. When the product X of the unit (nm) and the average atomic concentration A (unit: atomic%) of zero-valent Sn from the surface of the coating to the depth L satisfies the following formula (1), the appearance is more excellent.
0 ≦ X (= L × A) ≦ 60 (1)
本発明において、原子濃度分布は、皮膜の表面から、アルゴンスパッタリングした後にＸ線光電子分光法（X-ray Photoelectron Spectroscopy：ＸＰＳ）測定を行うことを繰り返して測定されたものとする。なお、皮膜の表面とは、皮膜のめっき鋼板側とは反対側の表面のことをいう。 In the present invention, it is assumed that the atomic concentration distribution is measured by repeatedly performing X-ray photoelectron spectroscopy (XPS) measurement after argon sputtering from the surface of the film. In addition, the surface of a film means the surface on the opposite side to the plated steel plate side of a film.
図１は、皮膜の表面からの深さ方向の原子濃度分布の例を示すグラフであり、横軸は、皮膜の表面からの距離である深さ（単位：ｎｍ）を表し、縦軸は、原子濃度（単位：原子％）を表す。
図１に示されるような原子濃度分布において、０価Ｓｎの原子濃度が、めっき層（錫めっき層）の０価Ｓｎの原子濃度（バルク濃度）の２５％と等しくなる深さ（皮膜の表面からの距離）をＬ（単位：ｎｍ）とし、皮膜の表面から深さＬまでの０価Ｓｎの平均原子濃度（単位：原子％）をＡとした場合に、両者の積Ｘ（＝Ｌ×Ａ）が、上述した式（１）を満たすことが好ましい。
FIG. 1 is a graph showing an example of the atomic concentration distribution in the depth direction from the surface of the film, the horizontal axis represents the depth (unit: nm) which is the distance from the surface of the film, and the vertical axis is Represents atomic concentration (unit: atomic%).
In the atomic concentration distribution as shown in FIG. 1, the depth at which the atomic concentration of zero-valent Sn is equal to 25% of the atomic concentration (bulk concentration) of zero-valent Sn in the plating layer (tin plating layer) The distance from the surface) is L (unit: nm), and the average atomic concentration (unit: atomic%) of zero-valent Sn from the surface of the film to the depth L is A, the product X of both (= L × It is preferable that A) satisfies the above-described formula (1).
ここで、バルク濃度の２５％と等しくなる深さＬ（単位：ｎｍ）を採用した理由は、皮膜の表面から深くスパッタするほどめっき層（錫めっき層）からの情報が混在し、反対に、皮膜表面のごく近傍では皮膜の深さ方向の情報が反映されにくいからである。
このような深さＬに、深さＬまでの０価Ｓｎの平均原子濃度Ａを乗じて得られるＸは、めっき層（錫めっき層）よりも確実に上層側に存在し、かつ、皮膜の中に存在する０価Ｓｎの含有量を示す指標となる。
Here, the reason why the depth L (unit: nm) that is equal to 25% of the bulk concentration is adopted is that information from the plating layer (tin plating layer) is mixed as the film is sputtered deeper from the surface of the film. This is because information in the depth direction of the film is hardly reflected in the very vicinity of the film surface.
X obtained by multiplying the depth L by the average atomic concentration A of zero-valent Sn up to the depth L is surely present on the upper layer side than the plating layer (tin plating layer), and It becomes an index indicating the content of zero-valent Sn present therein.
本発明者らは、容器用鋼板の試験材を作製し、作製した試験材について、Ｘ（＝Ｌ×Ａ）を求め、次いで、明度を表すＬ値を日本電色工業社製ＳＱ−２０００を用いて測定し、グラフにプロットした。
図２は、ＸとＬ値との関係の一例を示すグラフであり、横軸は、Ｘを表し、縦軸はＬ値を表す。図２のグラフから、ＸとＬ値とは良好な相関関係を示し、Ｘの値が大きくなるほど、Ｌ値は減少することが分かる。
ここで、Ｌ値が大きいほど、皮膜の着色が抑制されている（外観が良好である）と評価し得るものであり、例えば、Ｌ値は７０以上であることが好ましい。このため、Ｘは、６０以下が好ましく、３８以下がより好ましい。
The present inventors prepared a test material for a steel plate for containers, obtained X (= L × A) for the prepared test material, and then obtained an L value representing brightness by using SQ-2000 manufactured by Nippon Denshoku Industries Co., Ltd. And measured and plotted on a graph.
FIG. 2 is a graph showing an example of the relationship between X and L value, where the horizontal axis represents X and the vertical axis represents L value. From the graph of FIG. 2, it can be seen that the X value and the L value show a good correlation, and the L value decreases as the value of X increases.
Here, it can be evaluated that the coloration of the film is suppressed (the appearance is good) as the L value is large. For example, the L value is preferably 70 or more. For this reason, X is preferably 60 or less, and more preferably 38 or less.
なお、Ｘが０である場合は、皮膜中に０価Ｓｎが含まれていないことを表し、上述した推定メカニズムによれば、皮膜の着色が抑制され、外観が良好な状態となる。したがって、Ｘの下限値は、理論上は０となる。もっとも、アルゴンスパッタリングにより表面から順次掘り進めていくＸＰＳ測定では、測定を進めるうちに、多少なりともバルクの０価Ｓｎの影響が出てくる。このため、Ｘが０を示すことは実際にはなく、５未満となることはない。したがって、Ｘは５以上が好ましく、１０以上がより好ましい。 In addition, when X is 0, it represents that 0 valent Sn is not contained in the film, and according to the above-described estimation mechanism, coloring of the film is suppressed, and the appearance becomes good. Therefore, the lower limit value of X is theoretically 0. However, in the XPS measurement that is sequentially dug from the surface by argon sputtering, the influence of the bulk zero-valent Sn appears as the measurement proceeds. For this reason, X actually does not indicate 0, and never becomes less than 5. Therefore, X is preferably 5 or more, and more preferably 10 or more.
上述したように、Ｘを求める際の原子濃度分布は、皮膜の表面から、アルゴンスパッタリングした後にＸＰＳ測定を行うことを繰り返して測定される。
ＸＰＳ測定に用いるＸＰＳ装置は、ＵＬＶＡＣ−ＰＨＩ社製のＱｕａｎｔｅｒａＳＸＭを使用し、分析条件は、Ｘ線源モノクロＡｌ−Ｋα、電圧１５ｋＶ、出力２５Ｗ、測定領域１００μｍφとし、帯電中和は、電子線とＡｒイオン照射との同時照射とし、スパッタ条件は、Ａｒイオンによりスパッタレート１ｎｍ／分（ＳｉＯ2スパッタレート換算）とする。
ＸＰＳ測定に際しては、Ｃ１ｓスペクトルのＣ−Ｃ結合由来ピークが２８４．８ｅＶとなるように各元素スペクトルの帯電補正（シフト補正）を行い、原子濃度は、ナロースキャンにおける各元素ピークの面積強度と、各元素の相対感度係数とを用いて算出する。
なお、０価Ｓｎの原子濃度は、ＰＨＩのハンドブックおよびＮＩＳＴのデータベースを参照し、実測の検出傾向から、Ｓｎ３ｄ５／２スペクトルにおける０価Ｓｎ由来ピークおよびＳｎ酸化物由来ピークの検出エネルギー値の代表値を、それぞれ、４８４．８ｅＶおよび４８６．８ｅＶとして、ピーク分離を行って算出される値を用いる。
As described above, the atomic concentration distribution at the time of obtaining X is measured by repeating the XPS measurement after argon sputtering from the surface of the film.
The XPS apparatus used for XPS measurement uses Quantera SXM manufactured by ULVAC-PHI, analysis conditions are an X-ray source monochrome Al-Kα, a voltage of 15 kV, an output of 25 W, a measurement area of 100 μmφ, The simultaneous irradiation with Ar ion irradiation is performed, and the sputtering condition is Ar ion with a sputtering rate of 1 nm / min (in terms of SiO 2 sputtering rate).
In XPS measurement, charge correction (shift correction) of each element spectrum is performed so that the C—C spectrum-derived peak of the C1s spectrum is 284.8 eV, and the atomic concentration is determined by the area intensity of each element peak in the narrow scan, It calculates using the relative sensitivity coefficient of each element.
For the atomic concentration of zero-valent Sn, refer to the PHI handbook and the NIST database, and based on the actual detection tendency, representative detection energy values of the zero-valent Sn-derived peak and the Sn oxide-derived peak in the Sn3d 5/2 spectrum The values are 484.8 eV and 486.8 eV, respectively, and values calculated by performing peak separation are used.
〔錫酸化膜〕
本発明の容器用鋼板は、上述しためっき層と皮膜との間に、錫酸化物を含有する錫酸化膜を有する。そして、この錫酸化膜の錫酸化物の還元に要する電気量（以下、「還元電気量」ともいう）が２．０〜５．０ｍＣ／ｃｍ2である。
本発明の容器用鋼板においては、このような錫酸化膜を有することにより、上述した皮膜の着色や経時的な着色濃化を抑制でき、外観に優れる。
一方、還元電気量が２．０ｍＣ／ｃｍ2未満であると、錫めっき層から皮膜中へのＳｎドープを抑制する効果が不十分となり、外観に劣る。また、還元電気量が５．０ｍＣ／ｃｍ2を超えると、錫めっき層から皮膜中へのＳｎドープは抑制し得るが、錫酸化膜そのものの呈色により、やはり、外観に劣る。
[Tin oxide film]
The steel plate for containers of the present invention has a tin oxide film containing tin oxide between the plating layer and the coating described above. The amount of electricity required to reduce the tin oxide of the tin oxide film (hereinafter also referred to as “reduced amount of electricity”) is 2.0 to 5.0 mC / cm 2 .
In the steel plate for containers according to the present invention, by having such a tin oxide film, the above-described coloration of the film and color concentration with time can be suppressed, and the appearance is excellent.
On the other hand, if the amount of reducing electricity is less than 2.0 mC / cm 2 , the effect of suppressing Sn doping from the tin plating layer into the film becomes insufficient, resulting in poor appearance. If the amount of reduced electricity exceeds 5.0 mC / cm 2 , Sn doping from the tin plating layer into the film can be suppressed, but the appearance is still inferior due to the coloration of the tin oxide film itself.
錫酸化膜の還元電気量は、皮膜の着色や経時的な着色濃化をより抑制でき、容器用鋼板の外観がより優れるという理由から、３．０〜５．０ｍＣ／ｃｍ2が好ましく、３．６〜５．０ｍＣ／ｃｍ2がより好ましい。
また、錫酸化膜の還元電気量が５．０ｍＣ／ｃｍ2以下であれば、錫酸化膜内での凝集破壊による密着性の低下が生じにくくなるため好ましい。
The reduction electric quantity of the tin oxide film is preferably 3.0 to 5.0 mC / cm 2 , because it can further suppress the coloring of the film and the color concentration with time, and the appearance of the steel plate for containers is more excellent. More preferably, it is 6 to 5.0 mC / cm 2 .
In addition, it is preferable that the amount of reducing electricity of the tin oxide film is 5.0 mC / cm 2 or less because it is difficult for the adhesiveness to decrease due to cohesive failure in the tin oxide film.
錫酸化物の還元に要する電気量は、窒素ガスのバブリング等の手段によって溶存酸素を除去した０．００１ｍｏｌ／Ｌの臭化水素酸水溶液中で０．０５ｍＡ／ｃｍ2の定電流で本発明の容器用鋼板を陰極電解し、錫酸化物を還元除去する時間と電流との積から求めることができる。
なお、皮膜がＮｉを含有する場合には、上述の定電流法では水素発生電流が共存し、錫酸化物の還元電流を直接測定できない。そのため、浸漬電位から−０．７Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）の電位まで電位を掃引する過程で得られる１回目の還元電流曲線と、その後、同じく浸漬電位から−０．７Ｖ（ｖｓ．Ａｇ／ＡｇＣｌ）の電位まで電位を掃引する２回目の還元電流曲線との差分に相当する電気量から求めることができる。
The amount of electricity required for the reduction of the tin oxide is a constant current of 0.05 mA / cm 2 in a 0.001 mol / L hydrobromic acid aqueous solution from which dissolved oxygen has been removed by means such as bubbling of nitrogen gas. It can be determined from the product of time and current for cathodic electrolysis of the steel plate for containers and reduction and removal of tin oxide.
When the film contains Ni, hydrogen generation current coexists with the constant current method described above, and the reduction current of tin oxide cannot be measured directly. Therefore, the first reduction current curve obtained in the process of sweeping the potential from the immersion potential to the potential of −0.7 V (vs. Ag / AgCl), and then from the immersion potential to −0.7 V (vs. Ag / Ag / It can be determined from the amount of electricity corresponding to the difference from the second reduction current curve in which the potential is swept to the potential of AgCl).
［容器用鋼板の製造方法］
上述した本発明の容器用鋼板を製造する方法としては、例えば、後述する前処理工程および皮膜形成工程をこの順に備える方法（以下、便宜的に「本発明の製造方法」ともいう）が好適に挙げられる。以下、このような本発明の製造方法について説明を行う。
[Manufacturing method of steel plate for containers]
As a method for producing the container steel plate of the present invention described above, for example, a method comprising a pretreatment step and a film forming step described later in this order (hereinafter also referred to as “the production method of the present invention” for convenience) is suitably used. Can be mentioned. Hereinafter, the manufacturing method of the present invention will be described.
〔前処理工程〕
本発明の製造方法は、後述する皮膜形成工程の前に、前処理工程を備える。前処理工程は、酸化剤もしくは炭酸塩を含有する前処理液に、めっき鋼板を浸漬する、または、上記前処理液中で陽極電解処理することにより、当該めっき鋼板のめっき層側の表面上に、上述した錫酸化膜を形成する工程である。
めっき鋼板を上記前処理液に浸漬する、または、上記前処理液中で陽極電解処理することで、めっき鋼板が有するＳｎを含むめっき層の一部が、前処理液中の酸化剤もしくは炭酸塩によって酸化されて、錫酸化物を含有する錫酸化膜が形成される。
[Pretreatment process]
The production method of the present invention includes a pretreatment step before the film formation step described later. In the pretreatment step, the plated steel sheet is immersed in a pretreatment liquid containing an oxidizing agent or a carbonate, or is subjected to an anodic electrolytic treatment in the pretreatment liquid, so that the plating layer side surface of the plated steel sheet is applied. This is a step of forming the above-described tin oxide film.
By immersing the plated steel sheet in the pretreatment liquid or by anodic electrolytic treatment in the pretreatment liquid, a part of the plating layer containing Sn included in the plated steel sheet is oxidized in the pretreatment liquid or carbonate. Is oxidized to form a tin oxide film containing tin oxide.
前処理液に含有される酸化剤または炭酸塩は特に限定されない。
酸化剤としては、従来公知の酸化剤を用いることができる。例えば、二酸化塩素；過塩素酸、過ヨウ素酸などの過ハロゲン酸；過塩素酸ナトリウム、過塩素酸カリウム、過塩素酸アンモニウムなどの過塩素酸塩類；亜塩素酸ナトリウム、亜塩素酸カリウムなどの亜塩素酸塩類；次亜塩素酸ナトリウム、次亜塩素酸カルシウムなどの次亜塩素酸塩類；臭素酸ナトリウム、臭素酸カリウムなどの臭素酸塩類；ヨウ素酸ナトリウム、ヨウ素酸カリウムなどのヨウ素酸塩類；過ヨウ素酸ナトリウム、過ヨウ素酸カリウムなどの過ヨウ素酸塩類；過酸化ナトリウム、過酸化カリウム、過酸化マグネシウム、過酸化カルシウム、過酸化バリウムなどのアルカリ金属またはアルカリ土類金属の過酸化物；過酸化水素、過炭酸ナトリウムなどの過酸化水素またはその誘導体；等が挙げられる。
また、炭酸塩としては、従来公知の水溶性の炭酸塩を用いることができる。例えば、炭酸ナトリウム、炭酸カリウムなどのアルカリ金属の炭酸塩類が挙げられる。
The oxidizing agent or carbonate contained in the pretreatment liquid is not particularly limited.
As the oxidizing agent, a conventionally known oxidizing agent can be used. For example, chlorine dioxide; perhalogen acids such as perchloric acid and periodic acid; perchlorates such as sodium perchlorate, potassium perchlorate, ammonium perchlorate; sodium chlorite, potassium chlorite, etc. Chlorites; hypochlorites such as sodium hypochlorite and calcium hypochlorite; bromates such as sodium bromate and potassium bromate; iodates such as sodium iodate and potassium iodate; Periodates such as sodium periodate and potassium periodate; alkali metal or alkaline earth metal peroxides such as sodium peroxide, potassium peroxide, magnesium peroxide, calcium peroxide, barium peroxide; And hydrogen peroxide such as hydrogen oxide and sodium percarbonate or derivatives thereof.
As the carbonate, a conventionally known water-soluble carbonate can be used. Examples thereof include alkali metal carbonates such as sodium carbonate and potassium carbonate.
これらのうち、錫酸化膜を鋼板上に連続的かつ緻密に形成できるという理由から、酸化剤としては、過塩素酸塩類、アルカリ金属またはアルカリ土類金属の過酸化物、過酸化水素またはその誘導体が好ましく、炭酸塩としては、炭酸ナトリウムが好ましい。
また、前処理液中の酸化剤または炭酸塩の含有量は、錫酸化膜を鋼板上に連続的かつ緻密に形成できるという理由から、５〜３０ｇ／Ｌが好ましく、１０〜２０ｇ／Ｌがより好ましい。
Among these, as the oxidizing agent, a perchlorate, an alkali metal or alkaline earth metal peroxide, hydrogen peroxide or a derivative thereof can be used because a tin oxide film can be continuously and densely formed on a steel plate. The carbonate is preferably sodium carbonate.
Further, the content of the oxidizing agent or carbonate in the pretreatment liquid is preferably 5 to 30 g / L, more preferably 10 to 20 g / L, because the tin oxide film can be continuously and densely formed on the steel plate. preferable.
前処理工程において、処理を実施する際の前処理液の液温は、形成される錫酸化膜量が適量となって、皮膜の色調変化をより抑制できるという理由から、２０〜８０℃が好ましく、４０〜６０℃がより好ましい。
また、前処理液中への浸漬時間は、液温と同様の理由から、０．１〜５秒が好ましく、０．２〜２秒がより好ましい。
なお、前処理液への浸漬後においては、必要に応じて、水洗処理を施してもよい。
In the pretreatment step, the temperature of the pretreatment liquid at the time of carrying out the treatment is preferably 20 to 80 ° C. because the amount of tin oxide film to be formed becomes an appropriate amount and the color change of the film can be further suppressed. 40-60 ° C is more preferable.
Further, the immersion time in the pretreatment liquid is preferably 0.1 to 5 seconds, and more preferably 0.2 to 2 seconds, for the same reason as the liquid temperature.
In addition, after immersion in a pretreatment liquid, you may perform a water washing process as needed.
また、前処理液中での電解条件は、液温と同様の理由から、鋼板側が陽極になるよう電解し、電解電流密度は１．０〜１０．０Ａ／ｄｍ２が好ましく、３．０〜６．０Ａ／ｄｍ２がより好ましい。通電時間は、０．１〜５秒が好ましく、０．２〜２秒がより好ましい。
前処理液中での電解処理後においては、必要に応じて、水洗処理を施してもよい。
Moreover, the electrolysis conditions in the pretreatment liquid are electrolyzed so that the steel sheet side becomes the anode for the same reason as the liquid temperature, and the electrolysis current density is preferably 1.0 to 10.0 A / dm 2 , 3.0 to 6.0 A / dm 2 is more preferable. The energization time is preferably 0.1 to 5 seconds, and more preferably 0.2 to 2 seconds.
After the electrolytic treatment in the pretreatment liquid, a water washing treatment may be performed as necessary.
〔皮膜形成工程〕
皮膜形成工程は、前処理工程で形成された錫酸化膜の表面上に、上述した皮膜を形成する工程であって、後述する処理液中で錫酸化膜を形成しためっき鋼板に陰極電解処理を施す工程である。以下に、使用される処理液や陰極電解処理の条件などについて詳述する。
[Film formation process]
The film formation step is a step of forming the above-described film on the surface of the tin oxide film formed in the pretreatment step, and cathodic electrolytic treatment is applied to the plated steel sheet on which the tin oxide film is formed in the treatment liquid described later. It is a process to apply. Below, the processing solution used, conditions for cathodic electrolysis, and the like will be described in detail.
皮膜形成工程で使用される処理液は、上記皮膜にＴｉ（チタニウム元素）を供給するためのＴｉ成分（Ｔｉ化合物）を含有する。このＴｉ成分としては、特に限定されない。例えば、チタンアルコキシド、シュウ酸チタニルアンモニウム、シュウ酸チタニルカリウム二水和物、硫酸チタン、チタンラクテート、チタンフッ化水素酸（Ｈ2ＴｉＦ6）および／またはその塩などが挙げられる。なお、チタンフッ化水素酸の塩としては、例えば、六フッ化チタン酸カリウム（Ｋ2ＴｉＦ6）、六フッ化チタン酸ナトリウム（Ｎａ2ＴｉＦ6）、六フッ化チタン酸アンモニウム（（ＮＨ4）2ＴｉＦ6）等が挙げられる。
これらのうち、処理液の安定性、入手の容易性などの観点から、チタンフッ化水素酸および／またはその塩が好ましい。
処理液中のＴｉ成分の含有量は、チタンフッ化水素酸および／またはその塩を使用する場合、六フッ化チタン酸イオン（ＴｉＦ6 2-）に換算した量が、３．０〜１５．０ｇ／Ｌであるのが好ましく、５．０〜１０．０ｇ／Ｌがより好ましい。
The treatment liquid used in the film forming step contains a Ti component (Ti compound) for supplying Ti (titanium element) to the film. The Ti component is not particularly limited. Examples thereof include titanium alkoxide, titanyl ammonium oxalate, potassium titanyl oxalate dihydrate, titanium sulfate, titanium lactate, titanium hydrofluoric acid (H 2 TiF 6 ) and / or a salt thereof. Examples of the salt of titanium hydrofluoric acid include potassium hexafluorotitanate (K 2 TiF 6 ), sodium hexafluorotitanate (Na 2 TiF 6 ), and ammonium hexafluorotitanate ((NH 4 ). 2 TiF 6 ) and the like.
Of these, titanium hydrofluoric acid and / or a salt thereof is preferable from the viewpoints of stability of the treatment liquid, availability, and the like.
When using titanium hydrofluoric acid and / or its salt, the content of the Ti component in the treatment liquid is 3.0 to 15.0 g in terms of hexafluorotitanate ions (TiF 6 2− ). / L is preferable, and 5.0 to 10.0 g / L is more preferable.
また、上記皮膜がＮｉ（ニッケル元素）を含有する場合には、皮膜形成工程で使用される処理液は、上記皮膜にＮｉ（ニッケル元素）を供給するためのＮｉ成分（Ｎｉ化合物）を含有する。このＮｉ成分としては、特に限定されない。例えば、硫酸ニッケル（ＮｉＳＯ4）、硫酸ニッケル六水和物、塩化ニッケル（ＮｉＣｌ2）、塩化ニッケル六水和物などが挙げられる。
処理液中のＮｉ成分の含有量は、Ｎｉイオン（Ｎｉ２＋）に換算した量が、０．１〜３．０ｇ／Ｌであるのが好ましく、０．３〜１．０ｇ／Ｌがより好ましい。
Moreover, when the said film | membrane contains Ni (nickel element), the process liquid used at a film | membrane formation process contains Ni component (Ni compound) for supplying Ni (nickel element) to the said film | membrane. . The Ni component is not particularly limited. Examples thereof include nickel sulfate (NiSO 4 ), nickel sulfate hexahydrate, nickel chloride (NiCl 2 ), nickel chloride hexahydrate and the like.
The content of the Ni component in the treatment liquid is preferably 0.1 to 3.0 g / L, more preferably 0.3 to 1.0 g / L, in terms of Ni ions (Ni 2+ ). .
なお、処理液中の溶媒としては、通常水が使用されるが、有機溶媒を併用してもよい。
処理液のｐＨは、特に限定されないが、ｐＨ２．０〜５．０が好ましい。この範囲内であれば、処理時間を短くでき、かつ、処理液の安定性に優れる。ｐＨの調整には公知の酸成分（例えば、リン酸、硫酸）・アルカリ成分（例えば、水酸化ナトリウム、アンモニア水）を使用できる。
また、処理液には、必要に応じて、ラウリル硫酸ナトリウム、アセチレングリコールなどの界面活性剤が含まれていてもよい。また、付着挙動の経時的な安定性の観点から、処理液には、ピロリン酸塩などの縮合リン酸塩が含まれていてもよい。
In addition, as a solvent in a process liquid, although water is normally used, you may use an organic solvent together.
Although the pH of a process liquid is not specifically limited, pH 2.0-5.0 are preferable. Within this range, the treatment time can be shortened and the stability of the treatment liquid is excellent. A known acid component (for example, phosphoric acid, sulfuric acid) / alkali component (for example, sodium hydroxide, aqueous ammonia) can be used to adjust the pH.
Further, the treatment liquid may contain a surfactant such as sodium lauryl sulfate or acetylene glycol as necessary. Further, from the viewpoint of the stability of the adhesion behavior over time, the treatment liquid may contain a condensed phosphate such as pyrophosphate.
さらに、本発明の処理液は、伝導助剤を含有していてもよい。これにより、本発明の容器用鋼板の高速操業性が優れる。伝導助剤としては、例えば、硫酸カリウム、硫酸ナトリウム、硫酸マグネシウム、硫酸カルシウムなどの硫酸塩；硝酸カリウム、硝酸ナトリウム、硝酸マグネシウム、硝酸カルシウムなどの硝酸塩；塩化カリウム、塩化ナトリウム、塩化マグネシウム、塩化カルシウムなどの塩化物塩；等が挙げられる。
本発明の処理液における伝導助剤の含有量は、０．０１〜１ｍｏｌ／Ｌが好ましく、０．０２〜０．５ｍｏｌ／Ｌがより好ましい。
Furthermore, the treatment liquid of the present invention may contain a conduction aid. Thereby, the high-speed operativity of the steel plate for containers of this invention is excellent. Examples of the conduction aid include sulfates such as potassium sulfate, sodium sulfate, magnesium sulfate, and calcium sulfate; nitrates such as potassium nitrate, sodium nitrate, magnesium nitrate, and calcium nitrate; potassium chloride, sodium chloride, magnesium chloride, calcium chloride, and the like. And the like.
0.01-1 mol / L is preferable and, as for content of the conductive support agent in the processing liquid of this invention, 0.02-0.5 mol / L is more preferable.
皮膜形成工程において処理を実施する際の処理液の液温は、２０〜８０℃が好ましい。この範囲であれば、形成される皮膜中のＴｉ等が適量となって、密着性が優れる。
皮膜形成工程において、陰極電解処理を実施する際の電解電流密度は、形成される皮膜中のＴｉ等が適量となって、密着性が優れるという理由から、１．０〜２０．０Ａ／ｄｍ2が好ましい。
このとき、陰極電解処理の通電時間は、電解電流密度と同様の理由から、０．１〜５秒が好ましく、０．３〜２秒がより好ましい。なお、陰極電解処理の際の電気量密度は、電流密度と通電時間との積であり、適宜設定される。
As for the liquid temperature of the process liquid at the time of implementing a process in a film formation process, 20-80 degreeC is preferable. If it is this range, Ti in the membrane | film | coat formed will become suitable amount, and adhesiveness will be excellent.
In the film formation step, the electrolysis current density when the cathode electrolysis treatment is performed is 1.0 to 20.0 A / dm 2 because Ti in the film to be formed becomes an appropriate amount and the adhesiveness is excellent. Is preferred.
At this time, the energization time of the cathodic electrolysis treatment is preferably 0.1 to 5 seconds, and more preferably 0.3 to 2 seconds, for the same reason as the electrolytic current density. The quantity of electricity at the time of cathodic electrolysis is the product of the current density and the energization time, and is appropriately set.
なお、皮膜表面の不純物を除去する観点から、陰極電解処理の後、得られた鋼板の水洗処理を行うのが好ましい。
水洗処理の方法は特に限定されない。例えば、連続ラインで製造を行う場合、皮膜処理タンクの後に水洗タンクを設け、皮膜処理後に連続して水に浸漬する方法などが挙げられる。水洗処理に用いる水の温度は、４０〜９０℃が好ましい。
水洗時間は、水洗処理による効果がより優れるという理由から、０．５秒超が好ましく、１．０〜５．０秒が好ましい。
水洗処理に代えて、または、水洗処理の後に、乾燥を行ってもよい。乾燥の際の温度および方式は特に限定されず、例えば、通常のドライヤーや電気炉乾燥方式が適用できる。乾燥処理の際の温度としては、１００℃以下が好ましい。上記範囲内であれば、皮膜の酸化を抑制でき、皮膜組成の安定性が保たれる。なお、下限は特に限定されないが、通常室温程度である。
In addition, it is preferable to perform the water-washing process of the obtained steel plate after a cathodic electrolysis process from a viewpoint of removing the impurity of the membrane | film | coat surface.
The method for the water washing treatment is not particularly limited. For example, when manufacturing by a continuous line, the method etc. which provide a water-washing tank after a film processing tank, and are immersed in water continuously after a film processing are mentioned. The temperature of the water used for the water washing treatment is preferably 40 to 90 ° C.
The washing time is preferably more than 0.5 seconds, and more preferably 1.0 to 5.0 seconds, because the effect of the washing treatment is more excellent.
Drying may be performed instead of the water washing treatment or after the water washing treatment. The temperature and method during drying are not particularly limited, and for example, a normal dryer or an electric furnace drying method can be applied. The temperature during the drying treatment is preferably 100 ° C. or lower. If it is in the said range, the oxidation of a film | membrane can be suppressed and stability of a film | membrane composition is maintained. The lower limit is not particularly limited, but is usually about room temperature.
本発明の製造方法によって得られる本発明の容器用鋼板は、ＤＩ缶、食缶、飲料缶など種々の容器の製造に使用される。 The steel plate for containers of the present invention obtained by the manufacturing method of the present invention is used for manufacturing various containers such as DI cans, food cans, and beverage cans.
以下に、実施例を挙げて本発明を具体的に説明する。ただし、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
〈めっき鋼板の製造〉
以下の２つの方法［（Ｋ−１）および（Ｋ−２）］によって、めっき鋼板を製造した。
（Ｋ−１）
板厚０．２２ｍｍの鋼板（Ｔ４原板）について電解脱脂と酸洗とを行い、その後、第３表に示す片面当たりのＳｎ付着量の錫めっきを施した。引き続き、Ｓｎの融点以上の温度で加熱溶融処理を施し、Ｆｅ−Ｓｎ合金層とその上層にＳｎ層とを形成し、めっき鋼板を製造した。このようにして、下層側から順に、Ｆｅ−Ｓｎ合金層／Ｓｎ層からなるめっき層が両面に形成された。
（Ｋ−２）
板厚０．２２ｍｍの鋼板（Ｔ４原板）を電解脱脂し、ワット浴を用いて第３表に示す片面当たりのＮｉ付着量でニッケルめっき層を形成後、１０ｖｏｌ.％Ｈ2＋９０ｖｏｌ.％Ｎ2雰囲気中にて７００℃で焼鈍してニッケルめっきを拡散浸透させることによりＮｉ−Ｆｅ合金層（Ｎｉ含有層）（第３表にＮｉ付着量を示す）を両面に形成した。
引き続き、上記表層にＮｉ含有層を有する鋼板を、錫めっき浴を用い、第３表に示す片面当たりのＳｎ付着量の錫めっきを施した。その後、Ｓｎの融点以上の温度で加熱溶融処理を施し、Ｆｅ−Ｓｎ−Ｎｉ合金層とその上層に不連続のＳｎ層とを形成し、めっき鋼板を製造した。このようにして、下層側から順に、Ｎｉ−Ｆｅ合金層／Ｆｅ−Ｓｎ−Ｎｉ合金層／Ｓｎ層からなるめっき層が両面に形成された。
<Manufacture of plated steel sheets>
Plated steel sheets were produced by the following two methods [(K-1) and (K-2)].
(K-1)
Electrolytic degreasing and pickling were performed on a steel plate (T4 original plate) having a thickness of 0.22 mm, and then tin plating with an Sn adhesion amount per one side shown in Table 3 was performed. Subsequently, a heat-melting treatment was performed at a temperature equal to or higher than the melting point of Sn to form an Fe—Sn alloy layer and an Sn layer thereon, thereby producing a plated steel sheet. Thus, the plating layer which consists of a Fe-Sn alloy layer / Sn layer was formed in both surfaces sequentially from the lower layer side.
(K-2)
A steel plate (T4 original plate) having a thickness of 0.22 mm is electrolytically degreased and a nickel plating layer is formed with a Ni adhesion amount per one side shown in Table 3 using a Watt bath, and then 10 vol.% H 2 +90 vol.% N 2 An Ni—Fe alloy layer (Ni-containing layer) (showing the amount of Ni deposited in Table 3) was formed on both sides by annealing at 700 ° C. in an atmosphere and allowing nickel plating to diffuse and penetrate.
Subsequently, the steel plate having the Ni-containing layer as the surface layer was subjected to tin plating with a Sn adhesion amount per one side shown in Table 3 using a tin plating bath. Then, the heat-melting process was performed at the temperature more than melting | fusing point of Sn, the discontinuous Sn layer was formed in the Fe-Sn-Ni alloy layer and the upper layer, and the plated steel plate was manufactured. In this way, a plating layer composed of Ni—Fe alloy layer / Fe—Sn—Ni alloy layer / Sn layer was formed on both surfaces in order from the lower layer side.
〈前処理工程（錫酸化膜の形成）〉
製造しためっき鋼板を、水洗した後に、第１表（その１）に示す組成の前処理液（溶媒：水）中に、第２表に示す処理温度（液温）、ならびに、浸漬時間もしくは陽極電解条件により、両面に錫酸化膜を形成した。なお、前処理工程によって錫酸化膜を形成しなかった場合には、第２表に「−」を記載した。
〈皮膜形成工程〉
次いで、前処理工程を経ためっき鋼板を水洗し、第１表（その２）に示す組成およびｐＨの処理液（溶媒：水）を用い、第２表に示す処理温度（液温）および電解条件（電流密度、通電時間、電気量密度）で陰極電解処理を施した。その後、水洗処理して、ブロアを用いて室温で乾燥を行い、皮膜を両面に形成した。
<Pretreatment process (formation of tin oxide film)>
After the manufactured plated steel sheet is washed with water, the pretreatment liquid (solvent: water) having the composition shown in Table 1 (Part 1), the treatment temperature (liquid temperature) shown in Table 2, and the immersion time or anode A tin oxide film was formed on both sides depending on the electrolysis conditions. In the case where the tin oxide film was not formed by the pretreatment process, “-” is shown in Table 2.
<Film formation process>
Next, the plated steel sheet that has undergone the pretreatment process is washed with water, and using the treatment liquid (solvent: water) having the composition and pH shown in Table 1 (Part 2), the treatment temperature (liquid temperature) and electrolysis conditions shown in Table 2 Cathodic electrolysis treatment was performed at (current density, energization time, electric quantity density). Thereafter, it was washed with water and dried at room temperature using a blower to form a film on both sides.
その後、作製した容器用鋼板の試験材について、以下の方法で、外観および密着性を評価した。各成分量、および、評価結果を第３表にまとめて示す。
錫酸化膜の還元電気量、ならびに、皮膜のＴｉ付着量およびＮｉ付着量は、上述した方法により測定ないし計算した。
Then, about the produced test material of the steel plate for containers, the external appearance and adhesiveness were evaluated with the following method. The amount of each component and the evaluation results are summarized in Table 3.
The amount of reduced electricity of the tin oxide film and the amount of Ti and Ni deposited on the film were measured or calculated by the method described above.
〈外観〉
《初期色調》
作製した直後（作製後６０分以内）の容器用鋼板について、皮膜の茶系色の呈色について評価した。具体的には、Ｌ値を、日本電色工業社製ＳＱ−２０００を用いて測定し、下記基準で評価した。◎または○であれば、皮膜の着色が抑制され、外観に優れるものとして評価できる。
◎：Ｌ値７５以上
○：Ｌ値７０以上７５未満
△：Ｌ値６０以上７０未満
×：Ｌ値６０未満
<appearance>
<Initial color tone>
About the steel plate for containers immediately after preparation (within 60 minutes after preparation), the brown color of the film was evaluated. Specifically, L value was measured using SQ-2000 made by Nippon Denshoku Industries Co., Ltd., and evaluated according to the following criteria. If it is ◎ or ◯, coloring of the film is suppressed, and it can be evaluated as having excellent appearance.
◎: L value 75 or more ○: L value 70 or more and less than 75 Δ: L value 60 or more and less than 70 ×: L value 60 or less
《耐変色性》
上記のようにして色調を評価した容器用鋼板について、５０℃、相対湿度９８％の恒温恒湿槽内に７２時間放置した後、初期色調と同様にして、Ｌ値を測定し、下記基準で評価した。◎または○であれば、経時的な着色濃化が抑制されて、外観に優れるものとして評価できる。
◎：初期（作製後６０分以内）からのＬ値低下が３未満
○：初期（作製後６０分以内）からのＬ値低下が３以上７未満
△：初期（作製後６０分以内）からのＬ値低下が７以上１２未満
×：初期（作製後６０分以内）からのＬ値低下が１２以上
<Discoloration resistance>
The container steel plate whose color tone was evaluated as described above was left in a constant temperature and humidity chamber at 50 ° C. and a relative humidity of 98% for 72 hours, and then the L value was measured in the same manner as the initial color tone. evaluated. If it is ◎ or ◯, color concentration with time is suppressed, and it can be evaluated as being excellent in appearance.
A: L value decrease from initial (within 60 minutes after production) is less than 3 ○: L value decrease from initial (within 60 minutes after production) is 3 or more and less than 7 Δ: From initial (within 60 minutes after production) L value decrease is 7 or more and less than 12 ×: L value decrease from initial (within 60 minutes after production) is 12 or more
〈密着性〉
作製した容器用鋼板（幅１００ｍｍ×長さ１５０ｍｍ）の表面に、エポキシフェノール系塗料を塗布し、２１０℃で１０分間の焼付を行い、付着量が５０ｍｇ／ｄｍ2の塗装を施した。次いで、上記塗装を施した、同一の条件で作製した２枚の容器用鋼板を、ナイロン接着フィルムを挟んで塗装面が向かい合わせになるように積層した後、圧力２．９４×１０5Ｐａ、温度１９０℃、圧着時間３０秒の圧着条件下で貼り合わせた。その後、これを５ｍｍ幅の試験片に分割した。分割した試験片の２枚の容器用鋼板を引張試験機で引き剥がし、引き剥がしたときの引張強度を測定した。各試験材で、２つの試験片の平均値を下記基準で評価した。実用上、結果が○または△であれば、密着性に優れるものとして評価できる。
○：２．０ｋｇｆ以上
△：１．０ｋｇｆ以上２．０ｋｇｆ未満
×：１．０ｋｇｆ未満
<Adhesion>
An epoxy phenol-based paint was applied to the surface of the produced steel plate for containers (width 100 mm × length 150 mm), and baked at 210 ° C. for 10 minutes to give a coating amount of 50 mg / dm 2 . Next, after laminating the two coated steel plates prepared under the same conditions with the above coating so that the coated surfaces face each other across the nylon adhesive film, the pressure is 2.94 × 10 5 Pa, Bonding was performed under pressure bonding conditions of a temperature of 190 ° C. and a pressure bonding time of 30 seconds. Then, this was divided into 5 mm wide test pieces. Two container steel plates of the divided test pieces were peeled off by a tensile tester, and the tensile strength when peeled off was measured. For each test material, the average value of the two test pieces was evaluated according to the following criteria. Practically, if the result is ○ or Δ, it can be evaluated as having excellent adhesion.
○: 2.0 kgf or more Δ: 1.0 kgf or more and less than 2.0 kgf ×: Less than 1.0 kgf
上記第１表〜第３表に示す結果から明らかなように、本発明例１〜５１の容器用鋼板は、いずれも外観が優れることが確認された。
なかでも、Ｘの値が３８以下である本発明例は、Ｘの値が３９以上６０以下である本発明例とくらべて、外観がより良好であった。
As is clear from the results shown in Tables 1 to 3, it was confirmed that the steel plates for containers of Examples 1 to 51 of the present invention were all excellent in appearance.
In particular, the example of the present invention having an X value of 38 or less had a better appearance than the example of the present invention having an X value of 39 to 60.
これに対して、錫酸化膜の還元電気量が２．０ｍＣ／ｃｍ2未満または５．０ｍＣ／ｃｍ2超である比較例１〜４の容器用鋼板は、いずれも外観に劣ることが確認された。
なお、錫酸化膜の還元電気量が５．０ｍＣ／ｃｍ2超である比較例２〜４の容器用鋼板は、錫酸化膜によって、錫めっき層から皮膜中へのＳｎドープは抑制されている（そのため、Ｘの値が比較的小さい）が、錫酸化膜そのものの呈色のため、Ｌ値が低下し、外観が劣っているものと考えられる。
On the other hand, it was confirmed that the steel plates for containers of Comparative Examples 1 to 4 in which the amount of reducing electricity of the tin oxide film is less than 2.0 mC / cm 2 or more than 5.0 mC / cm 2 are all inferior in appearance. It was.
In addition, Sn doping from the tin plating layer into the film is suppressed by the tin oxide film in the steel plates for containers of Comparative Examples 2 to 4 in which the amount of reducing electricity of the tin oxide film exceeds 5.0 mC / cm 2 . (Therefore, the value of X is relatively small), however, it is considered that the L value decreases and the appearance is inferior because of the tin oxide film itself being colored.
Claims (7)
前記めっき層と前記皮膜との間に、錫酸化物を含有する錫酸化膜を有し、前記錫酸化物の還元に要する電気量が２．０〜５．０ｍＣ／ｃｍ2であり、
前記皮膜が、Ｔｉを含有し、前記めっき鋼板の片面あたりのＴｉ換算の付着量が２．５〜３０．０ｍｇ／ｍ2である、容器用鋼板。 A plated steel sheet covering at least a part of the surface of the steel sheet with a plated layer including at least one layer selected from a Sn layer, a Fe—Sn—Ni alloy layer, and a Fe—Sn alloy layer; and the plated layer of the plated steel sheet A steel plate for containers having a coating disposed on the surface on the side,
Between the plating layer and the coating, it has a tin oxide film containing tin oxide, and the amount of electricity required for reduction of the tin oxide is 2.0 to 5.0 mC / cm 2 ,
The steel plate for containers in which the said film contains Ti and the adhesion amount of Ti conversion per single side | surface of the said plated steel plate is 2.5-30.0 mg / m < 2 >.
０≦Ｘ（＝Ｌ×Ａ）≦６０・・・（１） In the atomic concentration distribution in the depth direction from the surface of the coating, a depth L (unit: nm) at which the atomic concentration of zero-valent Sn is equal to 25% of the atomic concentration of zero-valent Sn of the plating layer, and the coating The steel plate for containers according to claim 1 or 2, wherein the product X with the average atomic concentration A (unit: atomic%) of zero-valent Sn from the surface of the metal to the depth L satisfies the following formula (1).
0 ≦ X (= L × A) ≦ 60 (1)
鋼板の表面の少なくとも一部をＳｎ層、Ｆｅ−Ｓｎ−Ｎｉ合金層およびＦｅ−Ｓｎ合金層のうちから選ばれた少なくとも１層を含むめっき層が覆うめっき鋼板を、酸化剤もしくは炭酸塩を含有する前処理液に浸漬する、または、前記前処理液中で陽極電解処理することにより、当該めっき鋼板のめっき層側の表面上に、前記錫酸化膜を形成する前処理工程と、
Ｔｉ成分を含有する処理液中で、前記錫酸化膜を形成した前記めっき鋼板に陰極電解処理を施して、前記錫酸化膜の表面上に前記皮膜を形成する皮膜形成工程と、
を備える容器用鋼板の製造方法。 It is a manufacturing method of the steel plate for containers which obtains the steel plate for containers according to claim 1,
A plated steel sheet covering at least a part of the surface of the steel sheet with a plating layer including at least one layer selected from an Sn layer, an Fe—Sn—Ni alloy layer, and an Fe—Sn alloy layer contains an oxidizing agent or a carbonate. A pretreatment step of forming the tin oxide film on the surface of the plated steel sheet on the plating layer side by immersing in the pretreatment liquid or by anodic electrolytic treatment in the pretreatment liquid;
In a treatment liquid containing a Ti component, a film forming step of performing a cathodic electrolytic treatment on the plated steel sheet on which the tin oxide film is formed, and forming the film on the surface of the tin oxide film;
The manufacturing method of the steel plate for containers provided with.
鋼板の表面の少なくとも一部をＳｎ層、Ｆｅ−Ｓｎ−Ｎｉ合金層およびＦｅ−Ｓｎ合金層のうちから選ばれた少なくとも１層を含むめっき層が覆うめっき鋼板を、酸化剤もしくは炭酸塩を含有する前処理液に浸漬する、または、前記前処理液中で陽極電解処理することにより、当該めっき鋼板のめっき層側の表面上に、前記錫酸化膜を形成する前処理工程と、
Ｔｉ成分およびＮｉ成分を含有する処理液中で、前記錫酸化膜を形成した前記めっき鋼板に陰極電解処理を施して、前記錫酸化膜の表面上に前記皮膜を形成する皮膜形成工程と、
を備える容器用鋼板の製造方法。 It is a manufacturing method of the steel plate for containers which obtains the steel plate for containers according to claim 2,
A plated steel sheet covering at least a part of the surface of the steel sheet with a plating layer including at least one layer selected from an Sn layer, an Fe—Sn—Ni alloy layer, and an Fe—Sn alloy layer contains an oxidizing agent or a carbonate. A pretreatment step of forming the tin oxide film on the surface of the plated steel sheet on the plating layer side by immersing in the pretreatment liquid or by anodic electrolytic treatment in the pretreatment liquid;
A film forming step of performing a cathodic electrolytic treatment on the plated steel sheet on which the tin oxide film is formed in a treatment solution containing a Ti component and a Ni component, and forming the film on the surface of the tin oxide film;
The manufacturing method of the steel plate for containers provided with.
前記炭酸塩が、アルカリ金属の炭酸塩類である、請求項４または５に記載の容器用鋼板の製造方法。 The oxidizing agent is at least one selected from the group consisting of perchlorates, alkali metal or alkaline earth metal peroxides, and hydrogen peroxide or derivatives thereof;
The method for producing a steel plate for containers according to claim 4 or 5, wherein the carbonate is an alkali metal carbonate.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014216848A JP5910700B2 (en) | 2014-01-24 | 2014-10-24 | Steel plate for container and method for producing the same |
| PCT/JP2014/083205 WO2015111328A1 (en) | 2014-01-24 | 2014-12-16 | Steel sheet for container and manufacturing method therefor |
| KR1020167016087A KR101803219B1 (en) | 2014-01-24 | 2014-12-16 | Steel sheet for container and manufacturing method therefor |
| CN201480067192.6A CN105814240B (en) | 2014-01-24 | 2014-12-16 | Steel plate for container and its manufacture method |
| MYPI2016702639A MY174324A (en) | 2014-01-24 | 2014-12-16 | Steel sheet for container and manufacturing method therefor |
| TW103145511A TWI507537B (en) | 2014-01-24 | 2014-12-25 | Steel sheet for containers and method for manufacturing therefor |
| PH12016501046A PH12016501046B1 (en) | 2014-01-24 | 2016-06-02 | Steel sheet for container and manufacturing method therefor |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014011324 | 2014-01-24 | ||
| JP2014011324 | 2014-01-24 | ||
| JP2014216848A JP5910700B2 (en) | 2014-01-24 | 2014-10-24 | Steel plate for container and method for producing the same |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016013094A Division JP6094693B2 (en) | 2014-01-24 | 2016-01-27 | Steel plate for container and method for producing the same |
| JP2016013095A Division JP6094694B2 (en) | 2014-01-24 | 2016-01-27 | Manufacturing method of steel plate for containers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015158005A true JP2015158005A (en) | 2015-09-03 |
| JP5910700B2 JP5910700B2 (en) | 2016-04-27 |
Family
ID=53681146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014216848A Active JP5910700B2 (en) | 2014-01-24 | 2014-10-24 | Steel plate for container and method for producing the same |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP5910700B2 (en) |
| KR (1) | KR101803219B1 (en) |
| CN (1) | CN105814240B (en) |
| MY (1) | MY174324A (en) |
| PH (1) | PH12016501046B1 (en) |
| TW (1) | TWI507537B (en) |
| WO (1) | WO2015111328A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017082294A (en) * | 2015-10-29 | 2017-05-18 | Ｊｆｅスチール株式会社 | Manufacturing method of steel sheet for container |
| WO2020217663A1 (en) * | 2019-04-23 | 2020-10-29 | Ｊｆｅスチール株式会社 | Method for producing surface-treated steel sheet, and surface-treated steel sheet |
| IT202000014572A1 (en) * | 2020-06-18 | 2021-12-18 | Tenova Spa | PASSIVATION PROCEDURE FOR A TIN-PLATED STEEL BAND |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54142135A (en) * | 1978-04-28 | 1979-11-06 | Nippon Kokan Kk <Nkk> | Tin-plated steel plate and its manufacture |
| JP2001073185A (en) * | 1999-09-07 | 2001-03-21 | Toyo Kohan Co Ltd | Surface treated steel sheet and its production |
| JP2007217728A (en) * | 2006-02-15 | 2007-08-30 | Jfe Steel Kk | Surface-treated steel sheet, its production method, resin-coated steel sheet, can and can lid |
| JP2007239004A (en) * | 2006-03-07 | 2007-09-20 | Nippon Steel Corp | Plated steel sheet for can |
| JP2013127095A (en) * | 2011-12-19 | 2013-06-27 | Jfe Steel Corp | Method for manufacturing surface-treated steel sheet |
| WO2015001598A1 (en) * | 2013-07-01 | 2015-01-08 | Ｊｆｅスチール株式会社 | Steel sheet for containers |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4270768B2 (en) * | 2000-11-08 | 2009-06-03 | Ｊｆｅスチール株式会社 | Tin-plated steel sheet and chemical treatment liquid |
| JP3873642B2 (en) * | 2001-03-21 | 2007-01-24 | Ｊｆｅスチール株式会社 | Tinned steel sheet |
| US20080057336A1 (en) * | 2004-06-22 | 2008-03-06 | Toyo Seikan Kaisha, Ltd | Surface-Treated Metal Materials, Method of Treating the Surfaces Thereof, Resin-Coated Metal Materials, Cans and Can Lids |
| JP4487651B2 (en) | 2004-06-22 | 2010-06-23 | 東洋製罐株式会社 | Surface-treated metal material and surface treatment method thereof, resin-coated metal material, metal can, metal lid |
| TWI391530B (en) * | 2007-04-04 | 2013-04-01 | Nippon Steel Corp | A plated steel sheet for use in a tank and a method for manufacturing the same |
| JP5467719B2 (en) * | 2007-12-25 | 2014-04-09 | Ｊｆｅスチール株式会社 | Manufacturing method of surface-treated steel sheet |
| JP5633117B2 (en) * | 2008-05-12 | 2014-12-03 | Ｊｆｅスチール株式会社 | Method for producing tin-plated steel sheet, tin-plated steel sheet and chemical conversion treatment liquid |
| EP2551377B1 (en) * | 2010-03-23 | 2017-09-13 | Nippon Steel & Sumitomo Metal Corporation | Method for producing a steel sheet for a container |
| JP5845563B2 (en) * | 2010-09-15 | 2016-01-20 | Ｊｆｅスチール株式会社 | Manufacturing method of steel plate for containers |
| JP5742147B2 (en) * | 2010-09-15 | 2015-07-01 | Ｊｆｅスチール株式会社 | Surface-treated steel sheet, method for producing the same, and resin-coated steel sheet using the same |
-
2014
- 2014-10-24 JP JP2014216848A patent/JP5910700B2/en active Active
- 2014-12-16 CN CN201480067192.6A patent/CN105814240B/en active Active
- 2014-12-16 KR KR1020167016087A patent/KR101803219B1/en active IP Right Grant
- 2014-12-16 MY MYPI2016702639A patent/MY174324A/en unknown
- 2014-12-16 WO PCT/JP2014/083205 patent/WO2015111328A1/en active Application Filing
- 2014-12-25 TW TW103145511A patent/TWI507537B/en active
-
2016
- 2016-06-02 PH PH12016501046A patent/PH12016501046B1/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54142135A (en) * | 1978-04-28 | 1979-11-06 | Nippon Kokan Kk <Nkk> | Tin-plated steel plate and its manufacture |
| JP2001073185A (en) * | 1999-09-07 | 2001-03-21 | Toyo Kohan Co Ltd | Surface treated steel sheet and its production |
| JP2007217728A (en) * | 2006-02-15 | 2007-08-30 | Jfe Steel Kk | Surface-treated steel sheet, its production method, resin-coated steel sheet, can and can lid |
| JP2007239004A (en) * | 2006-03-07 | 2007-09-20 | Nippon Steel Corp | Plated steel sheet for can |
| JP2013127095A (en) * | 2011-12-19 | 2013-06-27 | Jfe Steel Corp | Method for manufacturing surface-treated steel sheet |
| WO2015001598A1 (en) * | 2013-07-01 | 2015-01-08 | Ｊｆｅスチール株式会社 | Steel sheet for containers |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017082294A (en) * | 2015-10-29 | 2017-05-18 | Ｊｆｅスチール株式会社 | Manufacturing method of steel sheet for container |
| WO2020217663A1 (en) * | 2019-04-23 | 2020-10-29 | Ｊｆｅスチール株式会社 | Method for producing surface-treated steel sheet, and surface-treated steel sheet |
| JPWO2020217663A1 (en) * | 2019-04-23 | 2021-05-06 | Ｊｆｅスチール株式会社 | Manufacturing method of surface-treated steel sheet and surface-treated steel sheet |
| US11926921B2 (en) | 2019-04-23 | 2024-03-12 | Jfe Steel Corporation | Method of producing surface-treated steel sheet and surface-treated steel sheet |
| IT202000014572A1 (en) * | 2020-06-18 | 2021-12-18 | Tenova Spa | PASSIVATION PROCEDURE FOR A TIN-PLATED STEEL BAND |
| WO2021255699A1 (en) * | 2020-06-18 | 2021-12-23 | Tenova S.P.A. | A passivation process of a steel tinplate, passivated tinplate and coated passivated tinplate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015111328A1 (en) | 2015-07-30 |
| CN105814240A (en) | 2016-07-27 |
| PH12016501046A1 (en) | 2016-08-15 |
| KR101803219B1 (en) | 2017-11-29 |
| JP5910700B2 (en) | 2016-04-27 |
| CN105814240B (en) | 2018-04-17 |
| MY174324A (en) | 2020-04-07 |
| TW201531572A (en) | 2015-08-16 |
| PH12016501046B1 (en) | 2016-08-15 |
| TWI507537B (en) | 2015-11-11 |
| KR20160088361A (en) | 2016-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6806152B2 (en) | Sn-based alloy plated steel sheet | |
| KR20180132119A (en) | Sn-coated steel sheet | |
| JP5986342B1 (en) | Surface-treated steel sheet, metal container, and method for producing surface-treated steel sheet | |
| JP5910700B2 (en) | Steel plate for container and method for producing the same | |
| KR101791374B1 (en) | Steel plate for container | |
| JP2010018835A (en) | Tin-plated steel sheet and method for producing the same | |
| JP2010018834A (en) | Tin-plated steel sheet and method for producing the same | |
| JP6197778B2 (en) | Steel plate for container and method for producing the same | |
| JP6094693B2 (en) | Steel plate for container and method for producing the same | |
| JP5978923B2 (en) | Steel plate for container, treatment liquid used for manufacturing the same, and method for manufacturing steel plate for container | |
| JP6048441B2 (en) | Steel plate for containers | |
| WO2019039044A1 (en) | Steel sheet for container and production method therefor | |
| JP6052305B2 (en) | Steel plate for containers | |
| JP6003910B2 (en) | Steel plate for container and method for producing the same | |
| JP6197911B2 (en) | Treatment liquid and method for producing steel plate for container | |
| JP6361628B2 (en) | Manufacturing method of steel plate for containers | |
| JP2016060925A (en) | Steel sheet for vessel, and production therefor | |
| JP2014231631A (en) | Steel sheet for container | |
| JP2016102252A (en) | Steel sheet for vessel | |
| JP2016102250A (en) | Steel sheet for vessel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20151027 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160127 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20160203 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160301 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160314 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5910700 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |