JP6650251B2 - Surface-treated steel sheet, method for producing the same, and container using the surface-treated steel sheet - Google Patents
Surface-treated steel sheet, method for producing the same, and container using the surface-treated steel sheet Download PDFInfo
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- JP6650251B2 JP6650251B2 JP2015223918A JP2015223918A JP6650251B2 JP 6650251 B2 JP6650251 B2 JP 6650251B2 JP 2015223918 A JP2015223918 A JP 2015223918A JP 2015223918 A JP2015223918 A JP 2015223918A JP 6650251 B2 JP6650251 B2 JP 6650251B2
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- steel sheet
- plating
- treated steel
- alloy
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- 229910000831 Steel Inorganic materials 0.000 title claims description 89
- 239000010959 steel Substances 0.000 title claims description 89
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000010410 layer Substances 0.000 claims description 160
- 238000007747 plating Methods 0.000 claims description 99
- 229910045601 alloy Inorganic materials 0.000 claims description 73
- 239000000956 alloy Substances 0.000 claims description 73
- 229910018100 Ni-Sn Inorganic materials 0.000 claims description 47
- 229910018532 Ni—Sn Inorganic materials 0.000 claims description 47
- 239000002335 surface treatment layer Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 28
- 239000011247 coating layer Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 23
- 229910017091 Fe-Sn Inorganic materials 0.000 claims description 20
- 229910017142 Fe—Sn Inorganic materials 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910005382 FeSn Inorganic materials 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 105
- 239000011135 tin Substances 0.000 description 97
- 230000007797 corrosion Effects 0.000 description 26
- 238000005260 corrosion Methods 0.000 description 26
- 239000002245 particle Substances 0.000 description 25
- 238000011282 treatment Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 16
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 229910052718 tin Inorganic materials 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000003973 paint Substances 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- -1 and the like Substances 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 230000000007 visual effect Effects 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 235000013361 beverage Nutrition 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910000655 Killed steel Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000005029 tin-free steel Substances 0.000 description 4
- 239000005028 tinplate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 240000000560 Citrus x paradisi Species 0.000 description 2
- 229910003271 Ni-Fe Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- PAALZGOZEUHCET-UHFFFAOYSA-N 1,4-dioxecane-5,10-dione Chemical compound O=C1CCCCC(=O)OCCO1 PAALZGOZEUHCET-UHFFFAOYSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 150000004782 1-naphthols Chemical class 0.000 description 1
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 1
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- ZVSXNPBSZYQDKJ-UHFFFAOYSA-N 3,8-dioxabicyclo[8.3.1]tetradeca-1(14),10,12-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=CC1=C2 ZVSXNPBSZYQDKJ-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000004302 potassium sorbate Substances 0.000 description 1
- 229940069338 potassium sorbate Drugs 0.000 description 1
- 235000010241 potassium sorbate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
本発明は、ニッケルめっきおよび錫めっき上に有機樹脂層を被覆してなる表面処理鋼板に関し、特に加工を施した際に加工後の耐食性・有機樹脂層の密着性が優れる有機樹脂被覆鋼板及びその製造方法並びにこの有機樹脂被覆鋼板を用いた金属缶などの容器に関する。 The present invention relates to a surface-treated steel sheet obtained by coating an organic resin layer on nickel plating and tin plating, and in particular, when subjected to processing, an organic resin-coated steel sheet having excellent corrosion resistance and adhesion of the organic resin layer after processing, and the same. The present invention relates to a manufacturing method and a container such as a metal can using the organic resin-coated steel sheet.
飲料用あるいは食品用などに好適な金属缶の分野では、従来より、缶胴、天蓋、底蓋からなるいわゆる３ピースタイプの缶（以下、３ピース缶とも称する）が広く用いられている。この３ピース缶においては、基材となるＴＦＳ（ティンフリースチール）やぶりきなどに対する塗料の密着性や耐食性向上を目的としてクロメート処理が行われていた。
しかしながら近年の世界的な環境負荷低減に向けた対応への要望から、６価クロムを用いないで表面処理を行うクロムフリー処理の検討が行われている。
例えば飲料や食品分野では、ぶりき、ＴＦＳ（電解クロメート処理鋼板）以外の表面処理鋼板としてニッケル（Ｎｉ）めっきを施した鋼板が使用されており、ＮｉめっきとＳｎめっきを組み合わせたものも使用されている。
In the field of metal cans suitable for beverages or foods, so-called three-piece cans (hereinafter, also referred to as three-piece cans) having a can body, a canopy, and a bottom lid have been widely used. In this three-piece can, a chromate treatment has been performed for the purpose of improving the adhesion and corrosion resistance of the paint to TFS (tin-free steel) and tinplate as a base material.
However, in view of recent demands for reduction of environmental load worldwide, chromium-free treatment for performing surface treatment without using hexavalent chromium has been studied.
For example, in the field of beverages and foods, a steel sheet plated with nickel (Ni) is used as a surface-treated steel sheet other than tinplate and TFS (electrolytic chromate-treated steel sheet), and a combination of Ni plating and Sn plating is also used. ing.
ＮｉはＳｎ中に拡散しやすいため、めっき条件次第ではＳｎ中にＮｉが拡散してしまい、これが原因の１つとして例えば３ピース缶では溶接性の低下が生じてしまう。
これに対してニッケルめっき鋼板の密着性と耐食性を向上させるため、不均一な島状ニッケルめっきを施した後に錫めっきを行う表面処理鋼板が提案されている（例えば特許文献１参照）。
更に、従来のニッケルめっき鋼板では有機被覆樹脂層との密着性が充分でないという課題を克服するため、クロムを使用せずに希薄なニッケルめっき浴によってニッケルから成る凹凸形状をした微細粒状を形成して有機被覆樹脂との加工密着性に優れる表面処理鋼板を実現する技術も知られている（例えば特許文献２参照）。
Since Ni easily diffuses into Sn, Ni diffuses into Sn depending on plating conditions. One of the causes is a decrease in weldability, for example, in a three-piece can.
On the other hand, in order to improve the adhesion and corrosion resistance of a nickel-plated steel sheet, there has been proposed a surface-treated steel sheet in which non-uniform island-like nickel plating is performed and then tin plating is performed (for example, see Patent Document 1).
Furthermore, in order to overcome the problem that the conventional nickel-plated steel sheet does not have sufficient adhesion to the organic coating resin layer, a fine nickel-plated uneven shape is formed by a dilute nickel plating bath without using chromium. There is also known a technique for realizing a surface-treated steel sheet having excellent processing adhesion with an organic coating resin (for example, see Patent Document 2).
たしかに特許文献１のごとく不均一な島状Ｎｉめっきを施したりすれば、ある程度は溶接性の向上が見込めるものの、依然としてＮｉはＳｎめっき中に拡散されやすい状態に変わりはない。
また、特許文献２においても、Ｎｉめっき浴中に微量なＳｎを添加しているため、やはりＮｉはＳｎめっき中に拡散されやすい状態であると言える。
発明者が鋭意検討した結果、上記耐食性や塗料との密着性を向上させるためにはＮｉの拡散を如何にして制御するかが重要であり、したがってＮｉの拡散を抑制すれば耐食性の向上に格段に寄与できることを突き止めた。
Certainly, if non-uniform island-shaped Ni plating is applied as in Patent Literature 1, although the weldability is expected to be improved to some extent, Ni is still easily diffused during Sn plating.
Also, in Patent Document 2, since a small amount of Sn is added to the Ni plating bath, it can be said that Ni is easily diffused during the Sn plating.
As a result of the inventor's intensive studies, it is important to control the diffusion of Ni in order to improve the corrosion resistance and the adhesion with the paint. Therefore, if the diffusion of Ni is suppressed, the corrosion resistance is significantly improved. That we can contribute to
本発明は、かような課題を解決することを鑑みてなされ、クロムを用いずに塗料などの有機樹脂との高い密着性と耐食性を維持しつつ溶接性にも優れた表面処理鋼板や有機樹脂被覆鋼板、及びこれらの製造方法並びにこの有機樹脂被覆鋼板を用いた容器を提供することを目的とする。 The present invention has been made in view of solving such problems, and surface-treated steel sheets and organic resins excellent in weldability while maintaining high adhesion and corrosion resistance to organic resins such as paints without using chromium. It is an object of the present invention to provide a coated steel sheet, a production method thereof, and a container using the organic resin-coated steel sheet.
上記課題を解決するため、本発明の一実施形態にかかる表面処理鋼板は、基材と、前記基材上に形成されるとともに、粒状又は針状のＮｉ−Ｓｎ合金層と、前記Ｎｉ−Ｓｎ合金の他部に配置されるＦｅ−Ｓｎ合金層及びＳｎ層とを含む表面処理層と、を備えたことを特徴とする。
さらに、前記した（１）の特徴を備えた表面処理鋼板においては、（２）前記表面処理層におけるＳｎとＮｉとの比であるＳｎ／Ｎｉが、ａｔ％の比において５．０〜７０であることが好ましい。
また、前記した（１）又は（２）の特徴を備えた表面処理鋼板においては、（３）前記Ｎｉ−Ｓｎ合金は、その構造が主としてＮｉ３Ｓｎ４であるとともにＦｅを更に含有し、前記Ｆｅの含有率が１０ａｔ％以下であることが好ましい。
In order to solve the above problems, a surface-treated steel sheet according to an embodiment of the present invention includes a base material, a granular or acicular Ni-Sn alloy layer formed on the base material, and a Ni-Sn alloy layer. And a surface treatment layer including an Fe—Sn alloy layer and a Sn layer disposed on the other part of the alloy.
Furthermore, in the surface-treated steel sheet having the above-mentioned feature (1), (2) Sn / Ni, which is the ratio of Sn to Ni in the surface-treated layer, is 5.0 to 70 at the ratio of at%. Preferably, there is.
Further, in the surface-treated steel sheet having the features of the above (1) or (2), (3) the Ni—Sn alloy has a structure mainly composed of Ni 3 Sn 4 and further contains Fe. It is preferable that the Fe content be 10 at% or less.
また前記した（１）〜（３）のいずれかの特徴を備えた表面処理鋼板においては、（４）前記Ｎｉ−Ｓｎ合金の他部に配置されるＦｅ−Ｓｎ合金層は、ＦｅＳｎ２を含むことが好ましい。
また前記した（１）〜（４）のいずれかの特徴を備えた表面処理鋼板においては、（５） 前記表面処理層における面内方向に関し、前記Ｎｉ−Ｓｎ合金層は、前記Ｆｅ−Ｓｎ合金層又は前記Ｓｎ層に囲まれてなることが好ましい。
また前記した（１）〜（５）のいずれかの特徴を備えた表面処理鋼板においては、（６）前記表面処理層上、又は前記基材のうち前記表面処理層とは反対側に、Ｚｒ、Ｔｉ、及びＡｌの少なくとも１つ以上の酸化物を含むコーティング層が形成されてなることが好ましい。
また前記した（６）の特徴を備えた表面処理鋼板においては、（７）前記コーティング層が、Ｐ（リン）の酸化物を含むことが好ましい。
In the surface-treated steel sheet having any of the features of the above (1) ~ (3), (4) FeSn alloy layer which is disposed on the other portion of the Ni-Sn alloy includes FeSn 2 Is preferred.
Further, in the surface-treated steel sheet having any of the above features (1) to (4), (5) the Ni-Sn alloy layer is formed of the Fe-Sn alloy with respect to an in-plane direction of the surface treatment layer. It is preferable to be surrounded by a layer or the Sn layer.
In the surface-treated steel sheet having any one of the features (1) to (5), (6) Zr is formed on the surface-treated layer or on the side of the substrate opposite to the surface-treated layer. It is preferable that a coating layer containing at least one oxide of Al, Ti, and Al is formed.
In the surface-treated steel sheet having the feature of (6), (7) the coating layer preferably contains an oxide of P (phosphorus).
また、上記課題を解決するため、本発明の一実施形態にかかる有機樹脂被覆鋼板は、前記した（１）〜（７）のいずれかに記載の表面処理鋼板の上に有機樹脂層が被覆されてなることを特徴とする。
また、上記課題を解決するため、本発明の一実施形態にかかる容器は、前記した有機樹脂被覆鋼板から成ることを特徴とする。なお、当該容器としては、例えば飲料や食料、医薬品などを貯留する金属缶や缶蓋、あるいは金属ケースなどが例示される。
In order to solve the above-mentioned problems, an organic resin-coated steel sheet according to one embodiment of the present invention includes an organic resin layer coated on the surface-treated steel sheet according to any one of the above (1) to (7). It is characterized by becoming.
Further, in order to solve the above problems, a container according to an embodiment of the present invention is made of the above-mentioned organic resin-coated steel sheet. In addition, as the container, for example, a metal can or a can lid for storing beverages, foods, pharmaceuticals, and the like, or a metal case is exemplified.
また、上記課題を解決するため、本発明の一実施形態にかかる表面処理鋼板の製造方法は、 基材にＮｉめっきを行うことで、当該基材上にＮｉ層を形成する工程と、前記Ｎｉ層が形成された基材に対してＳｎめっきを行うことで、前記Ｎｉ層上にＳｎ層を形成する工程と、前記Ｎｉ層および前記Ｓｎ層が形成された基材に対して溶融加熱処理を行うことで、粒状又は針状のＮｉ−Ｓｎ合金層と、前記Ｎｉ−Ｓｎ合金の他部に配置されるＦｅ−Ｓｎ合金層及びＳｎ層とを含む表面処理層を前記基材上に形成する工程と、を含むことを特徴とする。
なお、上記した表面処理鋼板の製造方法においては、前記ＮｉめっきにおけるＮｉめっき量は、０．０１〜０．３ｇ／ｍ２であり、前記ＳｎめっきにおけるＳｎめっき量は、０．４〜３．０ｇ／ｍ２であることが好ましい。
In order to solve the above-mentioned problems, a method for manufacturing a surface-treated steel sheet according to an embodiment of the present invention includes the steps of: forming a Ni layer on a base material by performing Ni plating on the base material; By performing Sn plating on the substrate on which the layer is formed, a step of forming a Sn layer on the Ni layer, and a melting and heating treatment on the substrate on which the Ni layer and the Sn layer are formed are performed. By doing so, a granular or acicular Ni-Sn alloy layer and a surface treatment layer including an Fe-Sn alloy layer and a Sn layer disposed on the other part of the Ni-Sn alloy are formed on the base material. And a step.
In the method for producing a surface-treated steel sheet described above, the amount of Ni plating in the Ni plating is 0.01 to 0.3 g / m 2 , and the amount of Sn plating in the Sn plating is 0.4 to 3.0. It is preferably 0 g / m 2 .
本発明によれば、粒状あるいは針状のＮｉ−Ｓｎ合金層を形成させつつ他部をＦｅ−Ｓｎ合金層又はＳｎ層とすることで、ＮｉがＳｎの中で安定して存在することが可能となってＮｉの拡散を抑制することができ、これにより耐食性と溶接性を共に備える優れた表面処理鋼板を実現することができる。 ADVANTAGE OF THE INVENTION According to this invention, Ni can stably exist in Sn by forming a granular or acicular Ni-Sn alloy layer and making another part into a Fe-Sn alloy layer or a Sn layer. As a result, the diffusion of Ni can be suppressed, whereby an excellent surface-treated steel sheet having both corrosion resistance and weldability can be realized.
≪実施形態≫
以下、本発明を実施するための実施形態について説明する。
本実施形態に係る表面処理鋼板は、基材と、この基材上に形成される表面処理層とを少なくとも含んで構成されている。そしてこの表面処理層は、当該表面処理層中におけるＮｉの拡散が抑制されるように、この表面処理層内でＮｉが安定した相（準安定状態）となっていることを特徴としている。
以下、本実施形態に係る表面処理鋼板につき個々の要素を詳述していく。
<< embodiment >>
Hereinafter, embodiments for carrying out the present invention will be described.
The surface-treated steel sheet according to the present embodiment includes at least a substrate and a surface-treated layer formed on the substrate. The surface treatment layer is characterized in that Ni is in a stable phase (metastable state) in the surface treatment layer so that diffusion of Ni in the surface treatment layer is suppressed.
Hereinafter, individual elements of the surface-treated steel sheet according to the present embodiment will be described in detail.
＜基材＞
表面処理鋼板の基材としては、鉄や各種の合金などの金属板が用いられる。この金属板には、例えば、ぶりき、ＴＦＳ、ニッケルめっき鋼板などの各種の表面処理がなされた鋼板も含まれる。
具体的に好適な鋼板としては、例えば一般的に缶用に用いられる炭素量０．０１〜０．１５質量％の低炭素アルミキルド鋼を用いることができる。更にはニオブやチタンを添加した炭素量０．０１質量％未満の非時効性極低炭素アルミキルド鋼も適用可能である。なお、これらのアルミキルド鋼の熱間圧延板を電解酸洗等で酸洗して表面のスケールを除去した後、冷間圧延し、次いで、電解洗浄、焼鈍、圧延など施したものを冷延鋼板として用いてもよい。
<Substrate>
As a base material of the surface-treated steel sheet, a metal plate such as iron or various alloys is used. The metal plate includes, for example, a steel plate subjected to various surface treatments such as tinplate, TFS, and a nickel-plated steel plate.
As a specifically suitable steel plate, for example, a low-carbon aluminum killed steel having a carbon content of 0.01 to 0.15 mass% generally used for cans can be used. Furthermore, a non-ageing ultra-low carbon aluminum killed steel with a carbon content of less than 0.01% by mass to which niobium or titanium is added is also applicable. The hot-rolled aluminum-killed steel sheet was pickled by electrolytic pickling or the like to remove the scale on the surface, then cold-rolled, and then subjected to electrolytic cleaning, annealing, rolling, etc. to obtain a cold-rolled steel sheet. May be used.
＜表面処理層＞
本実施形態の表面処理層は、基材の少なくとも一面側に形成され、粒状又は針状のＮｉ−Ｓｎ合金層と、Ｎｉ−Ｓｎ合金の他部に配置されるＦｅ−Ｓｎ合金層又はＳｎ層とを含んで構成されている。なお、以下では、Ｆｅ−Ｓｎ合金層とＳｎ層とを総称する場合には包囲層と称する。すなわち、個々の層を特定して説明する場合を除き、単に「包囲層」と記載した場合には、「Ｆｅ−Ｓｎ合金層」、「Ｓｎ層」、又は「Ｆｅ−Ｓｎ合金層とＳｎ層」のいずれかを指すこととする。
図１は、本実施形態に係る表面処理鋼板ＳＴの構造を模式的に示した断面図であり、より具体的には上記した基材１と表面処理層２とが模式的に示されている。このうち、表面処理層２は、Ｎｉ−Ｓｎ合金層２１、第一包囲層２２および第二包囲層２３とを含んで構成されている。
<Surface treatment layer>
The surface treatment layer of the present embodiment is formed on at least one surface side of the base material, and is a granular or acicular Ni-Sn alloy layer, and an Fe-Sn alloy layer or a Sn layer disposed at another part of the Ni-Sn alloy. It is comprised including. In the following, when the Fe-Sn alloy layer and the Sn layer are collectively referred to, they are referred to as an envelope layer. That is, unless the individual layers are specified and described, when simply described as “enclosure layer”, “Fe—Sn alloy layer”, “Sn layer”, or “Fe—Sn alloy layer and Sn layer” ".
FIG. 1 is a cross-sectional view schematically illustrating the structure of the surface-treated steel sheet ST according to the present embodiment, and more specifically, the substrate 1 and the surface-treated layer 2 described above are schematically illustrated. . The surface treatment layer 2 includes a Ni—Sn alloy layer 21, a first surrounding layer 22, and a second surrounding layer 23.
Ｎｉ−Ｓｎ合金層２１は、基材１上で粒状又は針状の様相を呈している。ここで、「粒状又は針状」とは、Ｎｉ成分に着目した場合における周囲の部位よりも高さ方向に盛り上がった形状をいう。例えば図１で見た場合、Ｎｉ−Ｓｎ合金層２１は、平面方向（基材の面方向）に関して、Ｎｉ成分を含有する部位が基材１の鉛直方向である高さ方向に凸状に突出しており、上記した周囲の部位よりも高さ方向に盛り上がった形状と言える。
なお図１は断面で示されているが、後述する図４などから明らかなとおり、基材１の上方から表面処理層２を平面視で見た場合には、Ｎｉ−Ｓｎ合金層２１は第一包囲層２２と第二包囲層２３に囲まれるように位置している。
換言すれば、本実施形態の表面処理層２は次のようにも表現できる。すなわち、表面処理層２内では、Ｎｉ−Ｓｎ合金層２１は基材１上で所定の距離だけ隔てて点在するとともに、この隣り合うＮｉ−Ｓｎ合金層２１の間には第一包囲層２２が介在するとともに、このＮｉ−Ｓｎ合金層２１と第一包囲層２２を覆うように第二包囲層２３が形成された形態となっている。
The Ni—Sn alloy layer 21 has a granular or needle-like appearance on the substrate 1. Here, “granular or acicular” refers to a shape that rises in the height direction from surrounding parts when focusing on the Ni component. For example, when viewed in FIG. 1, the Ni-Sn alloy layer 21 has a portion containing a Ni component protruding in a height direction that is a vertical direction of the base material 1 in a plane direction (a surface direction of the base material). Therefore, it can be said that the shape is raised in the height direction more than the above-described surrounding parts.
Although FIG. 1 is shown in cross section, as is apparent from FIG. 4 and the like described below, when the surface treatment layer 2 is viewed from above the base material 1 in a plan view, the Ni—Sn alloy layer 21 It is located so as to be surrounded by the one surrounding layer 22 and the second surrounding layer 23.
In other words, the surface treatment layer 2 of the present embodiment can be expressed as follows. That is, in the surface treatment layer 2, the Ni—Sn alloy layers 21 are scattered at a predetermined distance on the substrate 1, and the first surrounding layer 22 is located between the adjacent Ni—Sn alloy layers 21. And a second surrounding layer 23 is formed so as to cover the Ni-Sn alloy layer 21 and the first surrounding layer 22.
Ｎｉ−Ｓｎ合金層２１は、その構造が主としてＮｉ3Ｓｎ４であることが望ましい。ここで、「主として」とは、結晶構造を解析した際に一番多い形態であることを言う。なお、結晶構造の解析は、例えばＸ線回折装置、透過型電子顕微鏡などにより行うことができる。
Ｎｉ−Ｓｎ合金層２１は主としてＮｉ3Ｓｎ４であることが望ましい理由は以下のとおりである。すなわち、ＮｉとＳｎの結合態様にはＮｉ3Ｓｎ４以外にもＮｉ3ＳｎやＮｉ3Ｓｎ２のごときＮｉ−Ｓｎ合金に対する準安定状態（準安定相）が存在するのであるが、本実施形態で求められるＳｎめっき量を考慮するとＮｉ3Ｓｎ４が最適となる。Ｎｉ−Ｓｎ合金層２１のＳｎが少ない場合には金属Ｎｉ相あるいはＮｉ−Ｆｅ相が形成されてしまうのでＳｎめっき量が多い条件の方が好ましく、この場合にはＮｉ3Ｓｎ４が上記した準安定相となるためである。
It is desirable that the structure of the Ni—Sn alloy layer 21 is mainly Ni 3 Sn 4 . Here, “mainly” refers to the most common form when the crystal structure is analyzed. The analysis of the crystal structure can be performed by, for example, an X-ray diffractometer, a transmission electron microscope, or the like.
The reason why the Ni—Sn alloy layer 21 is preferably mainly made of Ni 3 Sn 4 is as follows. That is, the bonding state of Ni and Sn has a metastable state (metastable phase) for Ni—Sn alloys such as Ni 3 Sn and Ni 3 Sn 2 in addition to Ni 3 Sn 4. In consideration of the amount of Sn plating required in the above, Ni 3 Sn 4 is optimal. Preferably towards the Sn plated amount is large conditions because the metal Ni phase or Ni-Fe phase will be formed in the case of Sn Ni-Sn alloy layer 21 is small, quasi the Ni 3 Sn 4 in this case is the This is because it becomes a stable phase.
なおＮｉ−Ｓｎ合金層２１における粒子（粒状又は針状の状態も含む）の形態については、以下の構造となることが望ましい。すなわち、Ｎｉ−Ｓｎ合金層２１におけるＮｉ粒子の平均粒径は０．１〜１．０μｍが好適であり、より好ましくは０．２〜０．４μｍである。また、Ｎｉ−Ｓｎ合金層２１におけるＮｉ粒子の粒子密度は、１０〜１００個／μｍ２が好適であり、より好ましくは１０〜２０個／μｍ２である。 The form of the particles (including a granular or acicular state) in the Ni—Sn alloy layer 21 preferably has the following structure. That is, the average particle size of the Ni particles in the Ni—Sn alloy layer 21 is preferably 0.1 to 1.0 μm, and more preferably 0.2 to 0.4 μm. The particle density of the Ni particles in the Ni—Sn alloy layer 21 is preferably from 10 to 100 particles / μm 2 , and more preferably from 10 to 20 particles / μm 2 .
ここで「粒子密度」は、表面処理膜２の表面を走査型電子顕微鏡（ＳＥＭ）で観察し、粒子の平均粒径がおよそ０．５μｍ以下の範囲では１×１μｍの範囲について、該範囲内に存在する粒子の数をカウントすることで、単位面積当たりのニッケルの粒子数を測定して求める。この場合、１×１μｍの枠内に完全に収まっている粒子は１個、一部のみが枠内に入っている粒子については０．５個としてカウントした。そして、この操作を、ニッケルめっき層の表面の５箇所について行い、最大値、最小値の２つを除き、３箇所の測定結果を平均することにより、粒子密度を求めることができる。 Here, the “particle density” refers to a value obtained by observing the surface of the surface-treated film 2 with a scanning electron microscope (SEM), and within a range of 1 × 1 μm when the average particle size of the particles is approximately 0.5 μm or less. The number of particles of nickel per unit area is determined by counting the number of particles present in the sample. In this case, the number of particles completely contained in the 1 × 1 μm frame was counted as one, and the number of particles only partially contained in the frame was counted as 0.5. And this operation is performed about five places of the surface of a nickel plating layer, and a particle density can be calculated | required by averaging the measurement result of three places except two of a maximum value and a minimum value.
また、平均粒径がおよそ０．５μｍ以上の場合は、測定範囲を１０×１０μｍとして同様の操作を行い、得られた粒子数を１×１μｍ当たりの粒子数に換算することにより粒子密度を求めることができる。
なお「平均粒径」は、表面処理膜２の表面を走査型電子顕微鏡（ＳＥＭ）で観察して求めた１×１μｍの単位面積当たりの粒子密度から、粒子１個当たりの平均占有面積を計算し、その平均占有面積に相当する円の直径として算出し求めることができる。
When the average particle size is about 0.5 μm or more, the same operation is performed with the measurement range set to 10 × 10 μm, and the particle density is obtained by converting the obtained number of particles into the number of particles per 1 × 1 μm. be able to.
The “average particle diameter” is calculated from the particle density per unit area of 1 × 1 μm obtained by observing the surface of the surface-treated film 2 with a scanning electron microscope (SEM). Then, it can be calculated and obtained as the diameter of a circle corresponding to the average occupied area.
Ｎｉ−Ｓｎ合金層２１は、上記した準安定相を維持する限りにおいてＮｉ3Ｓｎ４に対して不純物（基材から元素拡散など製造時に不回避的に混入する物質）が含有されていてもよい。
基材の成分が鉄（Ｆｅ）の場合には、Ｎｉ−Ｓｎ合金層２１（Ｎｉ3Ｓｎ４）にＦｅが含有されることがある。この場合におけるＦｅの含有率（Ｆｅ／（Ｎｉ＋Ｓｎ＋Ｆｅ））の値は１０ａｔ％以下であることが望ましい。１０ａｔ％を超えると、内容物中へ溶解しやすくなり、耐食性が低下しやすくなるため、好ましくないからである。
The Ni—Sn alloy layer 21 may contain impurities (substances that are inevitably mixed during production such as element diffusion from the base material) into Ni 3 Sn 4 as long as the above-mentioned metastable phase is maintained. .
When the component of the base material is iron (Fe), the Ni—Sn alloy layer 21 (Ni 3 Sn 4 ) may contain Fe. In this case, the value of the Fe content (Fe / (Ni + Sn + Fe)) is desirably 10 at% or less. If it exceeds 10 at%, it is not preferable because it is easily dissolved in the contents and the corrosion resistance is easily lowered.
Ｎｉ−Ｓｎ合金層２１を包囲する包囲層は、第一包囲層２２と第二包囲層２３を含んでいる。
第一包囲層２２は、「Ｆｅ−Ｓｎ合金層」又は「Ｓｎ層」であり、基材１上に形成されてＮｉ−Ｓｎ合金層２１の間に位置している。
第二包囲層２３は、「Ｆｅ−Ｓｎ合金層」又は「Ｓｎ層」であり、Ｎｉ−Ｓｎ合金層２１及び第一包囲層２２を覆うように、これらの層上に位置している。なお第一包囲層２２と第二包囲層２３の成分に関しては、基材１からのＦｅ成分の拡散度合によって変化し得る。したがって本実施形態における第一包囲層２２と第二包囲層２３は、例えば次の表１に示すパターン１〜パターン３を取り得る。
The surrounding layer surrounding the Ni—Sn alloy layer 21 includes a first surrounding layer 22 and a second surrounding layer 23.
The first surrounding layer 22 is an “Fe—Sn alloy layer” or an “Sn layer”, and is formed on the substrate 1 and located between the Ni—Sn alloy layers 21.
The second surrounding layer 23 is an “Fe—Sn alloy layer” or “Sn layer”, and is located on these layers so as to cover the Ni—Sn alloy layer 21 and the first surrounding layer 22. Note that the components of the first surrounding layer 22 and the second surrounding layer 23 may change depending on the degree of diffusion of the Fe component from the base material 1. Therefore, the first surrounding layer 22 and the second surrounding layer 23 in the present embodiment can take, for example, patterns 1 to 3 shown in Table 1 below.
なお、第二包囲層２３は、必ずしもＮｉ−Ｓｎ合金層２１を覆う必要はなく、Ｎｉ−Ｓｎ合金層２１の一部が第二包囲層２３から突き出た形態でもよい。
また、第一包囲層２２又は第二包囲層２３がＦｅ−Ｓｎ合金層の場合には、当該Ｆｅ−Ｓｎ合金層はＦｅＳｎ２を含むことが望ましい。
また、表面処理層２におけるＳｎとＮｉとの比であるＳｎ／Ｎｉは、５．０〜７０であることが望ましい。Ｓｎ／Ｎｉが５．０以下ではＮｉ3Ｓｎ４のみで構成された構造となるため、溶接性、耐食性が悪くなる。Ｓｎ／Ｎｉが７０を超えると粒状に析出したＮｉによる効果が小さく、ぶりきに近い特性を示す。
The second surrounding layer 23 does not necessarily need to cover the Ni—Sn alloy layer 21, and may have a form in which a part of the Ni—Sn alloy layer 21 protrudes from the second surrounding layer 23.
When the first surrounding layer 22 or the second surrounding layer 23 is an Fe—Sn alloy layer, the Fe—Sn alloy layer preferably includes FeSn 2 .
Further, it is desirable that Sn / Ni, which is the ratio of Sn to Ni in the surface treatment layer 2, is 5.0 to 70. Since the Sn / Ni is constructed structure only Ni 3 Sn 4 in 5.0 below, weldability, corrosion resistance is deteriorated. If the value of Sn / Ni exceeds 70, the effect of Ni precipitated in the form of particles is small, and characteristics close to tinplate are exhibited.
＜表面処理鋼板＞
図１で示した表面処理鋼板ＳＴは、以下の態様にて製造される。すなわち、本実施形態ではＮｉめっきを微細粒状に析出させることにより、Ｓｎめっき後に行われる溶融加熱処理において、粒状あるいは針状のＮｉ−Ｓｎ合金を形成させ、これにより高い溶接性と耐食性を同時に備えた表面処理鋼板ＳＴを実現している。
なお、Ｎｉめっきを微細粒状に析出させる条件としては、例えば、めっき液の成分は硫酸ニッケル１０〜１００ｇ／Ｌ、より好ましくは４０〜８０ｇ／Ｌ、硫酸アンモニウム１０〜１００ｇ／Ｌ、より好ましくは４０〜８０ｇ／Ｌ、クエン酸５〜１００ｇ／Ｌ、より好ましくは１０〜２０ｇ／Ｌである。ｐＨは２．０〜５．０、より好ましくは３．５〜４．５である。また、陰極電解での条件としては電流密度３０〜１００Ａ／ｄｍ２、より好ましくは３０〜５０Ａ／ｄｍ２である。
以下、具体的な表面処理鋼板ＳＴの製造工程について、図２を用いて順を追って説明する。なお、以下の説明においては本実施形態の表面処理層２が基材１の少なくとも一面側に形成される例を示すが、この態様に限られず更に基材１の他側の面に形成されていてもよい。
<Surface treated steel sheet>
The surface-treated steel sheet ST shown in FIG. 1 is manufactured in the following mode. That is, in the present embodiment, the Ni plating is deposited in fine particles to form a granular or needle-like Ni-Sn alloy in the melt heat treatment performed after the Sn plating, thereby simultaneously providing high weldability and corrosion resistance. Surface-treated steel plate ST.
In addition, as conditions for precipitating Ni plating into fine particles, for example, the components of the plating solution are nickel sulfate 10 to 100 g / L, more preferably 40 to 80 g / L, and ammonium sulfate 10 to 100 g / L, more preferably 40 to 100 g / L. 80 g / L, citric acid 5-100 g / L, more preferably 10-20 g / L. The pH is between 2.0 and 5.0, more preferably between 3.5 and 4.5. The conditions for the cathodic electrolysis are a current density of 30 to 100 A / dm 2 , more preferably 30 to 50 A / dm 2 .
Hereinafter, a specific manufacturing process of the surface-treated steel sheet ST will be sequentially described with reference to FIG. In the following description, an example in which the surface treatment layer 2 of the present embodiment is formed on at least one surface of the substrate 1 is shown. However, the present invention is not limited to this mode, and the surface treatment layer 2 is further formed on the other surface of the substrate 1. You may.
図２に示すとおり、まず基材１にＮｉめっきを行うことで、当該基材１上にＮｉ層を形成する（ステップ１）。このＮｉめっきにおけるＮｉめっき量は、例えば０．０１〜０．３ｇ／ｍ２であることが好ましい。０．０１ｇ／ｍ２を下回るとＮｉめっきの効果が不十分であり、０．３ｇ／ｍ２を超えるとＳｎの必要量も多くなりコスト高となるからである。
ステップ１の後、続いてＮｉ層が形成された基材１に対してＳｎめっきを行うことで、Ｎｉ層上にＳｎ層を形成する（ステップ２）。このＳｎめっきにおけるＳｎめっき量は、０．４〜３．０ｇ／ｍ２であることが好ましい。０．４ｇ／ｍ２を下回るとＳｎめっきの効果が不十分であり、３．０ｇ／ｍ２を超えても大幅な改善効果は見込めずコスト高となるからである。
なお、より好ましくは、Ｎｉめっき量が０．０１〜０．１ｇ／ｍ２であり、且つ、Ｓｎめっき量が１．０〜２．８ｇ／ｍ２である。
As shown in FIG. 2, first, a Ni layer is formed on the base material 1 by performing Ni plating on the base material 1 (step 1). The amount of Ni plating in this Ni plating is preferably, for example, 0.01 to 0.3 g / m 2 . If the amount is less than 0.01 g / m 2 , the effect of Ni plating is insufficient. If the amount exceeds 0.3 g / m 2 , the required amount of Sn increases and the cost increases.
After step 1, Sn plating is performed on the substrate 1 on which the Ni layer has been formed, thereby forming an Sn layer on the Ni layer (step 2). The amount of Sn plating in the Sn plating is preferably 0.4 to 3.0 g / m 2 . If the amount is less than 0.4 g / m 2 , the effect of Sn plating is insufficient, and if the amount exceeds 3.0 g / m 2 , a significant improvement effect cannot be expected and the cost increases.
Incidentally, more preferably, Ni plating weight of 0.01 to 0.1 g / m 2, and, Sn plating weight of 1.0~2.8g / m 2.
ステップ２の後は、Ｎｉ層およびＳｎ層が形成された基材１に対して所定条件下でリフロー処理（溶融加熱処理）を行うことで、上述した表面処理層２（粒状又は針状のＮｉ−Ｓｎ合金層と、このＮｉ−Ｓｎ合金以外の他部（残部）に形成される包囲層としてのＦｅ−Ｓｎ合金層又はＳｎ層）を基材１上に形成する（ステップ３）。なお、リフロー処理の具体的な条件については、後述する実施例の中で詳述する。
以上説明したステップ１〜ステップ３の処理を経て、本実施形態の表面処理鋼板ＳＴが製造される。
After step 2, the substrate 1 on which the Ni layer and the Sn layer are formed is subjected to a reflow treatment (melt heat treatment) under a predetermined condition, thereby obtaining the surface treatment layer 2 (granular or needle-like Ni). An -Sn alloy layer and an Fe-Sn alloy layer or a Sn layer as an enclosing layer formed on the other part (remaining part) other than the Ni-Sn alloy are formed on the base material 1 (step 3). Note that specific conditions for the reflow process will be described in detail in an embodiment described later.
Through the processes of Steps 1 to 3 described above, the surface-treated steel sheet ST of the present embodiment is manufactured.
＜クロムフリー化処理としてのコーティング層＞
図２のステップ４及び図３に示すとおり、本実施形態の表面処理層２が形成された基材１に対しては、さらに表面処理層２上又は基材１のうち上述した他側の面に、Ｚｒ、Ｔｉ、及びＡｌの少なくとも１つ以上の酸化物（例えばＺｒＯ２、ＴｉＯ２、Ａｌ２Ｏ３など）の皮膜としてのコーティング層３が形成されていてもよい。すなわち、本実施形態においてコーティング層３は必須ではないが、表面処理層２上にコーティング層３があれば尚好ましい。
なお、本実施形態のコーティング層３は、上記した酸化物だけでなく水酸化物をも含むことがある。従って、本実施形態でいう「酸化物」とは、少なくともその一部に水酸化物が含まれていてもよい概念として用いられている。
<Coating layer as chrome-free treatment>
As shown in step 4 and FIG. 3 of FIG. 2, for the substrate 1 on which the surface treatment layer 2 of the present embodiment is formed, the surface on the surface treatment layer 2 or the other surface of the substrate 1 described above. Further, a coating layer 3 as a film of at least one oxide of Zr, Ti, and Al (for example, ZrO 2 , TiO 2 , Al 2 O 3, etc.) may be formed. That is, in the present embodiment, the coating layer 3 is not essential, but it is more preferable that the coating layer 3 is provided on the surface treatment layer 2.
In addition, the coating layer 3 of this embodiment may contain not only the above-mentioned oxide but also a hydroxide. Therefore, the “oxide” in the present embodiment is used as a concept that at least a part thereof may contain a hydroxide.
コーティング層３の形成は上記に限定されず、例えば（１）モリブデン酸（所定比率のリン酸を添加した形態を含む）やタングステン酸などの不動態化作用を利用した形態の皮膜、（２）Ｔｉ・Ｚｒ・Ｖ・Ｍｎ・Ｎｉ・Ｃｏなどの遷移金属のフッ化物やリン酸塩、硝酸塩および硫酸塩などをベースとする反応型形態の皮膜、さらにポリピニルフェノール誘導体やポリアクリル酸などをブレンドした塗布型形態の皮膜、（３）Ｙ・Ｌａ・Ｃｅなどの希士類元素の塩化物、硝酸塩などをベースとする反応型形態の皮膜、またはその酸素酸塩にモリブデン酸やタングステン酸などをブレンドした塗布型形態の皮膜、（４）タンニン酸など多価フェノールカルボン酸や硫黄や窒素を含むチオ尿素などのキレート剤をベースとする形態の皮膜など、公知の種々の形態の皮膜を用いてもよい。 The formation of the coating layer 3 is not limited to the above, and for example, (1) a film using a passivation action such as molybdic acid (including a form to which a predetermined ratio of phosphoric acid is added) or tungstic acid; Reaction type coatings based on fluorides, phosphates, nitrates and sulfates of transition metals such as Ti / Zr / V / Mn / Ni / Co, as well as polypinylphenol derivatives and polyacrylic acid Blend coating type coating, (3) Reaction type coating based on chlorides, nitrates, etc. of rare elements such as Y, La, Ce, etc., or molybdic acid, tungstic acid, etc. And known coatings such as (4) coatings based on chelating agents such as polyhydric phenol carboxylic acids such as tannic acid and thiourea containing sulfur and nitrogen. It may be used a film of various forms.
コーティング層３は、上記の酸化物以外にリンの酸化物を含んでもよい。コーティング層３を形成する前にＦｅあるいはＳｎからなるリン酸化合物層を形成させてもよいし、リン酸Ｚｒ，リン酸Ａｌなどのリン酸化合物の形態として形成させてもよい。リン酸を含むことにより、有機樹脂層との密着性を向上させるとともに、ピンホールなどのめっき欠陥を低減することができる。 The coating layer 3 may include an oxide of phosphorus in addition to the above oxide. Before forming the coating layer 3, a phosphate compound layer made of Fe or Sn may be formed, or may be formed in the form of a phosphate compound such as Zr phosphate or Al phosphate. By containing phosphoric acid, the adhesion to the organic resin layer can be improved and plating defects such as pinholes can be reduced.
なお、コーティング層３の皮膜量はＺｒ酸化物、Ａｌ酸化物、Ｔｉ酸化物のいずれも０．００１〜０．０３ｇ／ｍ２、リンの酸化物は０．０００１〜０．０５ｇ／ｍ２であることが好ましい。
このうち、リンの酸化物に関しては、Ｐ（リン）およびＡｌ（アルミニウム）の酸化物を主成分とするコーティング層を形成する場合には、好ましくはＡｌの皮膜量が０．００１〜０．０１５ｇ／ｍ２であり、このＡｌに対する好ましいＰの皮膜量は０．０００５〜０．００３ｇ／ｍ２である。
Incidentally, the coating amount of Zr oxide of the coating layer 3, Al oxide, both 0.001~0.03g / m 2 of Ti oxides, oxides of phosphorus in 0.0001~0.05g / m 2 Preferably, there is.
Among these, with respect to the oxide of phosphorus, when forming a coating layer mainly composed of oxides of P (phosphorus) and Al (aluminum), the coating amount of Al is preferably 0.001 to 0.015 g. / M 2 , and the preferable amount of P coating on Al is 0.0005 to 0.003 g / m 2 .
＜有機樹脂層＞
図２のステップ５及び図４に示すとおり、上記した表面処理鋼板ＳＴ上には、有機樹脂層４が形成されてもよい。より具体的には、上記した表面処理鋼板ＳＴの製造後、又は上記したコーティング層３が形成される場合にはそのコーティング層３形成の後に、これらの上に有機樹脂層４が形成されて有機樹脂被覆鋼板ＲＴが製造される。
なお有機樹脂層４としては種々の塗料などが適用可能である。熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、エチレン−プロピレン共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリルエステル共重合体、アイオノマー等のオレフィン系樹脂フィルム、ポリエチレンテレフタレートやポリブチレンテレフタレート等のポリエステルフィルム、ポリ塩化ビニルフィルムやポリ塩化ビニリデンフィルム等の未延伸フィルム又は二軸延伸したフィルム、又はナイロン６、ナイロン６，６、ナイロン１１、ナイロン１２等のポリアミドフィルムなどを用いることができる。その中でも、イソフタル酸を共重合化してなる無配向のポリエチレンテレフタレートが特に好ましい。また、このような有機樹脂層４を構成するための有機材料は、単独で用いてもよく、異なる有機材料をブレンドして用いてもよい。また複数の有機樹脂層からなる多層構成であってもよい。熱硬化性樹脂としては、エポキシ−フェノール樹脂、ポリエステル樹脂等を用いることができる。
<Organic resin layer>
As shown in step 5 of FIG. 2 and FIG. 4, an organic resin layer 4 may be formed on the surface-treated steel plate ST described above. More specifically, after the above-mentioned surface-treated steel sheet ST is manufactured, or when the above-mentioned coating layer 3 is formed, after the coating layer 3 is formed, the organic resin layer 4 is formed thereon to form an organic layer. The resin-coated steel sheet RT is manufactured.
Various paints and the like can be applied as the organic resin layer 4. As the thermoplastic resin, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, polyester such as polyethylene terephthalate and polybutylene terephthalate An unstretched film such as a film, a polyvinyl chloride film or a polyvinylidene chloride film or a biaxially stretched film, or a polyamide film such as nylon 6, nylon 6, 6, nylon 11, or nylon 12 can be used. Among them, non-oriented polyethylene terephthalate obtained by copolymerizing isophthalic acid is particularly preferable. Further, the organic material for forming the organic resin layer 4 may be used alone, or may be used by blending different organic materials. Further, it may have a multilayer structure composed of a plurality of organic resin layers. As the thermosetting resin, an epoxy-phenol resin, a polyester resin, or the like can be used.
このうちポリエステル樹脂は、塗装や焼付けが容易であり、加工性や金属との密着性、耐レトルト性に優れ、更には焼却時に有毒、腐食ガスを発生しない点から好適である。かようなポリエステル樹脂としては、例えば、エチレンテレフタレート、ブチレンテレフタレート、１，４−シクロヘキサンジメチルテレフタレート、エチレンイソフタレート、ブチレンイソフタレート、エチレンアジペート、ブチレンアジペート、エチレンナフタレート、ブチレンナフタレートのいずれか１種類以上のエステルを含有するポリエステル樹脂などが例示される。
さらに本実施形態の有機樹脂層４は、複数の層で構成された多層フィルムであってもよく、好ましくは２層あるいは３層のフィルムで構成されていてもよい。
Among them, the polyester resin is suitable because it is easy to apply and bake, is excellent in workability, adhesion to metal, and retort resistance, and is toxic and does not generate corrosive gas when incinerated. As such a polyester resin, for example, any one of ethylene terephthalate, butylene terephthalate, 1,4-cyclohexanedimethyl terephthalate, ethylene isophthalate, butylene isophthalate, ethylene adipate, butylene adipate, ethylene naphthalate, and butylene naphthalate Examples thereof include polyester resins containing the above esters.
Further, the organic resin layer 4 of the present embodiment may be a multilayer film composed of a plurality of layers, and preferably may be composed of a two-layer or three-layer film.
＜容器＞
図２のステップ６及び図５に示すとおり、上記した本実施形態の表面処理鋼板ＳＴや有機樹脂被覆鋼板ＲＴは、種々の容器Ｃに適用が可能である。本実施形態で適用が可能な容器Ｃとしては、飲料や食品を封入して保存する缶（公知の３ピース缶など）やケースなどが例示され、特に溶接を用いて所定の形状とする金属缶が好例である。
なお図５においては、構造把握の容易化のため、３ピース缶の完成品ではなく上蓋が未装着の缶胴を示している。
<Container>
As shown in Step 6 and FIG. 5 of FIG. 2, the surface-treated steel sheet ST and the organic resin-coated steel sheet RT of the present embodiment described above can be applied to various containers C. Examples of the container C applicable in the present embodiment include cans (such as well-known three-piece cans) for enclosing and storing beverages and foods, cases, and the like. Particularly, metal cans having a predetermined shape using welding. Is a good example.
Note that FIG. 5 shows a can body without an upper lid, instead of a completed three-piece can, for easy understanding of the structure.
≪実施例≫
以下に、実施例を挙げて本発明について、より具体的に説明する。
＜実施例１＞
厚さ０．２２５ｍｍの低炭素アルミキルド鋼の冷延鋼板を基材として用いた。まず、この基材をアルカリ水溶液中で電解脱脂して水洗いを行い、更に硫酸酸洗と水洗いを行った後に、ニッケルめっき浴でＮｉめっきの皮膜量を０．０１ｇ／ｍ２として凹凸形状をした微細粒状のＮｉめっき層を形成させた。その後、錫めっき浴でＳｎめっきの皮膜量を０．７ｇ／ｍ２として、Ｓｎめっき層を形成させた。
上記の条件にて得られた表面処理鋼板ＳＴに対し、リフロー処理（加熱処理）を行い、基材上にＮｉ−Ｓｎ合金層を形成させた。なお、このときのリフロー条件としては、Ｓｎの融点以上の温度２４０℃にて５．６秒で溶融加熱処理を行った。
なお、リフロー条件のうち、加熱温度については錫の融点以上という条件内であれば適宜選択可能であり、また、加熱時間については０．１〜８秒という条件内であれば適宜選択可能である。加熱温度あるいは加熱時間は、ＮｉとＳｎとの合金化が進み、Ｎｉ３Ｓｎ４が形成される条件であれば特に限定はされない。
<< Example >>
Hereinafter, the present invention will be described more specifically with reference to examples.
<Example 1>
A cold rolled low carbon aluminum killed steel sheet having a thickness of 0.225 mm was used as a base material. First, this base material was electrolytically degreased in an aqueous alkaline solution, washed with water, further washed with sulfuric acid and washed with water, and then formed into an uneven shape with a nickel plating bath having a Ni plating film amount of 0.01 g / m 2 . A fine-grained Ni plating layer was formed. Then, the Sn plating layer was formed in a tin plating bath with the amount of Sn plating being 0.7 g / m 2 .
The surface-treated steel sheet ST obtained under the above conditions was subjected to a reflow treatment (heating treatment) to form a Ni-Sn alloy layer on the base material. As the reflow conditions at this time, the melt heat treatment was performed at 240 ° C. or higher at the melting point of Sn for 5.6 seconds.
Among the reflow conditions, the heating temperature can be appropriately selected as long as it is within the condition of the melting point of tin or higher, and the heating time can be appropriately selected as long as it is within the range of 0.1 to 8 seconds. . The heating temperature or heating time is not particularly limited as long as the alloying of Ni and Sn proceeds and Ni 3 Sn 4 is formed.
なお、具体的なめっき浴の条件は次のとおりであった。
＜ニッケルめっき浴およびめっき条件＞
硫酸ニッケル ４０ｇ／Ｌ
硫酸アンモニウム ２０ｇ／Ｌ
クエン酸 １５ｇ／Ｌ
ｐＨ ４．０
浴温 ４５℃
電流密度５０Ａ／ｄｍ２
なお、硫酸ニッケルの量は、４０〜６０ｇ／Ｌであれば適宜調整してもよい。また、硫酸アンモニウムの量は、２０〜１００ｇ／Ｌであれば適宜調整してもよい。
表５では、本ニッケルめっき浴を用いたものには「微粒子Ｎｉ」と記した。
The specific conditions of the plating bath were as follows.
<Nickel plating bath and plating conditions>
Nickel sulfate 40g / L
Ammonium sulfate 20g / L
Citric acid 15g / L
pH 4.0
Bath temperature 45 ° C
Current density 50A / dm 2
The amount of nickel sulfate may be appropriately adjusted as long as it is 40 to 60 g / L. Further, the amount of ammonium sulfate may be appropriately adjusted as long as it is 20 to 100 g / L.
In Table 5, those using the present nickel plating bath are described as “fine particle Ni”.
＜錫めっき浴およびめっき条件＞
硫酸第一錫 ８０ｇ／Ｌ
フェノールスルホン酸 ６０ｇ／Ｌ
添加剤Ａ（エトキシ化−α−ナフトール） ３ｇ／Ｌ
添加剤Ｂ（エトキシナフトールスルホン酸） ３ｇ／Ｌ
ｐＨ １以下
浴温 ４０ ℃
電流密度 １０ Ａ／ｄｍ２
なお、硫酸第一錫の量は、１０〜２００ｇ／Ｌであれば適宜調整してもよい。また、フェノールスルホン酸の量は、５〜１００ｇ／Ｌであれば適宜調整してもよい。
表５では、本錫めっき浴を用いたものには「ＰＳＡ浴」と記した。
<Tin plating bath and plating conditions>
Stannous sulfate 80g / L
Phenolsulfonic acid 60g / L
Additive A (ethoxylated α-naphthol) 3 g / L
Additive B (ethoxynaphtholsulfonic acid) 3 g / L
pH 1 or lower Bath temperature 40 ° C
Current density 10 A / dm 2
In addition, the amount of stannous sulfate may be appropriately adjusted as long as it is 10 to 200 g / L. Further, the amount of phenolsulfonic acid may be appropriately adjusted as long as it is 5 to 100 g / L.
In Table 5, those using the present tin plating bath are described as “PSA bath”.
上記工程を経て製造された表面処理鋼板に対し、後処理として、硝酸アルミニウムを主成分とするｐＨ３．０の処理浴中にて陰極電解処理を行い、次いで水洗いを行って乾燥させることで、表面処理鋼板上にアルミニウムの酸化物を主成分とするコーティング層を形成させた（Ａｌの皮膜量が０．００５ｇ／ｍ２）。
コーティング層が形成された表面処理鋼板を温度１９０℃で１０分間の熱処理を行った後に、焼付け乾燥後の塗膜厚が７０ｍｇ／ｄｍ２となるようにエポキシフェノール系塗料を塗装後、温度２００℃で１０分間の焼付けを行うことで、表面処理鋼板上に有機樹脂層を形成してなる有機樹脂被覆鋼板を得た。
As a post-treatment, the surface-treated steel sheet manufactured through the above steps is subjected to a cathodic electrolysis treatment in a pH 3.0 treatment bath containing aluminum nitrate as a main component, followed by washing with water and drying to obtain a surface treatment. A coating layer mainly composed of aluminum oxide was formed on the treated steel sheet (the coating amount of Al was 0.005 g / m 2 ).
After heat-treating the surface-treated steel sheet on which the coating layer has been formed at a temperature of 190 ° C. for 10 minutes, an epoxyphenol-based paint is applied so that the coating thickness after baking and drying is 70 mg / dm 2, and then a temperature of 200 ° C. For 10 minutes to obtain an organic resin-coated steel sheet having an organic resin layer formed on a surface-treated steel sheet.
＜実施例２＞
Ｓｎめっき量を１．４ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Example 2>
Except that the Sn plated amount was 1.4 g / m 2 was carried out in the same manner as in Example 1.
＜実施例３＞
Ｎｉめっき量を０．０３ｇ／ｍ２とした以外は、実施例１と同様に行った。
なお、この実施例３における表面処理層２の表面形態に関するＳＥＭ画像を図６に示す。このＳＥＭ画像は、走査型電子顕微鏡（日本電子社製、ＪＳＭ−６３３０Ｆ）を用いて、加速電圧５ｋＶ、電流１２μＡの条件で表面を観察し、撮像を行って取得した。
<Example 3>
Except that the Ni coating weight was 0.03 g / m 2 was carried out in the same manner as in Example 1.
FIG. 6 shows an SEM image of the surface morphology of the surface treatment layer 2 in Example 3. This SEM image was obtained by observing the surface using a scanning electron microscope (JSM-6330F, manufactured by JEOL Ltd.) under conditions of an acceleration voltage of 5 kV and a current of 12 μA, and imaged.
＜実施例４＞
Ｎｉめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を１．４ｇ／ｍ２とした以外は、実施例１と同様に行った。
なお、この実施例４における表面処理層２の（ａ）表面形態に関するＳＥＭ画像、および（ｂ）脱錫後の表面形態に関するＳＥＭ画像を図７に示す。
さらに、表面処理層２におけるＥＤＸ分析結果とＮＢＤ（Ｎａｎｏ−Ｂｅａｍ−Ｄｉｆｆｒａｃｔｉｏｎ）を用いた結晶構造の解析につき、図８に測定点を示すＴＥＭ像を、表２にその分析結果をそれぞれ示す。なお、このＴＥＭ分析に際しては、日本電子製ＪＥＭ−２０１０Ｆ、ＥＤＸ分析に際しては、ノーラン製ＵＴＷ型Ｓｉ（Ｌｉ）半導体検出器を用いて行った。また、ＮＢＤ分析に際しては、ナノビーム解析（カメラ長５０ｃｍ、測定領域約直径３０ｎｍ）として行った。
また、表２から明らかなとおり、表面処理層２のうち包囲層（表２の他部）は、Ｎｉ−Ｓｎ合金層２１（表２ではＮｉ−Ｓｎ合金部に相当）を囲むように配置されるとともに、特性の異なる２つの層により構成されている。より具体的に本実施例４では、第一包囲層２２としてＦｅ−Ｓｎ合金層であるＦｅＳｎ２層が形成され、この第一包囲層２２（ＦｅＳｎ２層）上に第二包囲層２３としてＳｎ層が形成される形態となっている。
なお図７（ｂ）に示す脱錫後の表面形態を観察すると、図７（ａ）と同様に粒状あるいは針状のＮｉ−Ｓｎ合金層２１が確認され、包囲層はＦｅ−Ｓｎ合金層であることがわかる。腐食の欠点となるピンホールあるいは下地の金属成分（Ｆｅ）の露出は確認されず、外観上からも腐食しにくい構造であることが示唆される。
<Example 4>
Example 1 was repeated except that the amount of Ni plating was 0.03 g / m 2 and the amount of Sn plating was 1.4 g / m 2 .
FIG. 7 shows (a) an SEM image of the surface morphology of the surface treatment layer 2 in Example 4 and (b) an SEM image of the surface morphology after detinning.
Further, regarding the results of the EDX analysis on the surface treatment layer 2 and the analysis of the crystal structure using NBD (Nano-Beam-Diffraction), a TEM image showing measurement points is shown in FIG. The TEM analysis was performed using a JEM-2010F manufactured by JEOL Ltd., and the EDX analysis was performed using a UTW type Si (Li) semiconductor detector manufactured by Nolan. The NBD analysis was performed as a nanobeam analysis (camera length 50 cm, measurement area about 30 nm in diameter).
As is clear from Table 2, the surrounding layer (the other part of Table 2) of the surface treatment layer 2 is arranged so as to surround the Ni—Sn alloy layer 21 (corresponding to the Ni—Sn alloy part in Table 2). In addition, it is composed of two layers having different characteristics. More specifically, in the fourth embodiment, a FeSn 2 layer, which is an Fe—Sn alloy layer, is formed as the first surrounding layer 22, and Sn is formed as the second surrounding layer 23 on the first surrounding layer 22 (FeSn 2 layer). It has a form in which a layer is formed.
When observing the surface morphology after detinning shown in FIG. 7B, a granular or acicular Ni—Sn alloy layer 21 was confirmed as in FIG. 7A, and the surrounding layer was an Fe—Sn alloy layer. You can see that there is. No exposure of pinholes or the underlying metal component (Fe), which is a disadvantage of corrosion, was confirmed, suggesting that the structure is hard to corrode even from the appearance.
＜実施例５＞
Ｎｉめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を１．４ｇ／ｍ２とし、さらに後処理として、フッ化ジルコニウムを主成分とするｐＨ３．０の処理浴中にて陰極電解処理を行い、次いで水洗いを行って乾燥させることにより形成させたＺｒ酸化物（Ｚｒの皮膜量が０．０１ｇ／ｍ２）を用いた以外は、実施例１と同様に行った。
<Example 5>
The amount of Ni plating was set to 0.03 g / m 2 , the amount of Sn plating was set to 1.4 g / m 2, and as a post-treatment, a cathodic electrolysis treatment was performed in a pH 3.0 treatment bath containing zirconium fluoride as a main component. Then, it carried out similarly to Example 1 except having used the Zr oxide (Zr coating amount of 0.01 g / m < 2 >) formed by washing with water and drying.
＜実施例６＞
Ｎｉめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を２．８ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Example 6>
Example 1 was repeated except that the amount of Ni plating was 0.03 g / m 2 and the amount of Sn plating was 2.8 g / m 2 .
＜実施例７＞
Ｎｉめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を２．８ｇ／ｍ２とし、さらに後処理としてＺｒ酸化物を用いた以外は、実施例１と同様に行った。
<Example 7>
Example 1 was repeated except that the Ni plating amount was 0.03 g / m 2 , the Sn plating amount was 2.8 g / m 2, and a Zr oxide was used as a post-treatment.
＜実施例８＞
Ｎｉめっき量を０．１ｇ／ｍ２とし、Ｓｎめっき量を１．４ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Example 8>
Example 1 was repeated except that the amount of Ni plating was 0.1 g / m 2 and the amount of Sn plating was 1.4 g / m 2 .
＜実施例９＞
Ｎｉめっき量を０．２５ｇ／ｍ２とし、Ｓｎめっき量を２．８ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Example 9>
Example 1 was repeated except that the Ni plating amount was 0.25 g / m 2 and the Sn plating amount was 2.8 g / m 2 .
＜実施例１０＞
Ｎｉめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を０．９ｇ／ｍ２とした。後処理として、リン酸およびリン酸二水素ナトリウムを主成分とするｐＨ２．４の処理液中にて陽極電解を行い、水洗を行った。さらに、硝酸アルミニウムを主成分とするｐＨ３．０の処理浴中にて陰極電解処理を行い、次いで水洗いを行って乾燥させることで、表面処理鋼板上にＰ（リン）およびＡｌ（アルミニウム）の酸化物を主成分とするコーティング層を形成させた。コーティング層のＰおよびＡｌの皮膜量は０．００２ｇ／ｍ２および０．００５ｇ／ｍ２とした。上記以外は実施例１と同様に行った。
<Example 10>
The Ni plating amount was 0.03 g / m 2 , and the Sn plating amount was 0.9 g / m 2 . As a post-treatment, anodic electrolysis was performed in a treatment solution of pH 2.4 containing phosphoric acid and sodium dihydrogen phosphate as main components, and washing was performed with water. Further, by performing cathodic electrolytic treatment in a treatment bath containing aluminum nitrate as a main component and having a pH of 3.0, followed by washing with water and drying, oxidation of P (phosphorus) and Al (aluminum) on the surface-treated steel sheet is performed. A coating layer mainly composed of a product was formed. Coating amount of P and Al in the coating layer was 0.002 g / m 2 and 0.005 g / m 2. Except for the above, the procedure was the same as in Example 1.
＜実施例１１＞
Ｎｉめっき量を０．０４ｇ／ｍ２とし、Ｓｎめっき量を１．２ｇ／ｍ２、コーティング層のＰおよびＡｌの皮膜量は０．００２ｇ／ｍ２および０．００５ｇ／ｍ２とした。上記以外は実施例１０と同様に行った。
<Example 11>
Ni plating amount is 0.04g / m 2, Sn plating amount 1.2 g / m 2, coating amount of P and Al in the coating layer was 0.002 g / m 2 and 0.005 g / m 2. Except for the above, the procedure was the same as in Example 10.
＜実施例１２＞
Ｎｉめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を０．９ｇ／ｍ２、コーティング層のＰおよびＡｌの皮膜量は０．００２ｇ／ｍ２および０．０１ｇ／ｍ２とした。上記以外は実施例１１と同様に行った。
<Example 12>
The Ni plating amount was 0.03 g / m 2 , the Sn plating amount was 0.9 g / m 2 , and the coating amounts of P and Al of the coating layer were 0.002 g / m 2 and 0.01 g / m 2 . Except for the above, the procedure was the same as in Example 11.
＜実施例１３＞
Ｎｉめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を１．４ｇ／ｍ２、コーティング層のＰおよびＡｌの皮膜量は０．００２ｇ／ｍ２および０．０１ｇ／ｍ２とした。上記以外は実施例１１と同様に行った。 なお、実施例１２および１３について、ＡＴＣ値の測定を行った。測定値を表５にそれぞれ示す。
<Example 13>
The Ni plating amount was 0.03 g / m 2 , the Sn plating amount was 1.4 g / m 2 , and the coating amounts of P and Al of the coating layer were 0.002 g / m 2 and 0.01 g / m 2 . Except for the above, the procedure was the same as in Example 11. The ATC values of Examples 12 and 13 were measured. Table 5 shows the measured values.
＜比較例１＞
Ｎｉめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を０．３ｇ／ｍ２とした以外は、実施例１と同様に行った。
なお、この比較例１における表面処理層２の（ａ）表面形態に関する模式的な構造図、および（ｂ）表面形態に関するＳＥＭ画像を図９に示す。
さらに、表面処理層２におけるＥＤＸ分析結果とＮＢＤ（Ｎａｎｏ−Ｂｅａｍ−Ｄｉｆｆｒａｃｔｉｏｎ）を用いた結晶構造の解析につき、図１０に測定点を示すＴＥＭ像を、表３にその分析結果をそれぞれ示す。
<Comparative Example 1>
Example 1 was repeated except that the amount of Ni plating was 0.03 g / m 2 and the amount of Sn plating was 0.3 g / m 2 .
FIG. 9 shows (a) a schematic structural diagram of the surface morphology of the surface treatment layer 2 in Comparative Example 1, and (b) an SEM image of the surface morphology.
Further, regarding the results of the EDX analysis on the surface treatment layer 2 and the analysis of the crystal structure using NBD (Nano-Beam-Diffraction), a TEM image showing measurement points is shown in FIG.
＜比較例２＞
Ｎｉめっき量を０．５ｇ／ｍ２とし、Ｓｎめっき量を０．７ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Comparative Example 2>
Example 1 was repeated except that the Ni plating amount was 0.5 g / m 2 and the Sn plating amount was 0.7 g / m 2 .
＜比較例３＞
Ｎｉめっき量を０．５ｇ／ｍ２とし、Ｓｎめっき量を０．４ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Comparative Example 3>
Example 1 was repeated except that the amount of Ni plating was 0.5 g / m 2 and the amount of Sn plating was 0.4 g / m 2 .
＜比較例４＞
Ｎｉめっき量を０．１ｇ／ｍ２とし、Ｓｎめっき量を０．３ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Comparative Example 4>
Example 1 was repeated except that the amount of Ni plating was 0.1 g / m 2 and the amount of Sn plating was 0.3 g / m 2 .
＜比較例５＞
Ｎｉめっき量を０．９ｇ／ｍ２とし、Ｓｎめっき量を１．６ｇ／ｍ２とした以外は、実施例１と同様に行った。
なお、この比較例５における表面処理層２の（ａ）表面形態に関する模式的な構造図、および（ｂ）表面形態に関するＳＥＭ画像を図１１に示す。
<Comparative Example 5>
Example 1 was repeated except that the amount of Ni plating was 0.9 g / m 2 and the amount of Sn plating was 1.6 g / m 2 .
FIG. 11 shows (a) a schematic structural diagram of the surface morphology of the surface treatment layer 2 in Comparative Example 5, and (b) an SEM image of the surface morphology.
＜比較例６＞
Ｎｉめっき量を１．５ｇ／ｍ２とし、Ｓｎめっき量を０．４ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Comparative Example 6>
Example 1 was repeated except that the amount of Ni plating was 1.5 g / m 2 and the amount of Sn plating was 0.4 g / m 2 .
＜比較例７＞
Ｎｉめっき量を１．５ｇ／ｍ２とし、Ｓｎめっき量を２．８ｇ／ｍ２とした以外は、実施例１と同様に行った。
<Comparative Example 7>
Example 1 was repeated except that the amount of Ni plating was 1.5 g / m 2 and the amount of Sn plating was 2.8 g / m 2 .
＜参考例１＞
従来技術の一例として、Ｎｉめっきは行わず、Ｓｎめっき量を２．８ｇ／ｍ２としたＳｎめっきを施した以外は実施例１と同様に行った。
<Reference Example 1>
As an example of the prior art, the same procedure as in Example 1 was performed except that Ni plating was not performed and Sn plating was performed with the Sn plating amount being 2.8 g / m 2 .
＜参考例２＞
従来技術の一例として、Ｎｉめっきについては以下に示す条件のワット浴を用いてＮｉ−Ｆｅのめっき量を０．０３ｇ／ｍ２とし、Ｓｎめっき量を０．９ｇ／ｍ２とし、後処理としてクロメート処理を行った以外は実施例１と同様に行った。
なお、この参考例２における表面処理層２の（ａ）表面形態に関するＳＥＭ画像、および（ｂ）脱錫後の表面形態に関するＳＥＭ画像を図１２に示す。
<Reference Example 2>
As an example of the prior art, for Ni plating, the amount of Ni—Fe plating is set to 0.03 g / m 2 and the amount of Sn plating is set to 0.9 g / m 2 using a Watt bath under the following conditions. The same operation as in Example 1 was performed except that the chromate treatment was performed.
FIG. 12 shows an SEM image of (a) the surface morphology of the surface treatment layer 2 and (b) an SEM image of the surface morphology after detinning in Reference Example 2.
＜ワット浴でのめっき浴およびめっき条件＞
硫酸ニッケル ２４０ｇ／Ｌ
塩化ニッケル ４５ｇ／Ｌ
ホウ酸 ３０ｇ／Ｌ
添加剤（サッカリン等） ２ｇ／Ｌ
ｐＨ ４．０
浴温 ４５℃
電流密度 ５Ａ／ｄｍ２
<Plating bath and plating conditions in Watt bath>
Nickel sulfate 240g / L
Nickel chloride 45g / L
Boric acid 30g / L
Additives (saccharin etc.) 2g / L
pH 4.0
Bath temperature 45 ° C
Current density 5A / dm 2
＜参考例３＞
従来技術の一例として、Ｎｉめっきは行わず、Ｓｎめっき量を１．３ｇ／ｍ２としたＳｎめっきを施し、後処理としてクロメート処理を行った以外は実施例１と同様に行った。
なお、この参考例３における表面処理層２の（ａ）表面形態に関するＳＥＭ画像、および（ｂ）脱錫後の表面形態に関するＳＥＭ画像を図１３に示す。
さらに、表面処理層２におけるＥＤＸ分析結果とＮＢＤ（Ｎａｎｏ−Ｂｅａｍ−Ｄｉｆｆｒａｃｔｉｏｎ）を用いた結晶構造の解析につき、図１４に測定点を示すＴＥＭ像を、表４にその分析結果をそれぞれ示す。
<Reference Example 3>
As an example of the prior art, the same process as in Example 1 was performed except that Ni plating was not performed, Sn plating was performed with a Sn plating amount of 1.3 g / m 2, and chromate treatment was performed as a post-treatment.
FIG. 13 shows (a) an SEM image of the surface morphology of the surface treatment layer 2 in Reference Example 3 and (b) an SEM image of the surface morphology after detinning.
Further, regarding the results of the EDX analysis of the surface treatment layer 2 and the analysis of the crystal structure using NBD (Nano-Beam-Diffraction), a TEM image showing measurement points is shown in FIG.
また、参考例２および３について、ＡＴＣ値の測定を行った。測定値を表５にそれぞれ示す。なお、ＡＴＣ値とは、酸性食品中での耐食性を示す値である。 The ATC values of Reference Examples 2 and 3 were measured. Table 5 shows the measured values. The ATC value is a value indicating the corrosion resistance in an acidic food.
＜ＡＴＣ値の測定方法＞
表面処理板の金属Ｓｎ（フリーＳｎ）を水酸化ナトリウム水溶液中で電解を行うことにより溶解させ、合金層を露出した試験片を作製した。試験液として、グレープフルーツ（サントリー製サンフェスタグレープフルーツ１００）１３００ｍｌを蒸留水２００ｍｌで薄め、塩化第一錫０．２８５ｇおよびソルビン酸カリウム０．９ｇを添加熟成後、試験液とした。試験液中で試験片とＳｎとをカップルさせ窒素ガス雰囲気中、２７℃で２０時間後のカップル電流を測定した。
<Method of measuring ATC value>
Metal Sn (free Sn) of the surface-treated plate was dissolved by performing electrolysis in an aqueous sodium hydroxide solution to prepare a test piece with the alloy layer exposed. As a test solution, 1300 ml of grapefruit (Sunfesta Grapefruit 100 manufactured by Suntory) was diluted with 200 ml of distilled water, and 0.285 g of stannous chloride and 0.9 g of potassium sorbate were added and aged, and the test solution was obtained. The test piece and Sn were coupled in the test solution, and the couple current after 20 hours at 27 ° C. in a nitrogen gas atmosphere was measured.
以上の各実施例、比較例および参考例では、次に示す手法にて皮膜量の測定や表面形態の観察、各種評価を行った。
＜ＮｉおよびＳｎの皮膜量測定＞
表面処理鋼板のＮｉおよびＳｎの皮膜量は、蛍光Ｘ線装置（蛍光Ｘ線分析装置（リガク社製、ＺＳＸ１００ｅ）により測定した。
In each of the above examples, comparative examples, and reference examples, measurement of the amount of the film, observation of the surface morphology, and various evaluations were performed by the following methods.
<Measurement of Ni and Sn film amount>
The amounts of Ni and Sn films on the surface-treated steel sheet were measured by a fluorescent X-ray apparatus (X-ray fluorescent analyzer (ZSX100e, manufactured by Rigaku Corporation)).
＜表面形態の測定（観察）方法＞
表面処理層の表面形態は、ＳＥＭ（走査型電子顕微鏡）を用いた観察により行った。
析出粒子の構成はＴＥＭ（透過型電子顕微鏡）を用いた断面観察にて行った。
表面処理層中に存在する化合物の同定は結晶回折により行った。また、ＴＥＭ−ＥＤＸ（エネルギー分散型Ｘ線分光法）での点分析にて、表面処理層中に存在するＮｉ、ＳｎおよびＦｅの定量分析を行った。
<Surface morphology measurement (observation) method>
The surface morphology of the surface treatment layer was determined by observation using a scanning electron microscope (SEM).
The configuration of the precipitated particles was determined by cross-sectional observation using a TEM (transmission electron microscope).
The compound present in the surface treatment layer was identified by crystal diffraction. Further, quantitative analysis of Ni, Sn and Fe present in the surface treatment layer was performed by point analysis using TEM-EDX (energy dispersive X-ray spectroscopy).
＜塗料密着性および耐食性の評価方法＞
得られた有機樹脂被覆鋼板について、モデル液中での塗料密着性および耐食性を評価した。なお、モデル液としては、酢酸０．５重量％および塩化ナトリウム（食塩）１．５重量％の混合水溶液、酢酸０．５％重量％水溶液、およびクエン酸１．５％と塩化ナトリウム（食塩）１．５重量％の混合水溶液を用いた。
より具体的には、表面処理鋼板に有機樹脂層を形成してなる有機樹脂被覆鋼板を用いて絞り比２．０の浅絞り缶（容器）を作製し、缶側壁部に基材に達するキズ（クロスカット）を付与した。その後、モデル液中にて温度１２５℃で３０分間のレトルト処理を行った後、３７℃環境下で２週間経時した。２週間経時後のクロスカット周囲の腐食状況を目視にて観察し、以下の基準で評価した。
<Method for evaluating paint adhesion and corrosion resistance>
With respect to the obtained organic resin-coated steel sheet, paint adhesion and corrosion resistance in a model liquid were evaluated. Examples of the model liquid include a mixed aqueous solution of 0.5% by weight of acetic acid and 1.5% by weight of sodium chloride (salt), an aqueous solution of 0.5% by weight of acetic acid, and 1.5% of citric acid and sodium chloride (salt). A 1.5% by weight mixed aqueous solution was used.
More specifically, a shallow drawn can (container) having a draw ratio of 2.0 is produced using an organic resin-coated steel sheet obtained by forming an organic resin layer on a surface-treated steel sheet, and a scratch reaching the base material on the side wall of the can. (Cross cut). After that, a retort treatment was performed in a model solution at a temperature of 125 ° C. for 30 minutes, and then aged for 2 weeks in a 37 ° C. environment. The corrosion state around the cross cut after a lapse of 2 weeks was visually observed and evaluated according to the following criteria.
［塗料密着性評価］
塗料密着性評価は、後述する全ての実施例及び比較例について行った。
３点：目視で判定した結果、塗料の剥離がクロスカット部より２ｍｍ以内であった。
２点：目視で判定した結果、塗料の剥離がクロスカット部より２ｍｍを超え５ｍｍ以内で認められた。
１点：目視で判定した結果、塗料の剥離がクロスカット部より５ｍｍを超える範囲で認められた。
なお、塗料密着性の評価において、上記基準で評価が２点以上である場合には、かような表面処理鋼板を、飲食缶用途として用いた際に十分な塗料密着性を有するものであると判断した。
[Coating adhesion evaluation]
The paint adhesion evaluation was performed for all Examples and Comparative Examples described below.
3 points: As a result of the visual judgment, the peeling of the paint was within 2 mm from the cross cut portion.
2 points: As a result of visual judgment, peeling of the paint was recognized in a range of more than 2 mm and less than 5 mm from the cross cut portion.
1 point: As a result of visual judgment, the peeling of the paint was recognized in a range exceeding 5 mm from the cross cut portion.
In addition, in the evaluation of paint adhesion, if the evaluation is 2 or more in the above criteria, such a surface-treated steel sheet, when used as a food and beverage cans, it has sufficient paint adhesion It was judged.
［耐食性評価］
耐食性評価は、全ての実施例及び比較例について行った。
３点：目視で判定した結果、参考例２と比較して腐食の程度が同等であった。
２点：目視で判定した結果、参考例２と比較して腐食の程度がわずかに大きかった。
１点：目視で判定した結果、参考例２と比較して明らかに腐食の程度が大きかった。
なお、耐食性の評価においては、上記基準で評価が２点以上である場合に、表面処理鋼板を、飲食缶用途として用いた際に十分な耐食性を有するものであると判断した。
[Corrosion resistance evaluation]
The corrosion resistance evaluation was performed for all Examples and Comparative Examples.
3 points: As a result of visual judgment, the degree of corrosion was equivalent to that of Reference Example 2.
2 points: As a result of visual judgment, the degree of corrosion was slightly larger than that in Reference Example 2.
1 point: As a result of visual judgment, the degree of corrosion was clearly higher than that of Reference Example 2.
In the evaluation of corrosion resistance, it was determined that the surface-treated steel sheet had sufficient corrosion resistance when used for food and drink cans when the evaluation was 2 or more according to the above criteria.
＜溶接性の評価方法＞
有機樹脂被覆鋼板又は表面処理鋼板の溶接性は、表面抵抗を測定することにより評価した。より具体的には、例えば表面処理鋼板に接触荷重100gfを負荷し、負荷から除荷に至る１サイクルの中で、設定荷重（例えば１００ｇｆ）到達時にその抵抗を測定した。測定に際しては、（株）山崎精機研究所製の電気接点シミュレーターＣＲＳ−１５３−ＡＵ型を用いて行った。
なお溶接性評価は全ての実施例及び比較例について行った。
３点：抵抗値で判定した結果、参考例２と比較して同等かそれ以下であった。
２点：抵抗値で判定した結果、参考例２と比較して抵抗値が２倍以内であった。
１点：抵抗値で判定した結果、参考例２と比較して抵抗値が２倍を超えた。
なお、溶接性の評価においては、上記基準で評価が３点以上である場合に、表面処理鋼板を、飲食缶用途として用いた際に十分な溶接性を有するものであると判断した。
<Weldability evaluation method>
The weldability of the organic resin-coated steel sheet or the surface-treated steel sheet was evaluated by measuring the surface resistance. More specifically, for example, a contact load of 100 gf was applied to a surface-treated steel sheet, and the resistance was measured when a set load (for example, 100 gf) was reached in one cycle from loading to unloading. The measurement was performed using an electric contact simulator CRS-153-AU manufactured by Yamazaki Seiki Laboratory Co., Ltd.
The evaluation of the weldability was performed for all Examples and Comparative Examples.
3 points: As a result of the judgment based on the resistance value, it was equal to or less than that of Reference Example 2.
2 points: As a result of the judgment based on the resistance value, the resistance value was within 2 times as compared with Reference Example 2.
1 point: As a result of the judgment based on the resistance value, the resistance value was more than double as compared with Reference Example 2.
In the evaluation of weldability, it was determined that the surface-treated steel sheet had sufficient weldability when used for food and drink cans when the evaluation was 3 or more according to the above criteria.
以上説明した各実施例、比較例および参考例に関する材料と皮膜量、表面形態を表５に示すとともに、各種評価の結果を表６に示す。耐食性評価はモデル液での評価であり、従来技術（参考例１から３）では適用されていない内容物もある。本発明で得られた表面処理板のＡＴＣ値は比較例２および３よりも小さく、耐食性に優れることが示された。今回用いたモデル液での評価以外でも本発明が耐食性に優れることが示唆されるものである。 Table 5 shows the materials, film amounts, and surface morphologies for each of the examples, comparative examples, and reference examples described above, and Table 6 shows the results of various evaluations. The corrosion resistance evaluation is an evaluation using a model liquid, and there are some contents that are not applied in the related art (Reference Examples 1 to 3). The ATC value of the surface-treated plate obtained in the present invention was smaller than Comparative Examples 2 and 3, indicating that it had excellent corrosion resistance. It is suggested that the present invention is excellent in corrosion resistance other than the evaluation using the model liquid used this time.
実施例は写真のような粒子が確認されたが、比較例および参考例では確認されていない。表面処理鋼板の表面に存在する金属錫をアルカリ溶液中にて電解処理を行い、金属錫を溶解させた場合の合金層の形態を写真に示す。これにおいても、実施例は写真のような粒子が確認されたが、比較例および参考例では確認されていない。 In Examples, particles as shown in the photograph were confirmed, but not in Comparative Examples and Reference Examples. The photograph shows the form of the alloy layer when the metal tin existing on the surface of the surface-treated steel sheet is subjected to electrolytic treatment in an alkaline solution to dissolve the metal tin. Also in this example, particles as in the photograph were confirmed in the examples, but were not confirmed in the comparative examples and the reference examples.
なお上記した実施形態と各実施例は、本発明の趣旨を逸脱しない範囲で種々の変形が可能である。 The above-described embodiment and each example can be variously modified without departing from the spirit of the present invention.
以上説明したように、本発明の表面処理鋼板、有機樹脂被覆鋼板およびそれを用いた容器は、耐食性、塗料密着性および溶接性を同時に高い次元で備えており、広い分野の産業への適用が可能である。 As described above, the surface-treated steel sheet, the organic resin-coated steel sheet and the container using the same of the present invention have corrosion resistance, paint adhesion and weldability at the same time at a high level, and are applicable to a wide range of industries. It is possible.
１ 基材
２ 表面処理層
２１ Ｎｉ−Ｓｎ合金層
２２ 第一包囲層
２３ 第二包囲層
３ コーティング層
４ 有機樹脂層
ＳＴ 表面処理鋼板
ＲＴ 有機樹脂被覆鋼板
Ｃ 容器
DESCRIPTION OF SYMBOLS 1 Base material 2 Surface treatment layer 21 Ni-Sn alloy layer 22 First surrounding layer 23 Second surrounding layer 3 Coating layer 4 Organic resin layer ST Surface treated steel sheet RT Organic resin coated steel sheet C Container
Claims (11)
前記基材上に形成されるとともに、粒状又は針状のＮｉ−Ｓｎ合金層と、前記Ｎｉ−Ｓｎ合金の他部に配置されるＦｅ−Ｓｎ合金層及びＳｎ層とを含む表面処理層と、
を備え、
前記表面処理層において、前記Ｎｉ−Ｓｎ合金層は、前記Ｆｅ−Ｓｎ合金層及び前記Ｓｎ層に囲まれていることを特徴とする表面処理鋼板。 A substrate,
Formed on the base material, a granular or acicular Ni-Sn alloy layer, and a surface treatment layer including an Fe-Sn alloy layer and a Sn layer disposed on the other part of the Ni-Sn alloy,
Equipped with a,
The surface-treated steel sheet , wherein in the surface-treated layer, the Ni-Sn alloy layer is surrounded by the Fe-Sn alloy layer and the Sn layer .
前記Ｆｅの含有率が１０ａｔ％以下である請求項１又は２に記載の表面処理鋼板。 The Ni-Sn alloy further contains Fe with its structure is mainly Ni 3 Sn 4,
The surface-treated steel sheet according to claim 1 or 2, wherein the Fe content is 10 at% or less.
前記Ｎｉ層が形成された基材に対してＳｎめっきを行うことで、前記Ｎｉ層上にＳｎ層を形成する工程と、
前記Ｎｉ層および前記Ｓｎ層が形成された基材に対して溶融加熱処理を行うことで、粒状又は針状のＮｉ−Ｓｎ合金層と、前記Ｎｉ−Ｓｎ合金を囲むように配置するＦｅ−Ｓｎ合金層及びＳｎ層とを含む表面処理層を前記基材上に形成する工程と、
を含むことを特徴とする表面処理鋼板の製造方法。 Performing a Ni plating on the base material to form a Ni layer precipitated in a granular form on the base material;
Forming a Sn layer on the Ni layer by performing Sn plating on the substrate on which the Ni layer is formed;
By performing a melting heat treatment on the base material on which the Ni layer and the Sn layer are formed, a granular or acicular Ni—Sn alloy layer and Fe—Sn disposed so as to surround the Ni—Sn alloy Forming a surface treatment layer including an alloy layer and a Sn layer on the base material;
A method for producing a surface-treated steel sheet, comprising:
〜０．３ｇ／ｍ２であり、
前記ＳｎめっきにおけるＳｎめっき量は、０．４〜３．０ｇ／ｍ２である請求項１０に記載の表面処理鋼板の製造方法。 The amount of Ni plating in the Ni plating is 0.01
０．３0.3 g / m 2 ,
Sn plating amount in the Sn plating, a method for producing a surface-treated steel sheet according to claim 10 which is 0.4~3.0g / m 2.
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