CN105874107A - Surface-treated steel sheet, organic-resin-coated metal container, and method for producing surface-treated steel sheet - Google Patents
Surface-treated steel sheet, organic-resin-coated metal container, and method for producing surface-treated steel sheet Download PDFInfo
- Publication number
- CN105874107A CN105874107A CN201480069019.XA CN201480069019A CN105874107A CN 105874107 A CN105874107 A CN 105874107A CN 201480069019 A CN201480069019 A CN 201480069019A CN 105874107 A CN105874107 A CN 105874107A
- Authority
- CN
- China
- Prior art keywords
- steel plate
- treated steel
- surface treated
- layer
- group
- 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 207
- 239000010959 steel Substances 0.000 title claims abstract description 207
- 229920005989 resin Polymers 0.000 title claims abstract description 103
- 239000011347 resin Substances 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title abstract description 26
- 239000002184 metal Substances 0.000 title abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 57
- 239000011737 fluorine Substances 0.000 claims abstract description 55
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 127
- 239000010410 layer Substances 0.000 claims description 108
- 230000008569 process Effects 0.000 claims description 95
- 239000007864 aqueous solution Substances 0.000 claims description 52
- 239000011575 calcium Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910052791 calcium Inorganic materials 0.000 claims description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 11
- 239000007921 spray Substances 0.000 claims description 4
- 239000003595 mist Substances 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 31
- 238000005260 corrosion Methods 0.000 abstract description 31
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000002335 surface treatment layer Substances 0.000 abstract 2
- 238000010828 elution Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 45
- 230000006978 adaptation Effects 0.000 description 35
- 230000033228 biological regulation Effects 0.000 description 34
- 238000005868 electrolysis reaction Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 27
- 239000012530 fluid Substances 0.000 description 26
- 238000012545 processing Methods 0.000 description 23
- 150000002500 ions Chemical class 0.000 description 22
- 238000004090 dissolution Methods 0.000 description 21
- 239000000126 substance Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 16
- 229960005069 calcium Drugs 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229920001225 polyester resin Polymers 0.000 description 15
- 239000004645 polyester resin Substances 0.000 description 15
- -1 hexafluoro silicon Chemical compound 0.000 description 13
- 230000008859 change Effects 0.000 description 11
- 150000002222 fluorine compounds Chemical class 0.000 description 11
- 229940091250 magnesium supplement Drugs 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 150000002927 oxygen compounds Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 230000001105 regulatory effect Effects 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000010030 laminating Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000010025 steaming Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 6
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 208000037656 Respiratory Sounds Diseases 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 238000004876 x-ray fluorescence Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 235000010384 tocopherol Nutrition 0.000 description 4
- 229960001295 tocopherol Drugs 0.000 description 4
- 229930003799 tocopherol Natural products 0.000 description 4
- 239000011732 tocopherol Substances 0.000 description 4
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 3
- 239000001527 calcium lactate Substances 0.000 description 3
- 235000011086 calcium lactate Nutrition 0.000 description 3
- 229960002401 calcium lactate Drugs 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 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 2
- NNEUOGCLWCDYQM-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione;terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.O=C1OCCOC(=O)C2=CC=CC1=C2 NNEUOGCLWCDYQM-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 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 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
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910003134 ZrOx Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- GOZLPQZIQDBYMO-UHFFFAOYSA-N azanium;zirconium;fluoride Chemical compound [NH4+].[F-].[Zr] GOZLPQZIQDBYMO-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229940058494 beryllium Drugs 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical group [Be] ATBAMAFKBVZNFJ-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
- 238000005266 casting Methods 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 239000001755 magnesium gluconate Substances 0.000 description 2
- 235000015778 magnesium gluconate Nutrition 0.000 description 2
- 229960003035 magnesium gluconate Drugs 0.000 description 2
- IAKLPCRFBAZVRW-XRDLMGPZSA-L magnesium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate;hydrate Chemical compound O.[Mg+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IAKLPCRFBAZVRW-XRDLMGPZSA-L 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052705 radium Inorganic materials 0.000 description 2
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910019979 (NH4)2ZrF6 Inorganic materials 0.000 description 1
- 229910019977 (NH4)2ZrO Inorganic materials 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910003899 H2ZrF6 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020148 K2ZrF6 Inorganic materials 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910020900 Sn-Fe Inorganic materials 0.000 description 1
- 229910019314 Sn—Fe Inorganic materials 0.000 description 1
- 229910008998 Sn—Ni—Fe Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000001055 magnesium Nutrition 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000004337 magnesium citrate Substances 0.000 description 1
- 229960005336 magnesium citrate Drugs 0.000 description 1
- 235000002538 magnesium citrate Nutrition 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229960003390 magnesium sulfate Drugs 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002541 mycostatic Substances 0.000 description 1
- 230000001557 mycostatic effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000013138 pruning Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
- C23C22/62—Treatment of iron or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- 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
-
- 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
-
- 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
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The present invention pertains to a surface-treated steel sheet and to a method for producing the same, and is a surface-treated steel sheet which has a surface treatment layer containing fluorine and composed principally of zirconium and oxygen formed on at least one surface of the steel sheet, wherein, due to the presence of a Group II element on the surface side of the surface treatment layer, it is possible to provide a metal container having exceptional corrosion resistance and adhesion to an organic resin coating, as well as exceptional adhesion to the resin on a can outer surface, and resistance to fluorine elution.
Description
Technical field
The present invention relates to surface treated steel plate, organic resin cover surface treated steel plate, canister and
The manufacture method of surface treated steel plate.More particularly it relates to be characterized as excellence to organic resin
The adaptation of cover layer and the surface treated steel plate of excellent resistance to stripping property, and its manufacture method.
Background technology
Hitherto known use in the field of household electrical appliance, construction material, vehicle, airborne vehicle and container etc.
Chromate process as the process being used for improving adaptation between steel plate and organic coating layer, therefore by
It is widely used in corrosion resistance and the adaptation of its excellence.
The process using chromate relates to comprising chromic one in overlay film and not comprising in overlay film
Chromic one.But, in recent years, from environment and the viewpoint of work hygiene, the trend of increase is not
The state of pipe final products, prohibits the use of and comprises chromic any parent material.
Naturally, the manufacture materials'use of the canister of such as tank and lid etc. does not remains
The chromate of chromic type processes.In addition, material generally uses organic resin to cover.
Such as, by tin plate catholyte in the aqueous solution of sodium dichromate, by steel plate in the nothing of fluoride
Catholyte in water chromic acid aqueous solution, and use chromium phosphate to process aluminium alloy, the most then make
Cover with organic resin.
Under many circumstances, in order to be sterilized by content, the canister of such as tank and cover etc. makes
Process with the steaming and decocting of hot water.Therefore, material experience severe rugged environment cause resin coating layer and metal surface it
Between adaptation reduce problem.Therefore, in order to solve this problem, various research has been carried out so far.Mesh
Before, use the adaptation during hot water treatment to improve, will be used as producing the plating of the material of tank
Sheet tin and the steel plate using electrolysis chromic acid to process use warm water or hot water in the final step processing surface
Clean.That is, control process cover layer in such as sulfate ion and fluorion etc. anion from
And obtain metal surface (non-patent literature 1, the patent literary composition of the adaptation to organic overlay film being characterized as excellence
Offer 2).
Chrome-free surface as the research in recent years relevant to steel plate processes, it has been proposed that uses and comprises
The impregnation process (patent documentation 1) of the treatment fluid of Zr (zirconium) or Ti (titanium).But, by being immersed in containing Zr or
The cover layer of the steel plate processing its surface in the solution of Ti has poor corrosion resistance.In addition, with so far
The steel plate (TFS) of the electrolysis chromic acid process that the present already functions as the material for producing tank is compared, the analysis of overlay film
Go out speed little.Therefore, productivity is excessively poor.Accordingly, as the high speed processing of replacement impregnation process,
Processed and/or Al process by Zr and/or Ti of application catholyte through proposing.It is known that this two
Plant and process oxygen compound (patent documentation 3,4 and that can form metal with high speed on the surface of base material
5)。
Further, as improving the overlay film of oxygen compound of the metal side to the adaptation of organic resin layer
Method, it has been proposed that about the oxygen compound of the metal by forming the oxygen compound comprising Zr on base material
Overlay film and use the hot water of more than 80 DEG C to clean the surface of overlay film of oxygen compound of metal and manufacture
The technology of the method for steel plate for container, described steel plate for container has and comprises 1 to 100mg/m2The Zr of amount
And 0.1mg/m2The conversion processing film (conversion-treated film) (patent documentation 6) of the F of following amount.
Prior art literature:
Patent documentation:
Patent documentation 1: international publication WO2002/103080
Patent documentation 2:JP-A-7-11483
Patent documentation 3:JP-A-2004-190121
Patent documentation 4:JP-A-2005-97712
Patent documentation 5:JP-A-2006-348360
Patent documentation 6: international publication WO2012/036200
Non-patent literature:
Non-patent literature 1: " history (the History of Coated Steel of Japan's plate for surface treatment plate for can
Sheets for Cans in Japan) ", Foundation, Japanese Association of Steels, 1998
On October 30, in publishes, and page 87 last column is to page 90.
Summary of the invention
The problem that invention is to be solved
If attempting to be formed without thereon the coat of metal, and instead, at metal base directly on a surface
Form the situation of the overlay film of the oxygen compound of the metal of the oxygen compound mainly comprising such as Zr, Al or Ti etc.
The lower corrosion resistance improving metal base, becomes desirable for increasing the thickness (quilt of overlay film compared with the coat of metal
The amount of covering).Specifically, in the purposes of the seamless tank of big degree of finish, bedding iron can reveal due to processing
Go out or the adaptation of organic resin can be reduced.Therefore, promoted by increase amount of coating guarantee
Corrosion resistance, has simultaneously facilitated the adaptation improved organic resin.
Except relevant to adaptation to begin a project in addition to, still there is other that the invention solves the problems that and ask
Topic, i.e. prevent the component dissolution constituting canister to content.For canister, extremely important
The quality being to maintain content, therefore, it is necessary to special concern can from canister dissolution to content
Component.Generally, the representative of the dissolution of the metal component of container can be the dissolution owing to corroding the ferrum caused
Dissolution with the anion of such as sulfate ion and fluorion etc. in overlay film.Therefore, in except paying close attention to
Beyond tolerant pH and sterilization conditions, it is necessary to focus on the amount of coating in Treatment of Metal Surface, apparent condition
Closing force with the organic resin cover layer to such as film or film etc..
Patent document 2 discloses that by using hot water to clean the oxygen compound of metal on the coat of metal
The example of adaptation is improved on the surface of overlay film.But, form big amount of coating in requirement as mentioned above
In the case of, it was found that, have been used to be electrolysed the cleaning deficiency using hot water of chromic acid treated steel sheet so far
To realize surface treatment characteristics and suppression dissolution on demand.Therefore, it is applied to if electrolysis chromic acid processes line
Form the overlay film of the oxygen compound of metal, then, compared with traditional method, cleaning must carry out the longer time.
Hence, it is recognised that still there is a lot of problem, such as relevant to production load increases and energy expenditure
Amount increases, applies the speed of operation of surface disposing line to limit, need increase cleaning groove number and increase
Have to use for hot water amount.
Therefore, it is made that the present invention in this case, and its objective is that organic resin layer is worked as in offer
When being formed in its surface, it is characterized by the adaptation to organic resin layer of excellence and the corrosion-resistant of excellence
The surface treated steel plate of property；The surface treated steel plate covered with organic resin；There is provided and it is characterized by excellence
The adaptation of the resin on the surfaces externally and internally of tank and the organic resin of excellent fluorine-resistant stripping property are covered
Canister；With the manufacture method providing surface treated steel plate.
For solving the scheme of problem
According to the present invention, it is provided that a kind of surface treated steel plate, described surface treated steel plate have steel plate and
Surface-treated layer at least one surface of described steel plate, described surface-treated layer comprise zirconium, oxygen and
Fluorine, wherein said surface-treated layer comprises group il elements in its face side.
In the surface treated steel plate of the present invention, it is intended that
(1) described group il elements exists as fluorine compounds；
(2) described group il elements is at least one of calcium or magnesium；
(3) mol ratio AE/Zr of the group il elements in described surface-treated layer (AE) and zirconium (Zr) is 0.2
Above；With
(4) the weight thickness of the zirconium in described surface-treated layer is 100 to 200mg/m2。
According to the present invention, further, it is provided that the surface treated steel plate that a kind of organic resin covers, it leads to
Cross and on described surface treated steel plate, form organic resin coating layer obtain.
According to the present invention, further, it is provided that a kind of canister or cover, it is by described organic resin
The surface treated steel plate covered is made.
According to the present invention, further, it is provided that the manufacture method of a kind of surface treated steel plate, described surface
Process steel plate and there is steel plate and the surface-treated layer at least one surface of described steel plate, described surface
Process layer and comprise zirconium, oxygen and fluorine, said method comprising the steps of:
Overlay film is formed by steel plate described in catholyte in comprising the aqueous solution of Zr ion and F ion；
With
Afterwards, the surface modulation aqueous solution comprising group il elements by use carries out impregnation process, spray
More than any one of mist process or catholyte process regulate surface.
Manufacture method at the surface treated steel plate of the present invention, it is intended that
(1) described group il elements is at least one of calcium or magnesium；With
(2) regulation surface step in, the slip of the fluorine carrying out the step of self-forming overlay film be 30% with
Under.
The effect of invention
The present invention can provide when organic resin layer is formed in its surface, it is characterized by excellence to having
The adaptation of machine resin bed and the surface treated steel plate of excellent corrosion resistance；The table covered with organic resin
Face processes steel plate；The canister that organic resin as container covers can be provided, it is characterized by excellence
Fluorine-resistant stripping property, the excellent adaptation to organic resin and the corrosion resistance of excellence；Further, energy
The manufacture method of surface treated steel plate is enough provided.
In the present invention, specifically, the fluorine compounds making group il elements and specifically group il elements are deposited
It is in the face side of surface-treated layer.Therefore, fluorine is insoluble and suppresses dissolution.In addition, surely
Determine the structure of surface-treated layer, and do not made zirconium dissolve, and lacking of whole surface-treated layer can have been reduced
The portion of falling into.
Further, when being processed or during heat treatment, the organic tree formed from the teeth outwards can effectively be prevented
Lipid layer is peeled off.Therefore, the invention provides surface treated steel plate, even if it is at organic resin layer crackle also
And metal surface expose under wet environment in the case of also be not easy corrosion and suppress constitute container gold
Belong to the dissolution of component；Provide the canister using the organic resin of described surface treated steel plate to cover；
And provide the manufacture method of surface treated steel plate.
In the manufacture method of the surface treated steel plate of the present invention, the step on regulation surface is comprised by use
The surface modulation aqueous solution of group il elements implements what impregnation process, spraying treatment or catholyte processed
More than any one.Therefore, the electrolysis chromic acid steel plate using hot water to clean so far can use warm water now
Or normal-temperature water cleans so that the process time can be shortened compared with when only using hot water to be carried out
And reduce energy charge.
Additionally, by using through using the surface modulation aqueous solution comprising group il elements to regulate surface
Step, different from when using hot water to clean steel plate, do not remove the fluorine in overlay film and be expelled to ring
In border, but instead, the fluorine in overlay film and group il elements are reacted thus insoluble in overlay film.Therefore,
In the step forming overlay film, suppress to be less than 30% by the slip of the fluorine in surface treated steel plate,
Funing tablet in draining reduces, and drainage load reduces.Therefore while excellently maintaining environment
Provide the manufacture method of surface treated steel plate.
Accompanying drawing explanation
[Fig. 1] be illustrate as by use x-ray photoelectron spectroscopy instrument try to achieve in the depth direction this
The figure of the change of the atomic concentration in surface-treated layer on the surface treated steel plate of invention.
[Fig. 2] be illustrate as by use x-ray photoelectron spectroscopy instrument try to achieve in the depth direction than
The figure of the change of the atomic concentration in surface-treated layer on the relatively surface treated steel plate of example 4.
[Fig. 3] is the figure of the cross section structure of the surface treated steel plate schematically indicating that the present invention.
Detailed description of the invention
The surface treated steel plate of the present invention has at least one surface of steel plate and mainly comprises zirconium and oxygen
And comprising the surface-treated layer of fluorine, the most important feature is that group il elements is contained in surface and processes
In the face side of layer.
In the surface treated steel plate of the present invention, the group ii unit being contained in the face side of surface-treated layer
Element and fluorine compounds can be according to such as x-ray photoelectron spectroscopy (XPS), Auger electronics photometry (AES)
Or the various surface analyses of analytical electron microscope (SEM, TEM) etc. or cross-section analysis confirm.
As it has been described above, as shown in Fig. 3, the surface treated steel plate 1 obtained by the present invention is at steel plate 2
On at least one surface (being two surfaces in the drawings), there is surface-treated layer 3.Surface-treated layer 3 is at its table
Face comprises group il elements on side, specifically, and the fluorine compounds of group il elements.Normally, on surface
Process formation organic resin layer on layer 3 thus obtain the material of the canister being then used as such as tank etc.
The surface treated steel plate that organic resin covers.
The surface treated steel plate below describing the present invention, the organic resin using this surface treated steel plate cover
Container and the manufacture method of this surface treated steel plate.
(surface treated steel plate)
Surface-treated layer is formed on the surface treated steel plate of the present invention, mainly comprises zirconium and oxygen, comprises fluorine,
And think that supposition is such as ZrOx(OH)y-zFzAmorphism structure.Overlay film dehydrogenation when being dried and firing,
Removing F, being changed into the oxidation overlay film with a lot of crystallographic component, if heated further, the most finally becoming
For close to ZrO2Overlay film.But, the superheated in the thermal history that common tank material accepts is due to knot
The change of structure causes the crackle in overlay film and makes overlay film become more like pottery, not only causes processability to drop
Low, also cause the adaptation to resin coating layer to reduce, this is less desirable.Further, if F
Measure and substantially reduce in surface-treated layer, even if then the structure of overlay film tends to owing to use hot water etc. cleans
The most easily changed by the heating of slight degree, cause the cohesiveness of overlay film to reduce, cause at cross-hatching
The corrosion resistance of the metallic plate that the resin in test covers reduces, and causes the feelings impacted at tank body
Under condition, corrosion or adaptation reduce.
Accordingly, it is desirable to surface-treated layer keep comprise F and OH such as ZrOx(OH)y-zFzStructure.
The present inventor studies the overlay film component of the amount etc. of the amount of such as Zr, F the most for a long time, steaming and decocting processes
After draw lattice corrosion resistance and to the relation between the adaptation of cover layer resin.As a result, the present inventor is
It is found that the surface comprising a lot of zirconium and fluorine processes overlay film to realize above properties effective.
But, about fluorine, if the surface treated steel plate that significant amount comprises F in overlay film is for producing
Canister, the fluorine being present in the most in a large number in surface-treated layer is when by tank cooking disinfection or at high temperature storing
Dissolution is in content, and can damage the local flavor of content.On the other hand, if by overlay film
Fluorine is forced to remove by such as using hot water to clean, then surface treated steel plate is can easily cause overlay film
The placement of the state of structure change, causes the performance of such as corrosion resistance and adaptation etc. to reduce.Therefore,
When processing the surface treated steel plate of the present invention, by the process suppression fluorine for regulating surface from surface
Reason overlay film dissolution is effective at both performances aspect of the local flavor and holding canister that keep content.
On the other hand, if the amount of zirconium is little, then during defective part is present in surface process overlay film in a large number；That is,
Overlay film easily makes the ferrum dissolution of composition base material.Ferrum is dissolution in anode reaction.But, owing to resisting as it
Weighing apparatus reaction cathode reaction, alkali be formed at cover layer resin and metal film coated between interface on.Formed
Alkali promotes fluorine and processes overlay film dissolution from surface, and becomes between cover layer resin and surface-treated layer
The reason of interface peel.Therefore, after cooking disinfection, lattice corrosion resistance and to cover layer resin close are drawn
The viewpoint of conjunction property, it is desirable to use the surface comprising zirconium in a large number to process overlay film.
In the surface treated steel plate of the present invention, process on surface fluorine in overlay film with at surface modulation water
Group il elements reaction in solution, so that wherein the thawless fluorine compounds of fluorine are formed in face side.
Therefore, create after a while by the effect suppressing fluorine dissolution described and the defective part in surface-treated layer
The effect reduced.Therefore, although the amount of Zr is less than prior art, the surface treated steel plate of the present invention remains to
Enough keep corrosion resistance and adaptation.
For the amount of coating in the surface-treated layer on the surface treated steel plate of the present invention, it is desirable to
The amount of Zr is at 10 to 350mg/m2Scope.If the amount of Zr is less than 10mg/m2, then become to be difficult to
Realize drawing lattice corrosion resistance or filling and realize resin in sub-degree to tank after using organic resin to cover
The adaptation of surfaces externally and internally.On the other hand, more than 350mg/m2The use of Zr of amount be uneconomic,
In addition, cause adaptation during processing correspondingly to reduce, and be not desired.
The amount expecting F is 0.3 to 30mg/m2.If the amount of F is more than 30mg/m2Although, then in face side
The layer of the compound of upper formation group il elements, still becomes the dissolution being difficult to suppress fluorine.On the other hand, as
Really the amount of F is less than 0.3mg/m2, then the cohesiveness of overlay film affected by hydration due to the change of structure and
Reducing, therefore, cause adaptation and corrosion resistance to reduce, this is less desirable.
As the group il elements being contained in the surface of surface-treated layer by the process on regulation surface, can
With example is beryllium, magnesium, calcium, strontium, barium and radium.But, wherein, except being formed when reacting with fluorine
Beyond insoluble chemical compound, from safety, wholesomeness, the acquired and viewpoint of cost, it is desirable to use Ca
And Mg；And expectation uses Ca.
Specifically, if the amount of Zr is big, then overlay film comprises substantial amounts of fluorine and fluorine-resistant stripping property becomes heavier
Want.Accordingly, it is desirable to group il elements AE of such as calcium etc. in surface-treated layer and rubbing of zirconium
You are more than 0.2 than AE/Zr, and the weight thickness of group il elements AE of such as calcium etc. 7 to
150mg/m2In the range of.If weight thickness is less than 7mg/m2, then suppression fluorine dissolution and minimizing surface
The effect of defect is little.If weight thickness is more than 150mg/m2, the cohesiveness of overlay film reduces, and processability drops
Low and adaptation reduces, and this is less desirable.If comprising multiple group il elements, then AE represents it
Total amount.
The surface treated steel plate of the present invention has and mainly comprises zirconium and oxygen and the surface-treated layer comprising fluorine,
The most important feature is that surface-treated layer has the chemical combination of the group il elements being formed in its face side
The layer of thing.
Fig. 1 is the change of the atomic concentration illustrated in the depth direction in the surface treated steel plate of the present invention
Figure, described surface treated steel plate have in the face side being formed at surface-treated layer mainly comprise calcium and
The layer of the compound of fluoride, surface-treated layer is by mainly comprising zirconium and oxygen by having and comprise fluorine
The surface treated steel plate of surface-treated layer uses calcic aqueous solution to process by the step on regulation surface and obtains
?.
In FIG, the peak of C1s, O1s, F1s, Fe2p3, Zr3d and Ca2p3 is by using X-ray light
Electronic spectrograph (hereinafter referred to XPS) is measured, it is believed that these elements and be 100%, and will be from
The degree of depth of the Ar that sputtering is played on surface (is scaled SiO2) on transverse axis represent thus show the change of atomic concentration
Change.Such as, further, Fig. 2 is shown through using the water being used calcic by the step on regulation surface
The result of the distribution of atomic concentration in the depth direction of the surface treated steel plate detection before solution process.
Fig. 1 represents analysis result and Fig. 2 of the surface treated steel plate of preparation in the embodiment 11 shown after a while
Represent the analysis result of the surface treated steel plate of preparation in comparative example 4.
From Fig. 1 it will be appreciated that, in the surface treated steel plate of the present invention, Ca is present in surface-treated layer
Face side on.Compared with the Fig. 2 of the step not being adjusted surface, surface-treated layer in FIG exists
There is in its face side the F concentration of increase, but on the contrary, there is in its face side the Zr concentration of reduction
With the O concentration reduced.It is speculated that due to: by use the process of aqueous solution of calcic, fluorine and calcium that
This reaction, and in surface, form insoluble compound.In FIG, further, although by surface
Process layer to sputter dearly from its surface, but compared with Fig. 2, the atomic concentration of Fe raises hardly；
Hence, it is recognised that surface-treated layer has the structure making defect expose hardly.
Similar trend is shown in the embodiment 1 to 15 shown after a while with comparative example 1 to 5.That is, with
The comparative example represented by Fig. 2 is compared, and in an embodiment, as Fig. 1, group il elements is present in surface
On side, show that the F concentration in face side increases.
(manufacture method of surface treated steel plate)
<forming the step of overlay film>
In the manufacture method of the surface treated steel plate of the present invention, first, in the step forming overlay film,
Using steel plate as catholyte in the electrolysis treatment fluid of the aqueous solution comprising Zr ion and F ion, so that
With the amount of Zr at 10 to 350mg/m2, more preferably 10 to 200mg/m2In the range of and the amount of F 0.3
To 30mg/m2In the range of such mode, mainly comprise zirconium and oxygen and the Zr compound comprising fluorine
Overlay film be formed at least one surface of steel plate.Specifically, after a while by the regulation surface of description
In step, if the amount of overlay film is big, then can suppress the minimizing of fluorine greatly.Accordingly, it is desirable to
The amount of Zr is 100mg/m2Above, specifically, at 100 to 200mg/m2In the range of.
Steel plate after being formed on surface-treated layer is extruded by roller thus removes electricity
Solve treatment fluid, use water to clean, further, extruded by roller thus remove rinse water, and pass
Deliver to regulate the next step on surface.
In the electrolysis treatment fluid for the step forming overlay film, it is desirable to the concentration of Zr is 1,000
Concentration to 10,000ppm and F is 600 to 13,000ppm.It is desirable that, the pH of electrolysis treatment fluid
It is 2 to 5 and more preferably 2.5 to 4.Expect that the temperature being electrolysed treatment fluid is 30 to 60 DEG C.
After a while the various compounds described can be added the electrolysis process to the step being used for being formed overlay film
Liquid.Herein, in addition to comprising Zr ion and F ion, electrolysis treatment fluid comprises substantially for regulating pH
Nitrate ion and ammonium ion and from the Fe ion of base material dissolution.
The chemicals of the Zr ion for forming composition electrolysis treatment fluid is not particularly limited, it is possible to use
Such as K2ZrF6、(NH4)2ZrF6、(NH4)2ZrO(CO3)2、H2ZrF6、ZrO(NO3)2With
ZrO(CH3COO)2.In the present invention, above chemicals can individually or make with two or more combinations
With.
If the overlay film of Zr compound is processed by catholyte and is formed, the most normally, it is desirable to use and remove
The treatment fluid of F ion is comprised as electrolysis treatment fluid beyond above-mentioned Zr ion.It is contained in electrolysis treatment fluid
In F ion be used as to improve the deliquescent chelating agent of Zr ion in electrolysis treatment fluid.Therefore, Zrization
Compound can separate out and keep homogeneous thickness on substrate, and close between overlay film and organic resin layer
Conjunction property can be improved further.
If electrolysis treatment fluid comprises F ion in a small amount, then Zr local separates out, i.e. overlay film includes wherein
The mixture of part that Zr exists densely and the wherein part that Zr exists thinly.That is, overlay film lacks thickness
The uniformity of degree is as a result, have poor adaptation and corrosion resistance after the process.Therefore, formed
In the step of overlay film, it is important that by the mol ratio F/Zr control of the F atom in overlay film with Zr atom be
More than 0.6.
The chemicals being used for being formed the F ion in electrolysis treatment fluid is not particularly limited, and can make
With zirconium ammonium fluoride, aluminium fluoride, titanium fluoride, sodium fluoride, ammonium fluoride, Fluohydric acid., calcium fluoride, hexafluoro silicon
Acid and sodium hexafluorisilicate.Wherein, it is desirable to use those chemicals can being highly soluble in water.
Further, for the electrical conductivity improved in treatment fluid and the pH regulating treatment fluid, do not damage at it
Evil Zr compound overlay film formation in the range of, electrolysis treatment fluid can be added with nitrate ion and ammonium from
Son.
It addition, to electrolysis treatment fluid in, can add selected from such as citric acid, lactic acid, tartaric acid and
The organic acid of glycolic etc. or the macromolecular compound of such as polyacrylic acid, poly-itaconic acid and phenolic resin etc.
More than one of additive.The additive of such as organic acid and phenolic resin etc. is being added to electrolysis
During reason liquid, the additive of such as organic acid and phenolic resin etc. can be contained in the Zr compound overlay film of formation
In thus give the flexibility of the overlay film of the oxygen compound of metal and improve further organic resin layer
Adaptation.
Base material carry out catholyte process time, electric current density is not particularly limited, but preferably 1 to
30A/dm2。
If base material carries out catholyte process, then desirably employ the circulation that repeating is energized and is energized stops
Discontinuously electrolysis system (discrete electrolytic system).In the case, when being energized to base material total
Between (conduction time total when repeatedly carrying out being energized and be energized the circulation stopped) preferably 0.3 to 30 second.
Further, when base material carries out catholyte process, if it is carrying out the same of catholyte process
Time be not dissolved in electrolysis treatment fluid in, the most any kind of comparative electrode can be arranged on base material.But,
It is difficult to be dissolved in the sight being electrolysed treatment fluid from little oxygen overvoltage (oxygen overvoltage) and battery lead plate
Point, it is desirable to use the titanium plate using yttrium oxide to cover.
<step on regulation surface>
The key character of the present invention is to carry out after the step of above-mentioned formation overlay film by using group ii unit
Usually regulate the step on surface.
That is, form the step acquisition by forming overlay film mainly comprises zirconium and oxygen and the surface comprising fluorine
The surface modulation aqueous solution that the surface treated steel plate processing layer comprises group il elements by use soaks
More than any one of stain process, spraying treatment or catholyte process.By this process, make group ii
Element is present in the face side of surface-treated layer.Herein, as it has been described above, be especially desired to, fluorine with
Group il elements is reacted and insoluble so that it exists as fluorine compounds.
After the process of such as impregnation process etc., use roller to extrude steel plate thus remove and be used for regulating
The aqueous solution on surface, uses water to clean, and uses roller to extrude further thus removes rinse water, afterwards
Hot blast etc. is used to be dried.
If not being adjusted the step on surface, then by the organic resin using organic resin cover layer to apply
The container that the surface treated steel plate covered is made makes the fluorine in overlay film in the use heat of such as steaming and decocting process etc.
In the step of water sterilization processing, dissolution is to content.As a result, the change of structure of film is caused to cause such as
The performance of corrosion resistance, adaptation etc. reduces.
Therefore, before applying the resin coating layer for obtaining tank material, become it is essential that pre-
First pass through and in the step on regulation surface, form the layer of its compound reacted with group il elements and make
Fluorine is insoluble, and fluorine is already dispersed in the face side mainly comprising zirconium and oxygen and the surface-treated layer that comprises fluorine
On.
As the group il elements for surface modulation aqueous solution, can with example beryllium, magnesium, calcium, strontium,
Barium and radium.But, when using for these elements of surface modulation aqueous solution, it is necessary to pay close attention to chemistry
Whether product are dissolvable in water in water, and chemicals is the most easily bound to fluorine, and whether chemicals can form indissoluble
Property fluorine compounds, whether chemicals can excellently keep safety and wholesomeness, and whether chemicals is held high
Expensive.Therefore, from view of the above, it is desirable to use and can form slightly solubility CaF after reacting with fluorine2
Or MgF2Calcium or magnesium.
Herein, surface modulation aqueous solution can comprise calcium ion or magnesium ion, or both it.If bag
Containing the ion of any type, then most can expect that the aqueous solution comprising calcium is for regulating surface.
If the aqueous solution comprising calcium is for regulating surface, then any chemicals can be used not limit
System, condition is that they are soluble in water, and can use calcium lactate, calcium hydroxide, glucose
Acid calcium, calcium chloride, calcium nitrate, calcium sulfate, calcium citrate, calcium carbonate and calcium monohydrogenphosphate.Wherein,
Expect to use and there is big water miscible one.Further, if using magnesium, then to the change that can use
Product are not particularly limited, and condition is that they are dissolved in water.Preferably, it is possible to use magnesium chloride, nitre
Acid magnesium, magnesium sulfate, magnesium citrate, magnesium acetate and magnesium gluconate.If aqueous solution is alkaline, then
Can particularly preferably use magnesium gluconate.
As having the thawless work of fluorine making to be contained in surface process overlay film from surface modulation aqueous solution
With the fact it is evident that surface modulation aqueous solution can comprise fluorine or can when preparing chemicals
To have comprised fluorine along with its dissolving in the step on regulation surface.But, the present invention will not add wherein
Add fluorine or comprise fluorine wherein.
Further, in the step on regulation surface, it is desirable to the pH of surface modulation aqueous solution is 2
To 13, in the range of preferably 5 to 11, and more preferably 5.5 to 7.In this range, at surface-treated layer
In fluorine be speculated as free F ion but be not the state of complex ion, and can more effectively be bound to
Group il elements, thus form fluorine compounds with group il elements in the face side of surface-treated layer, protect
Keep steady qualitative, therefore, improve fluorine-resistant stripping property and the Funing tablet reducing in draining.
If pH is less than 2, peripheral equipment and as base material steel plate this in corrosion resistance aspect by unfavorable
Ground impact.If pH is accordingly changed into alkalescence more than 11, then in the face side of surface-treated layer stably
The ability forming fluorine compounds reduces.Especially, if pH is more than 13, then fluorine dissolves with the speed increased
In surface modulation aqueous solution, ultimately resulting in the Funing tablet in draining increases, and this is less desirable.
As the alkaline chemical of pH for regulating surface modulation aqueous solution, can simply use most
Such as Ca (OH)2Or Mg (OH)2Deng the hydrogen of group il elements showing alkalescence when being dissolved in water
Oxidized compound.But, these chemicals are dissolved in water with relatively small amount.Therefore, if regulated
The step on surface is by dipping or catholyte persistently carries out or if carried out catholyte, then chemicals must
Must frequently supply and typically require the experimental work for keeping and control aqueous solution.In such situation
Under, from easy to handle viewpoint, it is desirable to use and new surface modulation aqueous solution is sprayed at steel plate always
On spraying system.Even if the chemicals of group il elements is not dissolved in water and does not produce alkalescence, can
Regulate pH with one or more the chemicals comprising sodium, ammonium and potassium by interpolation, and this is molten
Liquid can serve as basic surface regulation aqueous solution.
As the chemicals in addition to group il elements of the pH for regulating surface modulation aqueous solution,
Can with example ammonia, ammonium zirconium carbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium phosphate, dibastic sodium phosphate,
Potassium hydroxide, potassium carbonate, sodium borate and sodium silicate, these can be with two or more uses.
Further, on demand, various surfactants and chelating agen can add to surface modulation with water-soluble
Liquid.
It is desirable that, the ion concentration of the group il elements being contained in surface modulation aqueous solution is 0.002
To 0.5mol/l.If ion concentration is less than 0.002mol/l, then on the surface of surface-treated layer
When using group il elements to form fluorine compounds on side, reaction efficiency becomes poor.If ion concentration exceedes
0.5mol/l, then group il elements separates out too much, and the cohesiveness of overlay film reduces, and this is less desirable.
In the step on regulation surface as above, impregnation process, spraying treatment or catholyte process
Can be carried out by the surface modulation aqueous solution that use comprises group il elements.From the sight processed rapidly
Point, it is desirable to also add catholyte in surface modulation aqueous solution and process.On the other hand, from simplicity
Viewpoint, spraying treatment and impregnation process are desirable means.From reducing surface modulation aqueous solution
Fluorine dissolving and reduce drainage load viewpoint, the pH of surface modulation aqueous solution should be in above-mentioned scope
In, specifically, in the range of 5.5 to 7.
Process if carried out catholyte, then it is desirable that, from the viewpoint for the treatment of effeciency, comprise group ii
The electrical conductivity of the surface modulation aqueous solution of element is more than 2mS/cm.
As set forth above, it is possible to make group il elements, specifically, the compound of group il elements is by regulation
The step on surface is present in the face side of surface-treated layer.Herein, in the face side of surface-treated layer
The compound preferred fluorinated compound of group il elements that formed, and more preferably slightly solubility.By making
The preferred calcium of insoluble chemical compound formed by group il elements and/or the compound of magnesium, can be maybe calcium or magnesium
Individually oriented compound, or calcium and the compound both magnesium.In the case of individually oriented compound, most expect shape
Become the fluorine compounds of the calcium of insoluble chemical compound.
In surface-treated layer, group il elements AE is preferably more than 0.2 with mol ratio AE/Zr of zirconium Zr, tool
Body ground, in the range of 0.4 to 1.8.More effectively, whether the weight thickness of group il elements is
7mg/m2Above, specifically, at 7 to 150mg/m2In the range of.
In the step on regulation surface, the temperature of surface modulation aqueous solution is not particularly limited.But,
From reactive and control the viewpoint of temperature, it is desirable to temperature is in 30 to 80 DEG C, specifically, 30 to
In the range of 60 DEG C.Further, the such as impregnation process, spraying treatment of surface modulation aqueous solution are used
With total processing time of catholyte process etc. at 0.1 to 5 second, and in the range of more preferably 0.5 to 3 second.
After using surface modulation aqueous solution to process in the step on regulation surface, it is also possible to add and pass through
The cleaning treatment being immersed at about 40 DEG C to about 95 DEG C in the warm water or hot water heated or use it to spray.
(as the steel plate of base material)
Steel plate as the surface treated steel plate as the present invention, it is possible to use such as based on casting continuously
The hot rolled steel plate of aluminum killed steel, by by the cold-rolled steel sheet of cold rolling for hot rolled steel plate acquisition with by comprising
The steel plate that the metal plating of Zn, Sn, Ni, Cu, Al etc. obtains on hot rolled steel plate or cold-rolled steel sheet.
Further, it is possible to use and there is in its part or whole surface such as Sn-Ni-Fe alloy, Sn-Fe
The steel plate of the alloy-layer of alloy or Ni-Fe alloy etc. and having is plated on above alloy-layer further
The steel plate of the layer of the metal of such as Sn or Ni.Wherein, from the viewpoint of cost, most expect not have metal-plated
Layer or there is the coat of metal but make the ferrum steel plate that exposes of local in decentralized manner be used as base material.
The thickness of base material is not particularly limited and can properly select according to purposes, but preferably 0.07
To 0.4mm.
(organic resin cover layer)
It is formed on surface-treated layer as it has been described above, the surface treated steel plate obtained by the present invention is had
Organic resin cover layer.The excellent adhesion of organic resin layer.Even if by surface treated steel plate boilery
In the case of reason, it is also prevented from organic resin layer and peels off.Further, though at organic resin layer crackle and
In the case of metal surface is exposed in wet environment, organic resin cover layer the most effectively prevents Corrosion developing,
Therefore, suppression constitutes the metal component dissolution of container.
The resin constituting organic resin cover layer is not particularly limited and can be according to the table of the present invention
Face processes the purposes (according to such as accommodating tank and the container of certain content thing) of steel plate and properly selects.
I.e., it is possible to the resin coating layer be made up of various thermoplastic resins of example and by thermohardening lacquer or thermoplasticity
The film that coating is made.As the resin coating layer being made up of thermoplastic resin, can with example such as polyethylene,
Polypropylene, ethylene-propylene copolymer, vinyl-vinyl acetate copolymer, vinyl-acrylate copolymer
Olefin-based resin molding with ionomer etc.；Such as polyethylene terephthalate and poly terephthalic acid fourth
The polyester film of diol ester etc.；The such as polyamide membrane of nylon 6, nylon 6,6, nylon 11 and nylon 12 etc.；
The such as thermoplastic resin film of polychloroethylene film and polyvinylidene chloride film etc., its can not yet stretch or
Can be the most biaxial stretch-formed.Wherein, gathering of the non-oriented particularly preferably obtained by copolymerization M-phthalic acid
Ethylene glycol terephthalate.The resin constituting organic resin cover layer can be with individually one or with difference
The blend of resin uses.
If thermoplastic resin cover layer is formed as organic resin cover layer, then cover layer can be single tree
Lipid layer or the multilamellar being formed by coextrusion.Multi-layered polyester resin bed provide the advantage that have excellent
The polyester resin of different cementability can serve as bottom i.e. on surface treated steel plate side, and has resistance to content
Physical property, i.e. there is resistance to extractability or there is the polyester resin of the performance not adsorbing sapidity ingredient can serve as
Surface layer.
The example of multi-layered polyester resin bed includes, it is expressed as surface layer/lower floor and is: poly terephthalic acid second
Diol ester/poly terephthalic acid ethylene isophthalate；Polyethylene terephthalate/poly-right
Phthalic acid ethylene glycol cyclohexylidene two methylene ester；There is the poly-to benzene of little M-phthalic acid ester content
The poly-terephthaldehyde of the big M-phthalic acid ester content of dioctyl phthalate ethylene isophthalate/have
Acid ethylene isophthalate；With poly terephthalic acid ethylene isophthalate/[poly-to benzene
Dioctyl phthalate ethylene isophthalate and the blend of poly-poly terephthalic acid tetramethylene adipate]
Deng, but, the present invention is by no means limited to this.It is desirable that, surface layer: the thickness ratio of lower floor is at 5:95
To 95:5.
Above organic coating layer can be blended according to known formula has known resin to be compounded agent, such as
Such as the antiblocking agents such as amorphous silica, inorganic filler, various antistatic additive, lubricant, antioxidation
Agent and UV absorbent.
Wherein, it is desirable to use tocopherol (vitamin e).Hitherto known, tocopherol is used as antioxidant,
And for preventing the molecular weight caused by the oxidation when by polyester resin heat treatment and decomposition from reducing also
And be used for improving resistance to pitting.Specifically, if added to by using polyester resin and as modification resin
The polymer blend that the above ethylene-based polymer compounding of component obtains, then tocopherol not only provides resistance to depression
Property, it is also used for preventing owing to experiencing harsh conditions at cooking disinfection with being stored in hot vending machine period
And the generation of the corrosion that the crackle formed in the overlay film caused causes, it is thus achieved that improve corrosion resistance greatly
Effect.
The addition expecting tocopherol is 0.05 to 3 weight %, specifically, and 0.1 to 2 weight %.
In the case of thermoplastic resin cover layer, it is applied to the surface treated steel plate obtained by the present invention
The thickness of organic resin cover layer in usual 3 to 50 μm, specifically, in the range of 5 to 40 μm,
In the case of film, its fire after thickness in 1 to 50 μm, specifically, in the range of 3 to 30 μm.As
Really thickness is less than range above, then corrosion resistance becomes insufficient.On the other hand, if thickness exceed with
Upper scope, then tend to the problem about processability.
The surface treated steel plate obtained by the present invention can be by such as, at thermoplastic resin cover layer
In the case of, any means such as cladding process, casting film thermal bonding or biaxially-stretched film thermal bonding of extruding use
Organic resin covers.In the case of extrusion cladding process, the polyester resin of molten condition is extruded to table
Face processes on steel plate and heat bonding.That is, by polyester resin by extruder melting mixing, by T mould
Be extruded as the form of thin film, and by the molten resin film of extrusion together with surface treated steel plate through a pair
Laminating roll thus be pressurised into the most together entirety structure, then chilling.If extruding many stratas
Ester resin bed, then use for the extruder of expression surface resin bed with for extruding lower-layer resin layer
Extruder.Resin stream from these extruders collaborates in multiple layers of molds.Afterwards, gained resin stream
Can be as extruding extruding in the case of single resin bed.Further, by by surface treated steel plate
Vertically pass through between a pair laminating roll and by molten resin net is supplied to its both sides, permissible
Polyester resin is used to cover on the two of base material surfaces.
The following specifically describes is having of the organic coating layer with polyester resin based on extrusion cladding process
The production of the surface treated steel plate that machine resin covers.Surface treated steel plate is come by heater on demand
Preheat, and the nip portion supplied between a pair laminating roll.On the other hand, polyester resin is passed through
The die head of extruder extrudes the form for thin film, supplies between laminating roll and surface treated steel plate, and
And by laminating roll pressurized adhesion to surface treated steel plate.Laminating roll is kept at a predetermined temperature.Will
The thin film of the thermoplastic resin of such as polyester etc. is forced on surface treated steel plate and heat bonding, then from
Its both sides cool down, thus obtain the surface treated steel plate that organic resin covers.Normally, by having of being formed
Machine resin cover surface treated steel plate import further in cooling water groove, and wherein chilling thus
Prevent thermal crystalline.
In extrusion cladding process, polyester resin layer has low-level degree of crystallinity, i.e. have with it without fixed
The difference of shape density is 0.05g/cm3Following density, this is because the resin selected forms and because passes through
Roller and the chilling in cooling bath.Therefore, polyester resin layer fills in the step forming tank and lid then
Code insurance demonstrate,proves its processability.Chilling operation is not limited only to above example, but can be to shape by cooling water spray
So that laminate chilling on the surface treated steel plate that the organic resin become covers.
Polyester resin is by utilizing the heat that had by molten resin layer and being had by surface treated steel plate
Heat and be thermally bonded to surface treated steel plate.Suitable scope in the temperature of laminating roll be 10 DEG C extremely
While 150 DEG C, the suitable scope of the temperature (T1) for heating surface treated steel plate is typically 90 DEG C extremely
290 DEG C, specifically, 100 DEG C to 280 DEG C.
Pre-by T modulus method or inflation method (inflation method) by heat bonding on surface treated steel plate
The polyester resin film being initially formed, organic resin cover layer can also be formed at the manufacture method by the present invention
On the surface treated steel plate obtained.As this film, it is possible to use by the cast form by extruded film chilling
The unstretching film that method is formed.Further, it is possible to use by by film under draft temperature successively or simultaneously
Ground is biaxial stretch-formed, and the biaxially-stretched film obtained by the film heat fixation after stretching.
(canister)
The canister (tank body) that the surface treated steel plate of the application of the invention is formed, it is desirable to
Surface treated steel plate is covered with organic resin foregoing by using according to any tank manufacture method
Surface and surface treated steel plate that the organic resin that obtains covers are to form container.Specifically, You Jishu
The surface treated steel plate that fat covers may be used for being formed and has jointed built-up tin (welded tank) on its lateral surface
With seamless tank (two piece can).But, as it has been described above, from the viewpoint of the adaptation to organic resin, the phase
Hope and be used for forming seamless tank by the surface treated steel plate comprising a large amount of Zr.
In the way of organic resin cover layer is in the inner face side of tank, according to the processing of such as drawing, drawing again
(stretching), based on drawing re-drawing is processed in drawing processing, bending based on drawing re-drawing-elongation
Bend-extend the traditional means of thinning processing or drawing attenuated processing etc. to produce seamless tank.
Such as based on drawing re-drawing bending-elongation processing (stretching) is carried out or based on drawing when it is changed into
During the seamless tank of the further processing of the bending of deep re-drawing-extend thinning processing etc., it is desirable to
Organic resin cover layer is the thermoplastic resin cover layer formed by extrusion cladding process.Organic resin covers
The feature of surface treated steel plate be the adaptation during excellent processing.I.e., i.e. it is subjected to harshness
Processing, cover layer still keeps the most closely sealed；And can provide and there is the seamless of excellent corrosion resistance
Tank.
(lid)
The cover being expected that by using the surface treated steel plate of the present invention to be formed is as above-mentioned canister
Formed by the surface treated steel plate using organic resin to cover, and come by known lid forming process
Formed.Specifically, this lid can be flat cover, stay chip (stay-on-tub type) drawn-can lid and standard-sized sheet
The drawn-can lid of formula.
According to the present invention, the table that various types of covers can cover with the organic resin of the application of the invention
Face processes steel plate and is formed unrestrictedly.
Embodiment
To be specifically described the present invention by the way of embodiment now, but, the present invention is by no means limited to
This.Material, dewaxing agent and organic coating layer to be covered is arbitrarily selected from those those commercially available, and
The manufacture method to the surface treated steel plate of the present invention does not applies to limit.
The manufacture method of surface treated steel plate described below and the evaluation methodology of its characteristic.
(forming the step of overlay film)
As raw steel plate, use thickness 0.225mm and the low carbon steel plate of width 200mm.Next step, make
For pretreatment, steel plate is by using the electrolysis of alkali to dewax and coming clear by being immersed in sulphuric acid use acid
Wash.Afterwards, steel plate is immersed in electrolysis treatment fluid and catholyte processes, so that steel plate is used
The main compound being made up of Zr and comprising F covers on two surface.Next step, make steel plate
Extrude with roller, use water to clean, and use roller extrudes thus removes rinse water further, from
And form overlay film.
Electrolysis treatment fluid: wherein dissolving the zirconium ammonium fluoride as Zr compound, the concentration of Zr is 6,000ppm
And the concentration of F is the aqueous solution of 7,500ppm
The pH:3.0 (using nitric acid and/or ammonia to regulate pH) of electrolysis treatment fluid
The temperature of electrolysis treatment fluid: 40 DEG C
Comparative electrode: use the titanium plate that yttrium oxide covers
Electrifying method during catholyte: at 3A/dm2Electric current density and each 0.15 second once
Or repeatedly energising (hereinafter referred to period)
(step on regulation surface)
Surface modulation aqueous solution is used to process pre-timing the steel plate after forming the step of overlay film
Between, use roller to extrude, use water to clean, use roller to extrude further, use hot blast afterwards
It is dried, thus obtains surface treated steel plate.
In the step on the regulation surface according to the present invention, the table of group il elements can be comprised by use
Regulation aqueous solution in face carries out more than any one of impregnation process, spraying treatment and catholyte process to be come
Carry out.But, in an embodiment of the present invention, carry out the surface modulation by use comprises calcium or magnesium and use
Aqueous solution carries out impregnation process, spraying treatment and catholyte and processes.The moon in the step on regulation surface
In the electrolysis of pole, the titanium plate using yttrium oxide to cover is used as comparative electrode, and power cycles is repeatedly,
Each circulation includes being energized 0.15 second, then stops energising 0.1 second.
(producing the surface treated steel plate that organic resin covers)
The surface treated steel plate that organic resin covers is obtained by following: taking with paying close attention to the suitable degree of film
While to, by the poly terephthalic acid/isophthalic diformazan of the isophthalic acid component by comprising 11mol%
The stretched film of 19 μ m-thick of acid glycol ester copolymerization composition is thermally bonded to surface treated steel plate achieved above
The inner surface becoming tank a surface on, with by the isophthalic acid component of 12mol% will be comprised
Poly terephthalic acid/ethylene isophthalate copolymerization composition and comprise further titanium oxide and
The stretched film of 13 μ m-thick of color white (colored white) is thermally bonded to become another surface of the outer surface of tank
On, by using laminating roll to use water to cool down the most rapidly.The surface that the organic resin obtained covers
Process sheet steel sections ground and draw lattice corrosion resistance for evaluating, and it is remaining for producing canister.
(production canister)
Paraffin is applied to statically two of the surface treated steel plate that organic resin achieved above covers
On surface.By circle that steel plate punched is diameter 143mm and be diameter according to ways customary drawing and forming
91mm and the cup of height 36mm.Meanwhile, drawing and forming cup is repeatedly carried out drawing attenuated processing two
Secondary thus formation has minor diameter and the cup of big height.Therefore the cup obtained has spy as described below
Property.
Cup diameter: 52.0mm
Cup is high: 111.7mm
Slip relative to the plate thickness in raw sheet thickness tank skin portion: 30%
After arching upward, by cup at 220 DEG C heat treatment 60 seconds thus from resin molding remove strain, connect
Pruning open end, print on curved surface, necking down is diameter and the flange processing of 50.8mm, from
And obtain the seamless tank of the capacity with 200ml.
(measuring amount and the amount (amount of group il elements) of AE of Zr)
By using x-ray fluorescence analyzer (model: ZSX100e, Rigaku Co. manufacture), measure with
The amount of the Zr being contained in metallic compound overlay film of the surface treated steel plate of upper acquisition and the amount of AE (are implemented
The amount of the Ca in example or the amount of Mg).Mol ratio AE/Zr is tried to achieve according to following formula,
AE/Zr=(atomic weight of the amount/AE of AE)/(atomic weight of the amount/Zr of Zr)
(measuring the amount of F)
The microanalysis of amount based on x-ray fluorescence analyzer F in the surface treated steel plate obtained causes pass
Restriction in quantitative accuracy.Specifically, it is difficult to measure the amount from F and be less than 1.5mg/m2Surface
Process the amount of the F of steel plate.Therefore, after various researchs, we survey the most in the manner as described below
Measure the amount of F.That is, by using the 160cm that can keep surface treated steel plate2A surface be in
The special groove (cell) of the state of the ultra-pure water of contact 183g, by surface treated steel plate steaming and decocting at 130 DEG C
Process 30 minutes.Afterwards, by release to the fluorion in ultra-pure water by ion chromatograph (DX-320,
DIONEX Co. manufactures) measure.The amount of the F being present in ultra-pure water is tried to achieve also from the concentration of the F obtained
And be converted to the amount of the F being present in the surface treated steel plate of per unit area, and as in overlay film
The amount of F.
Although the surface treated steel plate of the step passing through regulation surface shown in embodiment is carried out
Steaming and decocting processes, but fluorine dissolution hardly, it is thus impossible to the amount of the F being informed in surface treated steel plate.
Therefore, for passing through the surface treated steel plate of the step on regulation surface, the amount of F passes through XRF
Instrument is measured.But, the amount at F is less than 1.5mg/m2In the case of, the peak in x-ray fluorescence analyzer is not
Clear.Therefore, the amount of the area being equal to more than 10 times generally to be measured by x-ray fluorescence analyzer is come
Collect surface and process the scraping powder of overlay film, and measure fluorine by x-ray fluorescence analyzer and be converted to
The amount of its per unit area.
(measuring the slip of F)
Try to achieve from the amount of the F the surface treated steel plate only formed by the step forming overlay film
The minimizing percentage ratio of the amount of the F in the surface treated steel plate of the step on regulation surface.It is evaluated for use as
Index to the fluorine load of draining in the step on regulation surface.Expect that this index is less than 30%.
(evaluate and draw lattice corrosion resistance)
By using cutter, by become the part of the surface treated steel plate of the acquisition of the inner surface side of tank with
The mode intersected is carved into the degree of depth sufficiently achieving steel plate in the length of 4cm, thus prepares test sheet.Will
Test sheet be placed in bottle and be immersed in commercially available coffee (trade name, Blendy, bottled coffee, low sugar,
Ajinomoto General Foods Co. manufactures) in.This bottle is deaerated, stores 4 weeks at 37 DEG C thus comment
Valency etch state.In this process, by coffee periodic replacement thus press down mycostatic generation as far as possible.Rotten
Erosion state is by taking out evaluation by test sheet from coffee.That is, whether organic resin layer is peeled off or face
Whether color changes due to the formation of corrosion product, makes with the naked eye to observe and draws lattice part and about.
Color change or film are being drawn the test sheet that Breadth Maximum is more than 3mm that lattice portion is peeled off
Being calculated as a bit, being 2mm by the Breadth Maximum of stripping is calculated as 2 points less than the test sheet of 3mm, will
1mm is calculated as 3 points less than the test sheet of 2mm, by 0.5mm less than the test sheet of 1mm
It is calculated as 4 points, and the test sheet less than 0.5mm is calculated as 5 points.The test sheet being calculated as more than 3 is seen
Make acceptable.
(evaluating resin adaptation to the inner surface of tank)
Distilled water is used to fill in the seamless tank obtained, with covering double sealed cans, and steaming and decocting at 125 DEG C
Process 30 minutes.Afterwards, lid is removed from tank body, content is removed from tank, and by tank surface
The direction processing steel plate calendering 45 degree is cut into two halves as border.Next step, will be cut into the tank of two halves
It is immersed in water-soluble by the surfactant of 0.02 weight % is added to the sodium chloride containing 1 weight %
Liquid obtain solution in one hour.By use a shears, using tank with roll 135 degree direction as
Border is cut into two halves further from tank bottoms side.That observes within it face side final cuts tank bottoms footpath
To the cross section in portion, whether resin is peeled off, thus the adaptation of evaluating resin.By the stripping near facet
It is calculated as a bit from the tank for more than 10mm, is calculated as two by peeling off the tank for less than 10mm and more than 5mm
Point, is calculated as 3 points by peeling off the tank for less than 5mm and more than 2mm, will peel off as the tank meter less than 2mm
It is 4 points, and the tank peeled off will not had to be calculated as 5 points.The tank being calculated as more than 3 is regarded as acceptable.
(evaluating the stripping property of resistance to F)
The ultra-pure water that the seamless tank obtained uses 183g is filled, double sealed cans, and steam at 130 DEG C
Boil process 30 minutes.Afterwards, by release to the fluorion in ultra-pure water by ion chromatograph (DX-320,
DIONEX Co. manufactures) measure.The tank of release more than F0.1ppm is evaluated as × and will to discharge F little
Tank in 0.1ppm is evaluated as zero.
(drainage load evaluation)
Drainage load is evaluated from the slip of F.Situation when being below 30% by the slip of the amount as F
It is evaluated as zero and the situation when its slip is more than 30% is evaluated as △.Zero is better than △.
<embodiment 1>
In the step forming overlay film, first, the titanium plate using iridium to cover is used as in electrolysis treatment fluid
Relative electrolysis, steel plate is used as negative electrode, at 3A/dm2Electric current density under be energized once in 0.15 second,
Use roller to extrude steel plate thus remove electrolysis treatment fluid, use the water of room temperature to clean, and enter one
Step uses roller to extrude thus removes rinse water.Next step, processed by catholyte and regulate surface.
As surface modulation aqueous solution, calcium lactate and the electrical conductivity of the amount that use comprises 0.1mol/l are
6.57mS/cm and pH is the aqueous solution of 6.96.Surface modulation under being maintained at the liquid temperature of 30 DEG C is with water-soluble
In liquid, by being repeated twice at 4A/dm2Electric current density under be energized 0.15 second then energising stop 0.1 second
Circulation is adjusted the step on surface.Roller is used to extrude the steel plate after the step on regulation surface
Thus remove aqueous solution, use water to clean, again extrude with roller thus remove rinse water, and be dried
Thus obtain surface treated steel plate.
The amount of Zr of surface treated steel plate, the amount of AE and the amount of F obtained is measured by said method.Cover
The measurement result of film amount is as shown in table 1, and described table 1 also shows that the group il elements calculated from the amount of overlay film
(AE) with mol ratio AE/Zr of Zr and the slip of F.In table, "-" represent and do not measure.
<embodiment 2>
Except formed overlay film step at 10A/dm2Electric current density under be energized and repeat this circulation
Twice, and at 1A/dm in the step on regulation surface2Electric current density under energising beyond, with enforcement
The mode that example 1 is identical obtains surface treated steel plate.
<embodiment 3>
Except regulation surface step at 6.5A/dm2Electric current density under energising beyond, with enforcement
The mode that example 2 is identical obtains surface treated steel plate.
<embodiment 4>
Except in the step on regulation surface by steel plate at 60 DEG C in addition to impregnation process 3 seconds, with enforcement
The mode that example 2 is identical obtains surface treated steel plate.
<embodiment 5>
Except formed overlay film step at 10A/dm2Electric current density under be energized and repeat this circulation
Beyond 4 times, in the way of same as in Example 3, obtain surface treated steel plate.
<embodiment 6>
Preparing pH except the aqueous solution of calcium lactate by being added by ammonia to the amount comprising 0.1mol/l is
11.0 and surface modulation aqueous solution that electrical conductivity is 7.13mS/cm, and by being repeated twice at 40 DEG C
Under liquid temperature and at 2A/dm2Electric current density under the circulation of catholyte of energising be adjusted surface
Step beyond, in the way of same as in Example 5, obtain surface treated steel plate.
<embodiment 7>
Except passing through at 7A/dm in the step on regulation surface2Electric current density under energising carry out negative electrode
Beyond electrolysis, obtain surface treated steel plate in the same manner as in example 6.
<embodiment 8>
In addition in the step on regulation surface by steel plate spraying treatment 3 seconds, with same as in Example 6
Mode obtains surface treated steel plate.
<embodiment 9>
In addition to repeating this circulation 8 times in the step forming overlay film, in the same way as in example 2
Obtain surface treated steel plate.
<embodiment 10>
Except regulation surface step at 4A/dm2Electric current density under be energized and repeat this circulation 4
Beyond secondary, in the way of the same as in Example 9, obtain surface treated steel plate.
<embodiment 11>
Except regulation surface step at 6.5A/dm2Electric current density under energising beyond, with enforcement
The mode that example 10 is identical obtains surface treated steel plate.
<embodiment 12>
Except preparing electrical conductivity by the magnesium nitrate hexahydrate of the amount of use 0.1mol/l it is
15.1mS/cm and pH is the surface modulation aqueous solution of 5.61, and by being repeated twice the liquid at 40 DEG C
Under temperature and at 4A/dm2Electric current density under the circulation of catholyte of energising be adjusted surface
Beyond step, in the way of identical with embodiment 11, obtain surface treated steel plate.
<embodiment 13>
In addition to repeating this circulation 12 times in the step forming overlay film, with side same as in Example 10
Formula obtains surface treated steel plate.
<embodiment 14>
In addition to repeating this circulation 12 times in the step forming overlay film, with the side identical with embodiment 11
Formula obtains surface treated steel plate.
<embodiment 15>
Except using the calcium nitrate of the amount comprising 0.1mol/l and pH to be 5.6 in the step on regulation surface
Aqueous solution is as surface modulation aqueous solution, and is repeated twice under the liquid temperature of 40 DEG C and at 4A/dm2
Electric current density under energising catholyte circulation beyond, obtain in the way of identical with embodiment 13
Surface treated steel plate.
<comparative example 1>
In addition to not being adjusted the step on surface, obtain surface in the same manner as example 1
Process steel plate.
<comparative example 2>
In addition to not being adjusted the step on surface, obtain surface in the same way as in example 2
Process steel plate.
<comparative example 3>
In addition to not being adjusted the step on surface, in the way of same as in Example 5, obtain surface
Process steel plate.
<comparative example 4>
In addition to not being adjusted the step on surface, in the way of the same as in Example 9, obtain surface
Process steel plate.
<comparative example 5>
In addition to not being adjusted the step on surface, in the way of identical with embodiment 13, obtain surface
Process steel plate.
(investigation)
As evident from Table 1, in embodiment 1 to 15, the amount of the Zr in overlay film be set as 12 to
182mg/m2, and steel plate uses in the step on regulation surface the aqueous solution comprising group il elements come
Process thus obtain in overlay film, comprise 0.4 to 19.8mg/m2The steel plate of F of amount.Do not adjust
In the comparative example 1 to 3 of the step on joint surface, steel plate is gratifying about the stripping property of resistance to F, but about
Draw lattice corrosion resistance and adaptation is poor.Along with the amount of Zr increases, these performance improvements but resistance to F dissolution
Property reduce.The organic resin that the material from the step being adjusted surface of embodiment 1 to 15 obtains covers
Metallic plate show excellence draw lattice corrosion resistance, the adaptation of the excellent inner surface to canister,
The adaptation of the organic resin layer of the excellent stripping property of resistance to F and height.Even if formed tank processing and
After steaming and decocting process in the case of organic resin layer crackle, confirming, organic resin layer keeps the closeest
Close, and container excellently keeps the quality of content.
Further, in embodiment 1 to 15, if the amount of the Zr in overlay film is big, then the slip of F is little.
Specifically, if the amount of Zr is 100mg/m2Above, then the slip of F is less than 30%.That is, learn
Even if the slip of F is little, corrosion resistance, adaptation and the resistance to F with excellence still can be obtained
The steel plate of stripping property.
Further, as evident from Table 1, in embodiment 1 to 15, the amount of AE be 7.7 to
141mg/m2, and in a comparative example, the amount of AE is 1.4 to 5.1mg/m2.In a comparative example, do not carry out
The step on regulation surface, and the most wittingly group il elements is added extremely in the step forming overlay film
Aqueous solution or to rinse water.Think, at aqueous solution in the step of group il elements source leisure formation overlay film
Or Ca and Mg inevitably comprised as impurity in rinse water.Pay close attention to the AE/Zr ratio in table 1, exhibition
The AE/Zr ratio that the material of the embodiment 1 to 15 of good performance all has more than 0.2 is shown, and can not
The material of the comparative example 1 to 5 meeting performance all has the AE/Zr ratio less than 0.2.Therefore, AE/Zr ratio
Use can distinguish Ca and Mg inevitably comprised as impurity.
Claims (11)
1. a surface treated steel plate, described surface treated steel plate has steel plate and at described steel plate at least
Surface-treated layer on one surface, described surface-treated layer comprises zirconium, oxygen and fluorine, wherein said surface
Process and comprise group il elements in the face side of layer.
Surface treated steel plate the most according to claim 1, wherein said group il elements is as fluorination
Compound exists.
Surface treated steel plate the most according to claim 1 and 2, wherein said group il elements be calcium or
At least one of magnesium.
4., according to the surface treated steel plate described in any one of claims 1 to 3, wherein process on described surface
Group il elements AE and mol ratio AE/Zr of zirconium Zr in Ceng are more than 0.2.
5., according to the surface treated steel plate described in any one of Claims 1-4, wherein the weight thickness of zirconium is
100 to 200mg/m2。
6. the surface treated steel plate that organic resin covers, it is by arbitrary according to claim 1 to 5
Form organic resin coating layer on surface treated steel plate described in Xiang to obtain.
7. a canister, the surface that it is covered by organic resin according to claim 6 processes
Steel plate is made.
8. a cover, its surface treated steel plate covered by organic resin according to claim 6
Make.
9. a manufacture method for surface treated steel plate, described surface treated steel plate has steel plate and described
Surface-treated layer at least one surface of steel plate, described surface-treated layer comprises zirconium, oxygen and fluorine, institute
The method of stating comprises the following steps:
Overlay film is formed by steel plate described in catholyte in comprising the aqueous solution of Zr ion and F ion；With
Afterwards, the surface modulation aqueous solution comprising group il elements by use carries out impregnation process, spray
More than any one of mist process or catholyte process regulate surface.
The manufacture method of surface treated steel plate the most according to claim 9, wherein said group ii unit
Element is at least one of calcium or magnesium.
11. according to the manufacture method of the surface treated steel plate described in claim 9 or 10, wherein at reconciliation statement
In the step in face, the slip of the fluorine carrying out the step of self-forming overlay film is less than 30%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013260930A JP6530885B2 (en) | 2013-12-18 | 2013-12-18 | Surface-treated steel sheet, organic resin-coated metal container, and method for producing surface-treated steel sheet |
| JP2013-260930 | 2013-12-18 | ||
| PCT/JP2014/082239 WO2015093318A1 (en) | 2013-12-18 | 2014-12-05 | Surface-treated steel sheet, organic-resin-coated metal container, and method for producing surface-treated steel sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105874107A true CN105874107A (en) | 2016-08-17 |
| CN105874107B CN105874107B (en) | 2018-11-16 |
Family
ID=53402667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480069019.XA Expired - Fee Related CN105874107B (en) | 2013-12-18 | 2014-12-05 | The manufacturing method of surface treated steel plate, the canister of organic resin covering and surface treated steel plate |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20160289843A1 (en) |
| EP (1) | EP3085816B1 (en) |
| JP (1) | JP6530885B2 (en) |
| CN (1) | CN105874107B (en) |
| WO (1) | WO2015093318A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117793A (en) * | 2018-02-05 | 2019-08-13 | 嘉瑞科技（惠州）有限公司 | A kind of light-alloy organic coating layer preparation method, membrane equipment and environment-friendly type organic coating |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5886919B1 (en) * | 2014-09-12 | 2016-03-16 | 東洋製罐株式会社 | Surface-treated steel sheet, method for producing the same, and resin-coated surface-treated steel sheet |
| JP6119931B2 (en) | 2015-04-16 | 2017-04-26 | 新日鐵住金株式会社 | Steel plate for container and method for producing steel plate for container |
| TWI605155B (en) | 2015-04-16 | 2017-11-11 | 新日鐵住金股份有限公司 | Steel sheet for container and method of manufacturing the same |
| US20190390065A1 (en) * | 2018-06-22 | 2019-12-26 | Covestro Llc | Waterborne compositions containing organic ion-exchangers to improve corrosion resistance |
| CN115449712B (en) * | 2022-09-14 | 2023-06-09 | 浙江东南新材科技有限公司 | High-strength pickled plate and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1572912A (en) * | 2003-06-09 | 2005-02-02 | 日本油漆株式会社 | Method of treating metal surface and metal surface treated thereby |
| US20050175798A1 (en) * | 2002-11-25 | 2005-08-11 | Wataru Kurokawa | Surface-treated metallic material, method of surface treating therefor and resin coated metallic material, metal can and can lid |
| CN101010452A (en) * | 2004-06-22 | 2007-08-01 | 东洋制罐株式会社 | Surface-treated metal materials, method of treating the surfaces thereof, resin-coated metal materials, cans and can lids |
| CN101678644A (en) * | 2007-05-31 | 2010-03-24 | 东洋制罐株式会社 | Resin-coated metal sheet and formed object made therefrom |
| US20100176000A1 (en) * | 2006-09-08 | 2010-07-15 | Toshio Inbe | Method of treating surface of metal base, metallic material treated by the surface treatment method, and method of coating the metallic material |
| CN102066612A (en) * | 2008-03-17 | 2011-05-18 | 汉高两合股份公司 | Optimized passivation on Ti-/Zr-basis for metal surfaces |
| CN102918185A (en) * | 2010-05-28 | 2013-02-06 | 东洋制罐株式会社 | Surface treatment bath, method of manufacturing surface-treated steel plate using said surface treatment bath, and surface-treated steel plate formed with said manufacturing method |
| CN103097582A (en) * | 2010-09-15 | 2013-05-08 | 杰富意钢铁株式会社 | Steel sheet for container and method for manufacturing therefor |
| CN103097576A (en) * | 2010-06-30 | 2013-05-08 | 日新制钢株式会社 | Coated steel sheet having excellent corrosion resistance and alkali resistance |
| CN103108991A (en) * | 2010-09-15 | 2013-05-15 | 杰富意钢铁株式会社 | Manufacturing method for steel plates for containers |
| CN103108988A (en) * | 2010-09-15 | 2013-05-15 | 杰富意钢铁株式会社 | Steel plate for containers and manufacturing method for same |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2942105B2 (en) | 1993-06-24 | 1999-08-30 | 東洋鋼鈑株式会社 | Manufacturing method of tin-coated steel sheet with excellent paint adhesion over time under wet conditions |
| US5380374A (en) * | 1993-10-15 | 1995-01-10 | Circle-Prosco, Inc. | Conversion coatings for metal surfaces |
| AU763754B2 (en) * | 2000-04-21 | 2003-07-31 | Jfe Steel Corporation | Surface treated steel plate and method for production thereof |
| TWI268965B (en) | 2001-06-15 | 2006-12-21 | Nihon Parkerizing | Treating solution for surface treatment of metal and surface treatment method |
| JP4492103B2 (en) * | 2002-11-25 | 2010-06-30 | 東洋製罐株式会社 | Surface-treated metal material and surface treatment method thereof, resin-coated metal material, metal can, can lid |
| JP4205939B2 (en) | 2002-12-13 | 2009-01-07 | 日本パーカライジング株式会社 | Metal surface treatment method |
| JP4805613B2 (en) | 2005-06-17 | 2011-11-02 | 東洋製罐株式会社 | Surface-treated metal plate and surface treatment method thereof, and resin-coated metal plate, can and can lid |
| JP2008088553A (en) * | 2006-09-08 | 2008-04-17 | Nippon Paint Co Ltd | Method of treating surface of metal base, metallic material treated by the surface treatment method, and method of coating the metallic material |
| EP2551377B1 (en) * | 2010-03-23 | 2017-09-13 | Nippon Steel & Sumitomo Metal Corporation | Method for producing a steel sheet for a container |
| TWI449813B (en) * | 2010-06-29 | 2014-08-21 | Nippon Steel & Sumitomo Metal Corp | Steel sheet for container and manufacturing method thereof |
| JP5754099B2 (en) | 2010-09-15 | 2015-07-22 | Ｊｆｅスチール株式会社 | Manufacturing method of steel plate for containers |
-
2013
- 2013-12-18 JP JP2013260930A patent/JP6530885B2/en active Active
-
2014
- 2014-12-05 CN CN201480069019.XA patent/CN105874107B/en not_active Expired - Fee Related
- 2014-12-05 EP EP14872878.5A patent/EP3085816B1/en active Active
- 2014-12-05 US US15/035,940 patent/US20160289843A1/en not_active Abandoned
- 2014-12-05 WO PCT/JP2014/082239 patent/WO2015093318A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050175798A1 (en) * | 2002-11-25 | 2005-08-11 | Wataru Kurokawa | Surface-treated metallic material, method of surface treating therefor and resin coated metallic material, metal can and can lid |
| CN1572912A (en) * | 2003-06-09 | 2005-02-02 | 日本油漆株式会社 | Method of treating metal surface and metal surface treated thereby |
| CN101010452A (en) * | 2004-06-22 | 2007-08-01 | 东洋制罐株式会社 | Surface-treated metal materials, method of treating the surfaces thereof, resin-coated metal materials, cans and can lids |
| US20100176000A1 (en) * | 2006-09-08 | 2010-07-15 | Toshio Inbe | Method of treating surface of metal base, metallic material treated by the surface treatment method, and method of coating the metallic material |
| CN101678644A (en) * | 2007-05-31 | 2010-03-24 | 东洋制罐株式会社 | Resin-coated metal sheet and formed object made therefrom |
| CN102066612A (en) * | 2008-03-17 | 2011-05-18 | 汉高两合股份公司 | Optimized passivation on Ti-/Zr-basis for metal surfaces |
| CN102918185A (en) * | 2010-05-28 | 2013-02-06 | 东洋制罐株式会社 | Surface treatment bath, method of manufacturing surface-treated steel plate using said surface treatment bath, and surface-treated steel plate formed with said manufacturing method |
| CN103097576A (en) * | 2010-06-30 | 2013-05-08 | 日新制钢株式会社 | Coated steel sheet having excellent corrosion resistance and alkali resistance |
| CN103097582A (en) * | 2010-09-15 | 2013-05-08 | 杰富意钢铁株式会社 | Steel sheet for container and method for manufacturing therefor |
| CN103108991A (en) * | 2010-09-15 | 2013-05-15 | 杰富意钢铁株式会社 | Manufacturing method for steel plates for containers |
| CN103108988A (en) * | 2010-09-15 | 2013-05-15 | 杰富意钢铁株式会社 | Steel plate for containers and manufacturing method for same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110117793A (en) * | 2018-02-05 | 2019-08-13 | 嘉瑞科技（惠州）有限公司 | A kind of light-alloy organic coating layer preparation method, membrane equipment and environment-friendly type organic coating |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015093318A1 (en) | 2015-06-25 |
| CN105874107B (en) | 2018-11-16 |
| EP3085816B1 (en) | 2020-06-10 |
| EP3085816A4 (en) | 2017-08-23 |
| US20160289843A1 (en) | 2016-10-06 |
| EP3085816A1 (en) | 2016-10-26 |
| JP6530885B2 (en) | 2019-06-12 |
| JP2015117402A (en) | 2015-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105874107A (en) | Surface-treated steel sheet, organic-resin-coated metal container, and method for producing surface-treated steel sheet | |
| CN103097583B (en) | Steel plate for container and manufacture method thereof | |
| TWI439573B (en) | A method for producing a steel sheet for a container material having a low environmental burden, a steel sheet for a container material having a small environmental burden, a precoated steel sheet for a laminated steel sheet and a container material for use in the container material | |
| CN102812156B (en) | Surface treated steel plate and manufacture method thereof and utilize the resin-coated steel sheet of this surface treated steel plate | |
| CN103097582B (en) | Steel plate for container and manufacture method thereof | |
| CN103108988A (en) | Steel plate for containers and manufacturing method for same | |
| JP2008184630A (en) | Surface treated metallic plate and method of manufacturing the same, resin coated metallic plate, metallic can and can cap | |
| CN107208300A (en) | The manufacture method of surface treated steel plate, canister and surface treated steel plate | |
| EP2963159A1 (en) | Surface-treated steel sheet manufacturing method | |
| JP6065360B2 (en) | Manufacturing method of surface-treated steel sheet | |
| CN107429419B (en) | The manufacturing method of steel plate for container and steel plate for container | |
| CN105579622B (en) | The manufacturing method of surface treated steel plate, organic resin coating metal container and surface treated steel plate | |
| CN107075710B (en) | Surface treated steel plate, its manufacturing method and resin-coated surface treated steel plate | |
| JP6168101B2 (en) | Surface-treated steel sheet, method for producing the same, and resin-coated steel sheet using the same | |
| JP2010255065A (en) | Surface treated steel sheet and method of manufacturing the same | |
| CN105874106B (en) | Manufacture method, surface treated steel plate and the canister of organic resin covering of surface treated steel plate | |
| JP6156299B2 (en) | Steel plate for container and method for producing the same | |
| JP5884180B2 (en) | Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, resin-coated steel sheet, can and can lid | |
| JP5257192B2 (en) | Method for producing surface-treated steel sheet and resin-coated steel sheet | |
| JP5919990B2 (en) | Manufacturing method of surface-treated steel sheet | |
| JP6164206B2 (en) | Steel plate for container and method for producing the same | |
| JP2012062508A (en) | Surface-treated steel sheet, method for producing the same, and resin-coated steel sheet using the same | |
| JP2014177677A (en) | Manufacturing method of surface-treated steel plate and surface-treated steel plate, resin-coated steel plate, and can and can top |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20181012 Address after: Tokyo, Japan Applicant after: TOYO SEIKAN Co.,Ltd. Applicant after: TOYO KOHAN Co.,Ltd. Address before: Tokyo, Japan Applicant before: TOYO SEIKAN Co.,Ltd. Applicant before: TOYO KOHAN Co.,Ltd. Applicant before: NIPPON PAINT SURF CHEMICALS CO.,LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181116 Termination date: 20211205 |