WO2012036202A1 - 容器用鋼板およびその製造方法 - Google Patents
容器用鋼板およびその製造方法 Download PDFInfo
- Publication number
- WO2012036202A1 WO2012036202A1 PCT/JP2011/070983 JP2011070983W WO2012036202A1 WO 2012036202 A1 WO2012036202 A1 WO 2012036202A1 JP 2011070983 W JP2011070983 W JP 2011070983W WO 2012036202 A1 WO2012036202 A1 WO 2012036202A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- film
- steel sheet
- steel plate
- layer
- acid
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 105
- 239000010959 steel Substances 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 33
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 66
- 150000001261 hydroxy acids Chemical class 0.000 claims description 31
- 238000007747 plating Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002335 surface treatment layer Substances 0.000 claims description 8
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 3
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229960002510 mandelic acid Drugs 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 7
- 238000010306 acid treatment Methods 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000007739 conversion coating Methods 0.000 abstract 2
- 239000010408 film Substances 0.000 description 96
- 238000000034 method Methods 0.000 description 39
- 229920005989 resin Polymers 0.000 description 36
- 239000011347 resin Substances 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 230000007797 corrosion Effects 0.000 description 27
- 238000005260 corrosion Methods 0.000 description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 239000003973 paint Substances 0.000 description 15
- 238000012545 processing Methods 0.000 description 15
- 229910052718 tin Inorganic materials 0.000 description 14
- 239000000956 alloy Substances 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- -1 nitrate ions Chemical class 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 8
- 238000005097 cold rolling Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000005029 tin-free steel Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910020938 Sn-Ni Inorganic materials 0.000 description 4
- 229910008937 Sn—Ni Inorganic materials 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000007765 extrusion coating Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000010409 ironing Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 239000010452 phosphate Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910017091 Fe-Sn Inorganic materials 0.000 description 1
- 229910017136 Fe—Ni—Sn Inorganic materials 0.000 description 1
- 229910017142 Fe—Sn Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
- C23C22/83—Chemical after-treatment
-
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a steel plate for containers mainly used for processing into a container such as a can, and particularly a container steel plate excellent in adhesion to an organic resin such as a plastic film, and a method for producing the same.
- Various metal cans such as beverage cans, food cans, pail cans and 18 liter cans use metal plates such as electrolytic chromic acid treated steel plates called tin-plated steel plates or tin-free steel plates.
- tin-free steel sheets are produced by electrolytically treating steel sheets in a bath containing hexavalent chromium, and are characterized by having excellent resin adhesion to paints and the like.
- Patent Document 1 discloses a steel plate for containers that has been subjected to electrolytic treatment in a tungstic acid solution.
- Patent Document 2 proposes a surface-treated metal material having an inorganic surface-treated layer containing Zr, O, and F as main components and containing almost no phosphate ions.
- various types of metal cans have been manufactured by processing metal plates such as tin-free steel plates and then processing them into cans.
- a method of processing a laminated metal plate (resin-coated metal plate) obtained by laminating a resin such as a plastic film into a can body is frequently used.
- This laminated metal plate requires that the resin and the metal plate be in close contact with each other.
- the laminated metal plate used as a beverage can or a food can is squeezed and squeezed into the neck portion, Since a retort sterilization process may be performed after filling, a strong resin adhesion is required in which a steel plate-resin adhesion portion having a high processing rate does not peel even in a high-temperature wet environment.
- a steel plate for cans with a high processing rate which has excellent weldability, corrosion resistance, and paint adhesion, as well as film adhesion, particularly film adhesion in high-processed parts (hereinafter referred to as high film adhesion) is required. ing.
- An object of the present invention is to provide a steel plate for containers that is further excellent in high film adhesion.
- the present inventor has performed a hydroxy acid treatment on a Zr compound film formed on a steel sheet by dipping or electrolytic treatment in a solution containing Zr ions and F ions.
- the present inventors have found that a steel sheet having a layer is excellent in high film adhesion, and have reached the present invention.
- the present invention provides the following.
- (1) The amount of adhesion formed by immersing or electrolytically treating a steel sheet in a solution containing Zr ions and F ions is 0.1 to 100 mg / m 2 in terms of metal Zr, and 0.1 mg / m in terms of F.
- (2) The steel plate for containers according to (1), wherein the solution further contains phosphate ions, and the amount of the chemical conversion film further adhered is 0.1 to 50 mg / m 2 in terms of P amount.
- the steel sheet, on at least one surface is a surface treated steel sheet having a surface treatment layer containing 100 ⁇ 15000 mg / m 2 to 5 ⁇ 1000 mg / m 2 or Sn and Ni, one of (1) to (3)
- the steel sheet has a Ni layer containing Ni of 5 to 150 mg / m 2 and is an Ni plating or Fe—Ni alloy plating phase, and 300 to 3000 mg / m 2 of Sn plating on the Ni layer.
- a part or all of the underlying Ni layer and a part of the Sn plating layer are alloyed by a molten tin treatment, and an island-shaped Sn plating layer formed from the non-alloyed portion of the Sn plating layer
- a method for producing a steel plate for containers according to any one of (1) to (5) above In a solution containing Zr ions and F ions, the steel sheet is immersed or electrolytically treated, On the steel sheet, a chemical conversion film having an adhesion amount of 0.1 to 100 mg / m 2 in terms of metal Zr and 0.1 mg / m 2 or less in terms of F is formed, and the steel sheet having the chemical conversion film in an aqueous solution containing hydroxy acid
- the method for producing a steel plate for containers according to any one of (1) to (5) wherein the method is soaked in or coated with an aqueous solution containing a hydroxy acid on the chemical film and dried.
- a steel plate for containers that is excellent in weldability, corrosion resistance, paint adhesion, and high film adhesion, a method for producing the same, a metal can using the same, and a can lid.
- the original plate used in the present invention is not particularly restricted, and usually a steel plate used as a container material is used. There are no particular restrictions on the manufacturing method and material of the original plate, and the original plate is manufactured through normal steel slab manufacturing processes such as hot rolling, pickling, cold rolling, annealing, and temper rolling. A surface treatment layer containing one or more of Ni and Sn may be provided on the original plate or the original plate.
- the method for imparting is not particularly limited.
- the surface-treated steel sheet has a surface-treated layer containing Sn (tin) or Ni (nickel) on at least one surface of the steel sheet.
- Sn titanium
- Ni nickel
- surface treated layer is not particularly limited, per side, a 5 ⁇ 1000mg / m 2 or Sn and Ni preferably contains 100 ⁇ 15000mg / m 2.
- Sn exhibits excellent workability, weldability, and corrosion resistance
- the metal Sn is preferably 100 mg / m 2 or more to exhibit this effect.
- the adhesion amount of Sn is 15000 mg / m 2 or less as metal Sn.
- a Sn alloy layer is formed by performing a reflow process after Sn plating, and corrosion resistance further improves.
- Ni exerts its effect on paint adhesion, film adhesion, corrosion resistance, and weldability.
- Ni of 5 mg / m 2 or more is preferable as metal Ni.
- the adhesion amount of Ni is preferably 10 mg / m 2 or more and 1000 mg / m 2 or less as metal Ni.
- a plating layer using Ni or Sn is preferable.
- a preferable plating layer from the viewpoint of uniform coverage of the chemical conversion film, which is a film containing Zr formed thereon, is an Fe—Sn—Ni alloy layer, an intermediate layer composed of a single layer of Fe—Sn alloy layer, or an outermost layer.
- the surface-treated steel sheet has a Ni layer containing 5 to 150 mg / m 2 of Ni and is a Ni plating or Fe—Ni alloy plating phase, and 100 to 3000 mg / m 2 on the base Ni layer.
- a part or all of the underlying Ni layer and a part of the Sn plating layer are alloyed by molten tin treatment, and an island-shaped Sn formed from the unalloyed portion of the Sn plating layer.
- a surface-treated steel sheet having a plating layer If the Sn adhesion amount of the plating layer is less than 100 mg / m 2 , the corrosion resistance tends to be inferior. On the other hand, if it exceeds 3000 mg / m 2 , the plating layer becomes too thick, and thus the cost merit may be reduced.
- the Sn adhesion amount can be measured by electrolytic stripping or surface analysis using fluorescent X-rays.
- the molten tin treatment performed after Sn plating is applied to a steel plate or a plated steel plate to which nickel-based plating has been applied is also called reflow processing, and after Sn plating, the temperature is raised to 232 ° C. or higher, which is the melting point of Sn. This is performed in order to melt the surface Sn and to give a surface gloss. Also, by performing molten tin treatment, Sn on the surface is melted and alloyed with a base steel plate or a base metal to form a Sn—Fe alloy layer or a Sn—Fe—Ni alloy layer. Improve corrosion resistance. Moreover, island-shaped Sn can be formed by appropriately controlling the molten tin treatment.
- Chemical conversion film A chemical conversion film containing a Zr compound and F is applied directly on the steel sheet or on the upper layer of the surface treatment layer containing one or more of these Ni and Sn to obtain a chemical conversion film steel sheet.
- a method for applying these films there are a method of immersing a steel plate in an acidic aqueous solution in which Zr ions and F ions are dissolved, and a method of performing a cathode electrolytic treatment.
- the immersion treatment is disadvantageous for industrial production because various films are formed by etching the base, and the treatment time becomes long.
- cathodic electrolysis treatment a uniform film can be obtained in combination with forced charge transfer, surface cleaning by hydrogen generation at the steel plate interface, and adhesion promoting effect by pH increase. Further, in this cathodic electrolysis treatment, if nitrate ions and ammonium ions coexist in the treatment solution, Zr oxide or Zr phosphorylation that is excellent in improving corrosion resistance and adhesion in a short time treatment of several seconds to several tens of seconds. Since it is possible to promote the precipitation of the Zr compound film containing the product, it is industrially advantageous. Therefore, cathodic electrolysis is desirable for applying the chemical conversion film, and in particular, cathodic electrolysis with a treatment liquid in which nitrate ions and ammonium ions coexist is preferable.
- the concentration of ammonium ions in the treatment solution for cathodic electrolysis is in the range of about 100 to 10,000 ppm by mass, and the concentration of nitrate ions is in the range of about 1000 to 20000 ppm by mass, depending on the production equipment and production rate (capacity). Adjust it.
- the current density can be 0.05 to 50 A / dm 2
- the electrolysis time can be 0.01 to 10 seconds.
- the role of the Zr compound is to ensure corrosion resistance and adhesion.
- Zr compounds are thought to be Zr hydrated oxides and Zr phosphorous oxides composed of Zr oxide and Zr hydroxide, and these Zr compounds have excellent corrosion resistance and adhesion. Therefore, when the Zr film increases, the corrosion resistance and adhesion begin to improve, and when the amount of metal Zr is 0.1 mg / m 2 or more, a practically satisfactory level of corrosion resistance and adhesion are secured. Furthermore, when the amount of Zr film increases, the effect of improving corrosion resistance and adhesion also increases, but when the amount of Zr film exceeds 100 mg / m 2 in terms of metal Zr, the Zr film becomes too thick and the adhesion of the Zr film itself deteriorates.
- the Zr film adhesion amount is 0.1 to 100 mg / m 2 in terms of metal Zr amount.
- Coating weight of zirconium coating 0.1mg / m 2 ⁇ 9mg / m 2 is preferred in the metal zirconium content. More preferably, coating weight of zirconium coating is 1mg / m 2 ⁇ 8mg / m 2 of metal zirconium content.
- the amount of Zr phosphorous oxide when the amount of Zr phosphorous oxide is increased, more excellent corrosion resistance and adhesion are exhibited, but the effect can be clearly recognized by the amount of metal P being 0.1 mg / m 2 or more.
- the amount of phosphoric acid film increases, the effect of improving corrosion resistance and adhesion also increases.
- the amount of phosphoric acid film exceeds 50 mg / m 2 in terms of P amount, the phosphoric acid film becomes too thick and the adhesion of the phosphoric acid film itself is increased. As a result, the electrical resistance increases and the weldability deteriorates. Therefore, it is preferable that the phosphoric acid film adhesion amount is 0.1 to 50 mg / m 2 in terms of P amount.
- Deposition amount of phosphate film is preferably from 0.1mg / m 2 ⁇ 8mg / m 2 of metal P amount, more preferably the coating weight of phosphate coating, metal P amount 1mg / m 2 ⁇ 6mg / m 2 .
- F Since F is contained in the aqueous solution forming the chemical conversion film, it is taken into the film together with the Zr compound. F in the film does not affect the paint adhesion or film adhesion (primary adhesion), but the adhesion (secondary adhesion), rust resistance or coating during high temperature sterilization such as retort treatment It may cause deterioration of under corrosiveness. It is considered that this is because F in the film is eluted into water vapor or a corrosive liquid, and the bond with the organic film is decomposed or the base steel sheet is corroded.
- the amount of F in the film exceeds 0.1 mg / m 2 , the deterioration of these characteristics starts to become obvious, so the amount of F is preferably 0.1 mg / m 2 or less.
- a hydroxy acid treatment layer is formed on the chemical conversion film, and after drying, washing treatment may be performed by immersion treatment or spray treatment in warm water.
- the amount of F can be reduced by increasing the processing time or by increasing the processing time. Therefore, in order to reduce the F content in the film to 0.1 mg / m 2 or less, it is preferable to perform a dipping process or a spray process in warm water of 80 ° C. or higher. Dry after the cleaning process. Although drying temperature is not limited, 70 degreeC or more is preferable.
- the amount of metal Zr, the amount of P, and the amount of F contained in the chemical conversion film according to the present invention can be measured by a quantitative analysis method such as fluorescent X-ray analysis.
- Hydroxy acid treatment layer A hydroxy acid treatment layer is provided on the chemical conversion film obtained as described above.
- the method to provide is not limited, The method of immersing a chemical conversion film steel plate in hydroxy acid aqueous solution or apply
- hydroxy acid is selected from citric acid, tartaric acid, glycolic acid, lactic acid, glyceric acid, mandelic acid and the like At least one acid can be used. Hydroxy acids may be used alone or in combination of two or more. Moreover, you may mix and use a phenol resin for hydroxy acid. The mixing ratio is less than 50% by mass of the organic component.
- a method for forming this hydroxy acid-treated layer a method in which the above hydroxy acid is dissolved in water or an organic solvent, applied as a solution on a steel sheet, and then dried is preferable.
- a coating method various known coating methods can be used. In order to shorten the drying time, a step of heating the steel sheet may be provided as necessary.
- the adhesion amount of the hydroxy acid-treated layer is less than 0.05 mg / m 2 in terms of C amount, the effect of improving resin adhesion is insufficient, and if it exceeds 50 mg / m 2 , cohesive failure occurs in the organic film. Since there is a possibility that the resin adhesiveness is lowered, it is preferably 0.05 to 50 mg / m 2 .
- the amount of C contained in the hydroxy acid-treated layer can be measured by subtracting the amount of C existing in the steel plate using TOC (total organic carbon meter).
- TOC total organic carbon meter
- the steel plate for containers of the present invention can be produced by coating a resin on the chemical conversion film to produce a resin-coated steel plate.
- the steel plate for containers according to the present invention is excellent in film adhesion (high film adhesion) in a high-processed portion. This is presumably because the hydroxy acid-treated layer has a large number of functional groups and is chemically bonded to the resin film (organic resin).
- the resin coated on the container steel plate or the surface-treated steel plate and various thermoplastic resins and thermosetting resins can be exemplified.
- olefin resin film such as ionomer
- polyester film such as polybutylene terephthalate
- nylon 6 It may be a non-stretched or biaxially stretched thermoplastic resin film such as a nylon film such as nylon 6,6, nylon 11 or nylon 12, a polyvinyl chloride film or a polyvinylidene chloride film.
- a urethane adhesive an epoxy adhesive, an acid-modified olefin resin adhesive, a copolyamide adhesive, a copolyester adhesive (thickness: 0.1 to 5. 0 ⁇ m) is preferably used.
- a thermosetting paint may be applied to the surface-treated steel plate side or the film side in a thickness range of 0.05 to 2 ⁇ m, and this may be used as an adhesive.
- modified epoxy paints such as phenol epoxy and amino-epoxy, vinyl chloride-vinyl acetate copolymer, saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, epoxy-modified- Epoxyamino-modified, epoxyphenol-modified-vinyl paint or modified vinyl paint, acrylic paint, synthetic rubber-type paint such as styrene-butadiene copolymer, etc., or a combination of two or more thermoplastic or thermosetting paints It may be a combination.
- the thickness of the resin coating layer is desirably 3 to 50 ⁇ m, particularly 5 to 40 ⁇ m. This is because if the thickness is below the above range, the corrosion resistance becomes insufficient, and if the thickness exceeds the above range, problems are likely to occur in terms of workability.
- the resin coating layer can be formed on the hydroxy acid-treated steel sheet of the present invention by any means.
- it can be performed by an extrusion coating method, a cast film thermal bonding method, a biaxially stretched film thermal bonding method, or the like.
- the extrusion coating method it can be produced by extrusion coating a resin on a surface-treated steel sheet in a molten state and thermally bonding the resin.
- the resin is extruded from a T-die into a thin film, and the extruded molten resin film is passed through a pair of laminate rolls together with a surface-treated steel sheet to be pressed and integrated under cooling, and then rapidly cooled.
- extrusion coating a multi-layer resin coating layer use multiple extruders for each layer, merge the resin streams from each extruder in a multi-layer die, and then extrude as in the case of a single layer resin. Just coat it.
- a resin coating layer can be formed on both surfaces of a surface-treated steel sheet by passing a surface-treated steel sheet vertically between a pair of laminate rolls and supplying a molten resin web to both sides thereof.
- a resin-coated steel sheet can be applied to three-piece cans and seamless cans (two-piece cans) having side seams.
- the present invention can be applied to a stay-on-tab type easy open can lid, a full open type easy open can lid, and the like.
- Metal can and can lid As long as the method for producing the metal can is formed from the above-described resin-coated steel sheet, any can manufacturing method can be used.
- the metal can can be a three-piece can having a side seam, but is generally preferably a seamless can (two-piece can).
- This seamless can is drawn and redrawn, bent and stretched by drawing and redrawing (stretching), and stretched and drawn by drawing and redrawing so that the coated surface of the organic resin on the resin-coated steel sheet faces the inner surface of the can. It can be manufactured by a conventionally known processing method such as ironing processing, drawing / ironing processing, neck necking processing or the like.
- the can lid is formed of the above-described resin-coated steel plate, any conventionally known lid-making method can be used. Generally, it can be manufactured by a processing method of a stay-on-tab type easy open can lid or a full open type easy open can lid.
- a surface treatment layer on steel plate> A surface treatment layer was applied on a steel sheet having a thickness of 0.17 to 0.23 mm by using the following treatment methods (1) to (6).
- Treatment method 1 After cold rolling, the annealed and regulated original sheet was degreased and pickled, and then Sn was plated using a ferrostan bath to prepare an Sn-plated steel sheet.
- Treatment method 2 After cold rolling, Ni plating was performed using a Watt bath, a Ni diffusion layer was formed during annealing, and a Ni plated steel sheet was produced.
- Method A The steel sheet is immersed in a treatment solution in which fluorinated Zr 4000 ppm, phosphoric acid 300 ppm, phenol resin 0 or 700 ppm, and ammonium nitrate 10000 ppm are dissolved, and the Zr compound-phenol resin film is formed. Formed.
- Method B The above steel sheet was immersed in a treatment solution in which 1500 ppm by mass of Zr fluoride, 400 ppm by mass of phosphoric acid, 0 or 500 ppm by mass of phenol resin, and 5000 ppm by mass of ammonium nitrate were dissolved. A phenolic resin film was applied. Table 1 shows the current density (A / dm 2 ) and time (seconds) of cathodic electrolysis. “-” Indicates that no processing or detection was performed.
- (Method C) Zr compound is obtained by immersing or cathodically electrolyzing the steel sheet in a treatment solution in which 1500 to 4300 mass ppm of phosphorous Zr potassium, 300 to 1500 mass ppm of phosphoric acid, and 1000 to 7000 mass ppm of ammonium nitrate are dissolved.
- the chemical conversion film (Example) which has this was provided.
- Table 1 shows the current density (A / dm 2 ) and time (seconds) of cathodic electrolysis.
- the amount of metallic Ni and the amount of metallic Sn in the surface treatment layer were measured by a fluorescent X-ray method and specified using a calibration curve. Further, the amount of metal Zr, the amount of P, and the amount of F contained in the Zr compound film were measured by a quantitative analysis method such as fluorescent X-ray analysis. The amount of C contained in the hydroxy acid-treated layer was measured by subtracting the amount of C existing in the steel sheet using TOC (total organic carbon meter).
- the nip length is the length in the transport direction of the portion where the rubber roll and the steel plate are in contact.
- the appropriate current range on the secondary side was 1500 A or more.
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Abstract
Description
(1)Zrイオン、Fイオンを含む溶液中で、鋼板を浸漬又は電解処理して形成される、付着量が、金属Zr量で0.1~100mg/m2、F量で0.1mg/m2以下の化成皮膜と、該化成皮膜上に、付着量が、C量で0.05~50mg/m2であるヒドロキシ酸処理層とを有する、容器用鋼板。
(2)前記溶液中にさらにリン酸イオンを含み、前記化成皮膜の付着量が、さらにP量で0.1~50mg/m2である(1)に記載の容器用鋼板。
(3)前記ヒドロキシ酸が、クエン酸、酒石酸、グリコール酸、乳酸、グリセリン酸およびマンデル酸から選択される少なくとも1つである(1)または(2)に記載の容器用鋼板。
(4)前記鋼板は、少なくとも片面に、Niを5~1000mg/m2またはSnを100~15000mg/m2を含む表面処理層を有する表面処理鋼板である、(1)~(3)のいずれかに記載の容器用鋼板。
(5)前記鋼板は、Niを5~150mg/m2含む、NiめっきまたはFe-Ni合金めっき相である下地Ni層と、前記下地Ni層の上に300~3000mg/m2のSnめっきされ、溶融溶錫処理により前記下地Ni層の一部または全部と前記Snめっき層の一部が合金化され、前記Snめっき層の合金化していない残部から形成された島状のSnめっき層とを有する表面処理鋼板である、(1)~(4)のいずれかに記載の容器用鋼板。
(6)上記(1)~(5)のいずれかに記載の容器用鋼板の製造方法であって、
Zrイオン、Fイオンを含む溶液中で、鋼板を浸漬又は電解処理し、
鋼板上に付着量が、金属Zr量で0.1~100mg/m2、F量で0.1mg/m2以下の化成皮膜を形成し、該化成皮膜を有する鋼板をヒドロキシ酸を含む水溶液中に浸漬する、または該化成皮膜上にヒドロキシ酸を含む水溶液を塗布し、乾燥する、(1)~(5)のいずれかに記載の容器用鋼板の製造方法。
(7)前記乾燥工程の温度が、70℃以上である(6)に記載の容器用鋼板の製造方法。
(8)前記乾燥工程の後に、80℃以上の温度の水で洗浄し、さらに乾燥することを特徴とする、(6)または(7)に記載の容器用鋼板の製造方法。
表面処理鋼板は、鋼板の少なくとも一方の面にSn(錫)またはNi(ニッケル)を含む表面処理層を有する。表面処理層は特に限定されないが、片面当たり、Niを5~1000mg/m2またはSnを100~15000mg/m2含むのが好ましい。
めっき層のSn付着量が、100mg/m2未満では耐食性に劣る傾向がある。一方、3000mg/m2超えではめっき層が厚くなりすぎるため、コスト的なメリットが少なくなる場合がある。尚、Sn付着量は、電解剥離法又は蛍光X線による表面分析により測定することができる。
鋼板上に直接、または、これらのNi、Snの1種以上を含む表面処理層の上層に、Zr化合物とFとを含む化成皮膜が付与され化成皮膜鋼板を得る。これらの皮膜を付与する方法は、Zrイオン、Fイオンを溶解させた酸性水溶液に鋼板を浸漬する方法や陰極電解処理により行う方法がある。浸漬処理では、下地をエッチングして各種の皮膜が形成される為、処理時間が長くなる為、工業生産的には不利である。一方、陰極電解処理では、強制的な電荷移動および鋼板界面での水素発生による表面清浄化とpH上昇による付着促進効果も相俟って、均一な皮膜を得る事が出来る。更に、この陰極電解処理において、処理液中に硝酸イオンとアンモニウムイオンが共存すると、数秒から数十秒程度の短時間処理で耐食性や密着性の向上効果に優れたZr酸化物、またはZrリン酸化物を含むZr化合物皮膜の析出を促進する事が可能であることから、工業的に有利である。従って、化成皮膜の付与には陰極電解処理が望ましく、特に硝酸イオンとアンモニウムイオンを共存させた処理液での陰極電解処理が好ましい。
ジルコニウム皮膜の付着量は、金属ジルコニウム量で0.1mg/m2~9mg/m2が好ましい。より好ましくは、ジルコニウム皮膜の付着量は、金属ジルコニウム量で1mg/m2~8mg/m2である。ジルコニウム皮膜の付着量をこの範囲とすることにより、レトルト後の耐食性が確保できるとともに、均質性高く加工性に優れた皮膜を得ることができる。
上記のようにして得られた化成皮膜上にヒドロキシ酸処理層を付与する。付与する方法は限定されないが、ヒドロキシ酸水溶液に化成皮膜鋼板を浸漬するか、ヒドロキシ酸水溶液を化成皮膜上に塗布する方法が好適である。浸漬または塗布後に乾燥する。乾燥温度は限定されないが70℃以上が好ましい。短時間で充分な乾燥ができるからである。
ヒドロキシ酸は、1分子中にカルボキシル基とアルコール性水酸基とを持つ有機化合物の総称であり、本発明では、クエン酸、酒石酸、グリコール酸、乳酸、グリセリン酸、マンデル酸などの中から選ばれた少なくとも1種の酸を用いることができる。ヒドロキシ酸は1種でも2種以上混合して用いてもよい。また、ヒドロキシ酸にフェノール樹脂を混合して用いてもよい。混合率は有機物成分の50質量%未満とする。
このヒドロキシ酸処理層の形成方法としては、上記のヒドロキシ酸を水または有機溶剤に溶解し、溶液として鋼板上に塗布した後、乾燥する方法が好適である。塗布方法としては、各種公知のコーティング法を用いることができる。乾燥時間短縮のために、必要に応じて鋼板を加熱する工程を設けてもよい。なお、乾燥によって皮膜を形成した後は、水洗工程を経ることによって金属上に残存した過剰なヒドロキシ酸および・またはFを除去することが好ましい。この場合、特に強力な水洗である必要はなく、水槽に浸漬、あるいは水スプレー程度で十分である。水洗後は、再度乾燥し、実用に供することができる。
本発明の鋼板上にZr化合物化成皮膜とヒドロキシ酸処理層を有する本発明の密着性皮膜は、ヒドロキシ酸処理層が官能基の多い界面を構成するので、さらに上層に樹脂被覆層を形成するとヒドロキシ酸処理層とその上層とのフイルム密着性が高い。
本発明の容器用鋼板は、上記の化成皮膜上に、樹脂を被覆して樹脂被覆鋼板を製造することができる。上述したように、本発明の容器用鋼板は、高加工部のフイルム密着性(高フイルム密着性)に優れている。これは、ヒドロキシ酸処理層が多数の官能基を有し、樹脂フイルム(有機樹脂)と化学的に結合するためであると考えられる。
容器用鋼板原板または表面処理鋼板に被覆する樹脂としては、特に限定はなく、各種熱可塑性樹脂や熱硬化性樹脂を挙げることができる。例えば、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、エチレン-酢酸ビニル共重合体、エチレン-アクリルエステル共重合体、アイオノマー等のオレフィン系樹脂フィルム、またはポリブチレンテレフタラート等のポリエステルフィルム、もしくはナイロン6、ナイロン6,6、ナイロン11、ナイロン12等のポリアミドフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム等の熱可塑性樹脂フィルムの未延伸または二軸延伸したものであってもよい。積層の際に接着剤を用いる場合は、ウレタン系接着剤、エポキシ系接着剤、酸変性オレフィン樹脂系接着剤、コポリアミド系接着剤、コポリエステル系接着剤(厚さ:0.1~5.0μm)等が好ましく用いられる。さらに熱硬化性塗料を、厚み0.05~2μmの範囲で表面処理鋼板側、あるいはフィルム側に塗布し、これを接着剤としてもよい。
さらに、フェノールエポキシ、アミノ-エポキシ等の変性エポキシ塗料、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-酢酸ビニル共重合体けん化物、塩化ビニル-酢酸ビニル-無水マレイン酸共重合体、エポキシ変性-、エポキシアミノ変性-、エポキシフェノール変性-ビニル塗料または変性ビニル塗料、アクリル塗料、スチレン-ブタジエン系共重合体等の合成ゴム系塗料等の熱可塑性または熱硬化性塗料の単独または2種以上の組合わせであってもよい。
樹脂被覆層の厚みは3~50μm、特に5~40μmの範囲にすることが望ましい。厚みが上記範囲を下回ると耐食性が不十分となり、厚みが上記範囲を上回ると加工性の点で問題が生じやすいためである。
こうした樹脂被覆鋼板は、側面継ぎ目を有するスリーピース缶やシームレス缶(ツーピース缶)に適用することができる。また、ステイ・オン・タブタイプのイージーオープン缶蓋やフルオープンタイプのイージーオープン缶蓋等に適用することができる。
金属缶の製造方法は、前述した樹脂被覆鋼板から形成されている限り、任意の製缶法を用いることができる。この金属缶は、側面継ぎ目を有するスリーピース缶であることもできるが、一般にシームレス缶(ツーピース缶)であることが好ましい。このシームレス缶は、樹脂被覆鋼板の有機樹脂の被覆面が缶内面側となるように、絞り・再絞り加工、絞り・再絞りによる曲げ伸ばし加工(ストレッチ加工)、絞り・再絞りによる曲げ伸ばし・しごき加工、あるいは絞り・しごき加工、ネック部のネッキング加工等の従来公知の加工方法で製造できる。
上述の説明は、この発明の実施形態の一例を説明したに過ぎず、本発明の請求の範囲内において種々の変更を加えることができる。
以下の処理法(1)~(6)の方法を用いて、板厚0.17~0.23mmの鋼板上に表面処理層を付与した。
(処理法1)冷間圧延後、焼鈍、調圧された原板を脱脂、酸洗後、フェロスタン浴を用いてSnをめっきし、Snめっき鋼板を作製した。
(処理法2)冷間圧延後、ワット浴を用いてNiめっきを施し、焼鈍時にNi拡散層を形成させ、Niめっき鋼板を作製した。
(処理法3)冷間圧延後、焼鈍、調圧された原板を脱脂、酸洗後、フェロスタン浴を用いてSnをめっきし、その後、リフロー処理を行い、Sn合金層を有するSnめっき鋼板を作製した。
(処理法4)冷間圧延後、焼鈍、調圧された原板を脱脂、酸洗後、硫酸-塩酸浴を用いてFe-Ni合金めっきを施し、引き続き、フェロスタン浴を用いてSnめっきを施し、Ni、Snめっき鋼板を作製した。
(処理法5)冷間圧延後、焼鈍、調圧された原板を脱脂、酸洗後、硫酸-塩酸浴を用いてSn-Ni合金鍍金を施し、Ni、Snめっき鋼板を作製した。
(処理法6)
冷間圧延後、厚さが0.17~0.23mmの鋼基材(鋼板)を、脱脂及び酸洗した後、ワット浴を用いてNiめっきを施し、焼鈍によりNi拡散層を形成後、引き続き、フェロスタン浴を用いてSnめっきを施し、その後、溶融溶錫処理を行い、Sn-Ni合金層を有するSnめっき鋼板を作製した。
島状Sn形成状況を光学顕微鏡にて表面を観察し、実施例7、8で全体的に島が形成されていることを確認した。
上記の処理により表面処理層を付与した後、以下の処理法で化成皮膜を付与した。
(A法)フッ化Zr4000質量ppm、リン酸300質量ppm、フェノール樹脂0または700質量ppm、硝酸アンモン10000質量ppmを溶解させた処理液に、上記鋼板を浸漬し、Zr化合物-フェノール樹脂皮膜を形成した。
(B法)フッ化Zr1500質量ppm、リン酸400質量ppm、フェノール樹脂0または500質量ppm、硝酸アンモンニウム5000質量ppmを溶解させた処理液に、上記鋼板を浸漬、陰極電解してZr化合物-フェノール樹脂皮膜を付与した。陰極電解処理の電流密度(A/dm2)と時間(秒)を、表1に示した。「-」は処理しないまたは検出されなかったことを示す。
(C法)フッ化Zrカリウム1500~4300質量ppm、リン酸300~1500質量ppm、硝酸アンモンモニウム1000~7000質量ppmを溶解させた処理液に、上記鋼板を浸漬または、陰極電解してZr化合物を有する化成皮膜(実施例)を付与した。陰極電解処理の電流密度(A/dm2)と時間(秒)を、表1に示した。
形成された化成皮膜上に、表1に示すヒドロキシ酸の表1の濃度の水溶液をロールコーターを用いて塗布した。あるいは、浸漬してロール絞りを行った。
上記の処理によりヒドロキシ酸処理層を付与した後、下記工程で乾燥し水洗処理を行い、皮膜中のF量を制御し、その後乾燥した。
(W1法)70℃で乾燥し、80℃の温水に浸漬し、40℃で乾燥した。
(W2法)40℃で乾燥し、85℃の温水に浸漬し、70℃で乾燥した。
(W3法)30℃で乾燥し、80℃の温水に浸漬し、40℃で乾燥した。
(W4法)70℃で乾燥し、80℃の温水を噴霧し、70℃で乾燥した。
上記の処理を行った試験材について、以下に示す(A)~(G)の各項目について性能評価を行った。(A)の高フイルム密着性については、実施例の剥離面積率は1%未満であり、フイルム密着性に優れていたが、比較例はいずれも剥離面積率1%以上で、高加工部のフイルム密着性に問題があった。(B)~(G)の各項目については、実施例は比較例と同様に優れていた。
試験材の両面に厚さ20μmの延伸倍率3.1×3.1、厚さ25μm、共重合比12モル%、融点224℃のイソフタル酸共重合ポリエチレンテレフタラートフィルムを用い、フィルムの二軸配向度(BO値)が150になるようなラミネート条件、すなわち鋼板の送り速度:40m/min、ゴムロールのニップ長:17mm、圧着後水冷までの時間:1secでラミネートして、実施例、比較例の樹脂被覆鋼板を作製した。ここで、ニップ長とは、ゴムロールと鋼板が接する部分の搬送方向の長さのことである。得られた樹脂被覆鋼板を絞りしごき加工を行い、缶体を作製し、缶胴のネック部の加工(ネッキング加工)を行い、この缶体を120℃、30分間のレトルト処理を行い、缶胴のネック部の樹脂フィルムの剥離状況を観察し、剥離面積率から、5段階(◎:剥離面積率:0%、○:剥離面積率1%未満、△:剥離面積率1~2%、△×:剥離面積率:2%超~10%:、×:剥離面積率:10%超)で評価した。結果を表1に示す。
試験材の両面に厚さ20μmのPETフィルムを200℃でラミネートし、絞り加工としごき加工による製缶加工を段階的に行い、フィルムの疵、浮き、剥離を観察しそれらの面積率から成型を評価した結果、フィルムの疵、浮き、剥離がなかった。
(C)溶接性
ワイヤーシーム溶接機を用いて、溶接ワイヤースピード80m/minの条件で、電流を変更して試験材を溶接し、十分な溶接強度が得られる最小電流値とチリ及び溶接スパッタなどの溶接欠陥が目立ち始める最大電流値からなる適正電流範囲の広さから総合的に判断し、溶接性を評価した結果、二次側の適正電流範囲:1500A以上、であった。
(D)一次塗料密着性
試験材にエポキシ-フェノール樹脂を塗布し、200℃、30minで焼付けた後、1mm間隔で地鉄に達する深さの碁盤目を入れ、テープで剥離し、剥離状況を観察し、剥離面積率から、評価した結果、剥離面積率:0%であった。
(E)二次塗料密着性
試験材にエポキシ-フェノール樹脂を塗布し、200℃、30minで焼付けた後、1mm間隔で地鉄に達する深さの碁盤目を入れ、その後、125℃、30minのレトルト処理を行い、乾燥後、テープで塗膜を剥離し、剥離状況を観察し、剥離面積率から、4段階で評価した結果、剥離面積率:0%であった。
(F)塗膜下耐食性
試験材にエポキシ-フェノール樹脂を塗布し、200℃、30minで焼付けた後、地鉄に達する深さのクロスカットを入れ、1.5質量%クエン酸-1.5質量%食塩混合液からなる試験液に、45℃、72時間浸漬し、洗浄、乾燥後、テープ剥離を行い、クロスカット部の塗膜下腐食状況と平板部の腐食状況を観察し、塗膜下腐食の幅及び平板部の腐食面積率の両評価から、評価した結果、塗膜下腐食幅0.2mm未満かつ平板部の腐食面積率0%であった。
(G)レトルト耐錆性
試験材を125℃、30minのレトルト処理し、錆の発生状況を観察し、錆発生面積率から評価した結果、錆発生面積率0%、であった。
Claims (8)
- Zrイオン、Fイオンを含む溶液中で、鋼板を浸漬又は電解処理して形成される、付着量が、金属Zr量で0.1~100mg/m2、F量で0.1mg/m2以下の化成皮膜と、該化成皮膜上に、付着量が、C量で0.05~50mg/m2であるヒドロキシ酸処理層とを有する、容器用鋼板。
- 前記溶液中にさらにリン酸イオンを含み、前記化成皮膜の付着量が、さらにP量で0.1~50mg/m2である請求項1に記載の容器用鋼板。
- 前記ヒドロキシ酸が、クエン酸、酒石酸、グリコール酸、乳酸、グリセリン酸およびマンデル酸から選択される少なくとも1つである請求項1または2に記載の容器用鋼板。
- 前記鋼板は、少なくとも片面に、Niを5~1000mg/m2またはSnを100~15000mg/m2を含む表面処理層を有する表面処理鋼板である、請求項1~3のいずれか1項に記載の容器用鋼板。
- 前記鋼板は、Niを5~150mg/m2含む、NiめっきまたはFe-Ni合金めっき相である下地Ni層と、前記下地Ni層の上に300~3000mg/m2のSnめっきされ、溶融溶錫処理により前記下地Ni層の一部または全部と前記Snめっき層の一部が合金化され、前記Snめっき層の合金化していない残部から形成された島状のSnめっき層とを有する表面処理鋼板である、請求項1~4のいずれか1項に記載の容器用鋼板。
- 請求項1~5のいずれか1項に記載の容器用鋼板の製造方法であって、
Zrイオン、Fイオンを含む溶液中で、鋼板を浸漬又は電解処理し、
鋼板上に付着量が、金属Zr量で0.1~100mg/m2、F量で0.1mg/m2以下の化成皮膜を形成し、該化成皮膜を有する鋼板をヒドロキシ酸を含む水溶液中に浸漬する、または該化成皮膜上にヒドロキシ酸を含む水溶液を塗布し、乾燥する、請求項1~5のいずれか1項に記載の容器用鋼板の製造方法。 - 前記乾燥工程の温度が、70℃以上である請求項6に記載の容器用鋼板の製造方法。
- 前記乾燥工程の後に、80℃以上の温度の水で洗浄し、さらに乾燥することを特徴とする、請求項6または7に記載の容器用鋼板の製造方法。
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US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
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EP3000917B1 (en) | 2013-05-21 | 2020-03-11 | Nippon Steel Corporation | Steel sheet for containers, and method for producing steel sheet for container |
JP6530885B2 (ja) * | 2013-12-18 | 2019-06-12 | 東洋製罐株式会社 | 表面処理鋼板、有機樹脂被覆金属容器、及び表面処理鋼板の製造方法 |
US10294577B2 (en) * | 2014-10-09 | 2019-05-21 | Nippon Steel & Sumitomo Metal Corporation | Chemical treatment steel sheet, and method for producing chemical treatment steel sheet |
JP6510844B2 (ja) * | 2015-03-20 | 2019-05-08 | 株式会社神戸製鋼所 | 表面処理方法、表面処理装置およびアルミニウム表面処理材料 |
MX2019001874A (es) | 2016-08-24 | 2019-06-06 | Ppg Ind Ohio Inc | Composicion limpiadora que contiene hierro. |
CN111705314A (zh) * | 2020-06-23 | 2020-09-25 | 扬州耐盾桶业有限公司 | 一种耐腐蚀性好的钢桶内壁制备方法 |
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US10125424B2 (en) | 2012-08-29 | 2018-11-13 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
US10400337B2 (en) | 2012-08-29 | 2019-09-03 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates |
US10920324B2 (en) | 2012-08-29 | 2021-02-16 | Ppg Industries Ohio, Inc. | Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates |
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CN103097582B (zh) | 2015-11-25 |
TW201224206A (en) | 2012-06-16 |
MY162540A (en) | 2017-06-15 |
CN103097582A (zh) | 2013-05-08 |
JP2012082515A (ja) | 2012-04-26 |
TWI490370B (zh) | 2015-07-01 |
JP5729230B2 (ja) | 2015-06-03 |
US9637826B2 (en) | 2017-05-02 |
CO6680718A2 (es) | 2013-05-31 |
US20130209827A1 (en) | 2013-08-15 |
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