WO2012036201A1 - 容器用鋼板の製造方法 - Google Patents
容器用鋼板の製造方法 Download PDFInfo
- Publication number
- WO2012036201A1 WO2012036201A1 PCT/JP2011/070982 JP2011070982W WO2012036201A1 WO 2012036201 A1 WO2012036201 A1 WO 2012036201A1 JP 2011070982 W JP2011070982 W JP 2011070982W WO 2012036201 A1 WO2012036201 A1 WO 2012036201A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ions
- metal
- steel plate
- steel sheet
- layer
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 95
- 239000010959 steel Substances 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- 150000002500 ions Chemical class 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 36
- -1 boric acid ions Chemical class 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims description 53
- 238000007747 plating Methods 0.000 claims description 48
- 230000001737 promoting effect Effects 0.000 claims description 18
- 229910052718 tin Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 11
- 239000002335 surface treatment layer Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 63
- 239000000243 solution Substances 0.000 description 43
- 230000007797 corrosion Effects 0.000 description 33
- 238000005260 corrosion Methods 0.000 description 33
- 230000000694 effects Effects 0.000 description 22
- 239000010949 copper Substances 0.000 description 16
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910001128 Sn alloy Inorganic materials 0.000 description 5
- 238000005097 cold rolling Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000009924 canning Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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 group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020900 Sn-Fe Inorganic materials 0.000 description 1
- 229910019314 Sn—Fe Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 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
- 239000011889 copper foil Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 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
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
-
- 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
- C23C22/361—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 containing titanium, zirconium or hafnium compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
- C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/20—Inorganic coating
- B32B2255/205—Metallic coating
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
- B32B2439/66—Cans, tins
Definitions
- the present invention relates to a method for producing a steel plate for containers having excellent film adhesion.
- Metal containers used for beverages and foods are roughly divided into 2-piece cans and 3-piece cans.
- a two-piece can represented by a DI can is squeezed and ironed, then painted on the inner surface of the can and painted and printed on the outer surface of the can.
- the three-piece can is coated on the surface corresponding to the inner surface of the can and printed on the surface corresponding to the outer surface of the can, and then the can body is welded.
- a coating process is indispensable before and after canning.
- Solvent-based or water-based paints are used for painting, followed by baking.
- waste such as waste solvents
- exhaust gas mainly Carbon dioxide
- Patent Document 1 A steel plate for containers has been proposed (Patent Document 1). In patent document 1, it is described that this steel plate for containers shows the outstanding film adhesiveness.
- the inventors of the present invention continuously manufactured a steel sheet according to the method for manufacturing a steel sheet for containers described in Patent Document 1, and examined film adhesion regarding the neck portion.
- the steel sheet in the initial stage of manufacture exhibited desired film adhesion.
- an object of the present invention is to provide a method for producing a container steel plate that can stably and continuously produce a container steel plate exhibiting excellent film adhesion.
- the present inventors diligently studied to achieve the above object. As a result, at least one reaction promoting component selected from the group consisting of Al ions, borate ions, Cu ions, Ca ions, metal Al, and metal Cu was added. It has been found effective to use a solution containing. That is, the present inventors have found that the above problem is solved by the following configuration.
- the solution further contains phosphate ions, The method for producing a steel plate for containers according to any one of (1) to (3), wherein the amount of P in the Zr-containing coating is 0.1 to 50 mg / m 2 .
- the solution further contains a phenol resin, The method for producing a steel plate for containers according to any one of (1) to (4), wherein the amount of C in the Zr-containing coating is 0.1 to 50 mg / m 2 .
- the steel sheet, on at least one surface is a surface treated steel sheet having a surface treatment layer containing 100 ⁇ 15000mg / m 2 of metal Sn amount 10 ⁇ 1000mg / m 2 or Sn in amounts metallic Ni and Ni, ( (1) A method for producing a steel plate for containers according to any one of (6).
- the steel sheet is subjected to Ni plating or Fe—Ni alloy plating on the surface thereof to form a base Ni layer, and Sn plating is applied to the base Ni layer, and a part of the Sn plating and the base A part or all of the Ni layer is alloyed by molten tin treatment to form an Sn plating layer containing island-shaped Sn,
- the base Ni layer contains 5 to 150 mg / m 2 of Ni in the amount of metal Ni
- the substrate After forming a Zr-containing film on the surface of the steel sheet, the substrate is further subjected to a cleaning treatment by immersion treatment or spray treatment for 0.5 seconds or more with warm water of 40 ° C. or higher, according to any one of (1) to (8) Manufacturing method for steel plates for containers.
- the steel 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 is formed on the surface of the steel plate in order to ensure the corrosion resistance required for the container.
- the surface treatment layer containing 1 or more types of Ni (nickel) and Sn (tin) is provided, and it does not regulate in particular about the method to provide.
- a known technique such as an electroplating method, a vacuum deposition method, or a sputtering method may be used, and a heat treatment may be combined after plating in order to provide a diffusion layer. Further, even if Ni is plated with Fe—Ni alloy, the essence of the present invention remains unchanged.
- Ni in the surface treatment layer containing one or more of Sn, it is preferable Ni is 10 ⁇ 1000mg / m 2, Sn as the metal Ni is in the range of 100 ⁇ 15000mg / m 2 as metallic Sn .
- Sn exhibits excellent workability, weldability, and corrosion resistance, and it is preferable that this effect is manifested by 100 mg / m 2 or more as metal Sn. In order to ensure sufficient weldability, it is desirable to apply 200 mg / m 2 or more, and in order to ensure sufficient workability, it is desirable to apply 1000 mg / m 2 or more. As the Sn adhesion amount increases, the excellent workability and weldability improvement effects of Sn increase. However, if it exceeds 15000 mg / m 2 , the corrosion resistance improvement effect is saturated, which is economically disadvantageous. Therefore, it is preferable that the amount of deposited Sn be 15000 mg / m 2 or less as metallic Sn. Moreover, a Sn alloy layer is formed by performing a reflow process after Sn plating, and corrosion resistance further improves.
- the metal Ni exerts its effects on paint adhesion, film adhesion, corrosion resistance, and weldability.
- the metal Ni is preferably 10 mg / m 2 or more.
- the adhesion amount of Ni is preferably 10 mg / m 2 or more and 1000 mg / m 2 or less as metal Ni.
- the amount of metallic Ni and the amount of metallic Sn in the surface treatment layer can be measured by, for example, a fluorescent X-ray method.
- a calibration curve related to the amount of metal Ni is specified in advance using a sample of the amount of deposited Ni that has a known amount of metal Ni, and the amount of metal Ni is relatively specified using this calibration curve.
- a calibration curve related to the amount of metal Sn is specified in advance using a sample of the amount of Sn deposited with a known amount of metal Sn, and the amount of metal Sn is specified relatively using this calibration curve. To do.
- the composite plating layer which consists of the base Ni layer given to the steel plate surface and the island-like Sn plating layer formed on this base Ni layer is mentioned.
- the base Ni layer referred to here is a plating layer containing Ni formed on at least one surface of a steel plate, and is a metal Ni plating layer made of metal Ni, or Fe—Ni plated with Fe—Ni alloy. It may be an alloy plating layer.
- the island-like Sn plating layer is formed by performing Sn plating on the underlying Ni layer and alloying a part or all of the underlying Ni layer and a part of the Sn plating layer by a molten tin treatment. An alloy plating layer is preferred.
- an Fe—Ni alloy plating layer is used as the underlying Ni layer. It is preferable.
- the Ni plating layer and the island-shaped Sn plating layer will be described in detail.
- the base Ni layer made of Ni or Fe—Ni alloy is formed to improve the corrosion resistance. Since Ni is a highly corrosion-resistant metal, the corrosion resistance of the alloy layer containing Fe and Sn formed during the molten tin treatment is improved by plating Ni on the surface of the steel sheet as in the case of the steel sheet for containers of the present invention. be able to.
- the effect of improving the corrosion resistance of the alloy layer by the Ni plating is determined by the amount of Ni to be plated. If the amount of metallic Ni in the underlying Ni layer is 5 mg / m 2 or more, the effect of improving the corrosion resistance is remarkably increased. On the other hand, the effect of improving the corrosion resistance increases as the amount of Ni in the underlying Ni layer increases. However, when the amount of metallic Ni in the underlying Ni layer exceeds 150 mg / m 2 , the effect of improving the corrosion resistance is not only saturated. Is an expensive metal, it is economically disadvantageous to plate Ni in an amount exceeding 150 mg / m 2 . Therefore, the amount of Ni in the underlying Ni layer is preferably 5 mg / m 2 to 150 mg / m 2 .
- a diffusion treatment for forming the diffusion layer is performed in an annealing furnace.
- a nitriding process may be performed simultaneously with the diffusion process. Even when nitriding is performed, the effect of Ni as the underlying Ni layer and the effect of the nitriding layer in the present invention do not interfere with each other, and these effects can be achieved together.
- Ni plating and Fe—Ni alloy plating for example, a publicly known method (for example, cathode electrolysis method) generally performed in an electroplating method can be used.
- Sn plating in this specification includes not only plating with metal Sn but also a mixture of metal Sn with irreversible impurities and a mixture of metal Sn with a trace element.
- the Sn plating method is not particularly limited, and for example, a known electroplating method or a method of plating by dipping a steel plate in molten Sn may be used.
- the Sn plating layer by the above Sn plating is formed in order to improve corrosion resistance and weldability. Since Sn itself has high corrosion resistance, it has excellent corrosion resistance and weldability both as metal Sn and as an Sn alloy formed by molten tin treatment (reflow treatment) described below. Can be demonstrated.
- the Sn plating layer is formed so as to include island tin. This is because when the entire surface of the steel plate is plated with Sn, the steel plate may be exposed to a melting point (232 ° C.) or more during heat treatment after film lamination or coating, and by melting Sn or oxidizing Sn This is because the film adhesion cannot be secured. Therefore, Sn is made into islands, and the Fe—Ni base corresponding to the sea part is exposed (the part is not melted) to ensure film adhesion.
- the excellent corrosion resistance of Sn is remarkably improved from the amount of metal Sn of 300 mg / m 2 or more, and the degree of improvement in corrosion resistance increases as the Sn content increases. Therefore, the amount of metal Sn in the Sn plating layer containing island-shaped Sn is preferably 300 mg / m 2 or more. Moreover, since the corrosion resistance improving effect is saturated when the amount of metal Sn exceeds 3000 mg / m 2 , the Sn content is preferably 3000 mg / m 2 or less from an economical viewpoint.
- the amount of metal Sn is preferably set to 300 mg / m 2 or more and 3000 mg / m 2 or less.
- a molten tin treatment (reflow treatment) is performed.
- the purpose of the molten tin treatment is to melt Sn and alloy it with an underlying steel plate or an underlying metal (for example, an underlying Ni layer) to form an Sn—Fe alloy layer or an Sn—Fe—Ni alloy layer.
- the purpose is to improve the corrosion resistance of the layer and to form an island-shaped Sn alloy.
- This island-shaped Sn alloy can be formed by appropriately controlling the molten tin treatment.
- ⁇ Solution (treatment liquid)> As a method for imparting a Zr-containing film to the steel sheet, at least one reaction promoting component selected from the group consisting of Al ions, borate ions, Cu ions, Ca ions, metal Al, and metal Cu, and Zr ions, There are a method of immersing a steel plate in a solution containing F ions and a method of performing electrolytic treatment (particularly, cathodic electrolytic treatment).
- the immersion treatment is disadvantageous in industrial production because the base is etched to form various films, resulting in non-uniform adhesion and a longer treatment time.
- 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. Furthermore, in this cathodic electrolysis treatment, Zr oxide, Zr phosphorus excellent in the effect of improving the corrosion resistance and adhesiveness in a short time treatment of several seconds to several tens of seconds due to the coexistence of nitrate ions and ammonium ions in the solution. Since it is possible to promote the precipitation of the Zr-containing film containing an oxide, it is extremely advantageous industrially. Accordingly, cathodic electrolysis is desirable for the application of the Zr-containing coating of the present invention, and cathodic electrolysis with a treatment solution in which nitrate ions and ammonium ions coexist is particularly preferable.
- the concentration of Zr ions in the solution is preferably 0.008 to 0.07 mol / l in that the Zr-containing film is efficiently precipitated and the film adhesion of the resulting steel sheet is more excellent. More preferably, it is -0.05 mol / l.
- the supply source of Zr ions into the solution is not particularly limited, and examples thereof include K 2 ZrF 6 , Na 2 ZrF 6 , H 2 ZrF 6 , (NH 4 ) ZrF 6 and the like.
- F ions in the solution are necessary for the stable presence of Zr ions in the bath, and the concentration is preferably 0.024 to 0.63 mol / l, and preferably 0.048 to 0.42 mol. / L is more preferable.
- the source of F ions into the solution is not particularly limited.
- a form shared with Zr raw materials such as K 2 ZrF 6 , Na 2 ZrF 6 , H 2 ZrF 6 , (NH 4 ) ZrF 6 , Examples include a form in which NaF, HF, (NH 4 ) F, and the like are separately supplied.
- reaction promoting component examples include Al ions, borate ions, Cu ions, Ca ions, metallic Al, and metallic Cu.
- Zr ions form a complex with F ions and exist stably, but when the Zr-containing film is deposited, the F ions coordinated to the Zr ions are released, and as the time passes, free F The ion concentration increases.
- the free F ion concentration is increased, the efficiency of the deposition reaction of the Zr-containing film is reduced, and the stable film cannot be adhered.
- the component is present in the solution, it is easy to form a complex with F ions, and as a result, an increase in the free F ion concentration in the solution is suppressed.
- the addition effect of borate ions and metal Al is excellent and preferable in that a dense film having a uniform surface irregularity is formed and the film adhesion of the obtained steel sheet is more excellent.
- the content of the reaction promoting component in the solution is preferably 0.002 to 2 in terms of a molar ratio of the reaction promoting component to Zr ions (mole of Zr ions / mole of reaction promoting component), preferably 0.02 to 0 .2 is more preferable.
- the supply source of Al ions in the solution is not particularly limited, and examples thereof include Al 2 (SO 4 ) 3 .
- the source of borate ions in the solution is not particularly limited, and examples thereof include H 3 BO 3 .
- the source of Cu ions in the solution is not particularly limited, and examples thereof include CuSO 4 and CuCl 2 .
- the source of Ca ions in the solution is not particularly limited, and examples thereof include CaCl 2 .
- metal Al for example, a 3 mm ⁇ granular material having a purity of 99% or more can be preferably used.
- metal Cu for example, a copper plate having a purity of 99% or more, a granular material, and the like can be suitably used.
- the molar amount of each component in the solution can be appropriately measured by a known measuring apparatus (for example, an atomic absorption spectrophotometer).
- water is usually used.
- organic solvent etc. may be included in the range which does not impair the effect of this invention.
- the solution may further contain phosphate ions.
- P phosphorus
- the concentration of phosphate ions in the solution is appropriately adjusted so that the amount of P in the Zr-containing film, which will be described later, becomes a predetermined amount, but is generally about 0.007 to 0.15 mol / l. It is.
- the solution may further contain a phenol resin.
- C carbon
- the concentration of the phenol resin in the solution is appropriately adjusted so that the amount of C in the Zr-containing film described later becomes a predetermined amount, but is generally about 0.5 to 45 g / l.
- the concentration of ammonium ions or nitrate ions in the solution may be appropriately adjusted according to production equipment and production rate (capacity).
- the concentration of ammonium ions is preferably about 100 to 10,000 ppm by mass
- the concentration of nitrate ions is preferably about 1000 to 20000 ppm by mass, from the viewpoint of better film adhesion of the steel sheet to be obtained.
- the Zr-containing film is formed by dipping or electrolytically treating the steel sheet in the above solution.
- the conditions for immersing the steel sheet in the solution vary depending on the composition of the solution used, but are preferably 1 to 10 seconds and more preferably 3 to 5 seconds from the viewpoint of the formation of a desired amount of Zr-containing coating.
- the conditions for the electrolytic treatment vary depending on the composition of the solution used, but from the viewpoint of forming a Zr-containing film having a desired adhesion amount, the current density should be 0.01 to 20 A / dm 2. 0.5 to 10 A / dm 2 is more preferable.
- the electrolysis time is appropriately selected according to the current density, but is preferably 0.01 to 10 seconds, more preferably 1 to 5 seconds.
- the Zr-containing film formed by the above treatment contains a precipitate of Zr ions (Zr compound) in the solution.
- the role of the Zr compound is to ensure corrosion resistance and adhesion.
- Zr compounds are thought to be mainly Zr hydrated oxides and Zr phosphorous oxides composed of Zr oxide and Zr hydroxide, but these Zr compounds have excellent corrosion resistance and adhesion. Yes. Therefore, when the Zr-containing film increases, the corrosion resistance and adhesion begin to improve, and when the amount of metal Zr is 1 mg / m 2 or more, practically satisfactory levels of corrosion resistance and adhesion are secured. Furthermore, when the Zr-containing film increases, the effect of improving the corrosion resistance and adhesion also increases.
- the amount of Zr-containing film deposited is preferably 1 to 100 mg / m 2 in terms of metal Zr. Among these, 1 to 10 mg / m 2 is more preferable, and 1 to 8 mg / m 2 is more preferable.
- the amount of the Zr phosphorous oxide is increased, excellent corrosion resistance and adhesion are exhibited, but the effect can be clearly recognized when the amount of P in the Zr-containing film is 0.1 mg / m 2 or more. Furthermore, when the amount of P increases, the effect of improving corrosion resistance and adhesion also increases. However, when the amount of P exceeds 50 mg / m 2 , the adhesion of the Zr-containing film itself deteriorates and the electrical resistance increases and the weldability deteriorates. There is a case. Therefore, the amount of P in the Zr-containing film is preferably 0.1 to 50 mg / m 2 . Among these, 0.1 to 10 mg / m 2 is more preferable, and 0.1 to 8 mg / m 2 is more preferable.
- the Zr-containing film has excellent practical characteristics even when used alone, but the phenol resin film does not have sufficient practical performance even if it is used singly to some extent. However, when the Zr compound and the phenol resin are combined, a further excellent practical performance is exhibited.
- the role of the phenolic resin is to ensure adhesion. Since the phenol resin itself is an organic substance, it has very good adhesion to the laminate film. Therefore, when the phenol resin film increases, the adhesion starts to improve, and when the amount of C in the Zr-containing film is 0.1 mg / m 2 or more, a practically satisfactory level of adhesion is secured. Furthermore, when the amount of C increases, the effect of improving the adhesion also increases. However, if the amount of C exceeds 50 mg / m 2 , the electrical resistance may increase and the weldability may deteriorate. Accordingly, the C content in the Zr-containing film is preferably 0.1 to 50 mg / m 2 . Of these, 0.1 to 10 mg / m 2 is more preferable, and 0.1 to 8 mg / m 2 is even more preferable.
- F ions are contained in the solution, some amount is taken into the film together with the Zr compound.
- F atoms in the film do not significantly affect the normal adhesion (primary adhesion) of the film, but the adhesion (secondary adhesion), rust resistance or coating during high temperature sterilization such as retort treatment It causes deterioration of subfilm corrosion. It is considered that this is because F atoms in the film are eluted in water vapor or a corrosive liquid, and the bond with the organic film is decomposed or the base steel sheet is corroded.
- the F amount is preferably 0.1 mg / m 2 or less. Especially, 0.01 mg / m ⁇ 2 > or less is more preferable, and although a minimum in particular is not restrict
- the F amount can be reduced by increasing the length. Therefore, in order to reduce the F content in the film to 0.1 mg / m 2 or less, it is preferable to perform immersion treatment or spray treatment for 0.5 seconds or more with warm water of 40 ° C. or more.
- the amount of metal Zr (Zr), the amount of P (phosphorus), and the amount of F (fluorine) contained in the Zr-containing film according to the present invention can be measured by a quantitative analysis method such as fluorescent X-ray analysis. Is possible.
- the amount of C (carbon) can be measured by subtracting the amount of C existing in the steel sheet using TOC (total organic carbon meter).
- a surface treatment layer was applied on a steel plate having a thickness of 0.17 to 0.23 mm by using the following methods (Treatment Method 0) to (Treatment Method 3).
- (Treatment method 0) After cold rolling, a steel sheet was prepared by degreasing and pickling the annealed and pressure-adjusted original sheet.
- (Treatment method 1) After cold rolling, the annealed and pressure-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, the annealed and regulated original sheet was degreased and pickled, and then Ni-plated using a Watt bath to prepare a Ni-plated steel sheet.
- (Treatment method 3) After cold rolling, a steel substrate (steel plate) with a thickness of 0.17 to 0.23 mm is degreased and pickled, then Ni-plated using a watt bath, and Ni diffused during annealing After forming a layer, degreasing and pickling, Sn plating was performed using a ferrostan bath, and then molten tin treatment was performed to prepare a Ni and Sn plated steel sheet having a Sn alloy layer. In addition, when processing of (processing method 3) was performed, when the surface was observed with the optical microscope and the island-like Sn situation was evaluated, it was confirmed that the island was formed as a whole.
- the metal Al used in Table 1 is a 3 mm ⁇ granular material having a purity of 99% or more, and the metal Cu is a copper foil having a purity of 99% or more.
- the boric acid ion source is boric acid
- the calcium ion source is calcium chloride
- the copper ion source is copper chloride
- the aluminum ion source is Al 2 (SO 2. 4 ) Three .
- the amount of Ni and Sn attached to the base plating layer, and the amount of Zr, P and F of the Zr-containing coating are compared with the calibration plate obtained by chemical analysis of the amount of attachment in advance by fluorescent X-ray analysis.
- Ask. The amount of C was measured by subtracting the amount of C existing in the steel sheet using TOC (total organic carbon meter).
- ⁇ Initial film adhesion> After laminating a PET film having a thickness of 20 ⁇ m on both surfaces of each test material obtained in the examples and comparative examples in Table 1 at 200 ° C., a squeezing and ironing process was performed to produce a can body. A necking process was performed on the film, and a retort treatment was performed at 120 ° C. for 30 minutes. As a result, ⁇ indicates that there was no peeling at all, ⁇ indicates that there was slight peeling with no practical problems, ⁇ indicates that peeling occurred partially and there were practical problems, and most The case where peeling occurred was defined as x. Practically, it is necessary to be “ ⁇ ” and “ ⁇ ”.
- the steel plate for containers obtained by the production method of the present invention showed excellent initial film adhesion. Moreover, in each Example, there was almost no decrease in the adhesion amount of each component after a continuous process, the film adhesiveness was maintained stably, and the favorable continuous processability was shown. Further, in Example 12, where the molar ratio of the reaction promoting component to the Zr ion (mol of Zr ion / mol of the reaction promoting component) is included in the range of 0.002 to 2, the above molar ratio is not included in the range. Compared to Examples 13 and 14, it was confirmed that the film adhesion was superior.
- Comparative Examples 1 to 3 not containing a reaction promoting component the initial film adhesion was excellent, but the adhesion amount of each component was greatly reduced after continuous treatment, and the film adhesion deteriorated. The continuous processability was poor.
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Abstract
Description
近年、地球環境保全を目的とし、これら産業廃棄物や排ガスを低減しようとする取組みが行われている。この中で、塗装に代わるものとしてフィルムをラミネートする技術が注目され、急速に広まってきた。
また、工業化の観点からは、所望の特性を示す鋼板を、ロッド毎の品質のバラツキがないように連続して製造できることが重要である。特に、所定の成分を含む溶液を使用して鋼板の表面処理を行う場合、同一の溶液を長時間にわたって、繰り返し使用できれば、環境面およびコスト面からもその意義は大きい。
本発明者らは、特許文献1に記載の容器用鋼板の製造方法に従って鋼板を連続製造し、ネック部分に関するフィルム密着性について検討を行ったところ、製造初期の鋼板は所望のフィルム密着性を示すものの、連続製造を行うにつれ、フィルム密着性が劣化してしまうことを見出した。
即ち、本発明者らは、上記課題が下記構成により解決されることを見出した。
(3) 前記Zr含有皮膜の付着量が、金属Zr量で1~100mg/m2、F量で0.1mg/m2以下である、(1)または(2)に記載の容器用鋼板の製造方法。
前記Zr含有皮膜中のP量が、0.1~50mg/m2である、(1)~(3)のいずれかに記載の容器用鋼板の製造方法。
(5) 前記溶液がさらにフェノール樹脂を含み、
前記Zr含有皮膜中のC量が、0.1~50mg/m2である、(1)~(4)のいずれかに記載の容器用鋼板の製造方法。
(7) 前記鋼板は、少なくとも片面に、Niを金属Ni量で10~1000mg/m2またはSnを金属Sn量で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)~(6)のいずれかに記載の容器用鋼板の製造方法。
前記下地Ni層は、金属Ni量で5~150mg/m2のNiを含み、
前記Snめっき層は、金属Sn量で300~3000mg/m2のSnを含む、(1)~(7)のいずれかに記載の容器用鋼板の製造方法。
本発明の特徴としては、鋼板表面にZr含有皮膜を形成するために使用される溶液中に、Al(アルミニウム)イオン、ホウ酸イオン、Cu(銅)イオン、Ca(カルシウム)イオン、金属Al(アルミニウム)、および、金属Cu(銅)からなる群から選ばれる少なくとも一つの反応促進成分を含む点が挙げられる。
本発明者らは、特許文献1の発明に関して検討を行った結果、鋼板を溶液中で長時間浸漬または電解処理(特に、陰極電解処理)を行うと、皮膜の付着量が減少して、結果として鋼板特性が劣化することを見出した。この原因としては、必ずしも明らかでないが、時間の経過とともに溶液中のフリーFイオン濃度が増加し、皮膜の形成を阻害しているものと推測される。そこで、本発明者らは、上述した反応促進成分を溶液中に加えることにより、これら成分がFイオンと錯体を形成し、遊離したフリーFイオン濃度が減少することになり、結果として皮膜の形成が充分に進むことを見出している。
以下に、本発明で使用される鋼板、溶液に関して詳述する。
本発明で用いられる鋼板は特に規制されるものではなく、通常、容器材料として使用される鋼板を用いる。この原板の製造法、材質なども特に規制されるものではなく、通常の鋼片製造工程から熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等の工程を経て製造される。
表面処理層の第1の態様としては、Ni(ニッケル)、Sn(スズ)のうちの1種以上を含む表面処理層が付与されることが好ましく、付与する方法については特に規制するものでは無い。例えば、電気めっき法や真空蒸着法やスパッタリング法などの公知技術を用いれば良く、拡散層を付与するため、めっき後に加熱処理を組み合わせても良い。また、NiはFe-Ni合金めっきを行っても本発明の本質は不変である。
ここでいう下地Ni層とは、鋼板の少なくとも片面に形成されるNiを含むめっき層であって、金属Niによる金属Niめっき層である場合、または、Fe-Ni合金めっきを施したFe-Ni合金めっき層である場合がある。また、島状Snめっき層は、この下地Ni層上にSnめっきを施し、溶融溶錫処理により、下地Ni層の一部または全部とSnめっき層の一部が合金化することにより形成される合金めっき層であることが好ましい。ただし、Ni単独のめっき層上にSnめっきを施し、溶融溶錫処理を行っても、上記のような島状Snが形成しにくいため、下地Ni層としては、Fe-Ni合金めっき層を用いることが好ましい。以下、このようなNiめっき層及び島状Snめっき層について詳細に説明する。
上記鋼板にZr含有皮膜を付与する方法としては、Alイオン、ホウ酸イオン、Cuイオン、Caイオン、金属Al、および、金属Cuからなる群から選ばれる少なくとも一つの反応促進成分と、Zrイオンと、Fイオンとを含む溶液中で、鋼板を浸漬する方法や電解処理(特に、陰極電解処理)により行う方法がある。
ただし、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、付着が不均一になり、また、処理時間も長くなる為、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、溶液中に硝酸イオンとアンモニウムイオンが共存することに依り、数秒から数十秒程度の短時間処理と耐食性や密着性の向上効果に優れたZr酸化物、Zrリン酸化物を含むZr含有皮膜の析出を促進する事が可能である事から、工業的には極めて有利である。従って、本発明のZr含有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。
なお、溶液中へのZrイオンの供給源は特に制限されないが、例えば、K2ZrF6、Na2ZrF6、H2ZrF6、(NH4)ZrF6などが挙げられる。
なお、溶液中へのFイオンの供給源は特に制限されないが、例えば、K2ZrF6、Na2ZrF6、H2ZrF6、(NH4)ZrF6などZr原料と共有される形や、NaF、HF、(NH4)Fなどを別途供給する形などが挙げられる。
溶液中における反応促進成分の含有量は、反応促進成分とZrイオンとのモル比(Zrイオンのモル/反応促進成分のモル)で0.002~2であることが好ましく、0.02~0.2であることがより好ましい。
溶液中にホウ酸イオンの供給源は特に制限されないが、例えば、H3BO3などが挙げられる。
溶液中にCuイオンの供給源は特に制限されないが、例えば、CuSO4、CuCl2などが挙げられる。
溶液中にCaイオンの供給源は特に制限されないが、例えば、CaCl2などが挙げられる。
金属Alを使用する場合、例えば、純度99%以上の3mmφの粒状物などを好適に使用できる。
金属Cuを使用する場合、例えば、純度99%以上の銅板、粒状物などを好適に使用できる。
なお、溶液中におけるリン酸イオンの濃度は、後述するZr含有皮膜中におけるP量が所定量になるように適宜調整されるが、一般的には、0.007~0.15モル/l程度である。
なお、溶液中におけるフェノール樹脂の濃度は、後述するZr含有皮膜中におけるC量が所定量になるように適宜調整されるが、一般的には、0.5~45g/l程度である。
本発明においては、鋼板を上記溶液中で浸漬または電解処理することにより、Zr含有皮膜を形成する。
鋼板を溶液に浸漬の条件は、使用される溶液の組成などによって異なるが、所望の付着量のZr含有皮膜の形成性の観点からは、1~10秒間が好ましく、3~5秒間がより好ましい。
電解処理際の条件としては、使用される溶液の組成などによって異なるが、所望の付着量のZr含有皮膜の形成性の観点からは、電流密度を0.01~20A/dm2とすることが好ましく、0.5~10A/dm2とすることがより好ましい。また、電解時間は、電流密度に応じて適宜最適な条件が選択されるが、0.01~10秒が好ましく、1~5秒がより好ましい。
上記処理によって形成されるZr含有皮膜には、溶液中のZrイオンの析出物(Zr化合物)が含まれる。Zr化合物の役割は、耐食性と密着性の確保である。Zr化合物は、主に、酸化Zr、水酸化Zrで構成されているZr水和酸化物、Zrリン酸化物であると考えられるが、これらのZr化合物は優れた耐食性と密着性を有している。
従って、Zr含有皮膜が増加すると、耐食性や密着性が向上し始め、金属Zr量で、1mg/m2以上になると、実用上、問題ないレベルの耐食性と密着性が確保される。更に、Zr含有皮膜が増加すると耐食性、密着性の向上効果も増加するが、Zr皮膜量が金属Zr量で100mg/m2を超えると、Zr含有皮膜が厚くなり過ぎZr含有皮膜自体の密着性が劣化すると共に、電気抵抗が上昇し溶接性が劣化する場合がある。従って、Zr含有皮膜付着量は金属Zr量で1~100mg/m2にすることが好ましい。なかでも、1~10mg/m2がより好ましく、1~8mg/m2がさらに好ましい。
従って、フェノール樹脂皮膜が増加すると密着性が向上し始め、Zr含有皮膜中でのC量が0.1mg/m2以上になると、実用上、問題ないレベルの密着性が確保される。更に、C量が増加すると密着性の向上効果も増加するが、C量が50mg/m2を超えると、電気抵抗が上昇し溶接性が劣化する場合がある。従って、Zr含有皮膜中でのC量で0.1~50mg/m2にすることが好ましい。なかでも、0.1~10mg/m2がより好ましい、0.1~8mg/m2がさらに好ましい。
皮膜中のF量(F原子量)は0.1mg/m2を超えると、これらの諸特性の劣化が顕在化し始める事から、F量は0.1mg/m2以下にすることが好ましい。なかでも、0.01mg/m2以下がより好ましく、下限は特に制限されないが0が好ましい。
F量を0.1mg/m2以下にするには、Zr含有皮膜を形成した後、温水中での浸漬処理やスプレー処理により洗浄処理を行えば良く、この処理温度を高く、或いは、処理時間を長くすることによりF量を減少させる事が出来る。
従って、皮膜中のF量を0.1mg/m2以下にするには40℃以上の温水で0.5秒以上の浸漬処理あるいはスプレー処理をするのが好ましい。
以下の(処理法0)~(処理法3)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0)冷間圧延後、焼鈍、調圧された原板に脱脂、酸洗を施した鋼板を作製した。
(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をメッキし、Snめっき鋼板を作製した。
(処理法2)冷間圧延後、焼鈍、調圧された原板を脱脂、酸洗後、ワット浴を用いてNiメッキを施し、Niめっき鋼板を作製した。
(処理法3)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、焼鈍時にNi拡散層を形成させ、脱脂、酸洗後、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合金層を有するNi、Snめっき鋼板を作製した。
なお、(処理法3)の処理を行った場合には、光学顕微鏡にて表面を観察し、島状Sn状況を評価したところ、全体的に島が形成されていることが確認された。
(水洗処理)40℃以上の温水に3秒間浸漬した。
なお、表1中の溶液組成は、各成分の水溶液中の濃度を表す。
表1中で使用したフェノール樹脂は、N,N-ジエタノールアミン変成した水溶性フェノール樹脂(重量平均分子量:5000)である。
また、表1中で使用した金属Alは、純度99%以上の3mmφの粒状物であり、金属Cuは、純度99%以上の銅箔を使用した。
さらに、表1中、ホウ酸イオンの供給源はホウ酸であり、カルシウムイオンの供給源は塩化カルシウムであり、銅イオンの供給源は塩化銅であり、アルミニウムイオンの供給源はAl2(SO4)3である。
表1中の実施例及び比較例で得られた各試験材の両面に、厚さが20μmのPETフィルムを200℃でラミネートした後、絞りしごき加工を行って缶体を作製し、この缶体に対してネッキング加工を施し、120℃で30分間のレトルト処理を行い、缶のネック部分のフィルムの剥離状況で評価した。
その結果、剥離が全くなかったものを◎、実用上問題が無い程度の極僅かな剥離が生じていたものを○、部分的に剥離が生じて実用上問題があるものを△、大部分で剥離が生じていたものを×とした。
実用上、「○」「◎」であることが必要である。
表1中の各実施例及び各比較例の電解処理の条件で3日間連続して鋼板の製造を行った後、最後に得られた鋼板のフィルム密着性を上記<初期フィルム密着性>と同じ方法で評価した。
フィルム密着性の評価が変わらなかったものを「○」、フィルム密着性が劣化したものを「×」として評価した。
さらに、反応促進成分とZrイオンとのモル比(Zrイオンのモル/反応促進成分のモル)が0.002~2の範囲に含まれる実施例12は、上記モル比が該範囲に含まれない実施例13および14と比較して、より優れたフィルム密着性を示すことが確認された。
一方、反応促進成分を含まない比較例1~3においては、初期フィルム密着性は優れていたが、連続処理後において各成分の付着量が大幅に減って、フィルム密着性が劣化しており、連続処理性に劣っていた。
Claims (9)
- Alイオン、ホウ酸イオン、Cuイオン、Caイオン、金属Al、および、金属Cuからなる群から選ばれる少なくとも一つの反応促進成分と、Zrイオンと、Fイオンとを含む溶液中で、鋼板の浸漬または電解処理を行い、鋼板表面にZr含有皮膜を形成する、容器用鋼板の製造方法。
- 前記反応促進成分と前記Zrイオンとのモル比(Zrイオンのモル/反応促進成分のモル)が、0.002~2である、請求項1に記載の容器用鋼板の製造方法。
- 前記Zr含有皮膜の付着量が、金属Zr量で1~100mg/m2、F量で0.1mg/m2以下である、請求項1または2に記載の容器用鋼板の製造方法。
- 前記溶液がさらにリン酸イオンを含み、
前記Zr含有皮膜中のP量が、0.1~50mg/m2である、請求項1~3のいずれかに記載の容器用鋼板の製造方法。 - 前記溶液がさらにフェノール樹脂を含み、
前記Zr含有皮膜中のC量が、0.1~50mg/m2である、請求項1~4のいずれかに記載の容器用鋼板の製造方法。 - 前記溶液が、さらにアンモニウムイオンおよび/または硝酸イオンを含む、請求項1~5のいずれかに記載の容器用鋼板の製造方法。
- 前記鋼板は、少なくとも片面に、Niを金属Ni量で10~1000mg/m2またはSnを金属Sn量で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1~6のいずれかに記載の容器用鋼板の製造方法。
- 前記鋼板は、その表面にNiめっきまたはFe-Ni合金めっきが施されて下地Ni層が形成され、前記下地Ni層上にSnめっきが施され、当該Snめっきの一部と前記下地Ni層の一部または全部とが溶融溶錫処理により合金化されて島状Snを含むSnめっき層が形成され、
前記下地Ni層は、金属Ni量で5~150mg/m2のNiを含み、
前記Snめっき層は、金属Sn量で300~3000mg/m2のSnを含む、請求項1~7のいずれかに記載の容器用鋼板の製造方法。 - 鋼板表面にZr含有皮膜を形成した後、さらに40℃以上の温水で0.5秒以上の浸漬処理またはスプレー処理による洗浄処理を行う、請求項1~8のいずれかに記載の容器用鋼板の製造方法。
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2011
- 2011-09-14 TW TW100133006A patent/TWI471217B/zh active
- 2011-09-14 CN CN201180044328.8A patent/CN103108991B/zh active Active
- 2011-09-14 WO PCT/JP2011/070982 patent/WO2012036201A1/ja active Application Filing
- 2011-09-14 US US13/823,427 patent/US20130216714A1/en not_active Abandoned
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2013
- 2013-04-04 CO CO13082010A patent/CO6690787A2/es active IP Right Grant
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Also Published As
Publication number | Publication date |
---|---|
CN103108991B (zh) | 2016-05-25 |
JP2012062521A (ja) | 2012-03-29 |
JP5861249B2 (ja) | 2016-02-16 |
TW201223752A (en) | 2012-06-16 |
CO6690787A2 (es) | 2013-06-17 |
US20130216714A1 (en) | 2013-08-22 |
TWI471217B (zh) | 2015-02-01 |
CN103108991A (zh) | 2013-05-15 |
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