CN103085384B - Metal exterior material and manufacture method thereof with resin molding - Google Patents
Metal exterior material and manufacture method thereof with resin molding Download PDFInfo
- Publication number
- CN103085384B CN103085384B CN201210439629.7A CN201210439629A CN103085384B CN 103085384 B CN103085384 B CN 103085384B CN 201210439629 A CN201210439629 A CN 201210439629A CN 103085384 B CN103085384 B CN 103085384B
- Authority
- CN
- China
- Prior art keywords
- tunicle
- metal
- resin molding
- matrix material
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 175
- 239000002184 metal Substances 0.000 title claims abstract description 171
- 229920005989 resin Polymers 0.000 title claims abstract description 140
- 239000011347 resin Substances 0.000 title claims abstract description 140
- 238000000465 moulding Methods 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 102
- 239000011701 zinc Substances 0.000 claims abstract description 102
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000007747 plating Methods 0.000 claims abstract description 93
- 239000011159 matrix material Substances 0.000 claims abstract description 89
- 239000000758 substrate Substances 0.000 claims abstract description 84
- 238000006073 displacement reaction Methods 0.000 claims abstract description 53
- 238000012545 processing Methods 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 49
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 9
- 239000010959 steel Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 17
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 239000002904 solvent Substances 0.000 abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 55
- 239000010410 layer Substances 0.000 description 55
- 239000000243 solution Substances 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- -1 polyethylene terephthalate Polymers 0.000 description 25
- 239000007788 liquid Substances 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 20
- 238000001035 drying Methods 0.000 description 19
- 238000003475 lamination Methods 0.000 description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- 230000006978 adaptation Effects 0.000 description 12
- 239000007767 bonding agent Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 11
- 239000011790 ferrous sulphate Substances 0.000 description 11
- 235000003891 ferrous sulphate Nutrition 0.000 description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 206010013786 Dry skin Diseases 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- MSXHSNHNTORCAW-GGLLEASOSA-M sodium;(2s,3s,4s,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].O[C@H]1O[C@H](C([O-])=O)[C@@H](O)[C@H](O)[C@H]1O MSXHSNHNTORCAW-GGLLEASOSA-M 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 239000005030 aluminium foil Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000009820 dry lamination Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 238000000864 Auger spectrum Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 229920001903 high density polyethylene Polymers 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000002370 organoaluminium group Chemical group 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 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
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910000562 Gilding metal Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
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- 239000006166 lysate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 150000002927 oxygen compounds Chemical class 0.000 description 1
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B32B15/085—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 polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/20—Deep-drawing
-
- 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
-
- 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
-
- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/12—Deep-drawing
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/22—Nickel or cobalt
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/30—Iron, e.g. steel
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
The present invention provides a kind of metal exterior material with resin molding, even if at the matrix material metal overlayer pressurizing resin film such as aluminum or rustless steel or formation resin coating film, then in the case of carrying out the harsh forming such as deep-draw processing, thinning processing or stretch-draw processing, the high adhesion not making this laminated film or resin coating film peel off can also be given, even and if with acid or the Long contact time such as solvent, it may have the excellent resistance to chemical reagents of high adhesion can be kept.In order to solve the problems referred to above, the metal exterior material with resin molding of the present invention has: matrix material metal (1), is located at the substrate tunicle (2) of the one or both sides of matrix material metal (1) and is located at the laminated film on substrate tunicle (2) or resin coating film (3), and this substrate tunicle (2) is metallic zinc tunicle or the tunicle containing metallic zinc.Now, metallic zinc tunicle or the tunicle containing metallic zinc are formed preferably by displacement plating method or galvanoplastic.
Description
Technical field
The present invention relates to the metal exterior material with resin molding and manufacture method thereof.Specifically, relate to
Even and if matrix material metal and laminated film or resin can also be being kept in the case of electrolyte contacts
The metal exterior material with resin molding of the adaptation of film and manufacture method thereof.
Systems a kind of metal exterior material etc. with resin molding, even if at aluminum or not
The rust matrix material metal overlayer pressurizing resin film such as steel or form resin coating film, carry out behind deep-draw processing,
In the case of the harsh forming such as thinning processing or stretch-draw (stretch draw) processing, it is also possible to give
Do not make the high adhesion that this laminated film or resin coating film are peeled off, even and if connecing for a long time with acid or solvent etc.
Touch, it may have the excellent resistance to chemical reagents of high adhesion can be kept.
Background technology
Lamination process is that resinous film (hereinafter referred to as resin molding or laminated film) heating is pressed together on metal
The processing method of material surface, is the metal material surface for the purpose of protecting surface or giving design
One of method for coating, may be used in various field.With the table that resin combination is coated in metal material
Face is also dried and forms the method for resin coating film and compare, solvent that lamination process produces when dry or dioxy
The generation amount changing the waste gas such as carbon or greenhouse gases is few.Therefore, from the viewpoint of environmental conservation, excellent
Choosing use lamination process, its purposes expand, have been used for such as with aluminium sheet material, steel sheet material,
The main body of the food tank that Packaging Aluminum Foil or stainless steel foil etc. are raw material or cover material, containers for food use or
Aneroid battery container etc..
Particularly recently as use in mobile phone, electronic notebook, notebook computer or video camera etc.
The exterior material of portable lithium rechargeable battery, is preferably used light weight and the high aluminium sheet or stainless of barrier
The metallic plates such as steel plate, employ lamination process to the surface of such metallic plate.Additionally, studying work
For electric automobile or the lithium rechargeable battery of the drive energy of hybrid vehicle, and as its exterior material
Material, is also studied the metallic plate of laminated processing.
Laminated film for such lamination process is directly fitted with metal material, then carries out adding hot pressing
Close.Therefore, compared with application of resin compositions dry common resin coating film, having can
Suppress raw-material waste, pin hole (defective part) less and the advantage such as excellent in workability.Material as laminated film
Material, the usual use polyester resin such as polyethylene terephthalate and PEN,
The polyamide-based resins such as the polyolefin such as polyethylene and polypropylene, nylon.
By laminated film lamination process on the surface (hereinafter also referred to as " metal surface ") of metal material
Time, in order to improve the corrosion resistance of the adaptation between laminated film and metal surface and metal surface, be by
Metal surface carries out cleaning by degreasing, the most generally implements the chemical conversion treatment etc. such as chromium phosphate hydrochlorate.But,
Such chemical conversion treatment needs to implement after treatment matting, to remove remaining treatment fluid, right
Carry out waste water process in the rinse water discharged by this matting and want Expenses Cost.Especially chromium phosphate hydrochlorate
Etc. chemical conversion treatment etc. owing to employing chromyl treatment fluid, therefore, in recent years for environment
Worry, have the trend of avoidance.
On the other hand, chemical conversion treatment etc. is not implemented in metal surface if carried out during lamination process
, then there is the problem that laminated film is peeled off or metal material is susceptible to corrosion from metal surface in reason.Such as,
For exterior materials for lithium rechargeable battery etc., in its manufacturing process, degree to be subject to processing is high
Processing.The electrolyte of lithium rechargeable battery use the organic solvent such as ethyl carbonate or diethyl carbonate and
The fluorine such as lithium hexafluoro phosphate or LiBF4 system lithium complex.Therefore, if outside use is such for a long time
Package material, then function not only as the organic solvent of electrolyte, and the moisture in air also can immerse in container,
It reacts with electrolyte and generates Fluohydric acid., thus may create the problem that this Fluohydric acid. transmission layer press mold
And make metal surface and laminated film peeling-off, and can acid gilding metal surface.It addition, sometimes at layer
Before pressure, metal material is preheated (200 ~ 300 DEG C), can exist tunicle deteriorate under the action of heat,
So that the problem that adaptation reduces.
Packaging material as packaging lithium secondary battery, it is proposed that various have organic solvent or Fluohydric acid.
The laminated body of toleration, such as, in patent documentation 1, it is proposed that a kind of laminated body, its by outermost layer/
Barrier layer/innermost layer or be made up of, wherein, to described resistance outermost layer/barrier layer/intermediate layer/innermost layer
The innermost layer face side surface of interlayer carries out defat, or removes oxide on surface, and implements phosphate quilt
Film, by chromate, fluorides compound or organo-silicon compound, organic titanium compounds, organo-aluminium
The formation of the acid resistance tunicle that compounds is constituted and/or by silanes, organic titanium class, organo-aluminium class
The coupling processing etc. that material is formed.According to this technology, it is provided that the composition of following laminated body, i.e.
The stack membrane used in shell as storage polymer battery, it is to steam and other gas
Barrier is excellent, it addition, excellent in terms of the layers cementing intensity of content resistance and laminated body, and
There is the mechanical strength with puncture resistance etc. as representative, the most at high temperature can also use, to electrolyte
The most stable.
It addition, in patent documentation 2, it is proposed that following lithium ion battery packaging material, it is sealing
Layer one side be at least sequentially laminated with adhering resin layer, the first chemical conversion treatment layer, aluminium foil layer, second
Chemical conversion treatment layer, bond layer and base material layer, wherein, aluminium foil layer is etched by two sides
Aluminium foil formed, the first chemical conversion treatment layer and the second chemical conversion treatment layer are by zinc oxide tunicle shape
Become.According to this technology, it is provided that the lithium ion battery packaging material of a kind of high productivity, this lithium from
Sub-battery use packing material need not use the chromium being likely to cause environmental pressure, can obtain the resistance to electricity of excellence
Solve fluidity, hydrofluoric acid resistance, and chemical conversion treatment layer can be simply forming on the two sides of aluminium foil.
It addition, in patent documentation 3, it is proposed that following technology, it relates to plastics basement membrane, metal
The plastic layer press mold that paper tinsel and functional plastic layer are formed by stacking, wherein, in metal forming at least towards function
The property one side of plastic layer, the one side towards metal forming of functional plastic layer and functional plastic layer
Inside, or therein any one, utilize physical vaporous deposition formed at least 1 layer such as layers of chrome such
Metal protective layer.According to this technology, the adaptation of each interlayer can be improved, it may be preferred to as with
The plastic layer press mold of the covering making lithium ion polymer battery or lithium polymer battery uses.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2001-35453 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-76887 publication
Patent documentation 3: Japanese Unexamined Patent Application Publication 2009-544492 publication
Summary of the invention
The problem that invention is to be solved
But, the technology proposed in patent documentation 1 ~ 3 contributes to pack the laminated film of lithium secondary battery,
And it is not affected by the processing that degree of finish as elucidated before is high.Therefore, high to this laminated film degree of being processed
Processing after long-time use in the case of, it is not clear that the most still there is high electrolyte resistance.
It is an object of the invention to, it is provided that a kind of metal exterior material with resin molding and manufacturer thereof
Method, the described metal exterior material with resin molding is in the matrix material metal overlayer pressure such as aluminum or rustless steel
Resin molding or form resin coating film (also referred to as following " resin molding "), then carries out deep-draw processing, thinning
In the case of processing or the harsh forming such as stretch-draw processing, it is also possible to give will not make this laminated film or
The high adhesion that resin coating film is peeled off, even if additionally, with acid or the Long contact time such as solvent, it may have energy
Enough keep the excellent resistance to chemical reagents of high adhesion.
The method of solution problem
Exist for solving the feature with the metal exterior material of resin molding of the present invention of the problems referred to above
In, it has: matrix material metal, be located at the one or both sides of this matrix material metal substrate tunicle,
And it is located at the laminated film on this substrate tunicle or resin coating film, wherein, described substrate tunicle is metallic zinc
Tunicle or the tunicle containing metallic zinc.
According to this invention, by arranging metallic zinc tunicle or the tunicle containing metallic zinc as matrix material gold
Belong to the substrate tunicle between resin molding, can obtain following result: demonstrate will not make laminated film or
The high adhesion that resin coating film is peeled off, even and if also can keep highly dense with acid or the Long contact time such as solvent
Conjunction property.
In the metal exterior material with resin molding of the present invention, the most described laminated film or resin coating film
Containing polyolefin or acid modified polyolefin.
In the metal exterior material with resin molding of the present invention, the most described matrix material metal is choosing
Any one in aluminum or its alloy, rustless steel, copper or its alloy and nickel or its alloy.
In the metal exterior material with resin molding of the present invention, the described tunicle containing metallic zinc is permissible
Constituted in the way of comprising the one kind or two or more element in chosen from Fe, nickel and cobalt.
According to this invention, comprise one kind or two or more element in chosen from Fe, nickel and cobalt by setting
Tunicle containing metallic zinc is as substrate tunicle, such as in the situation utilizing displacement plating to form substrate tunicle
Can reduce down the replacement amount of matrix material metal, the machinery that additionally can improve this substrate tunicle is strong
Degree.
The metal exterior material with resin molding of the present invention can implement deep-draw processing, thinning processing or
Stretch-draw is processed and is constituted.
According to this invention, even if adding the metal exterior material after arranging resin molding is implemented deep-draw
In the case of the harsh forming such as work, thinning processing or stretch-draw processing, also can possess and not make resin molding
Even if the high adhesion peeled off and high adhesion can also be kept with acid or the Long contact time such as solvent
Resistance to chemical reagents.
For solving the manufacturer of the metal exterior material with resin molding of the present invention of the problems referred to above
Method is characterised by, it has: utilize displacement plating method or galvanoplastic matrix material metal one side or
The metallic zinc tunicle as substrate tunicle or the operation of the tunicle containing metallic zinc is formed on two sides；And
Cambium layer press mold or the operation of resin coating film on described substrate tunicle.
According to this invention, by utilizing displacement plating method or galvanoplastic in the one side or two of matrix material metal
The metallic zinc tunicle as substrate tunicle or the tunicle containing metallic zinc is formed, then at substrate tunicle on face
Upper cambium layer press mold or resin coating film, can obtain following result: the manufactured gold with resin molding
Belong to exterior material processed and demonstrate the high adhesion not making laminated film or resin coating film peel off, even and if with acid
Or the Long contact time such as solvent also can keep high adhesion.
The manufacture method with the metal exterior material of resin molding of the present invention can have a following composition:
There is in deep-draw processing, thinning processing and stretch-draw processing any 1 or more than 2 further
Manufacturing procedure.
The manufacture method with the metal exterior material of resin molding of the present invention can have a following composition:
Before the formation process of described substrate tunicle, have further for removing described matrix material metal watch
The operation of the oxide tunicle in face.
According to this invention, owing to also having for removing matrix material before the formation process of substrate tunicle
The operation of the oxide tunicle of metal surface, therefore can improve matrix material metal and substrate quilt further
Adaptation between film.
The effect of invention
The metal exterior material with resin molding according to the present invention and manufacture method thereof, by arranging gold
Belong to zinc tunicle or containing the tunicle of metallic zinc as the substrate tunicle between matrix material metal and resin molding,
Following result can be obtained: demonstrate the high adhesion not making laminated film or resin coating film peel off, and
Even if high adhesion also can be kept with acid or the Long contact time such as solvent.Even if to possessing the effect above
Harsh with the metal exterior material enforcement deep-draw processing of resin molding, thinning processing and stretch-draw processing etc.
In the case of forming, it is also possible to obtain following effect: can give and not make this laminated film or resin
The high adhesion that film is peeled off, even and if with acid or the Long contact time such as solvent, it is possible to have keep
The excellent resistance to chemical reagents of high adhesion.
Accompanying drawing explanation
[Fig. 1] is the type section of an example of the metal exterior material with resin molding illustrating the present invention
Figure.
Symbol description
1 matrix material metal
2 substrate tunicles (metallic zinc tunicle or the tunicle containing metallic zinc)
3 resin moldings (laminated film or resin coating film)
10 with the metal exterior material of resin molding
Detailed description of the invention
Hereinafter, the metal exterior material with resin molding and manufacture method thereof to the present invention are said
Bright.It should be noted that the technical scope of the present invention is not limited by the mode of the following description and accompanying drawing.
[with the metal exterior material of resin molding]
As it is shown in figure 1, the metal exterior material 10 with resin molding of the present invention has: matrix material
Expect metal 1, be located at the substrate tunicle 2 of the one or both sides of this matrix material metal 1 and be located at this
Laminated film or resin coating film on substrate tunicle 2 (below, as long as no particularly pointing out, refer to " resin
Film 3 ").In addition, it is characterised in that this substrate tunicle 2 is metallic zinc tunicle or the quilt containing metallic zinc
Film.It should be noted that in FIG, although the one side at matrix material metal 1 arranges substrate tunicle
2 and resin molding 3 but it also may on the two sides of matrix material metal 1, substrate tunicle 2 and resin molding are set
3。
Hereinafter, the composition of the present invention is described in detail.
(matrix material metal)
Matrix material metal 1 is the base of the metal exterior material 10 with resin molding becoming the present invention
The light sheet material of the metal of body material (base) or paper tinsel.As the material of matrix material metal 1, Ke Yiju
Go out any metal in aluminum or its alloy, rustless steel, copper or its alloy and nickel or its alloy.
Above-mentioned matrix material metal 1 both can be commercially available product, it is also possible to be that the sheet material of given thickness is carried out hot rolling
Or cold rolling and that obtain material.The thickness of matrix material metal 1 is not particularly limited, for example,
About 0.01mm ~ 2.0mm.And, in the situation utilizing displacement plating described later to arrange substrate tunicle 2
Under, owing to matrix material metal 1 is etched, therefore to consider that this etch quantity carrys out design thickness.
Alternatively, it is also possible to arrange other metal or alloy on these metal or alloy.As other
The forming method of metal or alloy, can enumerate plating (plating, non-electrolytic plating) method, evaporation coating method,
Clad method etc..As an example, can enumerate on copper or copper alloy, carried out electronickelling and
The nickel-clad copper etc. obtained.
(substrate tunicle)
Substrate tunicle 2 is provided at the metallic zinc tunicle of the one or both sides of matrix material metal 1 or containing gold
Belong to the tunicle of zinc.For the metal exterior material 10 with resin molding of the present invention, by inciting somebody to action
Metallic zinc tunicle or the tunicle containing metallic zinc are located at matrix material gold as the substrate tunicle 2 of resin molding 3
Belong on 1, can bring following result: that improves between resin molding 3 and matrix material metal 1 is closely sealed
Property, even if it addition, with acid or the Long contact time such as solvent, it is also possible to keep high adhesion.
Metallic zinc tunicle is the layer being only made up of metallic zinc, and the tunicle containing metallic zinc is by comprising metallic zinc
Metal tunicle formed layer.So-called " comprising " refers to the metallic element comprised beyond zinc, as so
Metallic element, the one kind or two or more iron group metal in chosen from Fe, nickel and cobalt can be enumerated.Bag
The tunicle containing metallic zinc containing these iron group metals has the advantage that machineries such as can improving hardness is strong
Spend and can suppress when displacement plating described later the etch quantity of matrix material metal 1.Containing metal
The content of the iron group metal in the tunicle of zinc is preferably the scope of 0.5 mass % ~ 15 mass %.Comprise above-mentioned
The tunicle containing metallic zinc of the iron family element of scope has the advantage that from suppressing matrix material
From the viewpoint of the etch quantity of metal 1, even if the most excessively thickening the thickness of substrate tunicle 2, it is also possible to fill
Ground is divided to form the substrate tunicle with the closely sealed retentivity of electrolyte resistance.It should be noted that metal now
Zinc tunicle is entirely metallic zinc in addition to inevitable impurity component (including micro amount of oxygen compound composition).
Metallic zinc tunicle as substrate tunicle 2 or the tunicle containing metallic zinc can utilize displacement plating
Method or galvanoplastic are formed.
Displacement plating method be according to the oxidation-reduction potential of the displacement matrix material metal 1 that contacts of plating solution,
And the size of the oxidation-reduction potential of the zinc ion contained by plating solution, utilize chemical reaction that base occurs simultaneously
The redox reaction that the oxidation dissolution of body material metal 1 and the reduction of zinc ion separate out, utilizes and matrix
Dissolving (also referred to as etching) the separating out of simultaneous zinc of material metal 1 forms substrate tunicle 2.Cause
This, displacement plating method depends on the matrix material metal 1 in displacement plating solution and the metal ion that can separate out
The size of oxidation-reduction potential, apply to the method that redox environment has obtained situation about adjusting,
In described redox environment, the chemistry that matrix material metal 1 residual electron and oxidation dissolution occur is anti-
Answer and occur the metal ion in liquid to accept this electronics and reduce separate out chemical reaction.It addition, plating
In liquid the most identical containing the one kind or two or more situation in chosen from Fe, nickel and cobalt, depend on matrix material
Expecting the size of metal 1 and the oxidation-reduction potential of the metal ion that can separate out, it is included in or does not comprises
In substrate tunicle 2.Such displacement plating method due to the shape regardless of matrix material metal 1,
The substrate tunicle 2 of uniform thickness can be formed, the most convenient, formed with utilizing galvanoplastic in addition
The mechanical strength such as substrate tunicle 2 is compared harder, hot strength.
Use the formation of substrate tunicle 2 of displacement plating method by making matrix material metal 1 with alkaline or sour
Property displacement plating solution contact carry out.For using which kind of alkaline or acid displacement plating solution, can basis
Whether can be because of the size of the matrix material metal 1 in displacement plating solution with the oxidation-reduction potential of metal ion
And occur to replace plating and properly select.The method " contacted " can be enumerated matrix material metal 1 and exist
Replace the dipping in plating solution, to matrix material metal 1 spray injection displacement plating solution etc..
Displacement plating solution is not particularly limited, and can enumerate the basic displacement used in embodiment the most described later
Plating solution (referred to as zincic acid salt bath, with zinc sulfate and sodium hydroxide as main constituent), acid displacement plating solution are (with sulphuric acid
Zinc and acid ammonium fluoride or Fluohydric acid. are main constituent) etc..And, in these displacement plating solutions, it is also possible to
Contain the additives such as polishing material, complexant, reducing agent, pH regulator, buffer agent, example as required
As gluconic acid sodium salt, other additive can be enumerated.It addition, in substrate tunicle 2 possibly together with chosen from Fe,
In the case of one kind or two or more metal in nickel and cobalt, in displacement plating solution, at random coordinate such as sulfur
Acid ferrous iron, nickel sulfate, cobaltous sulfate etc..
It should be noted that above-mentioned each salt is for illustrating, as long as can be in the one side of matrix material metal 1
Or two sides forms the metallic zinc tunicle as target or containing the tunicle of metallic zinc, it is possible to use above-mentioned with
Outer zinc salt, various slaines etc..It addition, the liquid composition of displacement plating solution is also not particularly limited.Example
As in the case of zincic acid salt bath, generally zinc sulfate 8 ~ 16g/L, sodium hydroxide 90 ~ 150g/L.
Galvanoplastic be to the matrix material metal 1 of plating solution contacts with in the same manner as with plating solution contacts
Between opposite electrode (also referred to as to electrode) apply electric current and by electroplate liquid on matrix material metal 1
The method that the mandatory reduction of metal ion separates out.
Use the formation of substrate tunicle 2 of galvanoplastic by making zinc plating solution contacts matrix material metal 1
Carry out with applying curtage under the state of opposite electrode.As opposite electrode, it is possible to use zine plate
Or insoluble electrode (such as carbon electrode, the Ti electrode etc. of cladding platinum).It addition, using containing zinc composition
In the case of the electroplate liquid of metal ingredient in addition forms the tunicle containing metallic zinc, it is possible to use bag
Containing the opposed electricity with the same amount of ratio of metal ingredient beyond zinc contained in the tunicle containing metallic zinc
Pole.So, can be corresponding with the decrement of the metal ingredient electroplate liquid from opposite electrode supply
Amount.Such galvanoplastic are different from displacement plating method, without chemical reaction, therefore can only pass through
Control curtage and be readily formed the substrate tunicle 2 of required thickness.Further, since with displacement
It is fast that plating method compares speed of separating out, therefore can realize formation at a high speed.
Zinc electroplate liquid is not particularly limited, such as, can enumerate the zinc sulfate used in embodiment described later
Plating solution.It should be noted that in electroplate liquid, it is also possible to be added as needed on polishing material, complexant,
The additives such as pH regulator, buffer agent.It addition, in substrate tunicle 2 possibly together with chosen from Fe, nickel and
In the case of one kind or two or more metal in cobalt, at random coordinate in electroplate liquid such as ferrous sulfate,
Nickel sulfate, cobaltous sulfate etc..
The thickness utilizing the substrate tunicle 2 that above-mentioned each method formed be usually 0.01 μm ~ 0.70 μm (with
Total attachment gauge corresponds approximately to 0.10g/m2~ about 5.0g/m2), preferably 0.03 μm ~ 0.28 μm is (with always
Attachment gauge corresponds approximately to 0.2g/m2~ about 2.0g/m2).If the thickness of substrate tunicle 2 is less than 0.01 μ
M, cannot obtain the closely sealed retentivity of enough electrolyte resistances the most sometimes.On the other hand, if substrate tunicle
The thickness of 2 is more than 0.70 μm, although then the closely sealed retentivity of electrolyte resistance is excellent, but substrate tunicle 2
Film forming can spend the time, thus has the situation of productivity difference.It should be noted that substrate tunicle 2
Total adhesion amount 1g/m2Be equivalent to thickness about 0.14 μm of substrate tunicle 2.
And, although for arranging metallic zinc tunicle or the tunicle containing metallic zinc as substrate tunicle 2
In the case of the reason of electrolyte resistance adaptation can be kept the most unclear, but substantially it is believed that may
Due to following reason: the metal exterior material 10 with resin molding of the present invention be impregnated in
LiPF6 etc. as in the case of in electrolyte solution, can confirm that concentrate in substrate tunicle 2 with
P elements between resin molding 3, therefore dipping time substrate tunicle 2 in zinc composition as LiPF6
Hydrolyzate Fluohydric acid. effect under and dissolution, this zinc composition with similarly as the hydrolysis of LiPF6
The phosphorus compound of product reacts and generates insoluble salt, so such insoluble salt just becomes the resistance to electricity of holding
Solve liquid adaptation will be because of.
(resin molding)
Resin molding 3 with the form of the laminated film at substrate tunicle 2 overlaminate resin-made membrane or
Arrange with the form of the resin coating film of coating resin on substrate tunicle 2.Resin molding 3 by polyolefin,
Acid modified polyolefin or the resin combination comprised as main constituent using them are formed.Such resin molding
Even if 3 is to be also possible to prevent matrix material metal 1 corroded with acid or the Long contact time such as solvent
Or etch and arrange.
As polyolefin, the polyethylene such as high density polyethylene (HDPE), Low Density Polyethylene can be enumerated；Ethylene with
The copolymer of alpha-olefin；Using homopolymer, random copolymer or block copolymer as the polypropylene of raw material；
The copolymer etc. of propylene and alpha-olefin, it is possible to use central one kind or two or more selected from them.Acid
Improved polyalkene can obtain by polyolefin maleic anhydride etc. is carried out graft modification.
Resin molding 3 both can be monolayer, it is also possible to the multilamellar that has been lamination and the multiple structure obtained.It addition,
Can also the resin such as copolymer of further lamination ethylene and cyclic olefin as required, be allowed to have damp proof
Property.It addition, resin molding 3 can also contain the additives such as antioxidant, fire retardant and viscosifier as required.
The thickness of resin molding 3 is usually 10 μm ~ 100 μm, preferably 20 μm ~ 50 μm.
For the lamination process for arranging laminated film, lamination methods, dry lamination method can be enumerated, squeeze
Go out laminating or coextruded layer platen press etc..
Being formed of resin molding 3 using lamination methods crimps resin molding by the surface heat of basad tunicle 2
3 and carry out.Temperature and pressure etc. when carrying out thermo-compressed arbitrarily can set according to the character of resin molding 3.
And, bond layer can also be arranged as required on the surface of resin molding 3, using this bond layer as
Thermo-compressed layer utilizes.As such bond layer, can enumerate by epoxy resin, phenolic resin, third
The layer that the resin combinations such as olefin(e) acid resin, polyurethane resin are formed, can be by being coated with such resin also
Be dried etc. arrange.
Use the formation of resin molding 3 of dry lamination method by forming bonding agent on the surface of substrate tunicle 2
Layer is also carried out at the surface room temperature crimping resin molding 3 of this bond layer.As bond layer, permissible
Enumerate polyesters bonding agent, polyethylene kind bonding agent, polyethers bonding agent, cyanoacrylate bonding
Agent, polyurethanes bonding agent, organic titanium class bonding agent, polyether-polyurethane class bonding agent, epoxies are bonding
The resin combination such as agent, polyester-polyurethane class bonding agent, isocyanates bonding agent, TPO bonding agent
Thing, bond layer above-mentioned resin combination can be coated on the surface of substrate tunicle 2 and be dried and
Formed.
After the formation of the resin molding 3 of employing extruding layer platen press or coextruded layer platen press can be by melting
Resin directly extrude to cool down after the surface of substrate tunicle 2 and carry out.Extrusion and cooling at resin
Time, such as can use flat-die method or melt extrude the equipment of forming process.
(with the metal exterior material of resin molding)
For the metal exterior material 10 with resin molding so constituted, the most as required
Be carried out deep-draw processing, thinning processing or stretch-draw processing, be configured to the shape that gives and for various uses.
Such as, as the portable lithium ion used in mobile phone, electronic notebook, notebook computer or video camera etc.
The exterior material of secondary cell uses.Alternatively, it is also possible to it is such just as smart mobile phone or panel computer
The framework taking type machine uses.Furthermore it is also possible to as driving as electric automobile or hybrid vehicle
The exterior material of the lithium rechargeable battery of kinetic energy uses.
As mentioned above, according to the metal exterior material 10 with resin molding of the present invention, pass through
Metallic zinc tunicle or the tunicle containing metallic zinc are set as between matrix material metal 1 and resin molding 3
Substrate tunicle 2, though can obtain demonstrating the high adhesion not making resin molding 3 peel off and with acid
Or the Long contact time such as solvent also can keep the result of high adhesion.Even if to possessing such effect
Metal exterior material 10 with resin molding implements deep-draw processing, thinning processing or stretch-draw processing etc. sternly
In the case of severe forming, it is also possible to obtain following effect: can give and not make this resin molding 3
The high adhesion peeled off, even and if with acid or the Long contact time such as solvent, it may have can keep highly dense
The excellent resistance to chemical reagents of conjunction property.
[with the manufacture method of metal exterior material of resin molding]
The manufacture method with the metal exterior material 10 of resin molding of the present invention has: utilize displacement
Plating method or galvanoplastic form the metal as substrate tunicle 2 at the one or both sides of matrix material metal 1
Zinc tunicle or containing metallic zinc tunicle substrate tunicle formation process and on this substrate tunicle 2 shape
Become laminated film or the resin molding formation process of resin coating film.It should be noted that so-called " having " refers to,
Can also have the operation beyond substrate tunicle formation process and resin molding formation process.For example, it is also possible to
There is any 1 of pretreatment procedure described later, manufacturing procedure and oxide tunicle removal step etc.
Or more than 2 operations.
Explanation for the details the most above-mentioned " with the metal exterior material of resin molding " of each operation
Shown in explanation in hurdle, the preparation of matrix material metal 1 or formation process, the formation work of substrate tunicle 2
The manufacturing procedures such as sequence, the formation process of resin molding 3, deep-draw processing describe at omitted below its.This manufacture
In method, it is also possible to forming the setting that takes a step forward of substrate tunicle 2 for removing matrix material metal 1
The operation of the oxide tunicle on surface.The removing of oxide tunicle such as can utilize and employ sulphuric acid, nitre
The common acid of the acid such as acid, hydrochloric acid, nitric hydrofluoric acid is cleaned and is carried out.As acid cleaning method, permissible
Enumerate impregnated cleaning or injecting type cleaning etc..Alternatively, it is also possible to carry out as required locating before common
The ungrease treatment of reason.It is generally disposed between each operation it should be noted that water cleans.
For the metal exterior material 10 with resin molding, process in deep-draw the most as required,
The manufacturing procedures such as thinning processing or stretch-draw processing are processed.Utilize such manufacturing procedure, be configured to
Given shape and for various uses.
Above, according to the manufacture method of the metal exterior material 10 with resin molding of the present invention, profit
Formed as substrate tunicle 2 at the one or both sides of matrix material metal 1 by displacement plating method or galvanoplastic
Metallic zinc tunicle or containing the tunicle of metallic zinc, thereafter, this substrate tunicle 2 forms resin molding
3 (laminated film or resin coating films), thus, have obtained following result: the manufactured gold with resin molding
Belong to exterior material 10 processed and demonstrate the high adhesion not making resin molding 3 peel off, even and if with sour or molten
The Long contact time such as agent also can keep high adhesion.
Embodiment
Hereinafter, the present invention will be described in more detail to utilize embodiment and comparative example.The present invention is not subject to
Below example limits.It should be noted that in the following description, " part " is " mass parts ",
" quality % " and " weight % " synonym, be the most also expressed simply as " % ".
[matrix material metal]
Following metallic plate or metal forming is employed as matrix material metal.
1a: aluminium sheet (JIS code name: A1100P, fine aluminium, thick 0.3mm)
1b: alloy foil (JIS code name: A8079, thick 0.03mm)
1c: stainless steel foil (JIS code name: SUS304, thick 0.1mm)
1d: copper coin (JIS code name: C1020P, oxygen-free copper, thick 0.3mm)
1e: nickel plate (more than purity 99 mass %, thick 0.3mm)
1f: nickel plating copper coin (oxygen-free copper of plating ambrose alloy, copper coin: C1020P, thick 0.3mm, nickel plating thickness
Spend 2 μm)
[forming method of substrate tunicle]
Method shown below is utilized to define substrate tunicle at matrix material metallic surface.
(2a: basic displacement plating)
ZINC SULFATE HEPTAHYDRATE 16.87 parts (in terms of zinc), sodium hydroxide 116 parts, gluconic acid sodium salt are made
20 parts and remainder are the basic displacement plating solution amounting to 1000 parts of water.Matrix material metal is existed
This plating solution impregnates 30 seconds in 30 DEG C, after washing, uses electric furnace 80 DEG C of heat dryings 1 minute.
(2b: basic displacement plating)
Made ZINC SULFATE HEPTAHYDRATE 16.87 parts (in terms of zinc), ferrous sulfate pentahydrate 1.16 parts (with
Ferrum meter), sodium hydroxide 116 parts, gluconic acid sodium salt 20 parts and remainder be water amount to 1000 parts
Basic displacement plating solution.Matrix material metal is impregnated 30 seconds in 30 DEG C in this plating solution, after washing,
Use electric furnace 80 DEG C of heat dryings 1 minute.
(2c: basic displacement plating)
ZINC SULFATE HEPTAHYDRATE 16.87 parts (in terms of zinc), nickel sulfate hexahydrate compound 2.0 parts are made (with nickel
Meter), sodium hydroxide 116 parts, gluconic acid sodium salt 20 parts and remainder be water amount to 1000 parts
Basic displacement plating solution.Matrix material metal is impregnated 30 seconds in 30 DEG C in this plating solution, after washing,
Use electric furnace 80 DEG C of heat dryings 1 minute.
(2d: basic displacement plating)
ZINC SULFATE HEPTAHYDRATE 16.87 parts (in terms of zinc), cobaltous sulfate heptahydrate 3.0 parts are made (with cobalt
Meter), sodium hydroxide 116 parts, gluconic acid sodium salt 20 parts and remainder be water amount to 1000 parts
Basic displacement plating solution.Matrix material metal is impregnated 30 seconds in 30 DEG C in this plating solution, after washing,
Use electric furnace 80 DEG C of heat dryings 1 minute.
(2e: basic displacement plating)
Made ZINC SULFATE HEPTAHYDRATE 16.87 parts (in terms of zinc), ferrous sulfate pentahydrate 1.16 parts (with
Ferrum meter), nickel sulfate hexahydrate compound 0.23 part (in terms of nickel), sodium hydroxide 116 parts, gluconic acid sodium salt 20 parts
And the basic displacement plating solution amounting to 1000 parts that remainder is water.By matrix material metal in this plating
Liquid impregnates 30 seconds in 30 DEG C, after washing, uses electric furnace 80 DEG C of heat dryings 1 minute.
(2f: basic displacement plating)
Made ZINC SULFATE HEPTAHYDRATE 16.87 parts (in terms of zinc), ferrous sulfate pentahydrate 1.16 parts (with
Ferrum meter), cobaltous sulfate heptahydrate 1.06 parts (in terms of cobalt), sodium hydroxide 116 parts, gluconic acid sodium salt 20 parts
And the basic displacement plating solution amounting to 1000 parts that remainder is water.By matrix material metal in this plating
Liquid impregnates 30 seconds in 30 DEG C, after washing, uses electric furnace 80 DEG C of heat dryings 1 minute.
(2g: acid displacement plating)
Make the following acid displacement plating solution amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 10 parts
(in terms of zinc), acid ammonium fluoride 7.65 parts, and remainder are water, also use the hydrogen of 10 mass %
Aqueous solution of sodium oxide is adjusted to pH3.0.Matrix material metal is impregnated 30 seconds in 30 DEG C in this plating solution
Clock, after washing, uses electric furnace 80 DEG C of heat dryings 1 minute.
(2h: acid displacement plating)
Make the following acid displacement plating solution amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 13 parts
(in terms of zinc), ferrous sulfate pentahydrate 3.6 parts (in terms of ferrum), 55 mass % hydrofluoric acid aqueous solutions 12.1
Part, and remainder is water, also uses the sodium hydrate aqueous solution of 10 mass % to be adjusted to pH2.0.
Matrix material metal is impregnated 30 seconds in 30 DEG C in this plating solution, after washing, uses electric furnace 80
DEG C heat drying 1 minute.
(2i: acid displacement plating)
Make the following acid displacement plating solution amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 13 parts
(in terms of zinc), nickel sulfate hexahydrate compound 0.8 part (in terms of nickel), 55 mass % hydrofluoric acid aqueous solutions 12.1 parts,
And remainder is water, the sodium hydrate aqueous solution of 10 mass % is also used to be adjusted to pH3.0.By base
Body material metal impregnates 30 seconds in 30 DEG C in this plating solution, after washing, uses electric furnace 80 DEG C of heating
It is dried 1 minute.
(2j: acid displacement plating)
Make the following acid displacement plating solution amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 13 parts
(in terms of zinc), cobaltous sulfate heptahydrate 2.1 parts (in terms of cobalt), 55 mass % hydrofluoric acid aqueous solutions 9.7 parts,
And remainder is water, the sodium hydrate aqueous solution of 10 mass % is also used to be adjusted to pH3.0.By base
Body material metal impregnates 30 seconds in 30 DEG C in this plating solution, after washing, uses electric furnace 80 DEG C of heating
It is dried 1 minute.
(2k: acid displacement plating)
Make the following acid displacement plating solution amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 13 parts
(in terms of zinc), ferrous sulfate pentahydrate 2.5 parts (in terms of ferrum), nickel sulfate hexahydrate compound 0.3 part (in terms of nickel),
55 mass % hydrofluoric acid aqueous solutions 12.1 parts, and remainder is water, also uses the ammonia of 10 mass %
Aqueous solution is adjusted to pH2.5.Matrix material metal is impregnated 30 seconds in 30 DEG C in this plating solution, water
After washing, use electric furnace 80 DEG C of heat dryings 1 minute.
(2l: acid displacement plating)
Make the following acid displacement plating solution amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 13 parts
(in terms of zinc), ferrous sulfate pentahydrate 1.5 parts (in terms of ferrum), cobaltous sulfate heptahydrate 0.4 part (in terms of cobalt),
55 mass % hydrofluoric acid aqueous solutions 12.1 parts, and remainder is water, also uses the ammonia of 10 mass %
Aqueous solution is adjusted to pH3.0.Matrix material metal is impregnated 30 seconds in 30 DEG C in this plating solution, water
After washing, use electric furnace 80 DEG C of heat dryings 1 minute.
(plating of 2m: zinc)
Make the zinc electroplate liquid of following 1000 part, i.e. ZINC SULFATE HEPTAHYDRATE 91.6 parts (in terms of zinc),
200 parts of sodium sulfate, and remainder is water, also uses the ammonia spirit of 10 mass % to be adjusted to
pH4.0.By matrix material metal impregnation in this plating solution, electrode is used zine plate, at 30 DEG C with 5A/dm2
Electric current density carry out the catholyte of 10 seconds.Then wash, use electric furnace to add at 80 DEG C
Heated drying 1 minute.
(plating of 2n: zinc)
Make the following zinc electroplate liquid amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 32.7 parts (with
Zinc meter), ferrous sulfate pentahydrate 27.5 parts (in terms of ferrum), 200 parts of sodium sulfate, and remainder
For water, the ammonia spirit of 10 mass % is also used to be adjusted to pH3.5.By matrix material metal impregnation at this
In plating solution, electrode is used zine plate, at 30 DEG C with 5A/dm2Electric current density carry out the moon of 10 seconds
Pole is electrolysed.Then wash, use electric furnace heat drying 1 minute at 80 DEG C.
(plating of 2o: zinc)
Make the following zinc electroplate liquid amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 32.7 parts (with
Zinc meter), nickel sulfate hexahydrate compound 25 parts (in terms of nickel), 200 parts of sodium sulfate, and remainder is water,
The ammonia spirit also using 10 mass % is adjusted to pH3.5.By matrix material metal impregnation in this plating solution,
Electrode is used zine plate, at 30 DEG C with 5A/dm2Electric current density carry out the catholyte of 10 seconds.
Then wash, use electric furnace heat drying 1 minute at 80 DEG C.
(plating of 2p: zinc)
Make the following zinc electroplate liquid amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 32.7 parts (with
Zinc meter), cobaltous sulfate heptahydrate 25 parts (in terms of cobalt), 200 parts of sodium sulfate, and remainder is water,
The ammonia spirit also using 10 mass % is adjusted to pH4.0.By matrix material metal impregnation in this plating solution,
Electrode is used zine plate, at 30 DEG C with 5A/dm2Electric current density carry out the catholyte of 10 seconds.
Then wash, use electric furnace heat drying 1 minute at 80 DEG C.
(plating of 2q: zinc)
Make the following zinc electroplate liquid amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 32.7 parts (with
Zinc meter), ferrous sulfate pentahydrate 27.5 parts (in terms of ferrum), nickel sulfate hexahydrate compound 25 parts (in terms of nickel),
200 parts of sodium sulfate, and remainder is water, also uses the ammonia spirit of 10 mass % to be adjusted to
pH3.5.By matrix material metal impregnation in this plating solution, electrode is used zine plate, at 30 DEG C with 5A/dm2
Electric current density carry out the catholyte of 10 seconds.Then wash, use electric furnace to add at 80 DEG C
Heated drying 1 minute.
(plating of 2r: zinc)
Make the following zinc electroplate liquid amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 32.7 parts (with
Zinc meter), ferrous sulfate pentahydrate 27.5 parts (in terms of ferrum), cobaltous sulfate heptahydrate 25 parts (in terms of cobalt),
200 parts of sodium sulfate, and remainder is water, also uses the ammonia spirit of 10 mass % to be adjusted to
pH3.5.By matrix material metal impregnation in this plating solution, electrode is used zine plate, at 30 DEG C with 5A/dm2
Electric current density carry out the catholyte of 10 seconds.Then wash, use electric furnace to add at 80 DEG C
Heated drying 1 minute.
(plating of 2s: zinc)
Make the following zinc electroplate liquid amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 91.6 parts (with
Zinc meter), 200 parts of sodium sulfate, and remainder is water, also uses the ammonia spirit of 10 mass % to adjust
Whole for pH4.0.Then, by matrix material metal nitric hydrofluoric acid aqueous solution (nitric acid 10 mass %,
Fluohydric acid. 5 mass %) at room temperature impregnate 1 minute, then wash.Thereafter, by above-mentioned matrix
Material metal is immersed in above-mentioned zinc electroplate liquid, electrode is used zine plate, at 30 DEG C with 5A/dm2Electricity
Current density carries out the catholyte of 10 seconds.Then wash, use electric furnace to heat at 80 DEG C dry
Dry 1 minute.
(plating of 2t: zinc)
Make the following zinc electroplate liquid amounting to 1000 parts, i.e. ZINC SULFATE HEPTAHYDRATE 91.6 parts (with
Zinc meter), ferrous sulfate pentahydrate 27.5 parts (in terms of ferrum), 200 parts of sodium sulfate, and remainder
For water, the ammonia spirit of 10 mass % is also used to be adjusted to pH4.0.Then, matrix material metal is existed
Nitric hydrofluoric acid aqueous solution (nitric acid 10 mass %, Fluohydric acid. 5 mass %) at room temperature impregnates 1 minute,
Then wash.Thereafter, by above-mentioned matrix material metal impregnation in above-mentioned zinc electroplate liquid, to electrode
Use zine plate, at 30 DEG C with 5A/dm2Electric current density carry out the catholyte of 10 seconds.Then enter
Row washing, uses electric furnace heat drying 1 minute at 80 DEG C.
(coating of 2u: zinc oxide)
With #3 bar coater coating zinc oxide colloidal sol (dispersion particle diameter 20nm, solid component concentration 1.5 mass %,
PH9.0) after, with 120 degree of heat dryings 1 minute in electric furnace.
(2v: without substrate tunicle)
For matrix material metal, it is formed without substrate tunicle, directly uses electric furnace to heat at 80 DEG C dry
Dry 1 minute.
[forming method of resin molding]
Any one following method is utilized to define resin molding.
(3a: heat lamination)
With 1MPa by the basad tunicle of maleated polypropylene thin film of thickness 50 μm at 190 DEG C
Surface heat crimp 10 seconds.
(3b: heat lamination)
With 1MPa by the maleated polypropylene layer of thickness 20 μm and thickness 30 μm at 190 DEG C
Polypropylene and resin molding maleic acid modified poly-of 2 Rotating fields of copolymer layer lamination of ethylene
The surface heat of Polypropylene film layer lateral substrate tunicle crimps 10 seconds.
(3c: heat lamination)
Use #8SUS wheat rod, utilize bar coater at the surface coated acid modified polypropene of substrate tunicle
(Mitsui Chemicals, Inc manufactures dispersion liquid, trade name: R-120K, nonvolatile component concentration: 20 matter
Amount %), then it is dried 1 minute with 200 DEG C in heated air circulation type drying oven, defines bond layer.
Thereafter, at 190 DEG C with 1MPa by polypropylene film (Tohcello Co., Ltd. system of thickness 30 μm
" CPPS " made) surface heat of bond layer on basad tunicle crimps 10 seconds.
(3d: extrusion lamination)
The surface extrusion acid modified polypropene of basad tunicle forms the molten resin layer of thickness 15 μm,
The polypropylene film (" CPPS " that Tohcello Co., Ltd. manufactures) of coating thickness 30 μm the most again,
Implement extrusion lamination.
(3e: dry lamination)
Use #8SUS wheat rod, utilize bar coater to be coated with polyurethanes dry type layer on the surface of substrate tunicle
(Morton Co., Ltd. of Japan manufactures pressure bonding agent, trade name: AD-503/CAT10, non-volatile one-tenth
Point concentration: 25 mass %) after, it is dried 1 minute with 80 DEG C in electric furnace, defines bond layer.So
After, by un-stretched polypropylene film (the two villages chemical industry strain formula meeting of this bond layer Yu thickness 30 μm
Society manufacture, trade name: FCZX) Corona discharge Treatment face at 100 DEG C with 1MPa crimp after,
Ripening 4 days at 40 DEG C.
[for the making of test material]
By above-mentioned matrix material metal in Fine Cleaner 359E (Nihon Parkerizing Co., Ltd.
(NIHON PARKERIZING CO., LTD.) manufacture, alkali cleaner) 2% aqueous solution in 50 DEG C
Carry out spraying defat in 10 seconds, then surface is washed, prepared the reality shown in table 1 ~ table 4
Execute matrix material metal used in example 1 ~ 71 and comparative example 1 ~ 12.
Then, to the embodiment 1 ~ 71 shown in table 1 ~ table 4 and the base used in comparative example 1 ~ 12
Each process shown in body material metal application table 1 ~ table 4, defines substrate tunicle.In table 1 ~ table 4
Shown embodiment 1 ~ embodiment 71 have selected any process in 2a ~ 2t, comparative example 1 ~ comparative example
The process of 2u or 2v is have selected in 12.
Here, owing to matrix material metal etches when replacing plating, therefore determine its erosion
Quarter measures (g/m2).The mensuration of etch quantity be utilize icp analysis (Shimadzu Scisakusho Ltd manufacture,
ICPE-9000) the matrix material metal in dissolution to displacement plating solution has been carried out quantitatively.The results are shown in
In table 1 ~ table 4.It addition, to metallic element (Zn, Fe, Ni, Co etc.) attached constituting substrate tunicle
The amount of wearing (g/m2) also utilize icp analysis to carry out quantitatively.This adhesion amount is by being provided with substrate tunicle
Matrix material metal impregnation dissolves in 60% nitric acid, this lysate is carried out icp analysis and measures
's.If it should be noted that attachment 1g/m2Metallic element, then the thickness of substrate tunicle is just about
0.5μm.The results are shown in table 1 ~ table 4.It addition, for the surface of substrate tunicle, carry out XPS
Analyze (Shimadzu Scisakusho Ltd manufactures, ESCA-850M), according to the peak of ZnLMM auger spectrum
Position identifies the chemical state of the zinc element in substrate tunicle.Peak position at ZnLMM auger spectrum
In the case of 993.6eV, zinc element is metallic state, and in the case of 988.6eV, zinc element is
The state of oxidation.The results are shown in table 1 ~ table 4.
Then, used in for the embodiment 1 ~ 71 shown in table 1 ~ table 4 and comparative example 1 ~ 12
With the matrix material metal of substrate tunicle, each lamination treatment shown in table 1 ~ table 4 is applied to be formed
Resin molding.
Then, exterior to the embodiment 1 ~ 71 of gained and the metal system with resin molding of comparative example 1 ~ 12
Material implements deep-draw processing.First, to the metal system with resin molding that stamping-out is diameter 160mm
Exterior material carries out drawing processing (for the first time), produces the cup of diameter 100mm.It follows that should
Cup drawing again processing (for the second time) becomes diameter 75mm, further drawing processing (for the third time) to become diameter
65mm, has made as the tank for test material.It should be noted that the processing of primary drawing,
Secondary drawing processing and third time drawing processing in reduction (thin-walled property mark) be respectively 5%,
15% and 15%.
[performance evaluation]
For the tank after the metal exterior material with resin molding is implemented deep-draw processing (for testing material
Material) initial stage adaptation, durable adaptation, the closely sealed retentivity of electrolyte resistance and liquid stability such as
Under evaluated.The results are shown in table 1 ~ table 4.
(initial stage adaptation)
The tank as confession test material after processing deep-draw have rated initial stage adaptation.Can make
Tank, do not have the stripping of resin molding, initial stage excellent adhesion be set to " 3 points ", by the one of resin molding
That point peels off is set to " 2 points ", and peeling-off resin molding is set to " 1 point " at whole.
(the closely sealed retentivity of electrolyte resistance)
The tank as confession test material after deep-draw being processed is immersed in the interpolation being filled in hermetic container
There is the electrolyte solution for lithium ion secondary battery (electrolyte: 1mol/L's of the ion exchange water of 1000ppm
LiPF6, solvent volume ratio is EC:DMC:DEC=1:1:1) in, then put into the temperature chamber of 60 DEG C
In 7 days.It should be noted that " EC " is ethylene carbonate, " DMC " is dimethyl carbonate,
" DEC " is diethyl carbonate.Then, take out for test material, in ion exchange water, impregnate 1 point
Clock, after shake is cleaned, is dried 10 minutes with 100 DEG C in electric furnace.Then, scrape with the tip of tweezers
Draw resin face, be set to " 4 points ", although will be peeling-off by what the stripping of resin molding do not occurred
But scratch resistance eminence and be set to " 3 points " in realistic scale, will can be peeling-off with very weak power
Be set to " 2 points ", the most stripped for resin molding is set to " 1 point ".
As shown in table 1 ~ table 4, embodiment 1 ~ 71 for test material (present invention with resin molding
Metal exterior material) compared with the confession test material of comparative example 1 ~ 12, even if in impregnated in electrolyte
In the case of can also keep adaptation, confirm that the closely sealed retentivity of its electrolyte resistance is excellent.
Claims (10)
1. with a metal exterior material for resin molding, it has: matrix material metal, be located at
The adhesion amount 0.10g/m of the one or both sides of this matrix material metal2～1.40g/m2Substrate tunicle, with
And it is located at the laminated film on this substrate tunicle or resin coating film, wherein, described substrate tunicle is metallic zinc quilt
Film or the tunicle containing metallic zinc.
Metal exterior material with resin molding the most according to claim 1, wherein, described
Laminated film or resin coating film contain polyolefin or acid modified polyolefin.
Metal exterior material with resin molding the most according to claim 1, wherein, described
Matrix material metal is in aluminum or its alloy, rustless steel, copper or its alloy and nickel or its alloy
Any one.
Metal exterior material with resin molding the most according to claim 2, wherein, described
Matrix material metal is in aluminum or its alloy, rustless steel, copper or its alloy and nickel or its alloy
Any one.
5. according to the metal exterior material with resin molding according to any one of Claims 1 to 4,
Wherein, the described tunicle containing metallic zinc comprises the one kind or two or more element in chosen from Fe, nickel and cobalt.
6. according to the metal exterior material with resin molding according to any one of Claims 1 to 4,
It is implemented deep-draw processing, thinning processing or stretch-draw processing and is formed.
Metal exterior material with resin molding the most according to claim 5, it is to implement deeply
Processing, thinning processing or stretch-draw processing is drawn to be formed.
8., with the manufacture method of metal exterior material for resin molding, the method has:
Displacement plating method or galvanoplastic are utilized to be formed as substrate at the one or both sides of matrix material metal
The metallic zinc tunicle of tunicle or the operation of the tunicle containing metallic zinc, the adhesion amount of described substrate tunicle is
0.10g/m2～1.40g/m2；And
Cambium layer press mold or the operation of resin coating film on described substrate tunicle.
The manufacture method of the metal exterior material with resin molding the most according to claim 8,
Wherein, also there is any 1 or more than 2 in deep-draw processing, thinning processing and stretch-draw processing
Manufacturing procedure.
The manufacturer of the metal exterior material with resin molding the most according to claim 8 or claim 9
Method, wherein, before the formation process of described substrate tunicle, also has for removing described matrix material
The operation of the oxide tunicle of metal surface.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-243944 | 2011-11-07 | ||
| JP2011243944A JP5980495B2 (en) | 2011-11-07 | 2011-11-07 | Metal exterior material with resin film and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| CN103085384A CN103085384A (en) | 2013-05-08 |
| CN103085384B true CN103085384B (en) | 2016-08-10 |
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| CN201210439629.7A Expired - Fee Related CN103085384B (en) | 2011-11-07 | 2012-11-06 | Metal exterior material and manufacture method thereof with resin molding |
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| Country | Link |
|---|---|
| JP (1) | JP5980495B2 (en) |
| KR (1) | KR101870455B1 (en) |
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| CN103847162B (en) * | 2014-02-21 | 2016-01-27 | 苏州米达思精密电子有限公司 | A kind of golden reinforcing chip of surface gold-plating and preparation technology thereof |
| JP6412323B2 (en) * | 2014-03-24 | 2018-10-24 | 昭和電工パッケージング株式会社 | Exterior material for electrochemical device and electrochemical device |
| JP6626258B2 (en) * | 2014-04-07 | 2019-12-25 | 昭和電工パッケージング株式会社 | Manufacturing method of laminate exterior material |
| KR102144161B1 (en) * | 2018-06-25 | 2020-08-12 | 현대제철 주식회사 | Plating solution for electro-galvanized steel sheet, manufacturing method for electro-galvanized steel sheet using the same, and electro-galvanized steel sheet prepared using the same |
| JP6733971B1 (en) * | 2019-04-23 | 2020-08-05 | 株式会社シミズ | Copper damage prevention film, method for producing copper member with copper damage prevention film, and copper damage prevention method |
| CN113381101A (en) * | 2021-05-07 | 2021-09-10 | 厦门大学 | Battery flexible packaging material with good heat dissipation performance and preparation method thereof |
| KR20230003964A (en) * | 2021-06-30 | 2023-01-06 | 삼성전자주식회사 | Electronic device comprising plate, plate, and manufacturing method of plate |
| WO2023128234A1 (en) | 2021-12-28 | 2023-07-06 | 주식회사 리베스트 | Apparatus and method for forming pattern on exterior material of battery |
| KR20230100585A (en) | 2021-12-28 | 2023-07-05 | 주식회사 리베스트 | Apparatus and method for forming pattern on exterior material of battery |
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| JP2904060B2 (en) * | 1995-06-27 | 1999-06-14 | 株式会社神戸製鋼所 | Surface-treated steel sheet with excellent punching workability and formability |
| CN1049697C (en) * | 1995-06-09 | 2000-02-23 | 株式会社神户制钢所 | Steel sheet having excellent processing characteristics manufacturing method therefor, and galvanized steel sheet and resin coating steel sheet |
| DE60036354T2 (en) * | 1999-04-08 | 2008-05-29 | Dai Nippon Printing Co., Ltd. | Laminated multilayer structure for lithium battery packaging |
| JP4440376B2 (en) | 1999-07-16 | 2010-03-24 | 大日本印刷株式会社 | Polymer battery packaging materials |
| JP2004176092A (en) * | 2002-11-25 | 2004-06-24 | Kobe Steel Ltd | Resin-coating galvanize-base coated steel sheet excellent in weldability and corrosion resistance, and its producing method |
| JP2007069354A (en) * | 2005-09-02 | 2007-03-22 | Sekisui Film Kk | Metal-like decorative sheet and decorative metal sheet |
| JP5045002B2 (en) * | 2006-06-26 | 2012-10-10 | ソニー株式会社 | Non-aqueous electrolyte secondary battery and battery pack, and non-aqueous electrolyte secondary battery and battery pack manufacturing method. |
| EP1884353A1 (en) | 2006-07-24 | 2008-02-06 | Alcan Technology & Management Ltd. | Plastic composite film |
| JP2008046477A (en) * | 2006-08-18 | 2008-02-28 | Toyo Kohan Co Ltd | Reflecting plate for liquid crystal backlight |
| JP4954775B2 (en) * | 2007-04-12 | 2012-06-20 | ソニー株式会社 | Battery pack |
| CN101396888B (en) * | 2007-09-27 | 2013-01-09 | 比亚迪股份有限公司 | Metal composite board and preparation method thereof |
| JP2010236022A (en) * | 2009-03-31 | 2010-10-21 | Jfe Steel Corp | Film laminate treatment hot-dip zinc-plated steel sheet |
| JP2011076887A (en) | 2009-09-30 | 2011-04-14 | Toppan Printing Co Ltd | Packaging material for lithium ion battery |
| JP2012212511A (en) * | 2011-03-30 | 2012-11-01 | Nisshin Steel Co Ltd | Laminate for battery exterior and secondary battery |
-
2011
- 2011-11-07 JP JP2011243944A patent/JP5980495B2/en not_active Expired - Fee Related
-
2012
- 2012-11-06 CN CN201210439629.7A patent/CN103085384B/en not_active Expired - Fee Related
- 2012-11-06 KR KR1020120124757A patent/KR101870455B1/en active IP Right Grant
- 2012-11-06 TW TW101141153A patent/TWI597161B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| TWI597161B (en) | 2017-09-01 |
| TW201325891A (en) | 2013-07-01 |
| JP5980495B2 (en) | 2016-08-31 |
| KR101870455B1 (en) | 2018-06-22 |
| JP2013099869A (en) | 2013-05-23 |
| KR20130050255A (en) | 2013-05-15 |
| CN103085384A (en) | 2013-05-08 |
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