TWI597161B - Metallic external material with resin film and its manufacturing method - Google Patents
Metallic external material with resin film and its manufacturing method Download PDFInfo
- Publication number
- TWI597161B TWI597161B TW101141153A TW101141153A TWI597161B TW I597161 B TWI597161 B TW I597161B TW 101141153 A TW101141153 A TW 101141153A TW 101141153 A TW101141153 A TW 101141153A TW I597161 B TWI597161 B TW I597161B
- Authority
- TW
- Taiwan
- Prior art keywords
- film
- metal
- zinc
- base
- resin
- Prior art date
Links
- 239000011347 resin Substances 0.000 title claims description 129
- 229920005989 resin Polymers 0.000 title claims description 129
- 239000000463 material Substances 0.000 title claims description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 140
- 239000002184 metal Substances 0.000 claims description 140
- 229910052725 zinc Inorganic materials 0.000 claims description 99
- 239000011701 zinc Substances 0.000 claims description 99
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 97
- 238000000034 method Methods 0.000 claims description 89
- 239000010953 base metal Substances 0.000 claims description 81
- 238000000576 coating method Methods 0.000 claims description 65
- 239000011248 coating agent Substances 0.000 claims description 64
- 238000007747 plating Methods 0.000 claims description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 238000006073 displacement reaction Methods 0.000 claims description 35
- 229910052742 iron Inorganic materials 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 20
- 238000012545 processing Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 238000010409 ironing Methods 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 description 48
- 239000010410 layer Substances 0.000 description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000007788 liquid Substances 0.000 description 28
- 239000002253 acid Substances 0.000 description 25
- -1 polyethylene terephthalate Polymers 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 21
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 21
- 238000011010 flushing procedure Methods 0.000 description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 17
- 238000011282 treatment Methods 0.000 description 17
- 238000009713 electroplating Methods 0.000 description 16
- 238000003475 lamination Methods 0.000 description 16
- 229910000368 zinc sulfate Inorganic materials 0.000 description 15
- 229960001763 zinc sulfate Drugs 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000011888 foil Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 239000011790 ferrous sulphate Substances 0.000 description 12
- 235000003891 ferrous sulphate Nutrition 0.000 description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 230000002378 acidificating effect Effects 0.000 description 8
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 8
- 229940044175 cobalt sulfate Drugs 0.000 description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 239000008151 electrolyte solution Substances 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 7
- 239000007767 bonding agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000000176 sodium gluconate Substances 0.000 description 7
- 235000012207 sodium gluconate Nutrition 0.000 description 7
- 229940005574 sodium gluconate Drugs 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000005022 packaging material 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
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 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
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 239000011686 zinc sulphate Substances 0.000 description 3
- 235000009529 zinc sulphate Nutrition 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 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
- 238000005253 cladding Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960001781 ferrous sulfate Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WQSRXNAKUYIVET-UHFFFAOYSA-N sulfuric acid;zinc Chemical compound [Zn].OS(O)(=O)=O WQSRXNAKUYIVET-UHFFFAOYSA-N 0.000 description 2
- 238000009823 thermal lamination Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001785 cerium compounds Chemical class 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
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 238000002203 pretreatment Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 239000000565 sealant Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- ISWJOCMVDARDLS-UHFFFAOYSA-L zinc;hydrogen sulfate Chemical compound [Zn+2].OS([O-])(=O)=O.OS([O-])(=O)=O ISWJOCMVDARDLS-UHFFFAOYSA-L 0.000 description 1
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
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- 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
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- 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
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- 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
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- 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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Description
本發明，是有關於附樹脂薄膜的金屬製外部材料及其製造方法。詳細的話，有關於附樹脂薄膜的金屬製外部材料及其製造方法，即使在與電解液接觸的情況也可以維持基材金屬及積層薄膜或樹脂塗膜的密合性。 The present invention relates to a metal external material to which a resin film is attached and a method for producing the same. In detail, there is a metal outer material with a resin film and a method for producing the same, and the adhesion between the base metal and the laminated film or the resin coating film can be maintained even when it is in contact with the electrolytic solution.
進一步詳細的話，有關於附樹脂薄膜的金屬製外部材料等，在鋁或不銹鋼等的基材金屬將樹脂薄膜積層或形成樹脂塗膜，其後即使施加了深拉深加工、熨燙加工或拉伸抽製加工等的嚴苛的成形加工的情況，也可以獲得：賦予高密合性使該積層薄膜或樹脂塗膜不剝離，進一步即使與酸或溶劑等長時間接觸也可優異地維持高密合性的耐藥品性。 More specifically, there is a metal outer material to which a resin film is attached, and a resin film is laminated or formed into a resin coating film on a base metal such as aluminum or stainless steel, and even deep drawing, ironing, or stretching is applied thereafter. In the case of a severe molding process such as a drawing process, it is possible to obtain high adhesion, and the laminated film or the resin coating film is not peeled off, and it is possible to maintain high adhesion even when exposed to an acid or a solvent for a long period of time. Chemical resistance.
積層加工，是將樹脂製的薄膜(以下稱為樹脂薄膜或積層薄膜)加熱擠壓在金屬材料的表面的加工手段，是為了賦予保護表面或外觀造形效果之目的之金屬材料表面的被覆方法的一種，被使用於各式各樣的領域。積層加工，是與藉由在金屬材料的表面將樹脂組成物塗抹乾燥而形成樹脂塗膜的方法相比，乾燥時所發生的溶劑和二氧化碳等的廢棄氣體或溫暖化氣體的發生量較少。因此，從環境保全的觀點會較佳且適用，其用途可擴大使用至例如將鋁薄板材、鐵薄板材、包裝用鋁箔或不銹鋼箔等作為素材的食 品用罐的殼體或蓋材、食品用容器、或乾電池容器等。 The laminating process is a processing method of heat-pressing a resin film (hereinafter referred to as a resin film or a laminated film) on the surface of a metal material, and is a coating method for a metal material surface for the purpose of imparting a protective surface or an appearance forming effect. One is used in a wide variety of fields. The lamination processing is performed in comparison with a method of forming a resin coating film by drying a resin composition on the surface of a metal material, and a generation amount of a waste gas or a warm gas such as carbon dioxide generated during drying is small. Therefore, it is better and applicable from the viewpoint of environmental preservation, and its use can be expanded to use, for example, a material such as an aluminum thin plate, an iron thin plate, an aluminum foil for packaging, or a stainless steel foil. A can body or lid material, a food container, or a dry battery container.
尤其是最近，作為行動電話、電子筆記本、筆記型個人電腦或攝影機等所使用的可攜裝置用鋰離子2次電池的外部材料，較佳是使用輕量且屏障性高的鋁板或不銹鋼板等的金屬板，在如此的金屬板的表面是適用積層加工。且，雖也被檢討作為電動汽車或混合動力汽車的驅動能量的鋰離子2次電池，但是即使其外部材料，也被檢討經積層加工的金屬板。 In particular, recently, as an external material of a lithium ion secondary battery for a portable device used for a mobile phone, an electronic notebook, a notebook personal computer, or a video camera, it is preferable to use an aluminum plate or a stainless steel plate which is lightweight and has a high barrier property. The metal plate on the surface of such a metal plate is suitable for lamination processing. In addition, although the lithium ion secondary battery which is the driving energy of an electric vehicle or a hybrid vehicle is also reviewed, the laminated metal sheet is reviewed even if it is an external material.
在如此的積層加工所使用的積層薄膜，是直接在被貼合於金屬材料之後進行加熱擠壓。因此，與將樹脂組成物塗抹乾燥的一般的樹脂塗膜相比，具有：可以抑制原材料的浪費、針孔(缺陷部)少、及加工性優異等的優點。積層薄膜的材料，一般是使用：聚對苯二甲酸乙二醇酯及聚乙烯萘等的聚酯系樹脂、聚乙烯及聚丙烯等的聚烯烴、耐綸等的聚醯胺系樹脂。 The laminated film used in such a lamination process is directly subjected to heat extrusion after being bonded to a metal material. Therefore, compared with the general resin coating film which smears a resin composition, it can suppress waste of a raw material, a pinhole (defect part), and the outstanding workability. As the material of the laminated film, a polyester resin such as polyethylene terephthalate or polyethylene naphthalene, a polyolefin such as polyethylene or polypropylene, or a polyamide resin such as nylon is used.
將積層薄膜在金屬材料的表面(以下也只稱為「金屬表面」)積層加工時，為了提高積層薄膜及金屬表面的密合性及金屬表面的耐腐蝕性，將金屬表面脫脂洗淨之後，通常會施加磷酸鉻等的化學轉化處理等。但是，如此的化學轉化處理，是在處理後需要將多餘的處理液除去用的洗淨過程，對於從該洗淨過程被排出的洗淨水的廢水處理很花費成本。尤其是磷酸鉻等的化學轉化處理等因為包含六價鉻的處理液的使用，所以從近年來的環境的考慮而有避免使用的傾向。 When the laminated film is laminated on the surface of a metal material (hereinafter also referred to simply as "metal surface"), in order to improve the adhesion between the laminated film and the metal surface and the corrosion resistance of the metal surface, the metal surface is degreased and washed. Usually, a chemical conversion treatment such as chromium phosphate or the like is applied. However, such a chemical conversion treatment is a washing process for removing excess treatment liquid after the treatment, and it is costly to treat the wastewater of the washing water discharged from the washing process. In particular, since chemical conversion treatment such as chromium phosphate or the like is used for the treatment liquid containing hexavalent chromium, it has a tendency to be avoided from the viewpoint of recent environmental considerations.
另一方面，在金屬表面不施加化學轉化處理等的處理而進行積層加工的話，會具有積層薄膜從金屬表面剝離、在金屬材料發生腐蝕的問題。例如在鋰離子2次電池的外部材料等中，由其製造過程受到加工度高的加工。鋰離子2次電池的電解質，是使用：碳酸乙酯或碳酸二乙酯等的有機溶劑、及六氟磷酸鋰或四氟硼酸鋰等的氟系鋰複鹽。因此，如此的外部材料若被長時間使用的話，不只電解質也就是有機溶劑，大氣中的水分也會滲入容器內，其與電解質反應而生成氟化氫酸，該氟化氫酸是透過積層薄膜而發生金屬表面及積層薄膜的剝離，並且會有將金屬表面腐蝕的問題。且，也有在積層之前預備加熱金屬材料(200~300℃)的情況，而具有因熱皮膜劣化而導致密合性下降的問題。 On the other hand, when the metal layer is subjected to a lamination process without a chemical conversion treatment or the like, there is a problem that the laminated film is peeled off from the metal surface and corroded in the metal material. For example, in an external material or the like of a lithium ion secondary battery, a process having a high degree of processing is processed by the manufacturing process. The electrolyte of the lithium ion secondary battery is an organic solvent such as ethyl carbonate or diethyl carbonate, or a fluorine-based lithium double salt such as lithium hexafluorophosphate or lithium tetrafluoroborate. Therefore, if such an external material is used for a long period of time, not only an electrolyte but also an organic solvent, moisture in the atmosphere will also permeate into the container, which reacts with the electrolyte to form hydrogen fluoride, which is a metal surface that passes through the laminated film. And the peeling of the laminated film, and there is a problem of corroding the metal surface. Further, there is a case where the metal material (200 to 300 ° C) is heated before the lamination, and there is a problem that the adhesion is deteriorated due to deterioration of the hot film.
將鋰2次電池包裝的包裝材，被提案各種對於有機溶劑和氟化氫酸具有耐性的層疊體是，例如，在專利文獻1中，被提案：在由最外層/屏障層/最內層，或最外層/屏障層/中間層/最內層所構成的層疊體，施加：將前述屏障層的最內層面側表面脫脂，或將表面氧化物除去，磷酸鹽皮膜、鉻酸鹽、氟化物系化合物，或是由有機矽化合物、有機鈦系化合物、有機鋁系化合物所構成的耐酸性皮膜的形成、及/或由矽烷系、有機鈦系、有機鋁系的物質所構成的聯接器處理等。依據此技術的話，可以提供一種使用於收納聚合物電池的殼的層疊薄膜，是對於水蒸氣及其他的氣體屏障性優異，且，對於耐內容物性及層疊體的層間的 接合強度也優異，且，具有耐刺透性等的機械強度，且在高溫也可使用，對於電解液也穩定的層疊體的構成。 A packaging material in which a lithium secondary battery is packaged is proposed to have various laminates resistant to an organic solvent and hydrogen fluoride. For example, in Patent Document 1, it is proposed to be in the outermost layer/barrier layer/inner layer, or a laminate composed of an outermost layer/barrier layer/intermediate layer/innermost layer applied by degreasing the innermost surface side surface of the barrier layer or removing surface oxide, phosphate film, chromate, fluoride system a compound, or an acid-resistant film composed of an organic cerium compound, an organic titanium-based compound, or an organoaluminum-based compound, and/or a coupler treatment composed of a decane-based, organotitanium-based, or organoaluminum-based material . According to this technique, it is possible to provide a laminated film for housing a polymer battery, which is excellent in barrier properties against water vapor and other gases, and is resistant to content properties and interlayers of the laminate. It is also excellent in the joint strength, and has mechanical strength such as puncture resistance, and can be used at a high temperature, and is also a structure of a laminate which is stable to an electrolytic solution.
且在專利文獻2中，被提案：對於在密封膠層的一方的面，至少接合樹脂層、第1化學轉化處理層、鋁箔層、第2化學轉化處理層、接合劑層及基材層依序被層疊的鋰離子電池用包裝材中，該鋁箔層，是由雙面被蝕刻的鋁箔所構成，第1化學轉化處理層及第2化學轉化處理層是由氧化鋅被膜所構成的鋰離子電池用包裝材。依據此技術的話，可以提供一種高生產性的鋰離子電池用包裝材，不需使用具有環境負荷可能性的鉻，就可獲得優異的耐電解液性、耐氫氟酸性，且在鋁箔的雙面可以簡便地形成化學轉化處理層。 Further, in Patent Document 2, it is proposed to bond at least a resin layer, a first chemical conversion treatment layer, an aluminum foil layer, a second chemical conversion treatment layer, a binder layer, and a substrate layer on one surface of the sealant layer. In the packaging material for a lithium ion battery to be laminated, the aluminum foil layer is composed of an aluminum foil which is etched on both sides, and the first chemical conversion treatment layer and the second chemical conversion treatment layer are lithium ions composed of a zinc oxide coating. Battery packaging materials. According to this technology, it is possible to provide a highly productive packaging material for a lithium ion battery, which can obtain excellent electrolyte resistance, hydrofluoric acid resistance, and double in aluminum foil without using chromium having an environmental load possibility. The chemical conversion treatment layer can be easily formed on the surface.
且在專利文獻3中，被提案：對於將塑膠製底基薄膜及金屬箔及功能性塑膠層重疊的塑膠積層薄膜，在：朝向金屬箔的至少功能性塑膠層側的面、及朝向功能性塑膠層的金屬箔側的面、及功能性塑膠層的內部、或是其中任一，藉由物理氣相蒸鍍法鍍膜如至少1鉻層的金屬製保護層的技術。依據此技術的話，可提高各層間的密合性，可以作為塑膠積層薄膜較佳使用在鋰離子聚合物電池和鋰聚合物電池的包層。 Further, in Patent Document 3, a plastic laminated film in which a plastic base film, a metal foil, and a functional plastic layer are superposed is formed on a surface facing the at least functional plastic layer side of the metal foil, and toward the functionality. A technique of coating a metal protective layer such as at least one chromium layer by a physical vapor deposition method on the metal foil side surface of the plastic layer and the inside of the functional plastic layer or either. According to this technique, the adhesion between the layers can be improved, and it can be preferably used as a plastic laminated film in a cladding of a lithium ion polymer battery and a lithium polymer battery.
[專利文獻1]日本特開2001-35453號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-35453
[專利文獻2]日本特開2011-76887號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-76887
[專利文獻3]日本特表2009-544492號公報 [Patent Document 3] Japanese Patent Publication No. 2009-544492
但是專利文獻1~3所提案的技術皆是將鋰2次電池包裝用的積層薄膜，不會受到前述的加工度高的加工。因此，對於其積層薄膜施加加工度高的加工之後被長時間使用的情況時，是否依然具有高耐電解液性並不明。 However, the techniques proposed in Patent Documents 1 to 3 are laminated films for packaging lithium secondary batteries, and are not subjected to the above-described high processing. Therefore, when it is used for a long period of time after the processing with high workability is applied to the laminated film, it is not clear whether or not the electrolyte resistance is still high.
本發明的目的，是提供一種附樹脂薄膜的金屬製外部材料及其製造方法，在鋁和不銹鋼等的基材金屬將樹脂薄膜積層或形成樹脂塗膜(以下也稱為「樹脂薄膜」)，其後即使施加了深拉深加工、熨燙加工或拉伸抽製加工等的嚴苛的成形加工的情況，也可以賦予高密合性使其積層薄膜或樹脂塗膜不剝離，進一步即使與酸或溶劑等長時間接觸也可優異地維持高密合性的耐藥品性。 An object of the present invention is to provide a metal outer material with a resin film and a method for producing the same, in which a resin film is laminated on a base metal such as aluminum or stainless steel, or a resin coating film (hereinafter also referred to as "resin film") is provided. After that, even if a severe molding process such as deep drawing, ironing, or drawing is applied, high adhesion can be imparted so that the laminated film or the resin coating film is not peeled off, and even with acid or The long-term contact with a solvent or the like can also excellently maintain high-adhesion chemical resistance.
為了解決上述課題的本發明的附樹脂薄膜的金屬製外部材料，其特徵為，具有：基材金屬、及設在該基材金屬的一方或雙方的面的基礎皮膜、及設在該基礎皮膜上的積層薄膜或樹脂塗膜，前述基礎皮膜是金屬鋅皮膜或含有金屬鋅的皮膜。 In order to solve the above-described problems, the metal external material with a resin film of the present invention is characterized in that it has a base metal and a base film provided on one or both of the base metal, and a base film provided on the base film. In the laminated film or the resin coating film, the base film is a metal zinc film or a film containing metal zinc.
依據本發明的話，藉由設置金屬鋅皮膜或含有金屬鋅的皮膜作為基材金屬及樹脂薄膜之間的基礎皮膜的特徵， 就可獲得：積層薄膜或樹脂塗膜不剝離的高密合性，且即使與酸或溶劑等長時間接觸也可維持高密合性的結果。 According to the present invention, by providing a metal zinc film or a film containing metal zinc as a feature of the base film between the base metal and the resin film, It is possible to obtain a high adhesion of the laminated film or the resin coating film without peeling off, and to maintain high adhesion even when it is in contact with an acid or a solvent for a long period of time.
對於本發明的附樹脂薄膜的金屬製外部材料，前述積層薄膜或樹脂塗膜，是包含聚烯烴或酸變性聚烯烴較佳。 In the metal outer material to which the resin film of the present invention is applied, the laminated film or the resin coating film is preferably a polyolefin or an acid-denatured polyolefin.
對於本發明的附樹脂薄膜的金屬製外部材料，前述基材金屬，是從鋁或其合金、不銹鋼、銅或其合金、及鎳或其合金選擇其中任一較佳。 In the metal external material to which the resin film of the present invention is applied, the base metal is preferably selected from aluminum or an alloy thereof, stainless steel, copper or an alloy thereof, and nickel or an alloy thereof.
對於本發明的附樹脂薄膜的金屬製外部材料，前述含有金屬鋅的皮膜，是包含從鐵、鎳及鈷選擇1種或2種以上的元素也可以。 In the metal external material with a resin film of the present invention, the metal zinc-containing coating film may contain one or two or more elements selected from the group consisting of iron, nickel, and cobalt.
依據本發明的話，藉由設置包含從鐵、鎳及鈷選擇1種或2種以上的元素的含有金屬鋅的皮膜作為基礎皮膜，例如在由置換鍍膜形成基礎皮膜的情況時可以減少基材金屬的置換量，進一步可以提高該基礎皮膜的機械的強度。 According to the present invention, a metal zinc-containing film containing one or two or more elements selected from iron, nickel, and cobalt is provided as a base film, for example, when a base film is formed by a displacement plating film, the base metal can be reduced. The amount of substitution can further increase the mechanical strength of the base film.
對於本發明的附樹脂薄膜的金屬製外部材料，被施加深拉深加工、熨燙加工或拉伸抽製加工的構成也可以。 The metal outer material to which the resin film of the present invention is applied may be subjected to deep drawing processing, ironing processing, or stretch drawing processing.
依據本發明的話，即使對於設置樹脂薄膜之後的金屬製外部材料施加深拉深加工、熨燙加工或拉伸抽製加工等的嚴苛的成形加工的情況，也具備：樹脂薄膜不剝離的高密合性、及即使與酸或溶劑等長時間接觸也可維持高密合性的耐藥品性。 According to the present invention, even when a severe molding process such as deep drawing, ironing, or drawing is applied to the metal outer material after the resin film is provided, the resin film does not have high adhesion without peeling off. It can maintain high adhesion and chemical resistance even when it is in contact with an acid or a solvent for a long period of time.
為了解決上述課題的本發明的附樹脂薄膜的金屬製外部材料的製造方法，其特徵為，具有：在基材金屬的一方或雙方的面，由置換鍍膜法或電鍍法將金屬鋅皮膜或含有 金屬鋅的皮膜作為基礎皮膜形成的過程；及在前述基礎皮膜上，形成積層薄膜或樹脂塗膜的過程。 In order to solve the above-described problems, a method for producing a metal-made external material of a resin film according to the present invention is characterized in that a metal zinc film or a film is formed by a substitution plating method or a plating method on one or both surfaces of a base metal. A process in which a film of metal zinc is formed as a base film; and a process of forming a laminated film or a resin coating film on the base film.
依據本發明的話，藉由在基材金屬的一方或雙方的面由置換鍍膜法或電鍍法將金屬鋅皮膜或含有金屬鋅的皮膜作為基礎皮膜形成，其後，在基礎皮膜上形成積層薄膜或樹脂塗膜的特徵，就可使被製造的附樹脂薄膜的金屬製外部材料，獲得：達成積層薄膜或樹脂塗膜不剝離的高密合性，且即使與酸或溶劑等長時間接觸也可維持高密合性的結果。 According to the present invention, a metal zinc film or a film containing a metal zinc is formed as a base film by a displacement plating method or a plating method on one or both surfaces of a base metal, and thereafter, a laminated film is formed on the base film or The resin coating film is characterized in that the metal outer material of the resin film to be produced can be obtained with high adhesion without forming a laminated film or a resin coating film, and can be maintained even after prolonged contact with an acid or a solvent. The result of high adhesion.
對於本發明的附樹脂薄膜的金屬製外部材料的製造方法，進一步具有從深拉深加工、熨燙加工及拉伸抽製加工選擇其中任一或二以上的加工過程也可以。 The method for producing a metal outer material with a resin film of the present invention may further include a process of selecting one or more of deep drawing, ironing, and drawing.
對於本發明的附樹脂薄膜的金屬製外部材料的製造方法，在前述基礎皮膜的形成過程之前，進一步具有將前述基材金屬的表面的氧化物皮膜除去的過程也可以。 The method for producing a metal outer material with a resin film of the present invention may further have a process of removing the oxide film on the surface of the base metal before the formation of the base film.
依據本發明的話，因為在基礎皮膜的形成過程之前，進一步具有將基材金屬的表面的氧化物皮膜除去的過程，所以可以更提高基材金屬及基礎皮膜的密合性。 According to the present invention, since the oxide film on the surface of the base metal is further removed before the formation of the base film, the adhesion between the base metal and the base film can be further improved.
依據本發明的附樹脂薄膜的金屬製外部材料及其製造方法的話，藉由設置金屬鋅皮膜或含有金屬鋅的皮膜作為基材金屬及樹脂薄膜之間基礎皮膜，就可獲得：可達成積層薄膜或樹脂塗膜不剝離的高密合性，且即使與酸或溶劑 等長時間接觸也可以維持高密合性的結果。即使在具備如此效果的附樹脂薄膜的金屬製外部材料施加深拉深加工、熨燙加工或拉伸抽製加工等的嚴苛成形加工的情況，也可以獲得：賦予高密合性使其積層薄膜或樹脂塗膜不剝離，進一步即使與酸或溶劑等長時間接觸也可維持高密合性的耐藥品性優異的效果。 According to the metal outer material of the resin film of the present invention and the method for producing the same, by providing a metal zinc film or a film containing metal zinc as a base film between the base metal and the resin film, it is possible to obtain a laminated film. Or the resin coating film does not peel off with high adhesion, and even with acid or solvent The result of high adhesion can be maintained even after prolonged contact. Even when a metal forming material having a resin film having such an effect is subjected to severe forming such as deep drawing, ironing, or drawing, it is possible to provide a film or a high adhesion property. The resin coating film is not peeled off, and the effect of excellent chemical resistance of high adhesion can be maintained even when it is contacted with an acid or a solvent for a long period of time.
以下，說明本發明的附樹脂薄膜的金屬製外部材料及其製造方法。又，以下的說明及圖面的形態並不限定本發明的技術的範圍。 Hereinafter, a metal external material with a resin film of the present invention and a method for producing the same will be described. Further, the following description and the form of the drawings do not limit the scope of the technology of the present invention.
本發明的附樹脂薄膜的金屬製外部材料10，是如第1圖所示，具有：基材金屬1、及設在其基材金屬1的一方或雙方的面的基礎皮膜2、及設在其基礎皮膜2上的積層薄膜或樹脂塗膜(以下除了特別規定以外皆稱為「樹脂薄膜3」)。且具有該基礎皮膜2，是金屬鋅皮膜或含有金屬鋅的皮膜之特徵。又，在第1圖中，雖在基材金屬1的單面設置基礎皮膜2及樹脂薄膜3，但是在基材金屬1的雙面設置基礎皮膜2及樹脂薄膜3也可以。 The metal outer material 10 with a resin film of the present invention has a base metal 1 and a base film 2 provided on one or both of the base metal 1 as shown in Fig. 1 and A laminated film or a resin coating film on the base film 2 (hereinafter referred to as "resin film 3" unless otherwise specified). Further, the base film 2 is characterized by a metal zinc film or a film containing metal zinc. In the first embodiment, the base film 2 and the resin film 3 are provided on one surface of the base metal 1, but the base film 2 and the resin film 3 may be provided on both sides of the base metal 1.
以下，詳細說明本發明的構成。 Hereinafter, the configuration of the present invention will be described in detail.
基材金屬1，是成為本發明的附樹脂薄膜的金屬製外部材料10的底基(基材)的金屬的薄板材或箔。基材金屬1的材質，是可以舉例從鋁或其合金、不銹鋼、銅或其合金、及鎳或其合金選擇其中任一。如此的基材金屬1，是購入品也可以，可獲得預定厚的板材熱間壓延和冷間壓延的者即可。基材金屬1的厚度並無特別限定，例如0.01mm~2.0mm程度。又，由後述的置換鍍膜設置基礎皮膜2的情況時，因為基材金屬1被蝕刻，所以考慮其蝕刻量來設計厚度。 The base metal 1 is a thin metal plate or foil which is a base (base material) of the metal outer material 10 to which the resin film of the present invention is applied. The material of the base material metal 1 can be selected, for example, from aluminum or an alloy thereof, stainless steel, copper or an alloy thereof, and nickel or an alloy thereof. Such a base metal 1 may be a purchased product, and a predetermined thick plate between hot rolling and cold rolling may be obtained. The thickness of the base metal 1 is not particularly limited, and is, for example, about 0.01 mm to 2.0 mm. Moreover, when the base film 2 is provided by the substitution plating film mentioned later, since the base metal 1 is etched, the thickness is designed considering the etching amount.
且在這些金屬或合金上設置其他的金屬或合金者也可以。其他的金屬或合金的形成手段，可以舉例鍍膜(電鍍、無電解鍍膜)手段、蒸鍍手段、包層手段等。其中一例，可以舉例在銅或銅合金上電鍍鎳的鎳鍍膜銅等。 It is also possible to provide other metals or alloys on these metals or alloys. Examples of other metal or alloy forming means include plating (electroplating, electroless plating) means, vapor deposition means, cladding means, and the like. As an example, nickel-plated copper or the like in which nickel is electroplated on copper or a copper alloy can be exemplified.
基礎皮膜2，是設於基材金屬1的一方或雙方的面的金屬鋅皮膜或含有金屬鋅的皮膜。在本發明的附樹脂薄膜的金屬製外部材料10中，藉由將金屬鋅皮膜或含有金屬鋅的皮膜設在基材金屬1上作為樹脂薄膜3的基礎皮膜2，也可以導致：提高樹脂薄膜3及基材金屬1的密合性，進一步即使與酸或溶劑等長時間接觸也可以維持高密合性的結果。 The base film 2 is a metal zinc film or a film containing metal zinc provided on one or both of the base metal 1 . In the metal outer material 10 with a resin film of the present invention, by providing a metal zinc film or a film containing metal zinc on the base metal 1 as the base film 2 of the resin film 3, it is also possible to: improve the resin film 3 and the adhesion of the base metal 1 can further maintain the high adhesion even if it contacts with an acid or a solvent for a long time.
金屬鋅皮膜，是只有由金屬鋅所構成的層，含有金屬鋅的皮膜，是由包含金屬鋅的金屬皮膜所構成的層。「包 含」雖是包含鋅以外的金屬元素的意思，但是如此的金屬元素，可以舉例從鐵、鎳及鈷選擇1種或2種以上的鐵族金屬。包含這些鐵族金屬的含有金屬鋅的皮膜，具有：可以提高硬度等的機械強度，並且後述的置換鍍膜時可以抑制基材金屬1的蝕刻量的優點。含有金屬鋅的皮膜中的鐵族金屬的含有量，是0.5質量%~15質量%的範圍較佳。包含如此範圍的鐵族元素的含有金屬鋅的皮膜，是從可以抑制基材金屬1的蝕刻量的觀點，具有：即使未將基礎皮膜2的厚度過度厚地形成，也可形成有充分耐電解液密合維持性的基礎皮膜的優點。又，此時的含有金屬鋅的皮膜，是除了包含不可避不純物成分(微量氧化物成分)以外，全部是金屬鋅。 The metal zinc film is a layer composed only of metal zinc, and a film containing metal zinc is a layer composed of a metal film containing metal zinc. "package The term "including" means a metal element other than zinc. However, as such a metal element, one or two or more kinds of iron group metals may be selected from iron, nickel and cobalt. The metal zinc-containing film containing these iron group metals has an advantage that the mechanical strength such as hardness can be improved, and the amount of etching of the base metal 1 can be suppressed at the time of replacement plating described later. The content of the iron group metal in the film containing metal zinc is preferably in the range of 0.5% by mass to 15% by mass. The metal zinc-containing film containing the iron group element in such a range is capable of suppressing the etching amount of the base metal 1 and has sufficient electrolyte resistance even if the thickness of the base film 2 is not excessively thick. The advantage of a tightly maintained base film. Further, the film containing metal zinc at this time is all metal zinc except for the inclusion of an unavoidable impurity component (a trace oxide component).
基礎皮膜2也就是金屬鋅皮膜或含有金屬鋅的皮膜，是由置換鍍膜法或電鍍法形成。 The base film 2, that is, a metal zinc film or a film containing metal zinc, is formed by a displacement plating method or an electroplating method.
置換鍍膜法，是依據：與置換鍍膜液接觸的基材金屬1的氧化還元電位、及被包含於鍍膜液的鋅離子的氧化還元電位的大小，使基材金屬1的氧化溶解及鋅離子的還元析出藉由化學反應同時發生氧化還元反應，藉由與基材金屬1的溶解(也稱為蝕刻)同時發生鋅的析出而形成基礎皮膜2。因此，置換鍍膜法，是依存於置換鍍膜液中的基材金屬1及可析出的金屬離子的氧化還元電位的大小，適用於：基材金屬1殘留電子並引起氧化溶解的化學反應，使該電子收取液中的金屬離子而還元析出的化學反應可發生的氧化還元環境整備的情況時的方法。且，在鍍膜液包 含從鐵、鎳及鈷選擇1種或2種以上的情況也同樣，依存於基材金屬1及可析出的金屬離子的氧化還元電位的大小，而包含或不包含在基礎皮膜2。如此的置換鍍膜法，因為是無關基材金屬1的形狀，皆可以形成均一的厚度的基礎皮膜2所以便利，進一步與由電鍍法形成的基礎皮膜2相比較硬，在拉伸強度等的機械的強度方面優異。 The displacement plating method is based on the oxidation reductive potential of the base metal 1 in contact with the displacement plating solution and the oxidation reductive potential of the zinc ions contained in the plating solution to oxidize and dissolve the base metal 1 and zinc ions. The precipitation further forms an oxidative reductive reaction by a chemical reaction, and the base film 2 is formed by simultaneous precipitation of zinc with the dissolution (also referred to as etching) of the base metal 1. Therefore, the displacement plating method is dependent on the magnitude of the oxidation reductive potential of the base metal 1 and the precipitateable metal ions in the displacement plating solution, and is suitable for a chemical reaction in which the substrate metal 1 remains electrons and causes oxidative dissolution. A method in which an electron is collected from a metal ion in a liquid and a chemical reaction which is precipitated in a chemical state can be generated by an oxidation-reduction environment. And, in the coating liquid package The same applies to the case where one or two or more kinds of iron, nickel, and cobalt are contained, depending on the magnitude of the oxidation reductive potential of the base metal 1 and the metal ions which can be precipitated, and may or may not be included in the base film 2. Such a displacement plating method is convenient for forming a base film 2 having a uniform thickness regardless of the shape of the base metal 1, and is further harder than the base film 2 formed by the plating method, and is a machine such as tensile strength. Excellent in terms of strength.
由置換鍍膜法所產生的基礎皮膜2的形成，是使基材金屬1、及鹼性或酸性的置換鍍膜液接觸來進行。雖使用鹼性或酸性的其中任一的置換鍍膜液，但是可以依據置換鍍膜液中的基材金屬1及金屬離子的氧化還元電位的大小適宜選擇是否發生置換鍍膜。「接觸」的手段，可以舉例：朝置換鍍膜液的基材金屬1的浸漬、和朝基材金屬1的置換鍍膜液的噴霧噴射等。 The formation of the base film 2 by the displacement plating method is carried out by bringing the base metal 1 into contact with a basic or acidic replacement coating liquid. Although a replacement plating solution of either alkaline or acidic is used, it is possible to appropriately select whether or not a replacement coating occurs depending on the magnitude of the oxidation reductive potential of the base metal 1 and the metal ions in the displacement plating solution. The means for "contacting" may be, for example, immersion of the base metal 1 of the replacement coating liquid, and spray spraying of the replacement coating liquid toward the base metal 1.
置換鍍膜液雖無特別限定，但是可以舉例例如在後述的實施例所使用的鹼性置換鍍膜液(稱作鋅酸鹽浴，以硫酸鋅及氫氧化鈉為主成分)、酸性置換鍍膜液(以硫酸鋅及酸性氟化銨或氫氟酸為主成分)等。又，在這些的置換鍍膜液中，依據需要包含光澤劑、絡合劑、還元劑、pH調整劑、緩衝劑等的添加劑也可以，可以舉例例如、葡萄糖酸鈉、其他的添加劑。且，在基礎皮膜2進一步含有從鐵、鎳及鈷選擇1種或2種以上的金屬的情況時，在置換鍍膜液可任意摻合例如硫酸亞鐵、硫酸鎳、硫酸鈷等。 The substitution coating liquid is not particularly limited, and examples thereof include an alkaline displacement plating solution (referred to as a zincate bath, zinc sulfate and sodium hydroxide as a main component) and an acid replacement coating liquid (for example, a zincate bath). Zinc sulfate and acidic ammonium fluoride or hydrofluoric acid as main components). In addition, an additive such as a glossing agent, a complexing agent, a reductant, a pH adjuster, a buffer, or the like may be contained in the replacement plating solution, and examples thereof include sodium gluconate and other additives. In addition, when the base film 2 further contains one or two or more kinds of metals selected from the group consisting of iron, nickel, and cobalt, for example, ferrous sulfate, nickel sulfate, cobalt sulfate, or the like may be blended in the replacement coating liquid.
又，上述的各鹽只是例示，可以將成為目的金屬鋅皮膜或含有金屬鋅的皮膜在基材金屬1的一方或雙方的面形 成的話，使用上述以外的鋅鹽、各種金屬鹽等也可以。且，置換鍍膜液的液組成也無特別限定。例如鋅酸鹽浴的情況時，一般是硫酸鋅8~16g/L，氫氧化鈉90~150g/L。 Moreover, each of the above-described salts is merely exemplified, and the surface of the target metal zinc film or the metal zinc-containing film may be formed on one or both of the base metal 1 . In the case of the above, a zinc salt other than the above, various metal salts, or the like may be used. Further, the liquid composition of the displacement plating solution is also not particularly limited. For example, in the case of a zincate bath, it is generally 8 to 16 g/L of zinc sulfate and 90 to 150 g/L of sodium hydroxide.
電鍍法，是在：與電鍍液接觸的基材金屬1、及與相同的電鍍液接觸的相對電極(也稱為對極)之間外加電流，在基材金屬1上將電鍍液中的金屬離子強制地還元析出的手段。 In the electroplating method, a current is applied between the substrate metal 1 in contact with the plating solution and a counter electrode (also referred to as a counter electrode) in contact with the same plating solution, and the metal in the plating solution is applied to the substrate metal 1. The means by which ions are forcibly returned.
由電鍍法所產生的基礎皮膜2的形成，是在將基材金屬1及相對電極與電鍍鋅液接觸的狀態下外加電流或電壓來進行。相對電極，可以使用：鋅板或不溶性電極(例如碳電極、白金被覆鈦電極等)。且，將含有金屬鋅的皮膜，使用包含鋅成分以外的金屬成分的電鍍液形成的情況時，使用包含與被包含於含有金屬鋅的皮膜的鋅以外的金屬成分同量比率的相對電極也可以。如此，可以將對應電鍍液中的金屬成分的減少量的量從相對電極供給。如此的電鍍法，因為是與置換鍍膜法相異不伴隨化學反應，所以只控制電流或電壓就可以容易地形成所期厚度的基礎皮膜2。且，與置換鍍膜法相比因為析出速度快，所以可由高速形成。 The formation of the base film 2 by the plating method is performed by applying a current or a voltage in a state where the base metal 1 and the counter electrode are in contact with the electroplating bath. As the counter electrode, a zinc plate or an insoluble electrode (for example, a carbon electrode, a platinum-coated titanium electrode, or the like) can be used. In addition, when a film containing a metal zinc is formed using a plating solution containing a metal component other than the zinc component, a counter electrode containing the same amount of metal components other than zinc contained in the film containing the metal zinc may be used. . In this manner, the amount of reduction of the metal component in the corresponding plating solution can be supplied from the counter electrode. Since such an electroplating method is different from the displacement plating method without a chemical reaction, the base film 2 of a desired thickness can be easily formed by controlling only a current or a voltage. Further, since the deposition rate is faster than the displacement plating method, it can be formed at a high speed.
電鍍鋅液雖無特別限定，但是可以舉例例如在後述的實施例所使用的硫酸鋅鍍膜液。又，在電鍍液中，依據需要包含光澤劑，絡合劑、pH調整劑、緩衝劑等的添加劑也可以。且，在基礎皮膜2進一步含有從鐵、鎳及鈷選擇 1種或2種以上的金屬的情況時，可在電鍍液任意摻合例如硫酸亞鐵、硫酸鎳、硫酸鈷等。 The electroplating zinc solution is not particularly limited, and for example, a zinc sulfate coating liquid used in the examples described later can be exemplified. Further, an additive such as a glossing agent, a complexing agent, a pH adjuster, or a buffer may be contained in the plating solution as needed. Moreover, the base film 2 further contains options selected from iron, nickel and cobalt. In the case of one or two or more kinds of metals, for example, ferrous sulfate, nickel sulfate, cobalt sulfate or the like may be blended in the plating solution.
由如此的各手段形成的基礎皮膜2的厚度，通常是0.01μm~0.70μm(總附著量相當於約0.10g/m2~約5.0g/m2)，較佳是0.03μm~0.28μm(總附著量相當於約0.2g/m2~約2.0g/m2)。基礎皮膜2的厚度是在0.01μm未滿時，有可能無法充分獲得耐電解液密合維持性。另一方面，基礎皮膜2的厚度是超過0.70μm的話，耐電解液密合維持性雖優異，但是需要基礎皮膜2的鍍膜時間，會使生產性劣化。又，基礎皮膜2的總附著量1g/m2是相當於基礎皮膜2的厚度約0.14μm。 The thickness of the base film 2 formed by such means is usually 0.01 μm to 0.70 μm (total adhesion amount is equivalent to about 0.10 g/m 2 to about 5.0 g/m 2 ), preferably 0.03 μm to 0.28 μm ( The total amount of adhesion corresponds to from about 0.2 g/m 2 to about 2.0 g/m 2 ). When the thickness of the base film 2 is less than 0.01 μm, the electrolyte solution adhesion maintaining property may not be sufficiently obtained. On the other hand, when the thickness of the base film 2 is more than 0.70 μm, the electrolyte solution adhesion maintaining property is excellent, but the plating time of the base film 2 is required, which deteriorates productivity. Further, the total adhesion amount of the base film 2 of 1 g/m 2 is equivalent to the thickness of the base film 2 of about 0.14 μm.
又，設置金屬鋅皮膜或是含有金屬鋅的皮膜作為基礎皮膜2的情況時，耐電解液密合性被被維持的理由在現時點仍不明確，但是大概是因為，在將LiPF6等作為電解質的電解液中將本發明的附樹脂薄膜的金屬製外部材料10浸漬的情況時，在基礎皮膜2及樹脂薄膜3之間被確認濃縮的磷元素，所以浸漬時藉由LiPF6的加水分解生成物也就是氫氟酸使基礎皮膜2中的鋅成分被溶出，該鋅成分，相同因為是與LiPF6的加水分解生成物也就是磷化合物反應而生成不溶性鹽，如此的不溶性鹽可能成為維持耐電解液密合性的要因。 When a metal zinc film or a film containing metal zinc is used as the base film 2, the reason why the electrolyte resistance is maintained is not clear at the present point, but it is probably because LiPF 6 or the like is used. In the electrolyte solution of the electrolyte, when the metal outer material 10 of the resin film of the present invention is immersed, the concentrated phosphorus element is confirmed between the base film 2 and the resin film 3, so that the water is decomposed by LiPF 6 during immersion. The product, that is, hydrofluoric acid, causes the zinc component in the base film 2 to be eluted. This zinc component is similarly formed by reacting with a hydrolyzed product of LiPF 6 , that is, a phosphorus compound, to form an insoluble salt, and such an insoluble salt may be maintained. The cause of resistance to electrolyte adhesion.
樹脂薄膜3，是作為在基礎皮膜2上將樹脂製薄膜積 層的積層薄膜，或是作為在基礎皮膜2上將樹脂塗抹的樹脂塗膜被設置。樹脂薄膜3，是由聚烯烴、酸變性聚烯烴、或將那些作為主成分包含的樹脂組成物形成。如此的樹脂薄膜3，是為了即使與酸或溶劑等長時間接觸也能防止基材金屬1被腐蝕和浸食而設置。 The resin film 3 is formed by laminating a resin film on the base film 2. The laminated film of the layer or the resin coating film which coats the resin on the base film 2 is provided. The resin film 3 is formed of a polyolefin, an acid-denatured polyolefin, or a resin composition containing those as a main component. Such a resin film 3 is provided to prevent the base metal 1 from being corroded and soaked even when it is in contact with an acid or a solvent for a long period of time.
聚烯烴，是可以舉例：高密度聚乙烯、低密度聚乙烯等的聚乙烯；乙烯及α-烯烴的共聚物；將均聚物、無規共聚物或嵌段共聚物作成原料的聚丙烯；丙烯及α-烯烴的共聚物等，可以使用從這些選擇1種或2種以上者。酸變性聚烯烴，是可以將聚烯烴由馬來酸酐等接枝變性而獲得。 The polyolefin is, for example, a polyethylene such as high density polyethylene or low density polyethylene; a copolymer of ethylene and an α-olefin; and a polypropylene obtained by using a homopolymer, a random copolymer or a block copolymer as a raw material; For the copolymer of propylene and an α-olefin, one or two or more kinds may be used. The acid-denatured polyolefin can be obtained by graft denaturation of a polyolefin with maleic anhydride or the like.
樹脂薄膜3，是單層也可以，將複數層層疊的多層構造也可以。且，依據需要，進一步層疊乙烯及環狀烯烴的共聚物等的樹脂，使具有防濕性也可以。且，樹脂薄膜3，是依據需要，包含：氧化防止劑、難燃劑及黏接賦予劑等的添加材也可以。樹脂薄膜3的厚度，通常是10μm~100μm、20μm~50μm較佳。 The resin film 3 may be a single layer or a multilayer structure in which a plurality of layers are laminated. Further, if necessary, a resin such as a copolymer of ethylene and a cyclic olefin may be further laminated to have moisture resistance. In addition, the resin film 3 may contain an additive such as an oxidation preventive agent, a flame retardant, and a tackifier. The thickness of the resin film 3 is usually 10 μm to 100 μm and preferably 20 μm to 50 μm.
設置積層薄膜用的積層加工，可以舉例熱層壓法、乾層壓法、擠出層壓法或多層共擠出層壓法等。 The lamination processing for the laminated film may be exemplified by a thermal lamination method, a dry lamination method, an extrusion lamination method, or a multilayer coextrusion lamination method.
由熱層壓法所產生的樹脂薄膜3的形成，是藉由將樹脂薄膜3熱擠壓在基礎皮膜2的表面來進行。熱擠壓時的溫度及壓力等，可對應樹脂薄膜3的性質任意設定。又，在樹脂薄膜3的表面中依據需要設置接合劑層，將該接合劑層作為熱擠壓層利用也可以。如此的接合劑層，可以舉例由環氧樹脂、酚樹脂、丙烯樹脂、尿烷樹脂等的樹脂組 成物所構成的層，可以將如此的樹脂塗抹並乾燥等而形成。 The formation of the resin film 3 by the thermal lamination method is performed by hot pressing the resin film 3 on the surface of the base film 2. The temperature, pressure, and the like at the time of hot extrusion can be arbitrarily set in accordance with the properties of the resin film 3. Further, a binder layer may be provided on the surface of the resin film 3 as needed, and the binder layer may be used as a hot extrusion layer. Such a binder layer may, for example, be a resin group such as an epoxy resin, a phenol resin, an acrylic resin, or a urethane resin. The layer formed of the object can be formed by applying such a resin, drying it, or the like.
由乾層壓法所產生的樹脂薄膜3的形成，是在基礎皮膜2的表面形成接合劑層，藉由將樹脂薄膜3常溫擠壓該接合劑層的表面來進行。接合劑層可以舉例：聚酯系接合劑、聚乙烯系接合劑、聚醚系接合劑、氰基丙烯酸酯系接合劑、尿烷系接合劑、有機鈦系接合劑、聚醚尿烷系接合劑、環氧系接合劑、聚酯尿烷系接合劑、異氰酸酯系接合劑、聚烯烴系接合劑等的樹脂組成物，接合劑層可以是將如此的樹脂組成物塗抹在基礎皮膜2的表面並乾燥而形成。 The resin film 3 produced by the dry lamination method is formed by forming an adhesive layer on the surface of the base film 2, and pressing the resin film 3 at a normal temperature to press the surface of the adhesive layer. Examples of the bonding agent layer include a polyester-based bonding agent, a polyethylene-based bonding agent, a polyether-based bonding agent, a cyanoacrylate-based bonding agent, a urethane-based bonding agent, an organic titanium-based bonding agent, and a polyether urethane bonding. A resin composition such as a solvent, an epoxy-based adhesive, a polyester urethane-based adhesive, an isocyanate-based adhesive, or a polyolefin-based adhesive, and the adhesive layer may be such that the resin composition is applied to the surface of the base film 2. And formed by drying.
由擠出層壓法或多層共擠出層壓法所產生的樹脂薄膜3的形成，是藉由將熔融的樹脂直接擠出在基礎皮膜2的表面之後冷卻來進行。在樹脂的擠出及冷卻中，可以使用例如扁平模法和熔融擠出成形法的設備。 The formation of the resin film 3 produced by the extrusion lamination method or the multilayer co-extrusion lamination method is carried out by directly extruding the molten resin on the surface of the base film 2 and then cooling it. In the extrusion and cooling of the resin, equipment such as a flat mold method and a melt extrusion molding method can be used.
如此構成的附樹脂薄膜的金屬製外部材料10，其後可依據需要，被施加深拉深加工、熨燙加工或拉伸抽製加工，成形成預定的形狀並使用於各種的用途。可作為例如行動電話、電子筆記本、筆記型個人電腦或攝影機等所使用的可攜裝置用鋰離子2次電池的外部材料使用。且，作為如智慧型手機和平板PC的可攜式型機器的框體使用也可以。且，使用於作為電動汽車或混合動力汽車的驅動能 量用的鋰離子2次電池的外部材料也可以。 The metal outer material 10 with a resin film thus constituted can be subjected to deep drawing processing, ironing processing, or stretch drawing processing as needed to form a predetermined shape and used for various purposes. It can be used as an external material of a lithium ion secondary battery for a portable device used for, for example, a mobile phone, an electronic notebook, a notebook personal computer, or a video camera. Moreover, it can be used as a casing of a portable type machine such as a smart phone and a tablet PC. And, used as the driving energy of an electric car or a hybrid car The external material of the lithium ion secondary battery for use can also be used.
如以上說明，依據本發明的附樹脂薄膜的金屬製外部材料10的話，藉由設置金屬鋅皮膜或含有金屬鋅的皮膜作為基材金屬1及樹脂薄膜3之間的基礎皮膜2，就可獲得：樹脂薄膜3不剝離的高密合性，且即使與酸或溶劑等長時間接觸也可以維持高密合性的結果。即使對於具備如此的效果的附樹脂薄膜的金屬製外部材料10施加深拉深加工、熨燙加工或拉伸抽製加工等的嚴苛成形加工的情況，也可獲得：可以使樹脂薄膜3不剝離地賦予高密合性，進一步即使與酸或溶劑等長時間接觸也可以維持高密合性的耐藥品性優異的效果。 As described above, according to the metal outer material 10 with a resin film of the present invention, by providing a metal zinc film or a film containing metal zinc as the base film 2 between the base metal 1 and the resin film 3, it is obtained. The resin film 3 has high adhesion without peeling off, and can maintain high adhesion even when it is in contact with an acid or a solvent for a long period of time. Even when the metal outer material 10 having the resin film having such an effect is subjected to severe molding processing such as deep drawing, ironing, or drawing, it is possible to obtain the resin film 3 without peeling off. The high adhesion is imparted, and the effect of excellent chemical resistance of high adhesion can be maintained even when it is contacted with an acid or a solvent for a long period of time.
本發明的附樹脂薄膜的金屬製外部材料10的製造方法，是具有：在基材金屬1的一方或雙方的面，由置換鍍膜法或是電鍍法將金屬鋅皮膜或是含有金屬鋅的皮膜作為基礎皮膜2形成的基礎皮膜形成過程；及在其基礎皮膜2上，形成積層薄膜或樹脂塗膜的樹脂薄膜形成過程。又，「具有」，是指即使具有基礎皮膜形成過程及樹脂薄膜形成過程以外的過程也可以的意思。例如，即使具有後述的前處理過程、加工過程、及將氧化物皮膜除去過程等的其中任一或二以上也可以。 The method for producing a metal outer material 10 with a resin film according to the present invention includes a metal zinc film or a film containing a metal zinc by a substitution plating method or a plating method on one or both surfaces of the base metal 1. A base film forming process formed as the base film 2; and a resin film forming process of forming a laminated film or a resin coating film on the base film 2 thereof. In addition, "having" means that it has a process other than the process of forming the base film and the process of forming the resin film. For example, it may have any one or two or more of a pretreatment process, a process, and an oxide film removal process which are mentioned later.
對於各過程的詳細，是如上述「附樹脂薄膜的金屬製外部材料」的說明欄所說明，基材金屬1的準備或形成過 程、基礎皮膜2的形成過程、樹脂薄膜3的形成過程、深拉深加工等的加工過程，在以下省略其記載。在此製造方法中，在形成基礎皮膜2之前，更設置將基材金屬1的表面的氧化物皮膜除去的過程也可以。氧化物皮膜的除去，是可以例如藉由使用硫酸、硝酸、鹽酸、硝氟化氫酸等的酸的一般的酸洗淨來進行。酸洗淨手段，可以舉例浸漬式洗淨或噴射式洗淨等。且，依據需要，也可以進行一般的前處理也就是脫脂處理。又，清水洗淨，通常是被配置於各過程間。 The details of each process are as described in the description column of the above-mentioned "metal external material with resin film", and the preparation or formation of the base metal 1 has been made. The process of forming the base film, the formation process of the base film 2, the formation process of the resin film 3, deep drawing processing, and the like are omitted below. In this manufacturing method, a process of removing the oxide film on the surface of the base metal 1 may be further provided before the formation of the base film 2. The removal of the oxide film can be carried out, for example, by general acid washing using an acid such as sulfuric acid, nitric acid, hydrochloric acid or nitrate hydrofluoric acid. The acid washing means can be exemplified by immersion washing or jet cleaning. Moreover, general pre-treatment, that is, degreasing treatment, can also be performed as needed. Moreover, the water is washed, and is usually disposed between the processes.
附樹脂薄膜的金屬製外部材料10，其後可依據需要，由深拉深加工、熨燙加工或拉伸抽製加工等的加工過程被加工。藉由如此的加工過程，成形成預定的形狀並使用於各種的用途。 The metal exterior material 10 with a resin film can be processed by a deep drawing process, an ironing process, or a drawing process, etc., as needed. By such a process, a predetermined shape is formed and used for various purposes.
以上，依據本發明的附樹脂薄膜的金屬製外部材料10的製造方法的話，在基材金屬1的一方或雙方的面由置換鍍膜法或電鍍法將金屬鋅皮膜或含有金屬鋅的皮膜作為基礎皮膜2形成，其後，在其基礎皮膜2上形成樹脂薄膜3(積層薄膜或樹脂塗膜)，就可使被製造的附樹脂薄膜的金屬製外部材料10，獲得：樹脂薄膜3不剝離的高密合性，且即使與酸或溶劑等長時間接觸也可維持高密合性的結果。 As described above, according to the method for producing the metal outer material 10 with a resin film of the present invention, the surface of one or both of the base metal 1 is based on a metal zinc film or a film containing a metal zinc by a displacement plating method or a plating method. The film 2 is formed, and thereafter, a resin film 3 (layered film or resin coating film) is formed on the base film 2, whereby the metal outer material 10 with the resin film to be produced can be obtained: the resin film 3 is not peeled off. It has high adhesion and maintains high adhesion even when it is in contact with an acid or a solvent for a long period of time.
以下，藉由實施例及比較例，進一步詳細說明本發 明。本發明是不是被以下的實施例限定者。又，在以下，「份」是指「質量份」，「質量%」是與「重量%」同義，以下也有只顯示「%」。 Hereinafter, the present invention will be further described in detail by way of examples and comparative examples. Bright. Whether the invention is defined by the following examples. In addition, in the following, "parts" means "mass parts", "mass%" is synonymous with "% by weight", and only "%" is displayed below.
基材金屬是使用以下的金屬板或金屬箔。 The base metal is the following metal plate or metal foil.
1a：鋁板(JIS記號：A1100P、純鋁、厚度0.3mm) 1a: Aluminum plate (JIS mark: A1100P, pure aluminum, thickness 0.3mm)
1b：鋁合金箔(JIS記號：A8079、厚度0.03mm) 1b: Aluminum alloy foil (JIS mark: A8079, thickness 0.03mm)
1c：不銹鋼箔(JIS記號：SUS304、厚度0.1mm)1d：銅板(JIS記號：C1020P、無氧銅、厚度0.3mm) 1c: stainless steel foil (JIS mark: SUS304, thickness 0.1 mm) 1d: copper plate (JIS mark: C1020P, oxygen-free copper, thickness 0.3 mm)
1e：鎳板(純度99質量%以上、厚度0.3mm) 1e: Nickel plate (purity of 99% by mass or more and thickness of 0.3 mm)
1f：Ni鍍膜Cu板(電鍍Ni的Cu，銅板：C1020P的無氧銅、厚度0.3mm、Ni鍍膜厚2μm) 1f: Ni-coated Cu plate (Cu plated with Ni, copper plate: oxygen-free copper of C1020P, thickness 0.3 mm, thickness of Ni plating film 2 μm)
在基材金屬的表面由以下所示的方法形成了基礎皮膜。 The base film was formed on the surface of the base metal by the method shown below.
製作了硫酸鋅7水合物16.87份(鋅)、氫氧化鈉116份、葡萄糖酸鈉20份及殘餘為水的合計1000份的鹼性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 An alkaline displacement plating solution of 16.87 parts (zinc), 116 parts of sodium hydroxide, 20 parts of sodium gluconate, and a total of 1000 parts of water remaining in water was prepared. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
製作了硫酸鋅7水合物16.87份(鋅)、硫酸亞鐵5水合物1.16份(鐵)、氫氧化鈉116份、葡萄糖酸鈉20份及殘餘為水的合計1000份的鹼性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 An alkaline displacement coating solution of 16.87 parts (zinc), ferrous sulfate 5 hydrate 1.16 parts (iron), 116 parts of sodium hydroxide, 20 parts of sodium gluconate and 1000 parts of water remaining in total was prepared. . The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
製作了硫酸鋅7水合物16.87份(鋅)、硫酸鎳6水合物2.0份(鎳)、氫氧化鈉116份、葡萄糖酸鈉20份及殘餘為水的合計1000份的鹼性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 An alkaline displacement plating solution of 16.87 parts (zinc), nickel sulfate hexahydrate 2.0 parts (nickel), 116 parts of sodium hydroxide, 20 parts of sodium gluconate, and a total of 1000 parts of water remaining in water was prepared. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
製作了硫酸鋅7水合物16.87份(鋅)、硫酸鈷7水合物3.0份(鈷)、氫氧化鈉116份、葡萄糖酸鈉20份及殘餘為水的合計1000份的鹼性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 An alkaline displacement plating solution of 16.87 parts (zinc) of sulfate zinc sulfate, 3.0 parts of cobalt sulfate 7 hydrate (cobalt), 116 parts of sodium hydroxide, 20 parts of sodium gluconate, and a total of 1000 parts of water remaining was prepared. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
製作了硫酸鋅7水合物16.87份(鋅)、硫酸亞鐵5 水合物1.16份(鐵)、硫酸鎳6水合物0.23份(鎳)、氫氧化鈉116份、葡萄糖酸鈉20份及殘餘為水的合計1000份的鹼性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 Made of zinc sulfate 7 hydrate 16.87 parts (zinc), ferrous sulfate 5 Hydrate 1.16 parts (iron), nickel sulfate 6 hydrate 0.23 parts (nickel), 116 parts of sodium hydroxide, 20 parts of sodium gluconate, and a total of 1000 parts of an alkaline displacement coating liquid remaining as water. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
製作了硫酸鋅7水合物16.87份(鋅)、硫酸亞鐵5水合物1.16份(鐵)、硫酸鈷7水合物1.06份(鈷)、氫氧化鈉116份、葡萄糖酸鈉20份及殘餘為水的合計1000份的鹼性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 Made of zinc sulfate 7 hydrate 16.87 parts (zinc), ferrous sulfate 5 hydrate 1.16 parts (iron), cobalt sulfate 7 hydrate 1.06 parts (cobalt), sodium hydroxide 116 parts, sodium gluconate 20 parts and residual A total of 1000 parts of alkaline displacement coating liquid of water. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物10份(鋅)、酸性氟化銨7.65份及殘餘為水，且進一步使用10質量%的氫氧化鈉水溶液製作了調整成pH3.0的合計1000份的酸性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 10 parts (zinc) of zinc sulfate 7-hydrate, 7.65 parts of acidic ammonium fluoride, and residual water, and further using a 10% by mass aqueous sodium hydroxide solution to prepare a total of 1000 parts of the acid replacement coating liquid adjusted to pH 3.0 . The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物13份(鋅)、硫酸亞鐵5水合物3.6份(鐵)、55質量%氟化氫酸水溶液12.1份及殘餘 為水，且進一步使用10質量%的氫氧化鈉水溶液製作了調整成pH2.0的合計1000份的酸性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 For zinc sulphate 7 hydrate 13 parts (zinc), ferrous sulfate 5 hydrate 3.6 parts (iron), 55 mass% hydrofluoric acid aqueous solution 12.1 parts and residual In the case of water, a total of 1000 parts of an acidic displacement plating solution adjusted to pH 2.0 was prepared using a 10% by mass aqueous sodium hydroxide solution. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物13份(鋅)、硫酸鎳6水合物0.8份(鎳)、55質量%氟化氫酸水溶液12.1份及殘餘為水，且進一步使用10質量%的氫氧化鈉水溶液製作了調整成pH3.0的合計1000份的酸性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 13 parts (zinc) of zinc sulfate 7 hydrate, 0.8 parts (nickel) of nickel sulfate hexahydrate, 12.1 parts of a 55 mass% aqueous hydrogen fluoride solution, and a residual water, and further adjusted using a 10% by mass aqueous sodium hydroxide solution. A total of 1000 parts of an acidic displacement plating solution having a pH of 3.0 was obtained. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物13份(鋅)、硫酸鈷7水合物2.1份(鈷)、55質量%氟化氫酸水溶液9.7份及殘餘為水，且進一步使用10質量%的氫氧化鈉水溶液製作了調整成pH3.0的合計1000份的酸性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 13 parts (zinc) of zinc sulfate 7-hydrate, 2.1 parts (cobalt) of cobalt sulfate 7-hydrate, 9.7 parts of a 55 mass% aqueous hydrogen fluoride solution, and a residual water, and further adjusted with a 10% by mass aqueous sodium hydroxide solution. A total of 1000 parts of an acidic displacement plating solution having a pH of 3.0 was obtained. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物13份(鋅)、硫酸亞鐵5水合物2.5份(鐵)、硫酸鎳6水合物0.3份(鎳)、55質量 %氟化氫酸水溶液12.1份及殘餘為水，且進一步使用10質量%的氨水溶液製作了調整成pH2.5的合計1000份的酸性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 For zinc sulphate 7 hydrate 13 parts (zinc), ferrous sulfate 5 hydrate 2.5 parts (iron), nickel sulfate 6 hydrate 0.3 parts (nickel), 55 mass In an amount of 12.1 parts of a hydrogen fluoride aqueous solution and a residual amount of water, a total of 1000 parts of an acidic displacement plating solution adjusted to pH 2.5 was prepared using a 10% by mass aqueous ammonia solution. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物13份(鋅)、硫酸亞鐵5水合物1.5份(鐵)、硫酸鈷7水合物0.4份(鈷)、55質量%氟化氫酸水溶液12.1份及殘餘為水，且進一步使用10質量%的氨水溶液製作了調整成pH3.0的合計1000份的酸性置換鍍膜液。在此鍍膜液中將基材金屬由30℃浸漬30秒鐘，沖水之後，使用電爐，由80℃加熱乾燥1分鐘。 For zinc sulphate 7 hydrate 13 parts (zinc), ferrous sulfate 5 hydrate 1.5 parts (iron), cobalt sulfate 7 hydrate 0.4 parts (cobalt), 55 mass% aqueous hydrogen fluoride solution 12.1 parts and residual water, and further A total of 1000 parts of the acid replacement plating solution adjusted to pH 3.0 was prepared using a 10% by mass aqueous ammonia solution. The base metal was immersed in the coating liquid for 30 seconds at 30 ° C, and after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物91.6份(鋅)、硫酸鈉200份及殘餘為水，且進一步使用10質量%的氨水溶液製作了調整成pH4.0的1000份的電鍍鋅液。將基材金屬浸漬在此鍍膜液中，在對極使用鋅板，由30℃以電流密度5A/dm2進行10秒鐘電子的陰極電解。其後，沖水後，使用電爐由80℃加熱乾燥1分鐘。 To zinc sulfate 7-hydrate 91.6 parts (zinc), 200 parts of sodium sulfate, and residual water, and 1000 parts of an electroplating zinc solution adjusted to pH 4.0 was further prepared using 10 mass % of aqueous ammonia solution. The base metal was immersed in this plating solution, and a zinc plate was used in the counter electrode, and cathodic electrolysis of electrons was performed at 30 ° C for 10 seconds at a current density of 5 A/dm 2 . Thereafter, after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物32.7份(鋅)、硫酸亞鐵5水合物27.5份(鐵)、硫酸鈉200份及殘餘為水，且進一 步使用10質量%的氨水溶液製作了調整成pH3.5的合計1000份的電鍍鋅液。將基材金屬浸漬在此鍍膜液中，在對極使用鋅板，由30℃以電流密度5A/dm2進行10秒鐘電子的陰極電解。其後，沖水後，使用電爐由80℃加熱乾燥1分鐘。 32.7 parts (zinc) of zinc sulfate 7 hydrate, 27.5 parts (iron) of ferrous sulfate 5 hydrate (iron), 200 parts of sodium sulfate, and residual water, and further adjusted to pH 3.5 by using a 10% by mass aqueous ammonia solution. A total of 1000 parts of electroplating zinc solution. The base metal was immersed in this plating solution, and a zinc plate was used in the counter electrode, and cathodic electrolysis of electrons was performed at 30 ° C for 10 seconds at a current density of 5 A/dm 2 . Thereafter, after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物32.7份(鋅)、硫酸鎳6水合物25份(鎳)、硫酸鈉200份及殘餘為水，且進一步使用10質量%的氨水溶液製作了調整成pH3.5的合計1000份的電鍍鋅液。將基材金屬浸漬在此鍍膜液中，在對極使用鋅板，由30℃以電流密度5A/dm2進行10秒鐘電子的陰極電解。其後，沖水後，使用電爐由80℃加熱乾燥1分鐘。 32.7 parts (zinc) of zinc sulfate 7 hydrate, 25 parts of nickel sulfate hexahydrate (nickel), 200 parts of sodium sulfate, and residual water, and further adjusted to a pH of 3.5 by using a 10% by mass aqueous ammonia solution. 1000 parts of electroplating zinc solution. The base metal was immersed in this plating solution, and a zinc plate was used in the counter electrode, and cathodic electrolysis of electrons was performed at 30 ° C for 10 seconds at a current density of 5 A/dm 2 . Thereafter, after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物32.7份(鋅)、硫酸鈷7水合物25份(鈷)、硫酸鈉200份及殘餘為水，進一步使用10質量%的氨水溶液製作了調整成pH4.0的合計1000份的電鍍鋅液。將基材金屬浸漬在此鍍膜液中，在對極使用鋅板，由30℃以電流密度5A/dm2進行10秒鐘電子的陰極電解。其後，沖水後，使用電爐由80℃加熱乾燥1分鐘。 32.7 parts (zinc) of zinc sulfate 7 hydrate, 25 parts of cobalt sulfate 7 hydrate (cobalt), 200 parts of sodium sulfate, and residual water, and a total of 1000 adjusted to a pH of 4.0 was prepared using a 10% by mass aqueous ammonia solution. Parts of electroplating zinc solution. The base metal was immersed in this plating solution, and a zinc plate was used in the counter electrode, and cathodic electrolysis of electrons was performed at 30 ° C for 10 seconds at a current density of 5 A/dm 2 . Thereafter, after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物32.7份(鋅)、硫酸亞鐵5水合物27.5份(鐵)、硫酸鎳6水合物25份(鎳)、硫酸鈉200份及殘餘為水，且進一步使用10質量%的氨水溶液製作了調整成pH3.5的合計1000份的電鍍鋅液。將基材金屬浸漬在此鍍膜液中，在對極使用鋅板，由30℃以電流密度5A/dm2進行10秒鐘電子的陰極電解。其後，沖水後，使用電爐由80℃加熱乾燥1分鐘。 For sulfuric acid zinc 7 hydrate 32.7 parts (zinc), ferrous sulfate 5 hydrate 27.5 parts (iron), nickel sulfate 6 hydrate 25 parts (nickel), sodium sulfate 200 parts and residual water, and further used 10% by mass The aqueous ammonia solution was prepared by adding a total of 1000 parts of electroplating zinc solution adjusted to pH 3.5. The base metal was immersed in this plating solution, and a zinc plate was used in the counter electrode, and cathodic electrolysis of electrons was performed at 30 ° C for 10 seconds at a current density of 5 A/dm 2 . Thereafter, after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物32.7份(鋅)、硫酸亞鐵5水合物27.5份(鐵)、硫酸鈷7水合物25份(鈷)、硫酸鈉200份及殘餘為水，且進一步使用10質量%的氨水溶液製作了調整成pH3.5的合計1000份的電鍍鋅液。將基材金屬浸漬在此鍍膜液中，在對極使用鋅板，由30℃以電流密度5A/dm2進行10秒鐘電子的陰極電解。其後，沖水後，使用電爐由80℃加熱乾燥1分鐘。 For sulfuric acid zinc 7 hydrate 32.7 parts (zinc), ferrous sulfate 5 hydrate 27.5 parts (iron), cobalt sulfate 7 hydrate 25 parts (cobalt), sodium sulfate 200 parts and residual water, and further used 10% by mass The aqueous ammonia solution was prepared by adding a total of 1000 parts of electroplating zinc solution adjusted to pH 3.5. The base metal was immersed in this plating solution, and a zinc plate was used in the counter electrode, and cathodic electrolysis of electrons was performed at 30 ° C for 10 seconds at a current density of 5 A/dm 2 . Thereafter, after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物91.6份(鋅)、硫酸鈉200份及殘餘為水，且進一步使用10質量%的氨水溶液製作了調整成pH4.0的合計1000份的電鍍鋅液。其後，將基材金屬，在硝氟化氫酸水溶液(硝酸10質量%、氟化氫酸5質量%)中，在室溫浸漬1分鐘之後，沖水。其後，在上述電鍍鋅液中，將上述基材金屬浸漬，在對極使用鋅板，由 30℃以電流密度5A/dm2進行10秒鐘電子的陰極電解。其後，沖水後，使用電爐由80℃加熱乾燥1分鐘。 To a zinc sulfate 7-hydrate, 91.6 parts (zinc), 200 parts of sodium sulfate, and a residual amount of water, and further using a 10 mass% aqueous ammonia solution, a total of 1000 parts of an electroplating zinc solution adjusted to pH 4.0 was prepared. Thereafter, the base metal was immersed in a nitric acid hydrofluoric acid aqueous solution (10% by mass of nitric acid and 5% by mass of hydrogen fluoride) at room temperature for 1 minute, and then flushed with water. Thereafter, in the above-mentioned electroplating zinc bath, the base metal was immersed, and a zinc plate was used in the counter electrode, and cathodic electrolysis of electrons was performed at 30 ° C for 10 seconds at a current density of 5 A/dm 2 . Thereafter, after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
對於硫酸鋅7水合物91.6份(鋅)、硫酸亞鐵5水合物27.5份(鐵)、硫酸鈉200份及殘餘為水，使用10質量%的氨水溶液製作了調整成pH4.0的合計1000份的電鍍鋅液。其後，將基材金屬硝在氟化氫酸水溶液(硝酸10質量%、氟化氫酸5質量%)中，在室溫浸漬1分鐘之後，沖水。其後，在上述電鍍鋅液中，將上述基材金屬浸漬，在對極使用鋅板，由30℃以電流密度5A/dm2進行10秒鐘電子的陰極電解。其後，沖水後，使用電爐由80℃加熱乾燥1分鐘。 91.6 parts (zinc) of zinc sulfate 7 hydrate, 27.5 parts of iron ferrous sulfate 5 hydrate (iron), 200 parts of sodium sulfate, and residual water, and a total of 1000 adjusted to pH 4.0 was prepared using a 10% by mass aqueous ammonia solution. Parts of electroplating zinc solution. Thereafter, the base metal nitrate was immersed in a hydrofluoric acid aqueous solution (10% by mass of nitric acid and 5% by mass of hydrogen fluoride) at room temperature for 1 minute, and then flushed with water. Thereafter, in the above-mentioned electroplating zinc bath, the base metal was immersed, and a zinc plate was used in the counter electrode, and cathodic electrolysis of electrons was performed at 30 ° C for 10 seconds at a current density of 5 A/dm 2 . Thereafter, after flushing, it was dried by heating at 80 ° C for 1 minute using an electric furnace.
將氧化鋅溶膠(分散粒經20nm、固態分濃度1.5質量%、pH9.0)以#3塗抹機塗抹之後，以電爐由120度加熱乾燥1分鐘。 The zinc oxide sol (dispersed particles were passed through a 20 nm, solid concentration of 1.5% by mass, pH 9.0) by a #3 applicator, and then dried by heating at 120 degrees in an electric furnace for 1 minute.
對於基材金屬，不形成基礎皮膜，直接使用電爐，由80℃加熱乾燥1分鐘。 For the base metal, the base film was not formed, and it was directly dried using an electric furnace at 80 ° C for 1 minute.
由以下的其中任一的方法形成樹脂薄膜。 A resin film is formed by any of the following methods.
在基礎皮膜的表面，將厚度50μm的馬來酸變性聚丙烯薄膜190℃，由1MPa熱擠壓10秒鐘。 On the surface of the base film, a maleic acid-denatured polypropylene film having a thickness of 50 μm was hot-pressed at 190 ° C for 10 seconds from 1 MPa.
將在基礎皮膜的表面使厚度20μm的馬來酸變性聚丙烯層及厚度30μm的丙烯及乙烯的共聚物層被層疊的2層構造的樹脂薄膜的馬來酸變性聚丙烯薄膜層側，190℃，由1MPa熱擠壓10秒鐘。 The maleic acid-denatured polypropylene film layer of the resin film of the two-layer structure in which the maleic-modified polypropylene layer having a thickness of 20 μm and the copolymer layer of propylene and ethylene having a thickness of 30 μm were laminated on the surface of the base film, at 190 ° C , hot extruded by 1MPa for 10 seconds.
在基礎皮膜的表面，將酸變性聚丙烯的分散體(三井化學股份有限公司製，商品名：R-120K，不揮發分濃度：20質量%)，使用#8SUS塗劑，由塗抹機塗抹之後，由熱風循環式乾燥爐內200℃，乾燥1分鐘而形成接合劑層。其後，在基礎皮膜上的接合劑層的表面，將厚度30μm的聚丙烯薄膜(東賽璐股份有限公司製，「CPPS」)，由190℃、1MPa熱擠壓10秒鐘。 On the surface of the base film, a dispersion of acid-denatured polypropylene (manufactured by Mitsui Chemicals, Inc., trade name: R-120K, nonvolatile concentration: 20% by mass) was applied by an applicator using #8SUS paint. The adhesive layer was formed by drying at 200 ° C in a hot air circulating drying oven for 1 minute. Thereafter, a polypropylene film ("CPPS", manufactured by Tosoh Corporation) manufactured by a thickness of 30 μm was hot-pressed at 190 ° C and 1 MPa for 10 seconds on the surface of the adhesive layer on the base film.
在基礎皮膜的表面，將酸變性聚丙烯作為厚度15μm的熔融樹脂層擠出，其後退一步實施將厚度30μm的聚丙 烯薄膜(東賽璐股份有限公司製，「CPPS」)貼合的擠出層壓。 On the surface of the base film, the acid-denatured polypropylene was extruded as a molten resin layer having a thickness of 15 μm, and a polypropylene having a thickness of 30 μm was carried out one step back. Extrusion lamination of an ene film ("CPPS" manufactured by Tosoh Corporation).
在基礎皮膜的表面，將尿烷系乾積層接合劑(東洋莫頓股份有限公司製，商品名：AD-503/CAT10、不揮發分濃度：25質量%)，使用#8SUS塗劑，由塗抹機塗抹之後，由電爐80℃，乾燥1分鐘而形成接合劑層。其後，將此接合劑層、及厚度30μm的未延伸聚丙烯薄膜(二村化學工業股份有限公司製，商品名：FCZX)的電暈放電處理面，由100℃、1MPa擠壓之後，由40℃以4天復原。 On the surface of the base film, a urethane-based dry laminate adhesive (manufactured by Toyo Morton Co., Ltd., trade name: AD-503/CAT10, nonvolatile concentration: 25% by mass) was applied by using #8SUS paint. After the machine was applied, it was dried by an electric furnace at 80 ° C for 1 minute to form a bonding layer. Then, the corona discharge treated surface of the adhesive layer and the unstretched polypropylene film (manufactured by Nakamura Chemical Co., Ltd., trade name: FCZX) having a thickness of 30 μm was extruded at 100 ° C and 1 MPa, and then 40 °C was restored in 4 days.
將上述的基材金屬由精密清洗機359E(日本帕卡瀨精股份有限公司製，鹼性脫脂劑)的2%水溶液50℃，10秒鐘噴霧脫脂，進一步將表面沖水，準備了如表1~表4所示的實施例1~71及比較例1~12所使用的基材金屬。 The above-mentioned base metal was spray-degreased by a 2% aqueous solution of a precision washing machine 359E (a basic degreaser manufactured by Paccarat Co., Ltd., Japan) at 50 ° C for 10 seconds, and the surface was further flushed to prepare a surface. 1 to the substrate metals used in Examples 1 to 71 and Comparative Examples 1 to 12 shown in Table 4.
接著，對於如表1~表4所示的實施例1~71及比較例1~12所使用的基材金屬，適用如表1~表4所示的各處理並形成基礎皮膜。在表1~表4所示的實施例1~實施例71中選擇2a~2t的其中任一的處理，在比較例1~比較例12中選擇2u或2v的處理。 Next, with respect to the base metals used in Examples 1 to 71 and Comparative Examples 1 to 12 shown in Tables 1 to 4, the respective treatments shown in Tables 1 to 4 were applied to form a base film. In the first to seventh embodiments shown in Tables 1 to 4, the processing of any one of 2a to 2t was selected, and in the comparative examples 1 to 12, the processing of 2u or 2v was selected.
在此，置換鍍膜處理的情況時因為基材金屬被蝕刻，所以測量了其蝕刻量(g/m2)。蝕刻量的測量，是分析在 置換鍍膜液中被溶出的基材金屬由ICP(股份有限公司島津製作所製，ICPE-9000)定量。將其結果如表1~表4所示。且，構成基礎皮膜的金屬元素(Zn、Fe、Ni、Co等)的附著量(g/m2)也由ICP分析定量。此附著量，是將設有基礎皮膜的基材金屬在60%硝酸中浸漬溶解，將其溶解液ICP分析並測量。又，1g/m2的金屬元素若附著的話，基礎皮膜的厚度是成為約0.5μm。將其結果如表1~表4所示。且，對於基礎皮膜的表面，進行XPS分析(股份有限公司島津製作所製，ESCA-850M)，將基礎皮膜中的鋅元素的化學狀態由ZnLMM歐傑譜的尖峰位置識別。ZnLMM歐傑譜的尖峰位置是993.6eV的情況時，鋅元素是金屬狀態，988.6eV的情況時，鋅元素是氧化狀態。將其結果如表1~表4所示。 Here, in the case of the displacement plating treatment, since the base metal was etched, the etching amount (g/m 2 ) thereof was measured. The measurement of the amount of etching was carried out by ICP (ICPE-9000, manufactured by Shimadzu Corporation) by the analysis of the base metal eluted in the displacement plating solution. The results are shown in Tables 1 to 4. Further, the amount of adhesion (g/m 2 ) of the metal element (Zn, Fe, Ni, Co, etc.) constituting the base film was also quantified by ICP analysis. The amount of adhesion was obtained by immersing and dissolving the base metal provided with the base film in 60% nitric acid, and analyzing and measuring the dissolved solution by ICP. Further, when a metal element of 1 g/m 2 is adhered, the thickness of the base film is about 0.5 μm. The results are shown in Tables 1 to 4. Further, XPS analysis (ESCA-850M, manufactured by Shimadzu Corporation) was performed on the surface of the base film, and the chemical state of the zinc element in the base film was recognized by the peak position of the ZnLMM Oujie spectrum. When the peak position of the ZnLMM Eugene spectrum is 993.6 eV, the zinc element is in a metallic state, and in the case of 988.6 eV, the zinc element is in an oxidized state. The results are shown in Tables 1 to 4.
接著，對於如表1~表4所示的實施例1~71及比較例1~12所使用的基礎皮膜附基材金屬，適用如表1~表4所示的各處積層處理而形成樹脂薄膜。 Next, the base film-attached base metal used in Examples 1 to 71 and Comparative Examples 1 to 12 shown in Tables 1 to 4 was subjected to lamination treatment as shown in Tables 1 to 4 to form a resin. film.
接著，將所獲得的實施例1~71及比較例1~12的附樹脂薄膜的金屬製外部材料施加深拉深加工。首先，將被沖成成直徑160mm的附樹脂薄膜的金屬製外部材料拉深加工(第1次)，製作直徑100mm的杯。接著，將其杯再度拉深加工(第2次)成直徑75mm，進一步拉深加工(第3次)成直徑65mm，製作成供試材也就是罐。又，第1次的拉深加工、第2次的拉深加工及第3次的拉深加工中的熨燙率(薄層化分率)，各別為5%、15%及15%。 Next, the obtained metal outer materials of the resin films of Examples 1 to 71 and Comparative Examples 1 to 12 were subjected to deep drawing. First, a metal outer material which was punched into a resin film having a diameter of 160 mm was drawn (first time), and a cup having a diameter of 100 mm was produced. Next, the cup was further deep-drawn (second time) into a diameter of 75 mm, and further drawn (third time) into a diameter of 65 mm to prepare a test piece, that is, a can. In addition, the ironing rate (thin layering ratio) in the first drawing process, the second drawing process, and the third drawing process are 5%, 15%, and 15%, respectively.
將附樹脂薄膜的金屬製外部材料深拉深加工後的罐(供試材)的初期密合性、耐久密合性、耐電解液密合維持性、及液穩定如以下地評價了。將其結果如表1~表4所示。 The initial adhesion, the durability adhesion, the electrolyte solution adhesion maintaining property, and the liquid stability of the can (test material) after the deep drawing of the metal outer material with the resin film were evaluated as follows. The results are shown in Tables 1 to 4.
對於深拉深加工之後的供試材也就是罐，評價了初期密合性。罐可以製作、沒有樹脂薄膜的剝離、初期密合性優異者為「3點」，樹脂薄膜的一部分剝離者為「2點」，樹脂薄膜全面剝離者為「1點」。 For the test material after deep drawing, that is, the can, the initial adhesion was evaluated. The can was produced, and the peeling of the resin film was not performed, and the initial adhesion was "3 points", the part of the resin film was "2 points", and the resin film was "1 point".
將深拉深加工之後的供試材也就是罐，將被充填於密閉容器中的離子交換水浸漬在被添加了1000ppm的鋰離子2次電池用電解液(電解質：1mol/L的LiPF6、溶劑體積比率；EC：DMC：DEC=1：1：1)之後，在60℃的恆溫槽中投入7天。又，「EC」，是指碳酸乙烯酯，「DMC」是指碳酸二甲酯，「DEC」，是指碳酸二乙酯。其後，將供試材取出，在離子交換水中浸漬1分鐘，擺動洗淨之後，以電爐由100℃乾燥10分鐘。其後，將樹脂薄膜面由銷單元的先端刮動，完全未引起樹脂薄膜的剝離者為「4點」，雖有剝離但是抗劃傷性高的實用等級者為「3 點」，由非常地弱的力就剝離者為「2點」，樹脂薄膜已經剝離者為「1點」。 The test material after deep drawing is a can, and the ion-exchange water filled in the closed container is immersed in a lithium ion secondary battery electrolyte to which 1000 ppm is added (electrolyte: 1 mol/L of LiPF 6 , solvent) After the volume ratio; EC: DMC: DEC = 1:1:1), it was placed in a thermostat at 60 ° C for 7 days. Further, "EC" means ethylene carbonate, "DMC" means dimethyl carbonate, and "DEC" means diethyl carbonate. Thereafter, the test piece was taken out, immersed in ion-exchanged water for 1 minute, shake-washed, and then dried in an electric furnace at 100 ° C for 10 minutes. Then, the surface of the resin film is scraped by the tip end of the pin unit, and the peeling of the resin film is not "4 points" at all, and the practical grade of the scratch resistance is high, which is "3 points". The weak force is "2 points" for the peeling and "1 point" for the resin film to be peeled off.
如表1~表4所示，實施例1~71的供試材(本發明的附樹脂薄膜的金屬製外部材料)，是與比較例1~12的供試材相比，確認在被浸漬於電解液的情況也可以維持密合性，耐電解液密合維持性優異。 As shown in Tables 1 to 4, the test materials of Examples 1 to 71 (the metal-made external materials of the resin film of the present invention) were confirmed to be impregnated as compared with the test materials of Comparative Examples 1 to 12. In the case of the electrolytic solution, the adhesion can be maintained, and the electrolyte solution adhesion maintaining property is excellent.
1‧‧‧基材金屬 1‧‧‧Substrate metal
2‧‧‧基礎皮膜(金屬鋅皮膜或含有金屬鋅的皮膜) 2‧‧‧Basic film (metal zinc film or film containing metal zinc)
3‧‧‧樹脂薄膜(積層薄膜或樹脂塗膜) 3‧‧‧Resin film (laminated film or resin film)
10‧‧‧附樹脂薄膜的金屬製外部材料 10‧‧‧Metal exterior materials with resin film
[第1圖]顯示本發明的附樹脂薄膜的金屬製外部材料的一例的示意剖面圖。 [Fig. 1] A schematic cross-sectional view showing an example of a metal outer material to which a resin film of the present invention is applied.
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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 |
| WO2023277431A1 (en) * | 2021-06-30 | 2023-01-05 | 삼성전자 주식회사 | Electronic device comprising plates, plates, and method for manufacturing plates |
| WO2023128234A1 (en) | 2021-12-28 | 2023-07-06 | 주식회사 리베스트 | Apparatus and method for forming pattern on exterior material of battery |
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| JPH04221052A (en) * | 1990-12-19 | 1992-08-11 | Nisshin Steel Co Ltd | Pretreatment of stainless steel material for hot dipping galvanizing |
| JPH04353439A (en) * | 1991-05-30 | 1992-12-08 | Sumitomo Metal Ind Ltd | Lightweight sandwich steel plate with good edge corrosion resistance |
| 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 |
| JP4440376B2 (en) | 1999-07-16 | 2010-03-24 | 大日本印刷株式会社 | Polymer battery packaging materials |
| EP1102336B1 (en) * | 1999-04-08 | 2007-09-12 | Dai Nippon Printing Co., Ltd. | Lithium battery packaging laminated multilayer structure |
| 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-laminated galvanized 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 |
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| KR20130050255A (en) | 2013-05-15 |
| TW201325891A (en) | 2013-07-01 |
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| CN103085384B (en) | 2016-08-10 |
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