TWI665081B - 成形用包裝材 - Google Patents
成形用包裝材 Download PDFInfo
- Publication number
- TWI665081B TWI665081B TW104129606A TW104129606A TWI665081B TW I665081 B TWI665081 B TW I665081B TW 104129606 A TW104129606 A TW 104129606A TW 104129606 A TW104129606 A TW 104129606A TW I665081 B TWI665081 B TW I665081B
- Authority
- TW
- Taiwan
- Prior art keywords
- resin
- layer
- molding
- packaging material
- protective coating
- Prior art date
Links
- 239000005022 packaging material Substances 0.000 title claims abstract description 77
- 238000000465 moulding Methods 0.000 title claims abstract description 63
- 239000010410 layer Substances 0.000 claims abstract description 167
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- 239000011888 foil Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 239000011253 protective coating Substances 0.000 claims abstract description 43
- 238000007789 sealing Methods 0.000 claims abstract description 43
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 29
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 28
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000011342 resin composition Substances 0.000 claims abstract description 24
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 11
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 10
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 description 31
- 239000012790 adhesive layer Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000000853 adhesive Substances 0.000 description 15
- 230000001070 adhesive effect Effects 0.000 description 15
- 239000010419 fine particle Substances 0.000 description 15
- -1 polybutylene terephthalate Polymers 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical class [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000000873 masking effect Effects 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920001661 Chitosan Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical class [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000009820 dry lamination Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229910052755 nonmetal Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 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
- 230000009993 protective function Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000037390 scarring Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
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- 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
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- B32B15/06—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 natural rubber or synthetic rubber
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- B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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Abstract
本發明係提供一種成形用包裝材1,其特徵為其係具有:由耐熱性樹脂所成之外側基材層13、由熱可塑性樹脂所成之內側密封層16、配設於前述外側基材層13與前述內側密封層16之間的金屬箔層11、及形成於與前述外側基材層13之金屬箔層11側為相反側的保護塗層14;且前述保護塗層14係由含有主劑樹脂及硬化劑之樹脂組成物所成,且主劑樹脂係含有苯氧基樹脂及胺基甲酸乙酯樹脂,且前述保護塗層之厚度為0.1~10μm者。
Description
本發明係關於例如可較佳地作為筆記型電腦用、行動電話用、車載用、固定型的鋰離子蓄電池的外殼而使用;除此之外,亦可較佳地作為食品的包裝材、醫藥品的包裝材的成形用包裝材及成形外殼而使用者。
關於上述的成形用包裝材,在耐熱性樹脂所成外層與熱可塑性樹脂所成內層之間,配設金屬箔層作為屏蔽層,並將此等積層一體化的包裝材已被揭露(參照專利文獻1~4)。此外,在外層之外側進一步積層其他層體以提高成形用包裝材之品質亦已被提案。
專利文獻2、3記載了一種包裝材,其係通過對外層施行保護處理或設置馬特塗層,使成形性及耐久性得以提高。此外,其亦記載了藉由形成馬特塗層,可提高包裝材的外觀品質,防止各個包裝材之間過於密著,從而容易處理。前述馬特塗層係由使固體微粒子分散於樹脂上所成的樹脂組成物,該樹脂係使用丙烯酸系樹脂、胺基甲酸乙酯樹脂系樹脂、醇酸系樹脂、氟系樹脂等,並使用二氧化矽、高嶺土等作為固體微粒子。
專利文獻4記載了一種包裝材,其係藉由使用在最外層之耐
熱樹脂層上,與聚酯樹脂層/接著樹脂/聚醯胺層共押出所成薄膜,從而改善耐電解液性。
【專利文獻1】日本特開2000-123799號公報
【專利文獻2】國際公開WO 2012/133663 A1號公報
【專利文獻3】日本特開2011-054563號公報
【專利文獻4】日本特開2014-017266號公報
將聚醯胺薄膜積層作為外層之成形用包裝材,以其作為鋰離子電池的外裝材使用時,在電池的製造中,會有聚醯胺薄膜上附著電解液,導致表面膨脹,並在電池製造中與設備等接觸造成表面產生裂傷而降低外觀品質之虞。此外,亦會有因電解液的附著而變色之情形。為了防止如此的外觀品質降低的問題,通常在製造電池時,會在成形後之電池外殼貼上遮蔽膠帶以保護外表面,並在電池製造後剝除遮蔽膠帶。惟如此之保護步驟,對於電池製造的作業性有很大的損害,且使用又捨棄遮蔽膠帶將有成
本較高之問題。
此外,將電池要素放入成形之外裝材,並熱密封外裝材之緣部以便密封電池要素時,會有外層之聚醯胺薄膜熔融軟化而無法從熱密封桿剝離、或剝離後密封面之外觀惡化的問題。
此外,亦有因聚醯胺薄膜吸濕(或乾燥)而膨脹(或收縮),導致成形用包裝材彎折之問題。
專利文獻2~4之包裝材,雖然係藉由在聚醯胺薄膜之外側進一步積層另外的層體,從而對於聚醯胺薄膜有某些保護機能,惟此等保護層各別皆有不同的問題存在,保護機能並不充分。
胺基甲酸乙酯樹脂系樹脂雖柔軟且可得良好的成形性,但較難有耐藥品性及耐溶劑性,電池外殼所訴求之耐電解液性較不足。
聚酯樹脂層與聚醯胺樹脂層隔著接著性樹脂層而共押出並積層的方法,雖可改善耐藥品性、耐溶劑性,但成本高且會降低成形性。
本發明,鑒於上述的技術背景,目的在於提供一種成形用包裝材及關連技術,其具有一種保護塗層,該保護塗層兼具優異的成形性、耐藥品性、耐溶劑性及耐裂痕性。
亦即,本發明係具有下述〔1〕~〔6〕所記載之構成。
〔1〕一種成形用包裝材,其特徵為其係具有:由耐熱性樹脂所成之外側基材層、由熱可塑性樹脂所成之內側密封層、配設於前述外側基材層與前述內側密封層之間的金屬箔層、及形成於
與前述外側基材層之金屬箔層側為相反側的保護塗層;且前述保護塗層係由含有主劑樹脂及硬化劑之樹脂組成物所成,且主劑樹脂係含有苯氧基樹脂及胺基甲酸乙酯樹脂,且前述保護塗層之厚度為0.1~10μm者。
〔2〕如前項1所記載之成形用包裝材,其中,前述主劑樹脂中的苯氧基樹脂與胺基甲酸乙酯樹脂的質量比,相對於苯氧基樹脂1,胺基甲酸乙酯樹脂係0.6~1.6者。
〔3〕如前項1所記載之成形用包裝材,其中,前述外側基材層係由聚醯胺樹脂所成。
〔4〕如前項1所記載之成形用包裝材,其中,前述金屬箔層之厚度為10~40μm。
〔5〕一種成形外殼,其特徵為其係將前項1~4中任一項所記載之成形用包裝材進行深引伸成形或鼓脹成形而成者。
〔6〕如前項5所記載之成形外殼,其中,其係作為電池外殼使用者。
根據〔1〕所記載之成形用包裝材,作為形成保護塗層之樹脂中的主劑樹脂,係使用具有高安定性的苯氧基樹脂和具有高柔軟性的胺基甲酸乙酯樹脂的混合樹脂,從而得到兼具成形性、耐藥品性、耐溶劑性及耐裂痕性之成形用包裝材。
根據〔2〕所記載之成形用包裝材,藉由前述主劑樹脂中的
苯氧基樹脂和胺基甲酸乙酯樹脂的混合比例,可得到成形性、耐藥品性、耐溶劑性之平衡特別良好的保護塗層。
根據〔3〕所記載之成形用包裝材,由於外側基材層係由聚醯胺樹脂所構成,故可得到特別具有優異成形性及強度之成形用包裝材。
根據〔4〕所記載之成形用包裝材,藉由將金屬箔層之厚度規定在10~40μm的範圍內,可得到具有成形性特別良好之成形用包裝材。
根據〔5〕所記載的發明,可提供兼具成形性、耐藥品性、耐溶劑性及耐裂痕性之成形外殼。
根據〔6〕所記載的發明,可提供兼具成形性、耐藥品性、耐溶劑性及耐裂痕性之電池外殼。此外,其係藉由保護塗層而保護外側基材層,故可防止在電池製造時因電解液的附著或與製造設備的接觸所導致的外觀品質降低。
1‧‧‧成形用包裝材
11‧‧‧金屬箔層
12‧‧‧外側接著劑層
13‧‧‧外側基材層
14‧‧‧保護塗層
15‧‧‧內側接著劑層
16‧‧‧內側密封層
【圖1】表示本發明的成形用包裝材的一實施型態的斷面圖。
【圖2】表示本發明的成形用包裝材的製造方法的概要說明圖。
〔成形用包裝材〕
圖1,表示本發明的成形用包裝材(1)的一實施型態。此成形用包裝
材(1),係被使用作為鋰離子蓄電池外殼用包裝材。亦即,前述成形用包裝材(1),係用以進行深引伸成形等的成形而作為蓄電池外殼使用者。
前述成形用包裝材(1),係由金屬箔層(11)的一側面隔著外側接著劑層(12)與外側基材層(13)積層一體化,同時於該外側基材層(13)的外面,亦即金屬箔層(11)的相反側面形成保護塗層(14)者。此外,前述金屬箔層(11)的另一側的面隔著內側接著劑層(15)與內側密封層(16)積層一體化。
以下對於各層進行詳細說明。
(外側基材層)
前述外側基材層(13)係由耐熱性樹脂所成。前述耐熱性樹脂,係使用在熱密封成形用包裝材(1)時不會因熱密封溫度而溶融的樹脂。前述耐熱性樹脂,係使用較構成內側密封層(16)的熱可塑性樹脂熔點高10℃以上的具有高熔點的耐熱性樹脂為佳,使用較熱可塑性樹脂熔點高20℃以上的熔點的耐熱性樹脂為特佳。前述耐熱性樹脂之種類雖無特別限定,但可列舉例如:聚醯胺薄膜、聚酯薄膜等,使用此等的延伸薄膜為佳。其中,根據成形性及強度之觀點來看,係以使用二軸延伸聚醯胺薄膜、二軸延伸聚對苯二甲酸丁二醇酯(PBT)膜、二軸延伸聚對苯二甲酸乙二醇酯(PET)膜、或二軸延伸聚萘二甲酸乙二醇酯(PEN)膜為特佳。前述聚醯胺薄膜,雖無特別限定,但可列舉例如:6-聚醯胺薄膜、6,6-聚醯胺薄膜、MXD聚醯胺薄膜等。又,前述外側基材層(13),可由單層所形成,亦可由例如PET膜/聚醯胺薄膜而成的複數層所形成者。
前述外側基材層(13)的厚度,係以9μm~50μm為
佳。使用聚酯薄膜時,厚度較佳為9μm~50μm,使用聚醯胺薄膜時,厚度較佳為10μm~50μm。藉由設定在上述較佳的下限值以上,可確保作為包裝材的充分強度,並且藉由設定在上述較佳的上限值以下,可降低鼓脹成形時或引伸成形時的應力而提升成形性。
(內側密封層)
前述內側密封層(16)係由熱可塑性樹脂所成,具備即使對於鋰離子蓄電池等使用的腐蝕性強的電解液等,亦具有優異的耐藥品性,並同時擔負賦予包材熱密封性之角色者。
構成前述內側密封層(16)的熱可塑性樹脂層並無特別限定,較佳係使用熱可塑性樹脂未拉伸薄膜。前述熱可塑性樹脂未延伸薄膜,並無特別限定,由耐藥品性及熱密封性的觀點來看,由選自聚乙烯、聚丙烯、烯烴系共聚物、此等之酸變性物及離子聚合物所成群之至少1種熱可塑性樹脂所形成之未延伸薄膜所構成者為佳。內側密封層(16),可為單層或複數層。作為複數層,例如有於嵌段聚丙烯的兩面積層無規聚丙烯的三層薄膜、將酸變性聚丙烯與無規聚丙烯積層所成2層薄膜、將均聚丙烯與無規聚丙烯積層所成2層薄膜作為例示。
前述內側密封層(16)之厚度,係設定於20μm~80μm為佳。藉由設定在20μm以上,可充分地防止針孔的產生,同時藉由設定在80μm以下,可降低樹脂用量而達到成本的降低。其中,內側密封層(16)的厚度設定於30μm~50μm為特佳。此外,前述內側密封層(16),可為單層或複數層。
(金屬箔層)
前述金屬箔層(11),係擔負賦予阻止氧或水分侵入於成形用包裝材(1)之氣體阻隔性之功能者。
前述金屬箔層(11),並無特別限定,可列舉例如:鋁箔、銅箔、鎳箔、不銹鋼箔、或此等的包覆箔、此等的燒鈍箔或未燒鈍箔等,而一般係使用鋁箔。前述金屬箔層(11)的厚度,係以10μm~100μm為佳。10μm以上時,於製造金屬箔時,可防止軋壓時之針孔的產生,同時,在100μm以下時,可降低鼓脹成形時或深引伸成形時之應力而提升成形性。
此外,為提升成形性,金屬箔的厚度特別係10~40μm為佳,且更佳係10~30μm。
此外,前述金屬箔層(11)的表面係形成有化成皮膜為佳。成形用包裝材(1)的外側層及內側層為樹脂層,此等的樹脂層雖極微量,但有光、氧氣、液體由外殼外部侵入的可能性,亦有內容物(電池的電解液、食品、醫藥品等)由內部滲入的可能性。此等的侵入物到達金屬箔層(11)會成為金屬箔層(11)的腐蝕原因。對於此現象,藉由在金屬箔層(11)的表面形成耐蝕性高的化成皮膜,可實現提高金屬箔層(11)的耐蝕性的目的。
化成皮膜為金屬箔表面施行化成處理所形成的皮膜,例如,在金屬箔進行鉻酸鹽處理,利用鋯化合物施行非鉻型化成處理皆可形成。例如,鉻酸鹽處理時,可在進行脫脂處理後的金屬箔表面上,塗佈下述1)~3)中任一項的混合物的水溶液後使其乾燥。
1)磷酸、鉻酸、氟化物的金屬鹽及氟化物的非金屬鹽中至少一種,
其混合物
2)磷酸、丙烯酸系樹脂、殼聚醣衍生物樹脂(Chitosan derivative resins)及苯酚系樹脂中至少一種,及鉻酸及鉻(III)鹽中至少一種,其混合物
3)磷酸、丙烯酸系樹脂、殼聚醣衍生物樹脂、苯酚系樹脂中至少一種,及鉻酸及鉻(III)鹽中至少一種,及氟化物的金屬鹽及氟化物的非金屬鹽中至少一種,其混合物
前述化成皮膜的鉻附著量為0.1~50mg/m2為佳,2~20mg/m2為特佳。由前述鉻附著量的化成皮膜可得到高耐蝕性的成形用包裝材。
(外側接著劑層)
前述外側接著劑層(12),係擔負將金屬箔層(11)與外側基材層(13)進行接合的層。
構成前述外側接著劑層(12)的接著劑,雖無特別的限定,但可列舉出例如:含有多元醇成分及異氰酸酯成分所成的二液硬化型的胺基甲酸酯系接著劑等。此二液硬化型的胺基甲酸酯系接著劑,特別係使用乾式層壓法進行接著為佳。作為前述多元醇成分,雖無特別限定,但可列舉例如聚酯多元醇、聚醚多元醇等。作為前述異氰酸酯成分,雖無特別限定,但可列舉例如TDI(甲苯二異氰酸酯)、HDI(六亞甲基二異氰酸酯)、MDI(亞甲基雙(4,1-伸苯基)二異氰酸酯)等的二異氰酸酯類等。前述外側接著劑層(12)的厚度,較佳係設定為2μm~5μm為佳,其中特佳係設定為3μm~4μm。
又,外側接著劑層(12),只要係在不妨礙本發明效果之範圍內,則亦可在前述構成樹脂中添加無機系或有機系的防結塊劑(anti-blocking agent)、醯胺系的潤滑劑。
(內側接着劑層)
前述內側接着劑層(15),係擔負將金屬箔層(11)與內側密封層(16)進行接合的層。
前述內側接着劑層(15),雖無特別限定,但可列舉為例如:由聚胺甲酸酯系接著劑、丙烯酸系接著劑、環氧系接著劑、聚烯烴系接著劑、彈性體系接著劑、氟系接著劑等所形成的接著劑層。其中,係以使用丙烯酸系接著劑、聚烯烴系接著劑為佳,此時,可提升包裝材(1)的耐電解液性及水蒸氣阻障性。
(保護塗層)
前述保護塗層(14)係於外側基材層(13)的外面所形成,其在成形用包裝材(1)的表面可賦予良好的滑動性以提高成形性,同時並賦予優良的耐藥品性、耐溶劑性、耐裂痕性的層。
此外,由於外側基材層(13)藉由前述保護塗層(14)而受到保護,故在將成形用包裝材作為電池外殼材料使用時,可防止在電池製造時電解液的附著或與製造設備的接觸所導致的外觀品質降低。此外,由於不需要保護用的遮蔽膠帶,故可提高作業性,並降低成本。且即使作為電池以外的用途,其外側基材層(13)亦可藉由保護塗層(14)而受到保護。
前述樹脂組成物的樹脂成分,係使用含有苯氧基樹脂及胺基
甲酸乙酯樹脂的主劑樹脂及硬化劑。
主劑樹脂中,胺基甲酸乙酯樹脂雖具有柔軟性並有優異的成形性,但相反的卻沒有充分的耐藥品性、耐溶劑性。另一方面,苯氧基樹脂是以雙酚類和環氧氯丙烷(Epichlorohydrin)所合成的線狀高分子,強韌且具有安定性,即使於廣範圍的加工溫度中亦具有優異的熱安定性。再者,構造內含有OH基,因此藉由交聯可成為具備優良密著性及耐藥品性的樹脂。具備這種特性的苯氧基樹脂雖具有優良的耐藥品性及耐溶劑性,但其柔軟性卻較胺基甲酸乙酯樹脂來的差。本發明中,作為主劑樹脂,係將具有相反特性的2種類樹脂混合,亦即將具有高度柔軟性的胺基甲酸乙酯樹脂和具有高耐藥品性及耐溶劑性的苯氧基樹脂混合使用,而得兼具成形性和耐藥品性及耐溶劑性的樹脂組成物。又,前述苯氧基樹脂可使用雙酚A型苯氧樹脂或雙酚F型苯氧樹脂中的其中一種,或亦可併用兩種,但根據是否有優良的耐溶劑性的觀點,推薦使用雙酚A型苯氧基樹脂。
此外,胺基甲酸乙酯樹脂具有非常良好的印字性,且苯氧基樹脂亦具有良好的印字性,此等的混合樹脂也會具有良好的印字性。
前述主劑樹脂,其胺基甲酸乙酯樹脂的含有率越高柔軟性越增加並提高成形性,但相對的苯氧基樹脂的含有率會下降而使耐藥品性及耐溶劑性降低。相反的,苯氧基樹脂的含有率越高越可提高耐藥品性及耐溶劑性,但相對的胺基甲酸乙酯樹脂的含有率會下降而使成形性提升的程度變小。本發明的主劑樹脂中混合比雖無限定,但在成形性和耐藥品性及耐溶劑性之間保持最佳的平衡的混合比,推薦以質量比為相對於苯氧基樹脂1時胺基甲酸乙酯樹脂在0.6~1.6的範圍內為佳。質量比為相對
於苯氧基樹脂1時胺基甲酸乙酯樹脂在0.8~1.4的範圍內為特佳。
前述保護塗層(14)硬化後的厚度係0.1~10μm為佳,若係為較前述下限值為薄的層則提高成形性的效果及提高耐藥品性‧耐溶劑性的效果都變小,而若為較前述上限值為厚的層則會使成本上升。特佳的厚度範圍係2~5μm。
此外,含有上述之苯氧基樹脂及胺基甲酸乙酯樹脂的主劑樹脂,可更進一步添加含氟樹脂、丙烯酸樹脂,從而更加提升強度及成形性。
此外,硬化劑雖無特別限定,但使用異氰酸酯成分為佳。作為異氰酸酯成分,可列舉例如:TDI(甲苯二異氰酸)、HDI(六亞甲基二異氰酸酯)、MDI(亞甲基雙(4,1-亞苯基)二異氰酸酯)等二異氰酸酯類等,並可使用1種或2種以上的混合物。
前述硬化劑相對於前述主劑樹脂100質量份,係以5~30質量份配合為佳。未滿5質量份時對外側基材層(13)的密著性及耐溶劑性會有降低的可能性。而超過30質量份時,保護塗層(14)會硬化,有降低成形性的可能性。硬化劑的配合量相對於前述主劑樹脂100質量份,係以10~20質量份配合為特佳。
此外,由前述主劑樹脂與硬化劑所成樹脂組成物的物性,係以20℃且固體成分濃度25質量%液且以黏度杯# 4測定時黏度在10~30秒的範圍內為佳,在15~25秒的範圍內為特佳。
又,本發明並不排除苯氧基樹脂及胺基甲酸乙酯樹脂以外的樹脂或添加劑,只要不損害成形性、耐藥品性及耐溶劑性,亦可添加其他的成分。
例如,前述保護塗層(14),可在前述樹脂組成物中,在不損及樹脂的光澤、外觀的範圍內,使用添加固體微粒子或潤滑劑所成的樹脂組成物。藉由固體微粒子或潤滑劑的添加,可賦予保護塗層(14)滑動性而提高成形性,同時並可防止各個包裝材之間過於密著,從而容易處理。
可發揮此等效果的固體微粒子,可使用無機微粒子、有機微粒子任何一種,亦可將其混合使用。在此,無機微粒子,可使用二氧化矽、礬土、氧化鈣、碳酸鈣、硫酸鈣、矽酸鈣、碳黑等1種或2種以上,其中使用二氧化矽為佳。又,有機微粒子,可使用丙烯酸酯系化合物、聚苯乙烯基系化合物、環氧系樹脂、聚醯胺系化合物,或其等的交聯物等的微粒子。
此等的微粒子,為得到良好的滑動性,其粒徑的平均粒徑係1μm~10μm為佳,其中又以2μm~5μm為更佳。使用粒徑未滿1μm的過小微粒子時,其會埋沒於塗佈液中而欲實現預期效果必須添加大量的微粒子,因此難以得到充分的滑動性。另一方面,使用粒徑超過10μm的粒徑的大微粒子時,粒徑會超過塗佈厚度而容易脫落。
此外,樹脂組成物中的固體微粒子的含有率,可對應於包裝材需要的滑動性程度、所添加微粒子的粒徑、種類等,在0.1~10質量%的範圍內適當地加以決定。含有率未達0.1質量%時提高滑動性的效果較小,而有造成無法充分得到成形性提高的效果的可能性。相反的超過10質量%而過量含有時,會有損及外觀的可能性。微粒子的含有量在0.1~5質量%的範圍為佳,在0.1~3質量%的範圍為特佳。無機微粒子如使用例如二氧化矽時,其粒徑、含有量於前述上下限範圍內時,
可賦予最適當的滑動性。
前述保護塗層(14)硬化後的厚度係0.1~10μm為佳。若該層較前述下限值還薄,則滑動性的提高效果會降低,而若較上限值還厚則成本會提高。特佳的厚度範圍係2~5μm。
(成形用包裝材的製作)
具有上述各層的成形用包裝材(1),係將金屬箔層(11)的一側的面隔著外側接著劑層(12)與外側基材層(13)貼合,另一側的面隔著內側接著劑層(15)與內側密封層(16)貼合,製作成五層的積層體(10),可藉由於此積層體(10)的外側基材層(13)的表面,塗佈調製為糊狀之保護塗層(14)用的樹脂組成物,乾燥後製作而成。
前述積層體(10)的製作中,其各層的貼合方法不限定於上述的方法,可例示如稱為乾式層壓的方法。具體的說,於金屬箔層(11)的上面或外側基材層(13)的下面,或係於此等二者的面塗布外側接著劑層(12)的接著劑,蒸發溶劑並乾燥皮膜後,將金屬箔層(11)與外側基材層(13)貼合。金屬箔層(11)和內側密封層(16)的貼合亦相同,於金屬箔層(11)的下面或內側密封層(16)的上面,或係於此等二者的面塗佈內側接著劑層(15)的接著劑,蒸發溶媒乾燥皮膜後,將金屬箔層(11)與內側密封層(16)貼合。並且進一步,根據接著劑的硬化條件使其硬化,製作出五層的積層體(10)。此外,藉由T模法,將外側基材層(13)和外側接著劑層(12)、內側密封層(16)和內側接著劑層(15)以積層薄膜押出,將此等積層薄膜與金屬箔層(11)進行熱壓著即可製作為積層體(10)。再者,金屬箔層(11)的二者的面可藉由不同的手法貼合。
另一方面,作為保護塗層(14)用之材料,應事先將苯氧基樹脂和胺基甲酸乙酯樹脂混合所得主劑樹脂與硬化劑混合並調製為糊狀之樹脂組成物、或者調製為使固體微粒子均勻分散之糊狀的樹脂組成物。
接著,於前述積層體(10)的外側基材層(13)的表面塗佈前述樹脂組成物後,使其乾燥。樹脂組成物的塗佈方法雖無限定,但可列舉為例如凹版輥法。藉由乾燥樹脂組成物,可形成保護塗層(14),同時使保護塗層(14)與外側基材層(13)接合而製得所期望的成形用包裝材(1)。
塗佈樹脂組成物後的乾燥方法,如圖2所示,可例示如將塗佈了樹脂組成物的積層體(10)通過滾輪間利用熱滾輪(20)加熱的方法。於此方法中與樹脂組成物接觸的滾輪作為熱滾輪(20),其滾輪的溫度可例如加熱至130~220℃。
又,本發明的成形用包裝材,其各層的貼合方法或保護塗層的形成方法,不限定於上述的方法及步驟,由其他方法或步驟製作時也包含於本發明中。
〔成形外殼〕
將本發明的成形用包裝材(1)進行成形(深引伸成形、鼓脹成形等),可得到電池外殼等之成形外殼。
接著,將說明關於本發明的具體的實施例,但本發明並不限定於此些實施例。
〈實施例1~10〉
製作如圖1所示積層構造的成形用包裝材(1)。實施例1~10僅係構成保護塗層(14)之樹脂組成物或厚度相異,除了保護塗層(14),各實施例之積層體(10)的材料及製作步驟均為共通。前述積層體(10)的材料及製作如以下所述。
〈積層體〉
金屬箔層(11)為厚度40μm的鋁箔,於此鋁箔的兩面,塗佈由聚丙烯酸、三價鉻化合物、水、醇類所成的化成處理液,進行180℃乾燥形成化成皮膜。此化成皮膜的鉻附著量為10mg/m2。
於形成化成皮膜的金屬箔層(11)的一側的面,使用二液硬化型的胺基甲酸乙酯樹脂系接著劑作為外側接著劑層(12),將厚度25μm的二軸延伸6-聚醯胺薄膜作為外側基材層(13),進行乾式層壓。
此外,內側接著劑層(15)的接著劑,係藉由對於金屬箔層(11)和聚丙烯兩者皆有接著性的馬來酸變性聚丙烯樹脂,藉由T模法,將該馬來酸變性聚丙烯樹脂和熔點為140℃、MFR為7g/10min的乙烯-丙烯無規共聚物樹脂所成的內側密封層(16),以馬來酸變性聚丙烯樹脂層7μm、乙烯-丙烯無規共聚物層以40μm的積層薄膜押出並準備。亦即,此積層薄膜為厚度40μm之內側密封層(16)與厚度7μm之內側接著劑層(15)積層所成的薄膜。
接著,在前述金屬箔層(11)的其他側的面,與前述積層薄膜的內側接著劑(15)重合,通過加熱至150℃的熱滾輪而得到五層構造之積層體(10)。
將所製得的前述積層體(10)作為共通材料使用,製作實施
例1~10的成形用包裝材。
保護塗層(14)用之樹脂組成物,係相對於苯氧基樹脂1以表1所示比率之質量比與胺基甲酸乙酯樹脂混合作為主劑樹脂,將甲苯二異氰酸酯(TDI)與六亞甲基二異氰酸酯(HDI)以質量比1:1混合作為硬化劑,並相對於主劑樹脂100質量份,配合硬化劑15質量份調製而得。
在前述積層體(10)之外側基材層(13)的表面,以凹版輥法將所調製的樹脂組成物塗佈於其上,乾燥後形成保護塗層(14)。保護塗層(14)乾燥後的厚度如表1所示。藉此得到成形用包裝材(1)。
〈比較例1〉
將實施例1~10所使用之五層構造之積層體(10)作為成形用包裝材。亦即,比較例1的成形用包裝材未具有保護塗層(14)。
〈比較例2〉
除了外側基材層係使用厚度12μm的PET薄膜與厚度15μm的二軸延伸6聚醯胺薄膜進行積層所成之複數層薄膜以外,其他皆使用與實施例1~10相同之方法而製作積層體,並將此做為成形用包裝材。比較例2之成形用包裝材為六層構造之積層體,且最外層為PET薄膜。
〈比較例3〉
除了保護塗層(14)之樹脂組成物的樹脂成分僅使用胺基甲酸乙酯樹脂以外,其他皆係使用與實施例1~10相同之方法而以五層構造之積層體(10)形成保護塗層。亦即,在其樹脂組成物中,相對於胺基甲酸乙酯樹脂100質量份,係配合TDI與HDI以1:1混合的硬化劑15質
量份而調製。
〈比較例4〉
除了保護塗層(14)之厚度為表1所示之厚度以外,係使用與實施例6相同之方法製作成形用包裝材。
關於上述所得的各成形用包裝材,對於下述之項目進行性能評估。其結果如表1所示。
〈成形性〉
使用株式會社雨田(Amada)製鼓脹成形機(編號:TP-25C-X2)對於成形用包裝材進行縱55mm×横35mm之鼓脹成形,直到成形深度至成形品的角R部產生針孔或裂痕,根據下述之基準對應未產生裂痕之成形界限值而進行成形性之評估。
「○」…成形界限值為7.5mm以上
「△」…成形界限值為未達7.5mm
〈耐電解液性〉
耐藥品性及耐溶劑性的評估,係將相對於乙烯碳酸酯與碳酸二乙酯以容量比1:1混合所成的混合溶劑,使用六氟磷酸鋰鹽進行溶解,而得濃度為1莫爾/L之溶液所成的電解液,滴至成形用包裝材的最外層,並放置在常溫24小時後,以乙醇將電解液拭去。藉由拭去電解液後的變色程度,根據下述基準進行評估。
「○」…無變色
「△」…輕微變色,但不明顯
「×」…變色
〈彎折性〉
將裁切為100mm×100mm之成形用包裝材放置於平台上時,
「○」…有彎折且其高度為10mm以下,或者完全沒有彎折
「△」…具有超過10mm之彎折
〈熱密封時封口板的附著性(對密封桿的貼附)〉
使2張成形用包裝材呈各內側密封層互相接觸之態樣進行重合,使用加熱至210℃的一對密封桿將其夾持並保持5秒,使內側密封層熱融著。此時,根據下述基準評估外層的樹脂是否貼附密封桿。
「○」…外層未附著密封桿,上升之密封桿並不會將成形用包裝材一同夾持上升。
「△」…外層雖輕微附著密封桿,但上升之密封桿並不會將成形用包裝材一同夾持上升。
「×」…外層附著密封桿,且上升之密封桿將成形用包裝材一同夾持上升。
〈耐裂痕性〉
將裁切為100mm×200mm之成形用包裝材使外層面朝上而放置於平台上時,在外層面上,使用重量450g、具有先端直徑為10mm且表面平整的鐵製治具重複來回20次(來回長度為100mm)。其後以目測觀察成形用包裝材的表面,根據以下基準評估是否產生傷痕。
「○」…未產生傷痕。
「△」…產生輕微傷痕,但不明顯。
「×」…產生傷痕。
在實施例1~10與比較例1、4的比較中,藉由形成保護塗層可提高耐電解液性。實施例1~10之成形性良好,未發現因形成保護塗層而成形性降低。此外,藉由形成保護塗層,可抑制裂痕的產生,且可防止在熱密封時,最外層樹脂貼附密封桿之情形。另一方面,無保護塗層之比較例1,其耐電解液性較差,而保護塗層之厚度不足的比較例4,其提升耐電解液之效果並無法被認可。由於比較例2之最外層為PET,其耐電解液性良好但成形性差,且使用複數層薄膜作為外層之製造成本較高。比較例3之保護塗層係由胺基甲酸乙酯樹脂與硬化劑構成,故成形性良好,但其耐電解液性較差。
本申請案,係伴隨著在2014年9月30日提出申請的日本專利申請案的特願2014-200099號的優先權主張,其揭示內容直接構成本申請案的一部分。
在此所使用的用語及說明,係用以說明本發明的實施形態所使用,但本發明並不限定於此。在本發明所揭示且敘述的特徵事項的任何均等物皆不應被排除,且在本發明所請求的範圍內的各種變形亦應被理解為係可被接受的。
本發明的成形用包裝材,可較佳地使用作為鋰離子蓄電池等的電池外殼、食品的包裝材、醫藥品的包裝材。
Claims (6)
- 一種成形用包裝材,其特徵為其係具有:由耐熱性樹脂所成之外側基材層、由熱可塑性樹脂所成之內側密封層、配設於前述外側基材層與前述內側密封層之間的金屬箔層、及形成於與前述外側基材層之金屬箔層側為相反側的保護塗層;且前述保護塗層係由含有主劑樹脂及硬化劑之樹脂組成物所成,且主劑樹脂係含有苯氧基樹脂及胺基甲酸乙酯樹脂,且前述保護塗層之厚度為0.1~10μm;前述主劑樹脂中的苯氧基樹脂與胺基甲酸乙酯樹脂的質量比,相對於苯氧基樹脂1,胺基甲酸乙酯樹脂係0.5~2者。
- 如申請專利範圍第1項所記載之成形用包裝材,其中,前述主劑樹脂中的苯氧基樹脂與胺基甲酸乙酯樹脂的質量比,相對於苯氧基樹脂1,胺基甲酸乙酯樹脂係0.6~1.6者。
- 如申請專利範圍第1項所記載之成形用包裝材,其中,前述外側基材層係由聚醯胺樹脂所成。
- 如申請專利範圍第1項所記載之成形用包裝材,其中,前述金屬箔層之厚度為10~40μm。
- 一種成形外殼,其特徵為其係將申請專利範圍第1~4項中任一項所記載之成形用包裝材進行深引伸成形或鼓脹成形而成者。
- 如申請專利範圍第5項所記載之成形外殼,其中,其係作為電池外殼使用者。
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KR20160038763A (ko) | 2016-04-07 |
CN105459501A (zh) | 2016-04-06 |
JP6412388B2 (ja) | 2018-10-24 |
US20160089861A1 (en) | 2016-03-31 |
DE102015218736A1 (de) | 2016-04-14 |
JP2016068391A (ja) | 2016-05-09 |
US9649827B2 (en) | 2017-05-16 |
KR102372035B1 (ko) | 2022-03-07 |
CN112060717A (zh) | 2020-12-11 |
TW201612004A (en) | 2016-04-01 |
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