JPS6149113B2 - - Google Patents
Info
- Publication number
- JPS6149113B2 JPS6149113B2 JP6239281A JP6239281A JPS6149113B2 JP S6149113 B2 JPS6149113 B2 JP S6149113B2 JP 6239281 A JP6239281 A JP 6239281A JP 6239281 A JP6239281 A JP 6239281A JP S6149113 B2 JPS6149113 B2 JP S6149113B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- plastic layer
- composite
- metal foil
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000011888 foil Substances 0.000 claims description 66
- 229910052751 metal Inorganic materials 0.000 claims description 63
- 239000002184 metal Substances 0.000 claims description 63
- 229920003023 plastic Polymers 0.000 claims description 53
- 239000004033 plastic Substances 0.000 claims description 53
- 229920005989 resin Polymers 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 44
- 239000002131 composite material Substances 0.000 claims description 37
- 239000011253 protective coating Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000853 adhesive Substances 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000004826 seaming Methods 0.000 claims description 10
- 239000012744 reinforcing agent Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000012766 organic filler Substances 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 239000004831 Hot glue Substances 0.000 claims description 3
- 229920006026 co-polymeric resin Polymers 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims 2
- 229920005668 polycarbonate resin Polymers 0.000 claims 2
- 239000004431 polycarbonate resin Substances 0.000 claims 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 238000004873 anchoring Methods 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- 125000005587 carbonate group Chemical group 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 47
- 238000000576 coating method Methods 0.000 description 22
- -1 hydroxyalkyl ester Chemical class 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 19
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 230000004888 barrier function Effects 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 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 8
- 229920001577 copolymer Polymers 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 235000013405 beer Nutrition 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 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 4
- 230000005484 gravity Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 235000014171 carbonated beverage Nutrition 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000013353 coffee beverage Nutrition 0.000 description 2
- 238000007765 extrusion coating Methods 0.000 description 2
- 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 2
- 238000010030 laminating Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- FRDVGLLSCPBABZ-UHFFFAOYSA-N 1,6-dimethylcyclohexa-2,4-diene-1-carbaldehyde Chemical compound CC1C=CC=CC1(C)C=O FRDVGLLSCPBABZ-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical group CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical group C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000015197 apple juice Nutrition 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- KZIKDWMVGLXOTB-UHFFFAOYSA-N chloranylethene Chemical compound ClC=C.ClC=C KZIKDWMVGLXOTB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 description 1
- UPSIAUXDGWYOFJ-UHFFFAOYSA-N formaldehyde;furan Chemical compound O=C.C=1C=COC=1 UPSIAUXDGWYOFJ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019674 grape juice Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 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
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 239000007968 orange flavor Substances 0.000 description 1
- 235000015205 orange juice Nutrition 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、複合罐及びその製造方法に関するも
ので、より詳細には、金属罐に匹敵するバリヤー
性、保存性を有し、しかも軽量で焼却処理も可能
な複合罐及びその製造方法に関する。
種々の容器の内でも金属罐は、内容物を外気か
ら完全に遮断するというバリヤー性及び内容物の
保存性に特に優れたものであるが、容器重量が比
較的大であり、更に空罐の廃棄処理が困難である
という問題がある。
金属罐自体の重量を軽くし、使用する金属コス
トを低減させるために、金属罐の素材厚を減少さ
せる試みが種々なされている。しかしながら、こ
れらの試みは未だ十分に成功するに至つていな
い。例えば、ビールや炭酸飲料等の自生圧力を有
する内容物を充填する罐、即ち内圧罐の場合に
は、罐胴の厚みをかなり減少させても、内圧によ
る罐の変形等が問題となることは殆んどないが、
罐胴と罐蓋との巻締時に加わる圧下力によつて、
罐胴が座屈等の変形を生じるため、罐胴の肉厚を
或る限界値以上に薄くすることは到底困難であ
る。また、果汁飲料罐や通常の食罐のように内容
物が減圧状態で保存される罐、即ちバキユーム罐
においては、罐胴の厚みを内圧罐に比べてかなり
厚くしなければ罐胴に加わる外圧によつて罐胴が
容易に変形することになる。
近年、金属が有する優れたガスバリヤー性を利
用し、金属を複合材料の一素材成分として利用す
ることにより、容器を軽量化することも既に行わ
れている。このような複合材料容器の最も代表的
なものは、積層パウチと呼ばれるものであり、金
属箔の内側にヒートシール可能な樹脂層及び外側
により耐熱性のプラスチツクフイルム層を設けて
成る可撓性積層シートを、ヒートシーラントが対
面するように重ね合せ、周囲をヒートシールした
ものである。この積層パウチは容器としての自立
性及び形態保持性に欠けるばかりではなく、内容
物の保存性にも未だ問題があり、例えば酸性飲料
や酸性果実等を充填した場合には、ヒートシーラ
ント層と金属箔との間に所謂ブリスターと呼ばれ
るフクレ等が生じてバリヤー性の低下により、内
容物の長期保存性が期待できない。のみならず、
このタイプの容器においては、ヒートシールによ
る密封を行わねばならないという生産性上の制約
がある。ヒートシールは、ヒートシーラント層へ
の伝熱及びヒートシーラント層の溶融により密封
が始めて可能となるものであるから、密封に１乃
至２秒間もの長時間を必要とし、密封操作を機械
的に行なう二重巻締では250乃至1200罐／分の高
速充填が可能であるのに対して、生産性が著しく
悪いことが明らかである。
従つて、本発明の目的は、金属箔、金属箔の外
面側に設けられたプラスチツク層及び金属箔の内
面側に設けられた保護塗膜から成り、しかも金属
罐に匹敵するバリヤー性と保存性とを有し、更に
二重巻締による密封が可能な複合罐を提供するに
ある。
本発明の他の目的は、バリヤー性や二重巻締性
を損わずに、用いる金属素材の厚みが箔のレベル
に薄肉化されており、その結果軽量性でしかも価
格も安価な複合罐を提供するにある。
本発明の更に他の目的は、空罐を焼却により容
易に廃棄処理に付し得る複合罐を提供するにあ
る。
本発明の更に他の目的は、複合素材を用いる点
を除けば従来の製罐操作と同様の操作で、しかも
従来の製罐設備を使用して、製罐が可能な複合罐
の製造方法を提供するにある。
本発明の更に他の目的は、高生産速度で製罐及
び密封が可能な複合罐の製造方法を提供するにあ
る。
本発明によれば、プレス成形により形成された
罐胴部材と罐端部材とを二重巻締して成る罐にお
いて、前記罐胴部材は内面側に位置し且つ内表面
に保護塗膜を有する金属箔と外面側に位置するプ
ラスチツク層との積層体から形成され、前記保護
塗膜はカルボニル基、水酸基、エーテル基及びエ
ポキシ基から成る群より選ばれた極性基を10乃至
2000ミリモル／100ｇ樹脂の濃度で含有する樹脂
乃至は樹脂組成物から成り、前記プラスチツクは
少くとも30パーセント以上の引張伸び率を有し且
つ罐胴部材に自己保持性を与えるに十分な厚みを
有することを特徴とする複合罐が提供される。
本発明によれば更に、
(A) 少なくとも30％以上の引張伸び率を有し且つ
罐胴部材に自己保持性を与えるに十分な厚みを
有するプラスチツク層と、金属箔とを貼合せた
積層体を、前記金属箔の内側となるようにプレ
ス成形する工程、
(B) 前記プレス成形の前或いは後に金属箔の内側
となる面に、カルボニル基、水酸基、エーテル
基及びエポキシ基から成る群より選ばれた極性
基を10乃至2000ミリモル／100ｇ樹脂の濃度で
含有する樹脂乃至は樹脂組成物から成る保護塗
膜を形成する工程、
(C) プレス成形により得られる罐胴部材をフラン
ジ付罐胴に塑性加工する工程、
(D) フランジ付罐部と罐端部材とを二重巻締工
程、
とから成ることを特徴とする複合罐の製造方法が
提供される。
本発明を以下に、添付図面に示す具体例を参照
しつつ説明する。
本発明の複合罐を示す第１図において、複合罐
は全体として１で示す罐胴部材と、全体として２
で示す罐端部材とから成つており、両者は二重巻
締により一体化され且つ密封されている。
この罐胴部材１は、以下に詳述する複合素材の
プレス成形により形成されており、周壁４と底壁
５とを備えており、周壁４にも、周壁４と底壁５
との境界部にも継目は存在しない。
本発明の複合罐の重要な特徴の一つは、第２図
の断面図に示す通り、この罐胴部材３が、内面側
に位置し且つ内表面に保護塗膜６を有する金属箔
７と外面側に位置するプラスチツク層８との積層
体から形成されていることに存する。即ち、本発
明は、罐の内面側から外面側に向けて、保護塗膜
６／金属箔７／プラスチツク層８の順の積層構造
とすることにより、無継目罐胴へのプレス成形や
フランジ加工、更には二重巻締操作が最も容易に
行われると共に、最も優れたバリヤー性と内容物
の保存性とが達成されるという知見に基づくもの
である。この場合前記金属箔７とプラスチツク層
８の間には良好な成形性を確保し、さらに成形後
の自己保持性をより強固なものとするために接着
層９を設けることが好ましい。既に述べた如く、
金属箔７の内面にプラスチツク層を設けた複合容
器においては、腐食性の強い内容物を充填したと
き、プラスチツク層と金属箔との間にブリスター
が発生し、金属箔の腐食やこれに伴なうガスバリ
ヤー性の低下が生じる。しかして、金属箔にこの
ような腐食による孔アキが１点でも発生すると、
プラスチツク層は程度の差はあれ、かなり大きな
気体透過性を有し、しかも罐の内外では大きな圧
力差があるため、リークが生じ、内容物の保存性
が低下する。この原因は、未だ十分には明らかで
ないが、プラスチツク層自体、イオンや水等の腐
食性成分に対して無視し得ない透過性を有してお
り、プラスチツク層と金属箔との間に密着不良の
部分に、腐食性成分の透過が進行して、遂にブリ
スターの発生に至るものと思われる。これに対し
て、本発明によれば、金属箔の内側に保護塗膜を
設けたことにより、金属箔との間の密着性を著し
く向上するばかりではなく、腐食性成分の金属箔
方向への透過も抑制され、金属箔のブリスター発
生や腐食が防止されて、金属箔による永続したガ
スバリヤー効果が達成されるのである。のみなら
ず、金属箔自体は著しく機械加工性に劣り、この
ものをプレス成形により外表面が滑らかな無継目
罐胴の形に成形することや、二重巻締に賦するこ
とは不可能に近い。これに対して、本発明によれ
ば、金属箔の外側にプラスチツクを貼り合せて積
層体としたことにより、金属箔の内面層にしわ
や、クラツク、ピンホール等を発生させることな
しに、内面が滑らかな無継目罐胴の形にプレス成
形が可能となり、更にこの罐胴はフランジへの塑
性加工や、罐端部材との二重巻締も可能となるも
のである。
本発明においては、前記保護塗膜が、カルボニ
ル
The present invention relates to a composite can and a method for manufacturing the same, and more particularly to a composite can that has barrier properties and preservability comparable to metal cans, is lightweight, and can be incinerated, and a method for manufacturing the same. Among various types of containers, metal cans have particularly excellent barrier properties that completely isolate the contents from the outside air and preserve the contents, but they are relatively heavy and are difficult to store when empty. There is a problem that disposal is difficult. In order to reduce the weight of the metal can itself and reduce the cost of the metal used, various attempts have been made to reduce the material thickness of the metal can. However, these attempts have not yet been fully successful. For example, in the case of cans that are filled with contents that have their own pressure, such as beer or carbonated drinks, that is, internal pressure cans, deformation of the can due to internal pressure will not become a problem even if the thickness of the can body is considerably reduced. There aren't many, but
Due to the rolling force applied when tightening the can body and can lid,
Since the can body undergoes deformation such as buckling, it is extremely difficult to reduce the thickness of the can body beyond a certain limit value. In addition, in cans where the contents are stored under reduced pressure, such as fruit juice cans and regular food cans, in other words, baquium cans, the thickness of the can body must be considerably thicker than that of internal pressure cans, otherwise external pressure will be applied to the can body. As a result, the can body is easily deformed. In recent years, the weight of containers has already been reduced by taking advantage of the excellent gas barrier properties of metals and using metals as a component of composite materials. The most typical type of composite material container is called a laminated pouch, which is a flexible laminated pouch consisting of a metal foil with a heat-sealable resin layer on the inside and a more heat-resistant plastic film layer on the outside. The sheets are stacked one on top of the other with the heat sealant facing each other, and the periphery is heat sealed. This laminated pouch not only lacks self-reliance and shape retention as a container, but also has problems with the preservation of the contents. For example, when filled with acidic drinks or acidic fruits, the heat sealant layer The long-term storage stability of the contents cannot be expected due to the formation of so-called blisters between the foil and the resulting deterioration of the barrier properties. As well,
This type of container has a productivity limitation in that it must be sealed by heat sealing. With heat sealing, sealing is only possible through heat transfer to the heat sealant layer and melting of the heat sealant layer, so it requires a long time of 1 to 2 seconds to seal, and the sealing operation is mechanically performed. Although it is possible to fill at high speeds of 250 to 1200 cans/min with heavy seaming, it is clear that productivity is extremely poor. Therefore, an object of the present invention is to provide a metal foil, a plastic layer provided on the outer surface of the metal foil, and a protective coating film provided on the inner surface of the metal foil, and to have barrier properties and storage properties comparable to those of metal cans. It is an object of the present invention to provide a composite can which has the following features and which can be sealed by double seaming. Another object of the present invention is to reduce the thickness of the metal material used to the same level as foil without impairing barrier properties or double-sealing properties, and as a result, to create a composite can that is lightweight and inexpensive. is to provide. Still another object of the present invention is to provide a composite can that allows the empty can to be easily disposed of by incineration. Still another object of the present invention is to provide a method for manufacturing a composite can, which can be manufactured using conventional can manufacturing equipment, with the same operation as a conventional can manufacturing operation, except for the use of composite materials. It is on offer. Still another object of the present invention is to provide a method for manufacturing a composite can that can be manufactured and sealed at a high production rate. According to the present invention, in a can formed by double-sealing a can body member and a can end member formed by press molding, the can body member is located on the inner side and has a protective coating on the inner surface. It is formed from a laminate of a metal foil and a plastic layer located on the outer surface side, and the protective coating film contains 10 to 10 polar groups selected from the group consisting of carbonyl groups, hydroxyl groups, ether groups, and epoxy groups.
consisting of a resin or resin composition containing a concentration of 2000 mmol/100 g resin, said plastic having a tensile elongation of at least 30 percent and a thickness sufficient to provide self-retention properties to the can body member. A composite can is provided. According to the present invention, (A) a laminate comprising a metal foil and a plastic layer having a tensile elongation rate of at least 30% and having a thickness sufficient to provide self-retention properties to the can body member; (B) a step of press-molding the metal foil so that it becomes the inner side of the metal foil; (C) forming a can body member obtained by press molding into a flanged can body; A method for manufacturing a composite can is provided, which comprises the following steps: (D) a step of double-sealing a flanged can portion and a can end member. The invention will now be described with reference to specific examples shown in the accompanying drawings. In FIG. 1 showing a composite can of the present invention, the composite can includes a can body member generally designated by 1 and a can body member generally designated by 2.
and a can end member shown by , both of which are integrated and sealed by double seaming. This can body member 1 is formed by press molding of a composite material, which will be described in detail below, and includes a peripheral wall 4 and a bottom wall 5.
There is no seam at the boundary between the two. One of the important features of the composite can of the present invention is that, as shown in the cross-sectional view of FIG. It consists in being formed from a laminate with a plastic layer 8 located on the outer side. That is, the present invention has a laminated structure in the order of protective coating 6/metal foil 7/plastic layer 8 from the inner surface to the outer surface of the can, thereby making it possible to press-form or flange a seamless can body. Furthermore, it is based on the knowledge that the double seaming operation is the easiest to perform and achieves the best barrier properties and preservation of the contents. In this case, it is preferable to provide an adhesive layer 9 between the metal foil 7 and the plastic layer 8 in order to ensure good moldability and further strengthen self-retention after molding. As already mentioned,
In a composite container in which a plastic layer is provided on the inner surface of the metal foil 7, when highly corrosive contents are filled, blisters are generated between the plastic layer and the metal foil, resulting in corrosion of the metal foil and accompanying blisters. Deterioration of carious gas barrier properties occurs. However, if even one hole occurs in the metal foil due to corrosion,
The plastic layer has a fairly high gas permeability to varying degrees, and there is a large pressure difference between the inside and outside of the can, which can lead to leaks and reduce the shelf life of the contents. The cause of this is not yet fully clear, but the plastic layer itself has a non-negligible permeability to corrosive components such as ions and water, resulting in poor adhesion between the plastic layer and the metal foil. It is thought that the permeation of corrosive components progresses through these areas, eventually leading to the formation of blisters. In contrast, according to the present invention, by providing a protective coating on the inside of the metal foil, not only the adhesion between the metal foil and the metal foil is significantly improved, but also corrosive components are directed toward the metal foil. Permeation is also suppressed, blistering and corrosion of the metal foil is prevented, and a permanent gas barrier effect of the metal foil is achieved. In addition, the metal foil itself has extremely poor machinability, making it impossible to press-form it into a seamless can body with a smooth outer surface, or to double-seal it. close. On the other hand, according to the present invention, by bonding plastic to the outside of the metal foil to form a laminate, the inner layer of the metal foil can be coated without wrinkles, cracks, pinholes, etc. It is now possible to press-form the can body into a smooth, seamless can body, and this can body can also be plastic-processed into flanges and can be double-sealed with can end members. In the present invention, the protective coating film is carbonyl
【式】水酸基、エーテル基及びエポキ
シ基から成る群より選ばれた極性基を10乃至2000
ミリモル／100ｇ樹脂、特に50乃至1600ミリモ
ル／100ｇ樹脂の濃度で含有する樹脂乃至は樹脂
組成物から成ることも金属箔との密着性の点で極
めて重要である。即ち、極性基を上記濃度の下限
よりも多い量で含むものは、金属箔への密着性に
優れており、上記上限よりも少い量で含むもの
は、塗膜自体の諸耐久性においても良好である。
更に、この保護塗膜は、1.0ｇ／c.c.よりも大き
い密度、特に1.1乃至1.4ｇ／c.c.の密度を有するこ
とが、腐食性成分に対するバリヤー性の点で望ま
しい。
本発明の保護塗膜の極性基において、カルボニ
ル[Formula] 10 to 2000 polar groups selected from the group consisting of hydroxyl group, ether group and epoxy group
It is also extremely important from the point of view of adhesion to the metal foil that the resin or resin composition contains a resin or a resin composition containing a concentration of mmol/100g resin, particularly 50 to 1600 mmol/100g resin. In other words, those containing polar groups in an amount greater than the lower limit of the above concentration have excellent adhesion to metal foil, and those containing polar groups in an amount less than the above upper limit have poor durability of the coating film itself. In good condition. Furthermore, it is desirable for the protective coating to have a density of greater than 1.0 g/cc, particularly from 1.1 to 1.4 g/cc, from the viewpoint of barrier properties against corrosive components. In the polar group of the protective coating film of the present invention, carbonyl
【式】基としては、カルボン酸、カルボ
ン酸塩、カルボン酸エステル、カルボン酸アミ
ド、炭酸エステル、ウレア或いはウレタン結合に
基ずくカルボニル基であつてよく、前述した極性
基は、樹脂の分子鎖中、分子鎖上のペンダント基
或いは末端基として含有されていてよい。
保護塗膜の適当な例は、熱硬化性樹脂塗料、例
えば、フエノール−ホルムアルデヒド樹脂、フラ
ン−ホルムアルデヒド樹脂、キシレン−ホルムア
ルデヒド樹脂、ケトン−ホルムアルデヒド樹脂、
尿素ホルムアルデヒド樹脂、メラミン−ホルムア
ルデヒド樹脂、アルキド樹脂、不飽和ポリエステ
ル樹脂、エポキシ樹脂、ビスマレイミド樹脂、ト
リアリルシアヌレート樹脂、熱硬化型アクリル樹
脂、シリコーン樹脂、油性樹脂、或いは熱可塑性
樹脂塗料、例えば塩化ビニル−酢酸ビニル共重合
体、塩化ビニル−酢酸ビニル共重合体部分ケン化
物、塩化ビニル−マレイン酸共重合体、塩化ビニ
ル−マレイン酸−酢酸ビニル共重合体、アクリル
重合体、飽和ポリエステル樹脂等である。これら
の樹脂塗料は単独でも２種以上の組合せでも使用
される。
金属箔基体への密着性や耐腐食性の見地から
は、60℃のクロロホルム中で60分間抽出すること
により求めたゲル分率が50乃至100％の範囲にあ
る熱硬化性の塗膜が好適である。
本発明の目的に最も好適な保護塗膜は、エポキ
シ樹脂と他の樹脂とを含有する組成物である。
エポキシ樹脂成分としては、分子中に１個より
も多いオキシラン環を有するエポキシ化合物、特
にビスエポキシドが使用され、好適なエポキシ樹
脂成分は、450乃至5500、特に1000乃至5000のエ
ポキシ当量を有する。
最も好適なエポキシ樹脂成分は、ビスフエノー
ル類とエピハロヒドリンとから誘導された芳香族
エポキシ樹脂である。
前述した他の樹脂成分（硬化剤成分）として
は、分子鎖上にエポキシ樹脂と反応し得る官能
基、例えば水酸基、カルボキシル基、酸無水物
基、アミノ基或いはアミド基を有し且つ好適には
それ自体も塗膜形成能を有する樹脂が単独または
２種以上の組合せで使用される。好適な硬化剤樹
脂成分の例はこれに限定されるものではないが、
次の通りである。
水酸基含有樹脂：
レゾール型フエノール・アルデヒド樹脂、キシ
レン−アルデヒド樹脂、尿素−アルデヒド樹脂、
メラミン−アルデヒド樹脂、塩化ビニル−酢酸ビ
ニル共重合体部分乃至は完全ケン化物、ヒドロキ
シアルキルエステル型アクリル樹脂。
酸乃至は酸無水物含有樹脂：
塩化ビニル−無水マレイン酸共重合体、塩化ビ
ニル−酢酸ビニル−無水マレイン酸共重合体、カ
ルボン酸含有型アクリル樹脂。
アミノ基乃至アミド基含有樹脂：
ダイマー酸変性ポリアミド樹脂、アミノアルキ
ルエステル型アクリル樹脂。
本発明の目的に好適な硬化剤樹脂成分は、水酸
基含有型或いは酸乃至は酸無水物含有型のもので
ある。
エポキシ樹脂成分と硬化剤樹脂成分とは、95：
５乃至１：99、特に90：10乃至５：95の重量比で
組合せて使用するのがよい。即ち、エポキシ樹脂
成分の量が上記範囲よりも少ない場合には、アル
ミ箔との密着性が低下する傾向があに、一方上記
範囲よりも多い場合には耐腐食性が低下する傾向
がある。
本発明においては、プラスチツク層は少なくと
も30パーセント以上の引張伸び率を有し且つ罐胴
部材に自己保持性を与えるに十分な厚みを有する
ことも、プレス成形や、フランジ形成用の塑性加
工、更に二重巻締を可能ならしめるために極めて
重要である。本明細書において、引張伸び率と
は、本発明に用いる積層体とは別個にプラスチツ
ク層単独を引張り試験に付したときの破断迄の伸
び率、即ち式
Ｅ＝ｘ１−ｘ０／ｘ０×100
式中、x1は破断時の伸び、x0はもとのプラスチ
ツクの長さ、Ｅは伸び率である、
の伸び率（Ｅ）として定義される。この伸び率が
30パーセントよりも少ないプラスチツク層を金属
箔と貼合せた積層体は、罐胴部材へのプレス成形
が困難であり、強いて罐胴部材へプレス成形した
としても罐胴部材との二重巻締が不可能である。
本発明によれば、引張伸び率が30％以上、特に50
％以上の範囲にあるプラスチツク層を金属箔と貼
合せた素材を用いることにより、プレス成形、フ
ランジの塑性加工及び二重巻締が可能となり、更
にプラスチツク層の厚みを十分にとることによ
り、自己形態保持性を有し、罐胴内外の圧力差に
耐える複合罐を得ることが可能となる。
このようなプラスチツク層の適当な例は、これ
に限定されるものでないが、低一、中一或いは高
密度ポリエチレン、アイソタクテイツク・ポリプ
ロピレン、結晶性プロピレン−エチレン共重合
体、プロピレン−エチレン−ブテン共重合体、エ
チレン−酢酸ビニル共重合体、エチレン−アクリ
ル共重合体、イオン架橋オレフイン共重合体（ア
イオノマー）等のオレフイン系樹脂；ポリ塩化ビ
ニル、塩化ビニル−酢酸ビニル共重合体、塩化ビ
ニル−塩化ビニリデン共重合体等の塩化ビニル系
樹脂；ポリスチレン、スチレン−ブタジエン・ブ
ロツク共重合体、スチレン−イソブレン・ブロツ
ク共重合体、ABS樹脂（アクリロニトリル−ブ
タジエン−スチレン共重合体）等のスチレン系樹
脂；ポリエチレン−テレフタレート、ポリテトラ
メチレンテレフタレート、ポリエチレンテレフタ
レート／イソフタレート、ポリエチレン／ブチレ
ン・テレフタレート、ポリエチレンナフトエート
等のポリエステル樹脂；ポリカーボネート：ナイ
ロン６、ナイロン６，６、ナイロン６／ナイロン
６，６コポリマー、ナイロン12、ナイロン13、ナ
イロン６／ナイロン10コポリマー等のポリアミド
系樹脂等の熱可塑性樹脂である。用いるプラスチ
ツクはフイルムあるいはシートを形成するに足る
分子量を有していればよい。
これらのプラスチツクは単独でも或いは２種以
上のブレンド物の形でも用いることができ、更に
プラスチツク層は単層でも或いは２層以上の積層
プラスチツクであつてもよい。
プラスチツク層には、それを増量し、またプラ
スチツク層の延びを損うことなく、特にプレス成
形性を向上し更にプラスチツク層の自己形態保持
性を向上させるために充填剤乃至は補強剤を配合
せしめることができる。かかる充填剤としては、
軽質乃至は重質の炭酸カルシウム、気相分解法シ
リカ、中和法乃至酸法シリカ等の各種シリカ；酸
化マグネシウム、水酸化マグネシウム、炭酸マグ
ネシウム等のマグネシウム系充填剤；ケイ酸カル
シウム、ケイ酸マグネシウム、タルク、アスベス
ト粉等のケイ酸塩；カオリン、ベントナイト、焼
成カオリン、その他の粘土類等のアルミノケイ酸
塩、或いは無水石膏等の硫酸カルシウムを挙げる
ことができる。補強剤としては、カーボンブラツ
ク、ホワイトカーボン等の粉末補強剤、ガラス繊
維、ロツクウール等の繊維剤、マイカ、金属フレ
ーク、フレーク状ガラス等の薄片状補強剤が使用
される。更に、木粉、殻繊維、木綿、芳香族ポリ
アミド等の有機充填剤も使用可能である。
熱可塑性樹脂を比較的低温にてプレス成形した
場合、成形後の弾性回復（スプリングバツク）が
発生する。特に成形後の複合罐がレトルト処理な
いしは内容物をホツトパツクする如き高温度に曝
される場合、スプリングバツクにより罐の変形が
生じる。しかるに前記充填剤を混合する事によつ
てスプリングバツクが著しく抑制される事を見い
出した。更にプラスチツク層の耐熱温度（熱変形
温度）自体が上昇する事によつて本発明による複
合罐の熱・温度に対する形態自立性が著しく上昇
する事を見い出した。
次に充填剤は、シート或いはフイルムへの成形
性及びプレス成形性、フランジ塑性加工性及び二
重巻締性を損わない範囲内で熱可塑性樹脂へ混入
出来る。
すなわち、これらの充填剤乃至は補強剤は樹脂
100重量部当り５乃至500重量部、特に10乃至200
重量部の量で使用すると、前述した目的（スプリ
ングバツクの抑制、プレス成形性、フランジ加工
性及び二重巻締性）に関して良好な結果が得られ
る。
用いるプラスチツク層には、それ自体公知の配
合剤、例えば着色剤、酸化防止剤、紫外線吸収
剤、熱安定剤、滑剤、可塑剤、帯電防止剤等を公
知の処方に従つて配合できる。
金属箔としては、アルミ箔等の軽金属箔、鉄
箔、鋼箔、ブリキ箔等が有利に使用される。これ
らの金属箔は保護塗膜やプラスチツク層等の密着
性の点で、リン酸及び／又はクロム酸処理、ベー
マイト処理、アルマイト処理、電解クロム酸処理
等の表面処理をされていることが望ましい。
本発明において、金属箔は、ガスバリヤー性の
点で、５ミクロン以上、特に９ミクロン以上の厚
みを有することが望ましく、一方経済性の点で
は、100ミクロン以下、特に60ミクロン以下の厚
みを有することが望ましい。
プラスチツク層の厚みは、金属箔との組合せで
罐胴に自己形態保持性を与えるものであり、一般
に0.3乃至1.5mm、特に0.4乃至1.0mmの厚みを有す
ることが、加工性との兼ね合いで有利である。
金属箔とプラスチツク層との厚みの比は、経済
性と内容物保存性との見地からは、１：３乃至
１：300、特に、１：８乃至１：100の範囲にある
ことが望ましい。
保護塗膜は、耐腐食性や加工性の見地から、１
乃至20ミクロン、特に３乃至15ミクロンの厚みを
有することが望ましい。
本発明に用いる積層体は、金属箔の一方の面に
プラスチツク層を貼り合せ、他方の面に保護塗膜
を設けることにより製造される。
金属箔とプラスチツク層との貼り合せは、プラ
スチツク層そのものが金属への熱接着性を有する
場合には、この熱接着性を利用して、或いはホツ
トメルト接着剤、イソシアネート系接着剤、酸変
性乃至は酸無水物変性熱可塑性樹脂或いはアンカ
ー剤を両者の間に介在させて行うことができる。
プラスチツク層は、予め形成されたフイルム乃至
はシートの形で金属箔と接着させてもよく、また
押出されたプラスチツク層を、押出コートと呼ば
れる方法で熱接着させてもよい。この際、前記接
着剤やアンカー剤は、金属箔側に設けても、プラ
スチツク層に設けてもよい。ホツトメルト接着剤
としては、ポリエチレン、エチレン−酢酸ビニル
共重合体等のベース樹脂に、スチレン系樹脂、石
油樹脂、ロジン、変性ロジン等を粘着剤として使
用され、イソシアネート系接着剤としてはそれ自
体公知の一液型或いは二液型イソシアネート接着
剤が、酸乃至は酸無水物変性熱可塑性樹脂として
は、マレイン酸、無水マレイン酸、アクリル酸、
メタクリル酸、無水シトラコン酸、無水イタコン
酸等でグラフト変性されたオレフイン系樹脂、石
油樹脂等が、またアンカー剤としては有機チタネ
ート系、イソシアネート系のアンカー剤が使用さ
れる。
これらの接着剤の塗布は、溶液、サスペンジヨ
ン、エマルジヨン等の形で行つてもよいし、また
粉末塗装、押出コート、多層共押出し、サンドイ
ツチラミネーシヨン等により行つてもよい。
保護塗膜の形成は、前述した樹脂成分を、トル
エン、キシレン等の芳香族系溶媒；メチルエチル
ケトン等のケトン系溶媒；ブチルセロソルブ等の
セロソルブ系溶媒等に、固形分が10乃至50％とな
るように溶解し、この溶液を塗布した後、これを
焼付けることにより形成される。塗膜の焼付は、
塗料の種類によつても相違するが150乃至400℃で
１秒乃至20分間の条件がよい。
本発明の複合罐の製造工程を示す第３図におい
て、先ず工程（ａ）において、塗装金属箔１０と
プラスチツク層１１とを貼合せて成る円板状の積
層体１２を用意する。この円板は、例えば積層体
の大板シートをパンチング等の手段で打抜くこと
により製造される。
この積層体を、それ自体公知のポンチとダイス
との組合せ（共に図示せず）等を用いて一段或い
は複数段のプレス成形に賦する。
第３図に示す具体例では、このプレス成形工程
は、(b)，(c)，(d)及び(e)の４段階で行われ、金属箔
層１０が内面、プラスチツク層１１が外側となつ
た無継目カツプにプレス成形する。この際、工程
(b)におけるカツプ１２ａ、工程(c)におけるカツプ
１２ｂ、工程(d)におけるカツプ１２ｃはこの順序
に側壁部の径が小となり且つその高さが大となつ
ており、最後のプレス成形工程(e)において、所定
の径及び高さを有する罐胴１２に成形される。
次いで、トリミング工程(f)において、罐胴１２
の先端部１３を剪断して除去する。
フランジ加工工程(g)において、トリミング後の
罐胴１２をポンチ１４とダイス１５とで保持し、
罐胴１２の先端部をパツド１６に押し当てること
により外方にほぼ直角方向に折曲げてフランジ１
７を形成される。
充填工程(h)において、罐胴１２の内部に内容物
１８を充填し、最後に二重巻締工程(i)において、
罐蓋１９を罐胴１２上に被蓋させ、罐蓋周縁部と
フランジ１７との間で二重巻締して、最終複合罐
とする。
本発明において、下記式
ＲD＝Ｄ／ｄ
式中、Ｄは積層体素材１２の径を表わし、ｄは
カツプ乃至罐胴の内径を表わす、
で定義される絞り比ＲDは、全体として1.1乃至
４、特に1.3乃至3.5の範囲にあるのが望ましい。
一段のプレス加工での絞り比ＲDは、1.05乃至
2.2、特に1.1乃至1.5の範囲とし、深絞り罐胴の場
合には、多段に深絞りを行なうことが望ましい。
尚、最終段のプレス加工では、罐胴に表面平滑性
を与えたために若干のしごき加工（ironing）乃
至は延伸を加えるようにしてもよい。
本発明で使用する前述した積層体は加工性に優
れているため、プレス成形は室温で行うことがで
きる。しかしながら、プレス加工性、特にプレス
加工の速度を高めるために、樹脂の融点乃至は軟
化点よりも低に温度であるという条件で、加工す
べき積層体を加熱することもできる。また、同様
の加熱は、フランジ加工すべき罐胴先端及び二重
巻締すべき罐胴についても行うことができる。
第３図には図示していないが、フランジ加工工
程(g)に先立つて、罐胴先端乃至はこれに近接した
部分を、それ自体公知のダイ方式或いはスピン方
式（ロール方式）により、側壁部よりも小径に絞
つてネツクを形成させることもできる。
プレス加工時に金属箔７に傷が入るのを防止す
るために、積層体の金属箔側外表面には予じめ前
述した塗膜を設けておくことが望ましい。しかし
ながら、勿論、この塗膜は、積層体を罐胴にプレ
ス成形した後、その内表面に設けてもよい。ま
た、プレス成形に先立つて、金属箔外表面に予じ
め塗膜を施こし、更に成形後の罐胴内面に第二の
塗膜をトツプコートとして施こしてもよい。この
態様によれば、金属箔の保護が一層完全なものと
なる。
本発明を次の例で説明する。
実施例 １
50μｍの銅箔表面を電解クロム酸処理した箔の
片面にブチルエーテル化ユリア樹脂15重量部と分
子量3800、エポキシ当量2500のビスフエノールＡ
型エポキシ樹脂85重量部を溶剤で溶解した塗料を
厚さが５μｍになるよう塗布、乾燥硬化し、塗膜
（極性基1200ミリモル／100ｇ樹脂比重1.22）を形
成せしめた。
一方メルトインデツクス１のポリプロピレン
100重量部とタルク100重量部の混合物からなる伸
張率80％の0.5mm厚みのシートとメルトインデツ
クス50の無水マレイン酸変性ポリプロピレン15μ
ｍの接着層を有する溶融共押し出し二層構造積層
体を用意した。
次に、前述鋼箔を250℃に加熱し、箔の電解ク
ロム酸処理表面側に二層構造積層体の接着層側に
押圧し、再加熱し、急冷し鋼箔積層体を作成し
た。
該鋼箔積層体を直径170mmの円形ブランクに打
ちぬき、ただちに直径98.9mmの円筒ポンチによつ
て該ブランクを塗膜が内側になるように円筒状カ
ツプに深絞り成形した。その後、おのおの直径が
76.9mm、62.5mm、52.3mmのポンチを使用して３回
の再絞り成形によつて円筒状カツプの内径を52.3
mmとした後に該円筒状カツプ開口部をトリミング
してカツプ底面からの高さを104mmとした。
次にトリミングされたカツプの外壁を円形ダイ
スによりしごき、該カツプ外壁部のポリプロピレ
ンとタルク混合物の高さをカツプ底面から104mm
以上とすると同時にダイスと対向して該カツプ中
心と同心に配置されたパツドによつて該カツプ開
口部のフランジ成形を行つた。このようにしてえ
られたプレス成形複合罐にオレンジジユース、ア
ツプルジユース、グレープジユース、コーヒード
リンクを熱間充填し、通常のアルミニウム製イー
ジーオープン蓋を二重巻締し罐詰とした。コーヒ
ードリンクは115℃20分間殺菌を行い、各々の罐
詰を一年間保存した。保存後の内容品は、変敗は
なく、味、色には変化はみられなかつた。
実施例 ２
30μｍの鉄箔の表面を電気すずめつきした箔の
片面に、石炭酸とクレゾール（オルト、パラ、メ
タクレゾールの混合物）とからなるレゾールタイ
プ混合フエノール樹脂（石炭酸：クレゾール＝
１：２）20重量部と、分子量2900、エポキシ当量
2000のビスフエノールＡ型エポキシ樹脂80重量部
を溶剤で溶解した塗料を厚さが５μｍになるよう
塗布、乾燥硬化し、塗膜（極性基1170ミリモル／
100ｇレンジ比重1.24）を形成せしめた。更に、
鉄箔のもう一方の片面にメルトインデツクス100
の無水マレイン酸変性ポリプロピレンを厚さ約３
μｍになるように静電粉末塗装をを行つた。
次に、前述の表面に塗膜と無水変性ポリプロピ
レンである接着剤層を有する鉄箔を200℃に予備
加熱した。一方メルトインデツクス１のボリプロ
ピレン100重量部と炭酸カルシウム50重量部、伸
張率70％の混合物をＴダイを備えた押し出し機に
より厚さ0.8mmになるようにシートを押し出し、
前述の200℃に加熱された鉄箔の接着剤層表面
に、炭酸カルシウム配合ポリプロピレンを溶融接
着し、冷却し、鉄箔積層体を作成した。
該鉄箔積層体を直径192mmの円形ブランクに打
ちぬき、ただちに直径128mmの円筒ポンチによつ
て該ブランクを塗膜が内側になるように円筒状カ
ツプに深絞り成形した。その後おのおの直径が
99.8mm、81.7mm、65.3mmのポンチを使用して３回
の再絞り成形によつて円筒状カツプの内径を65.3
mmとした後に該円筒状カツプ開口部をトリミング
してカリツプ底面からの高さを121mmとした。
次にトリミングされたカツプの外壁を円形ダイ
スによりしごき、該カツプ外壁部のポリプロピレ
ンと炭酸カルシウムの混合物の高さをカツプ底面
から121mm以上とすると同時にダイスと対向して
該カツプ中心と同心に配置されたパツドによつて
該カツプ開口部のフランジ成形を行つた。このよ
うにしてえられたプレス成形罐に人参、レンコ
ン、マグロの水煮を詰め通常のブリキ製蓋を二重
巻締し、105℃60分殺菌を行い罐詰とし、１年間
保存した。１年保存後の内容品はそれぞれ変敗も
なく味にも変化はなかつた。
実施例 ３
20μｍのアルミニウム箔の片面に、塩化ビニル
87モル％、酢酸ビニル12モル％、無水マレイン酸
１モル％からなる共重合体の樹脂を溶剤で溶解し
た塗料を厚さが５μｍになるよう塗布、乾燥、硬
化し、塗膜（極性基310ミリモル／100ｇ樹脂比重
1.35）を形成せしめた。
次にアルミニウム箔のもう一方の片面にイソシ
アネート系接着剤を厚さ２μｍになるように塗布
し、メルトインデツクス3.0のポリエチレン100重
量部とシリカ20重量部の混合物からなる0.6mm厚
みのシートを張り合わせ、50℃３日間硬化接着
し、アルミニウム積層体を成形した。
次に該アルミニウム積層体を直径170mmの円形
ブランクに打ちぬき、ただちに直径98.6mmのポン
チを使用して該ブランクを塗膜が内側になるよう
に円筒状カツプに深絞り成形した。その後おのお
の直径が76.9mm、62.5mm、52.3mmのポンチを使用
して３回の再絞り成形によつて円筒状カツプ内径
を52.3mmとした後に該円筒状カツプ開口部をトリ
ミングしてカツプ底面からの高さを107mmとし
た。次にトリミングされたカツプの外壁に円筒状
リングを設け、フランジ成形用工具をカツプ開口
部に挿入し円筒状リング端面との間で加圧するこ
とによりカツプの高さを底面から104mmとすると
同時に開口部のフランジ成形を行つた。
このようにしてえられたプレス成形複合罐に、
ビール、コーラ、透明炭酸飲料を冷却充填し、通
常のアルミニウム製イージーオープン蓋を二重巻
締し、ビールは70℃20分間の滅菌を行い、常温で
１年間保存した。保存後の内容品は味、色等に変
化はなかつた。
実施例 ４
50μｍのアルミニウム箔の片面にレゾールタイ
プビスフエノールＡ樹脂30重量部と分子量2900、
エポキシ当量2000のビスフエノールＡ型エポキシ
樹脂70重量部を溶剤で溶解した塗料を厚さが５μ
ｍになるよう塗布し、乾燥、硬化し、塗膜（極性
基990ミリモル／100ｇ樹脂比重1.26）を形成せし
めた。
一方、ポリ塩化ビニル（重合度800）、ABS樹
脂（アクリロニトリル／ブタジエン／スチレン＝
28／25／46（重量比））、ポリブチレンテレフタレ
ート（０−クロルフエノール溶媒中で25℃におけ
る固有粘度が0.12／ｇ）のプラスチツクス100
重量部に対し80重量部タルクを配合した引張伸び
60乃至100％の0.4mmのシートを成形した。
次に、前記塗装アルミニウム箔の塗装をほどこ
されていない表面にイソシアネート系接着剤を塗
布し、前記それぞれのプラスチツクフイルムを張
合せ50℃３日間硬化接着し、アルミニウム積層体
を成形した。
次に該アルミニウム積層体を直径170mmの円形
ブランクに打ち抜き、その後該円形ブランクを温
度70℃に保持した後に該ブランクの塗膜が内側に
なるように直径98.6mmのポンチを使用して深絞り
成形により円筒状カツプを成形し、その後ただち
に直径が76.99mm、62.5mm、52.3mmのポンチを使用
して円筒状カツプの内径を52.3mmとした。その後
円筒状カツプ開口部をトリミングしてカツプ底面
からの高さを107mmとした。次にトリミングされ
たカツプの外壁に円筒状リングを設け、フランジ
成形用工具をカツプ開口部に挿入し円筒状リング
端面との間で加圧成形することによりカツプの高
さを底面から104mmとすると同時に開口部のフラ
ンジ成形を行つた。このようにしてえられたプレ
ス成形罐にビール、炭酸入オレンジフレーバー、
透明炭酸飲料を冷却充填し、通常のアルミニウム
製イージーオープン蓋を二重巻締し、ビールは70
℃20分滅菌を行い一年保存した。
一年後の内容品は変敗はもちろんのこと味、色
等の品質に変化はなかつた。[Formula] The group may be a carbonyl group based on a carboxylic acid, a carboxylate, a carboxylic ester, a carboxylic acid amide, a carbonic ester, a urea or a urethane bond, and the above polar group is , may be contained as a pendant group or a terminal group on the molecular chain. Suitable examples of protective coatings include thermosetting resin coatings, such as phenol-formaldehyde resins, furan-formaldehyde resins, xylene-formaldehyde resins, ketone-formaldehyde resins,
Urea-formaldehyde resins, melamine-formaldehyde resins, alkyd resins, unsaturated polyester resins, epoxy resins, bismaleimide resins, triallyl cyanurate resins, thermosetting acrylic resins, silicone resins, oil-based resins, or thermoplastic resin coatings, such as chloride Vinyl-vinyl acetate copolymer, partially saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-maleic acid copolymer, vinyl chloride-maleic acid-vinyl acetate copolymer, acrylic polymer, saturated polyester resin, etc. be. These resin coatings may be used alone or in combination of two or more. From the standpoint of adhesion to the metal foil substrate and corrosion resistance, a thermosetting coating film with a gel fraction in the range of 50 to 100%, determined by extraction in chloroform at 60°C for 60 minutes, is preferred. It is. The most suitable protective coatings for the purposes of this invention are compositions containing epoxy resins and other resins. As epoxy resin component, epoxy compounds with more than one oxirane ring in the molecule, especially bisepoxides, are used; preferred epoxy resin components have an epoxy equivalent weight of 450 to 5500, especially 1000 to 5000. The most preferred epoxy resin components are aromatic epoxy resins derived from bisphenols and epihalohydrins. The other resin component (curing agent component) mentioned above has a functional group that can react with the epoxy resin on its molecular chain, such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group, or an amide group, and is preferably Resins which themselves have coating film-forming ability may be used alone or in combination of two or more. Examples of suitable curing agent resin components include, but are not limited to:
It is as follows. Hydroxyl group-containing resin: resol type phenol aldehyde resin, xylene-aldehyde resin, urea-aldehyde resin,
Melamine-aldehyde resin, vinyl chloride-vinyl acetate copolymer partially or completely saponified product, hydroxyalkyl ester type acrylic resin. Acid- or acid anhydride-containing resin: vinyl chloride-maleic anhydride copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, carboxylic acid-containing acrylic resin. Resins containing amino groups or amide groups: dimer acid-modified polyamide resins, aminoalkyl ester type acrylic resins. Curing agent resin components suitable for the purpose of the present invention are those containing hydroxyl groups or those containing acids or acid anhydrides. The epoxy resin component and hardener resin component are 95:
They are preferably used in combination at a weight ratio of 5 to 1:99, particularly 90:10 to 5:95. That is, when the amount of the epoxy resin component is less than the above range, the adhesion to aluminum foil tends to decrease, while when it exceeds the above range, the corrosion resistance tends to decrease. In the present invention, the plastic layer has a tensile elongation rate of at least 30% and has a thickness sufficient to provide self-retention properties to the can body member. This is extremely important to enable double seaming. In this specification, the tensile elongation rate refers to the elongation rate up to breakage when the plastic layer alone is subjected to a tensile test separately from the laminate used in the present invention, that is, the formula E=x 1 -x 0 /x 0 ×100 where x 1 is the elongation at break, x 0 is the length of the original plastic, and E is the elongation rate, defined as the elongation rate (E). This growth rate
A laminate in which less than 30% of the plastic layer is laminated with metal foil is difficult to press-form into a can body, and even if press-formed into a can body, double seaming with the can body is difficult. It's impossible.
According to the present invention, the tensile elongation rate is 30% or more, especially 50%.
By using a material in which a plastic layer with a thickness of 10% or more is laminated with metal foil, press forming, plastic forming of flanges, and double seaming are possible. It becomes possible to obtain a composite can that has shape retention and can withstand pressure differences inside and outside the can body. Suitable examples of such plastic layers include, but are not limited to, low, medium or high density polyethylene, isotactic polypropylene, crystalline propylene-ethylene copolymer, propylene-ethylene-butene. Olefin resins such as copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic copolymers, and ionically crosslinked olefin copolymers (ionomers); polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, vinyl chloride- Vinyl chloride resins such as vinylidene chloride copolymer; styrene resins such as polystyrene, styrene-butadiene block copolymer, styrene-isobrene block copolymer, ABS resin (acrylonitrile-butadiene-styrene copolymer); Polyester resins such as polyethylene terephthalate, polytetramethylene terephthalate, polyethylene terephthalate/isophthalate, polyethylene/butylene terephthalate, polyethylene naphthoate; polycarbonate: nylon 6, nylon 6,6, nylon 6/nylon 6,6 copolymer, nylon 12 , nylon 13, and thermoplastic resins such as polyamide resins such as nylon 6/nylon 10 copolymers. The plastic used need only have a molecular weight sufficient to form a film or sheet. These plastics can be used alone or in the form of a blend of two or more types, and the plastic layer can be a single layer or a laminated plastic layer of two or more layers. A filler or reinforcing agent is added to the plastic layer in order to increase its weight and to particularly improve press formability and self-shape retention of the plastic layer without impairing the elongation of the plastic layer. be able to. Such fillers include:
Various types of silica such as light to heavy calcium carbonate, vapor phase decomposition silica, neutralized silica or acid silica; magnesium fillers such as magnesium oxide, magnesium hydroxide, and magnesium carbonate; calcium silicate, magnesium silicate Examples include silicates such as , talc, and asbestos powder; aluminosilicates such as kaolin, bentonite, calcined kaolin, and other clays; and calcium sulfate such as anhydrite. As the reinforcing agent, powdered reinforcing agents such as carbon black and white carbon, fiber agents such as glass fiber and rock wool, and flaky reinforcing agents such as mica, metal flakes, and flaky glass are used. Furthermore, organic fillers such as wood flour, shell fibers, cotton, aromatic polyamides, etc. can also be used. When thermoplastic resin is press-molded at a relatively low temperature, elastic recovery (spring back) occurs after molding. In particular, when a composite can after molding is exposed to high temperatures such as during retorting or hot-packing the contents, springback causes deformation of the can. However, it has been found that springback can be significantly suppressed by mixing the filler described above. Furthermore, it has been found that by increasing the heat resistance temperature (heat deformation temperature) of the plastic layer itself, the form independence against heat and temperature of the composite can according to the present invention increases significantly. Next, the filler can be mixed into the thermoplastic resin within a range that does not impair the moldability into a sheet or film, press moldability, flange plastic workability, and double seamability. In other words, these fillers or reinforcing agents are
5 to 500 parts by weight per 100 parts by weight, especially 10 to 200 parts by weight
When used in amounts of parts by weight, good results are obtained with respect to the aforementioned objectives (suppression of springback, press formability, flanging property and double seaming property). The plastic layer to be used may contain compounding agents known per se, such as colorants, antioxidants, ultraviolet absorbers, heat stabilizers, lubricants, plasticizers, antistatic agents, etc., according to known formulations. As the metal foil, light metal foil such as aluminum foil, iron foil, steel foil, tin foil, etc. are advantageously used. These metal foils are desirably subjected to surface treatment such as phosphoric acid and/or chromic acid treatment, boehmite treatment, alumite treatment, electrolytic chromic acid treatment, etc. from the viewpoint of adhesion to protective coatings, plastic layers, etc. In the present invention, the metal foil desirably has a thickness of 5 microns or more, especially 9 microns or more in terms of gas barrier properties, while it has a thickness of 100 microns or less, especially 60 microns or less in terms of economy. This is desirable. The thickness of the plastic layer, in combination with the metal foil, gives the can body self-shape retention, and it is generally advantageous to have a thickness of 0.3 to 1.5 mm, particularly 0.4 to 1.0 mm, in terms of workability. It is. The thickness ratio of the metal foil to the plastic layer is preferably in the range of 1:3 to 1:300, particularly 1:8 to 1:100, from the viewpoint of economy and content preservation. From the viewpoint of corrosion resistance and processability, the protective coating film is
Preferably it has a thickness of between 20 and 20 microns, particularly between 3 and 15 microns. The laminate used in the present invention is produced by laminating a plastic layer on one side of a metal foil and providing a protective coating on the other side. If the plastic layer itself has thermal adhesive properties to metal, the metal foil and the plastic layer can be bonded together by utilizing this thermal adhesive property, or by using hot melt adhesive, isocyanate adhesive, acid modified adhesive, or adhesive. This can be carried out by interposing an acid anhydride-modified thermoplastic resin or an anchor agent between the two.
The plastic layer may be adhered to the metal foil in the form of a preformed film or sheet, or the extruded plastic layer may be thermally bonded by a process called extrusion coating. At this time, the adhesive or anchor agent may be provided on the metal foil side or on the plastic layer. Hot melt adhesives use a base resin such as polyethylene or ethylene-vinyl acetate copolymer and a styrene resin, petroleum resin, rosin, modified rosin, etc. as an adhesive.Isocyanate adhesives are known per se. One-component or two-component isocyanate adhesives include acid- or acid anhydride-modified thermoplastic resins such as maleic acid, maleic anhydride, acrylic acid,
Olefin resins, petroleum resins, etc. graft-modified with methacrylic acid, citraconic anhydride, itaconic anhydride, etc. are used, and organic titanate-based and isocyanate-based anchor agents are used as the anchor agent. These adhesives may be applied in the form of solutions, suspensions, emulsions, etc., or may be applied by powder coating, extrusion coating, multilayer coextrusion, sandwich lamination, etc. To form the protective coating, the above-mentioned resin component is mixed with an aromatic solvent such as toluene or xylene; a ketone solvent such as methyl ethyl ketone; or a cellosolve solvent such as butyl cellosolve, etc., so that the solid content is 10 to 50%. It is formed by dissolving, applying this solution, and then baking it. The baking of the paint film is
Although it varies depending on the type of paint, conditions of 1 second to 20 minutes at 150 to 400°C are best. In FIG. 3 showing the manufacturing process of the composite can of the present invention, first in step (a), a disc-shaped laminate 12 made by laminating a painted metal foil 10 and a plastic layer 11 is prepared. This disk is manufactured, for example, by punching a large sheet of a laminate by punching or the like. This laminate is press-formed in one or more stages using a punch and die combination (both not shown), which are known per se. In the specific example shown in FIG. 3, this press forming process is carried out in four stages (b), (c), (d) and (e), with the metal foil layer 10 being the inner surface and the plastic layer 11 being the outer surface. Press-form into a seamless seamless cup. At this time, the process
In the cup 12a in (b), the cup 12b in step (c), and the cup 12c in step (d), the diameter of the side wall portion becomes smaller and the height becomes larger in this order, and the final press forming step ( In e), the can body 12 is formed to have a predetermined diameter and height. Next, in the trimming step (f), the can body 12
The tip portion 13 of the wafer is sheared off and removed. In the flange processing step (g), the trimmed can body 12 is held with a punch 14 and a die 15,
By pressing the tip of the can body 12 against the pad 16, the flange 1 is bent outward at a substantially right angle.
7 is formed. In the filling step (h), the contents 18 are filled inside the can body 12, and finally in the double seaming step (i),
The can lid 19 is placed on the can body 12 and double seamed between the peripheral edge of the can lid and the flange 17 to form the final composite can. In the present invention, the drawing ratio R D defined by the following formula R D =D/d, where D represents the diameter of the laminate material 12 and d represents the inner diameter of the cup or can body, is 1.1 as a whole. It is preferably in the range of 1.3 to 3.5, particularly 1.3 to 3.5.
The drawing ratio R D in one-stage pressing is 1.05 to 1.05.
2.2, especially in the range of 1.1 to 1.5, and in the case of deep-drawn can bodies, it is desirable to perform deep drawing in multiple stages.
Incidentally, in the final stage of pressing, some ironing or stretching may be applied to impart surface smoothness to the can body. Since the above-described laminate used in the present invention has excellent workability, press molding can be performed at room temperature. However, in order to increase the pressability, in particular the speed of pressing, it is also possible to heat the laminate to be processed, provided that the temperature is below the melting or softening point of the resin. Further, similar heating can be performed on the tip of the can body to be flanged and the can body to be double seamed. Although not shown in FIG. 3, prior to the flange processing step (g), the tip of the can body or a portion close to it is cut into a side wall by a die method or a spin method (roll method), which is known per se. It is also possible to form a net by narrowing the diameter to a smaller diameter. In order to prevent the metal foil 7 from being scratched during press working, it is desirable to provide the above-mentioned coating film in advance on the outer surface of the laminate on the metal foil side. However, of course, this coating film may be provided on the inner surface of the can body after the laminate is press-molded into the can body. Further, prior to press molding, a coating film may be applied to the outer surface of the metal foil in advance, and a second coating film may be applied as a top coat to the inner surface of the can body after the molding. According to this aspect, the protection of the metal foil becomes even more complete. The invention is illustrated by the following example. Example 1 15 parts by weight of butyl etherified urea resin and bisphenol A with a molecular weight of 3800 and an epoxy equivalent of 2500 were applied to one side of a 50 μm copper foil surface treated with electrolytic chromic acid.
A paint containing 85 parts by weight of mold epoxy resin dissolved in a solvent was applied to a thickness of 5 μm, dried and cured to form a coating film (polar group 1200 mmol/100 g resin specific gravity 1.22). On the other hand, polypropylene with a melt index of 1
A 0.5 mm thick sheet with an elongation rate of 80% consisting of a mixture of 100 parts by weight and 100 parts by weight of talc and 15 μm of maleic anhydride-modified polypropylene with a melt index of 50.
A melt coextruded two-layer laminate with m adhesive layers was prepared. Next, the aforementioned steel foil was heated to 250°C, the electrolytic chromic acid treated surface side of the foil was pressed against the adhesive layer side of the two-layer structure laminate, reheated, and rapidly cooled to create a steel foil laminate. The steel foil laminate was punched into a circular blank with a diameter of 170 mm, and the blank was immediately deep drawn into a cylindrical cup using a cylindrical punch with a diameter of 98.9 mm so that the coating film was on the inside. Then the diameter of each
The inner diameter of the cylindrical cup was reduced to 52.3 by redrawing three times using 76.9 mm, 62.5 mm, and 52.3 mm punches.
mm, the opening of the cylindrical cup was trimmed to give a height of 104 mm from the bottom of the cup. Next, the trimmed outer wall of the cup is squeezed using a circular die, and the height of the polypropylene and talc mixture on the outer wall of the cup is 104 mm from the bottom of the cup.
At the same time as above, the opening of the cup was flange-formed using a pad placed concentrically with the center of the cup, facing the die. The thus obtained press-molded composite cans were hot filled with orange juice, apple juice, grape juice, and coffee drink, and a regular aluminum easy-open lid was double-sealed to seal the cans. The coffee drinks were sterilized at 115°C for 20 minutes, and each canned product was stored for one year. There was no deterioration of the contents after storage, and no change in taste or color was observed. Example 2 A resol-type mixed phenolic resin (carbolic acid:cresol=
1:2) 20 parts by weight, molecular weight 2900, epoxy equivalent
A coating prepared by dissolving 80 parts by weight of 2000 bisphenol A type epoxy resin in a solvent was applied to a thickness of 5 μm, dried and cured to form a coating film (1170 mmol of polar groups/
100g microwave specific gravity 1.24). Furthermore,
Melt index 100 on the other side of the iron foil
of maleic anhydride-modified polypropylene with a thickness of approximately 3
Electrostatic powder coating was performed to achieve a thickness of μm. Next, the above-mentioned iron foil having a coating film and an adhesive layer made of anhydrous modified polypropylene on its surface was preheated to 200°C. On the other hand, a mixture of 100 parts by weight of polypropylene with a melt index of 1, 50 parts by weight of calcium carbonate, and an elongation rate of 70% was extruded into a sheet with a thickness of 0.8 mm using an extruder equipped with a T-die.
Calcium carbonate-containing polypropylene was melt-bonded to the surface of the adhesive layer of the iron foil heated to 200°C, and cooled to create an iron foil laminate. The iron foil laminate was punched into a circular blank with a diameter of 192 mm, and the blank was immediately deep-drawn into a cylindrical cup using a cylindrical punch with a diameter of 128 mm so that the coating film was on the inside. After that, the diameter of each
The inner diameter of the cylindrical cup was made 65.3 by redrawing three times using 99.8 mm, 81.7 mm, and 65.3 mm punches.
mm, the opening of the cylindrical cup was trimmed to give a height of 121 mm from the bottom of the cup. Next, the trimmed outer wall of the cup is squeezed using a circular die, and the mixture of polypropylene and calcium carbonate on the outer wall of the cup is placed at a height of 121 mm or more from the bottom of the cup, and at the same time is placed concentrically with the center of the cup, facing the die. The cup opening was flanged with a pad. The press-molded can thus obtained was filled with boiled carrots, lotus root, and tuna, double-sealed with a regular tin lid, sterilized at 105°C for 60 minutes, sealed in a can, and stored for one year. After one year of storage, the contents remained unchanged and the taste remained unchanged. Example 3 PVC on one side of 20μm aluminum foil
Copolymer resin consisting of 87 mol% vinyl acetate, 12 mol% vinyl acetate, and 1 mol% maleic anhydride dissolved in a solvent was applied to a thickness of 5 μm, dried, and cured. mmol/100g resin specific gravity
1.35). Next, apply isocyanate adhesive to the other side of the aluminum foil to a thickness of 2 μm, and paste a 0.6 mm thick sheet made of a mixture of 100 parts by weight of polyethylene with a melt index of 3.0 and 20 parts by weight of silica. After curing and bonding at 50°C for 3 days, an aluminum laminate was formed. The aluminum laminate was then punched into a circular blank with a diameter of 170 mm, and the blank was immediately deep drawn into a cylindrical cup using a punch with a diameter of 98.6 mm, with the coating on the inside. After that, the inner diameter of the cylindrical cup was made 52.3mm by re-drawing three times using punches with diameters of 76.9mm, 62.5mm, and 52.3mm, respectively, and the opening of the cylindrical cup was trimmed to form the bottom surface of the cup. The height was set to 107 mm. Next, a cylindrical ring is provided on the outer wall of the trimmed cup, and a flange forming tool is inserted into the cup opening and pressure is applied between the end face of the cylindrical ring to raise the height of the cup to 104 mm from the bottom and simultaneously open the cup. The flange molding was carried out on the part. In the press-formed composite can obtained in this way,
Beer, cola, and clear carbonated drinks were chilled and filled, and a normal aluminum easy-open lid was double-sealed. The beer was sterilized at 70°C for 20 minutes and stored at room temperature for one year. There was no change in taste, color, etc. of the contents after storage. Example 4 30 parts by weight of resol type bisphenol A resin and a molecular weight of 2900 were applied to one side of a 50 μm aluminum foil.
A paint made by dissolving 70 parts by weight of bisphenol A type epoxy resin with an epoxy equivalent of 2000 in a solvent is applied to a thickness of 5 μm.
It was coated to give a coating weight of m, dried and cured to form a coating film (polar group 990 mmol/100 g resin specific gravity 1.26). On the other hand, polyvinyl chloride (polymerization degree 800), ABS resin (acrylonitrile/butadiene/styrene =
28/25/46 (weight ratio)), polybutylene terephthalate (intrinsic viscosity at 25°C in 0-chlorophenol solvent: 0.12/g) 100
Tensile elongation containing 80 parts by weight of talc
A 0.4 mm sheet of 60 to 100% was molded. Next, an isocyanate adhesive was applied to the unpainted surface of the painted aluminum foil, and the respective plastic films were laminated together and cured and bonded at 50° C. for 3 days to form an aluminum laminate. Next, the aluminum laminate was punched into a circular blank with a diameter of 170 mm, and after the circular blank was maintained at a temperature of 70°C, it was deep drawn using a punch with a diameter of 98.6 mm so that the coating film of the blank was on the inside. A cylindrical cup was formed, and then the inner diameter of the cylindrical cup was immediately set to 52.3 mm using punches with diameters of 76.99 mm, 62.5 mm, and 52.3 mm. The opening of the cylindrical cup was then trimmed to give a height of 107 mm from the bottom of the cup. Next, a cylindrical ring is provided on the outer wall of the trimmed cup, and a flange forming tool is inserted into the cup opening and pressure formed between the end surface of the cylindrical ring and the height of the cup is set to 104 mm from the bottom. At the same time, the opening was flanged. Beer, carbonated orange flavor,
Clear carbonated drinks are chilled and filled, and the regular aluminum easy-open lid is double-sealed.
It was sterilized at ℃ for 20 minutes and stored for one year. After one year, there was no change in the quality of the contents, such as taste or color, let alone deterioration.
第１図は、本発明の複合罐を示す一部断面斜視
図、第２図は、第１図の罐の周壁の一部拡大断面
図、第３図は、本発明の複合罐の製造工程を示す
図であつて、
引照数字１は罐胴部材、２は罐端部材、４は周
壁、５は底壁、６は保護塗膜、７は金属箔、８は
プラスチツク層、９は接着層、１０は塗装金属箔
層、１１はプラスチツク層、１２は積層体、１４
はポンチ、１５はダイス、１６はパツド、１７は
フランジ、１８は内容物、１９は罐蓋を夫々示
す。
FIG. 1 is a partially sectional perspective view showing a composite can of the present invention, FIG. 2 is a partially enlarged sectional view of the peripheral wall of the can of FIG. 1, and FIG. 3 is a manufacturing process of the composite can of the present invention. In this figure, reference number 1 is the can body member, 2 is the can end member, 4 is the peripheral wall, 5 is the bottom wall, 6 is the protective coating, 7 is the metal foil, 8 is the plastic layer, and 9 is the adhesive layer. , 10 is a painted metal foil layer, 11 is a plastic layer, 12 is a laminate, 14
15 is a punch, 15 is a die, 16 is a pad, 17 is a flange, 18 is a contents, and 19 is a can lid.
Claims (1)
部材とを二重巻締して成る罐において、 前記罐胴部材は内面側に位置し且つ内表面に保
護塗膜を有する金属箔と外面側に位置するプラス
チツク層との積層体から形成され、前記保護塗膜
はカルボニル基、水酸基、エーテル基及びエポキ
シ基から成る群より選ばれた極性基を10乃至2000
ミリモル／100ｇ樹脂の濃度で含有する樹脂乃至
は樹脂組成物から成り、前記プラスチツク層は少
なくとも30パーセント以上の引張伸び率を有し且
つ罐胴部材に自己保持性を与えるに十分な厚みを
有することを特徴とする複合罐。 ２ 前記プラスチツク層がオレフイン系樹脂、塩
化ビニル系樹脂、スチレン系共重合樹脂、ポリエ
ステル系樹脂、ポリカーボネート系樹脂或いはポ
リアミド系樹脂から選ばれた熱可塑性樹脂或いは
該熱可塑性樹脂のブレンド物或いは複合体である
特許請求の範囲第１項記載の複合罐。 ３ 前記プラスチツク層が前記熱可塑性樹脂と該
樹脂100重量部当り５乃至500重量部の無機充填剤
乃至は補強剤とのブレンド物である特許請求の範
囲第１項記載の複合罐。 ４ 前記無機充填剤乃至は補強剤が、炭酸塩、ケ
イ素酸化物、金属酸化物、金属水酸化物、硫酸
塩、ケイ酸塩、アルミノケイ酸塩、カーボンブラ
ツク、炭素繊維或いはガラス繊維である特許請求
の範囲第３項記載の複合罐。 ５ 前記プラスチツク層が前記熱可塑性樹脂と該
樹脂100重量部当り５乃至は500重量部の有機充填
剤とのブレンド物である特許請求の範囲第１項記
載の複合罐。 ６ 前記有機充填剤乃至は補強剤が、木粉、パル
プ、殻繊維、木綿或いは芳香族ポリアミド繊維で
ある特許請求の範囲第５項記載の複合罐。 ７ 前記複合罐は、金属箔とプラスチツク層との
厚み比が１：３乃至１：300の範囲内にあるもの
である特許請求の範囲第１項記載の複合罐。 ８ 前記金属箔とプラスチツク層とはホツトメル
ト接着剤、イソシアネート系接着剤、酸変性熱可
塑性樹脂、酸無水物変性熱可塑性樹脂或いはアン
カー剤を介して接合されている特許請求の範囲第
１項記載の複合罐。 ９ (A) 少なくとも30％以上の引張伸び率を有し
且つ罐胴部材に自己保持性を与えるに十分な厚
みを有するプラスチツク層と、金属箔とを貼合
せた積層体を、前記金属箔の内側となるように
プレス成形する工程、 (B) 前記プレス成形の前或いは後に金属箔の内側
となる面に、カルボニル基、水酸基、エーテル
基及びエポキシ基から成る群より選ばれた極性
基を10乃至2000ミリモル／100ｇ樹脂の濃度で
含有する樹脂乃至は樹脂組成物から成る保護塗
膜を形成する工程、 (C) プレス成形により得られる罐胴部材をフラン
ジ付罐胴に塑性加工する工程、 (D) フランジ付罐胴と罐端部材とを二重巻締する
工程、 とから成ることを特徴とする複合罐の製造方法。 １０ 前記プラスチツク層がオレフイン系樹脂、
塩化ビニル系樹脂、スチレン系共重合樹脂、ポリ
エステル系樹脂、ポリカーボネート系樹脂或いは
ポリアミド系樹脂から選ばれた熱可塑性樹脂或い
は該熱可塑性樹脂のブレンド物或いは複合体であ
る特許請求の範囲第９項記載の方法。 １１ 前記プラスチツク層が前記熱可塑性樹脂と
該樹脂100重量部当り５乃至500重量部の無機充填
剤とのブレンド物である特許請求の範囲第９項記
載の方法。 １２ 前記プラスチツク層が前記熱可塑性樹脂と
該樹脂100重量部当り５乃至500重量部の有機充填
剤とのブレンド物である特許請求の範囲第９項記
載の方法。 １３ プラスチツク層を予めシートに形成し、該
シートと金属箔とを接着剤で接合して積層体とす
る特許請求の範囲第９項記載の方法。 １４ プラスチツク層を、所望により接着剤或い
はアンカー剤が施された金属箔上に押出コートし
て積層体に形成する特許請求の範囲第９項記載の
方法。[Scope of Claims] 1. A can formed by double-sealing a can body member and a can end member formed by press molding, wherein the can body member is located on the inner surface side and has a protective coating film on the inner surface. The protective coating film contains 10 to 2000 polar groups selected from the group consisting of carbonyl groups, hydroxyl groups, ether groups, and epoxy groups.
consisting of a resin or resin composition containing a concentration of mmol/100 g resin, the plastic layer having a tensile elongation of at least 30 percent and having a thickness sufficient to provide self-retention to the can body member. A composite can featuring: 2. The plastic layer is made of a thermoplastic resin selected from olefin resin, vinyl chloride resin, styrene copolymer resin, polyester resin, polycarbonate resin, or polyamide resin, or a blend or composite of the thermoplastic resin. A composite can according to claim 1. 3. The composite can according to claim 1, wherein the plastic layer is a blend of the thermoplastic resin and an inorganic filler or reinforcing agent in an amount of 5 to 500 parts by weight per 100 parts by weight of the resin. 4. A patent claim in which the inorganic filler or reinforcing agent is carbonate, silicon oxide, metal oxide, metal hydroxide, sulfate, silicate, aluminosilicate, carbon black, carbon fiber, or glass fiber. Composite cans as described in item 3 of the scope. 5. A composite can according to claim 1, wherein said plastic layer is a blend of said thermoplastic resin and 5 to 500 parts by weight of organic filler per 100 parts by weight of said resin. 6. The composite can according to claim 5, wherein the organic filler or reinforcing agent is wood flour, pulp, shell fiber, cotton, or aromatic polyamide fiber. 7. The composite can according to claim 1, wherein the thickness ratio of the metal foil to the plastic layer is in the range of 1:3 to 1:300. 8. The metal foil and the plastic layer are bonded via a hot melt adhesive, an isocyanate adhesive, an acid-modified thermoplastic resin, an acid anhydride-modified thermoplastic resin, or an anchor agent. Composite can. 9 (A) A laminate of a metal foil and a plastic layer having a tensile elongation of at least 30% and having a thickness sufficient to provide self-retention properties to the can body member, (B) Before or after the press forming, 10 polar groups selected from the group consisting of a carbonyl group, a hydroxyl group, an ether group, and an epoxy group are added to the inner surface of the metal foil. (C) A step of plastically working a can body member obtained by press molding into a flanged can body; D) A method for manufacturing a composite can, comprising the steps of double seaming a flanged can body and a can end member. 10 the plastic layer is an olefin resin;
Claim 9 is a thermoplastic resin selected from vinyl chloride resin, styrene copolymer resin, polyester resin, polycarbonate resin, or polyamide resin, or a blend or composite of the thermoplastic resin. the method of. 11. The method of claim 9, wherein said plastic layer is a blend of said thermoplastic resin and from 5 to 500 parts by weight of inorganic filler per 100 parts by weight of said resin. 12. The method of claim 9, wherein said plastic layer is a blend of said thermoplastic resin and from 5 to 500 parts by weight of organic filler per 100 parts by weight of said resin. 13. The method according to claim 9, wherein the plastic layer is formed into a sheet in advance, and the sheet and metal foil are bonded with an adhesive to form a laminate. 14. The method of claim 9, wherein the plastic layer is extrusion coated onto a metal foil optionally provided with an adhesive or an anchoring agent to form a laminate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6239281A JPS57178744A (en) | 1981-04-27 | 1981-04-27 | Composite can and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6239281A JPS57178744A (en) | 1981-04-27 | 1981-04-27 | Composite can and its manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57178744A JPS57178744A (en) | 1982-11-04 |
| JPS6149113B2 true JPS6149113B2 (en) | 1986-10-28 |
Family
ID=13198807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6239281A Granted JPS57178744A (en) | 1981-04-27 | 1981-04-27 | Composite can and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57178744A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS581643A (en) * | 1981-06-24 | 1983-01-07 | 東洋製罐株式会社 | Composite can and its manufacture |
| JPS6090136U (en) * | 1983-11-28 | 1985-06-20 | キタノ製作株式会社 | airtight container |
| JPS60164019U (en) * | 1984-04-09 | 1985-10-31 | 釜屋化学工業株式会社 | Laminate tube |
| JPS61120734A (en) * | 1984-11-16 | 1986-06-07 | 東洋製罐株式会社 | Vessel made of steel having excellent disposal property |
-
1981
- 1981-04-27 JP JP6239281A patent/JPS57178744A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57178744A (en) | 1982-11-04 |
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