JPS6330216B2 - - Google Patents
Info
- Publication number
- JPS6330216B2 JPS6330216B2 JP57186110A JP18611082A JPS6330216B2 JP S6330216 B2 JPS6330216 B2 JP S6330216B2 JP 57186110 A JP57186110 A JP 57186110A JP 18611082 A JP18611082 A JP 18611082A JP S6330216 B2 JPS6330216 B2 JP S6330216B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- vinyl chloride
- lower body
- copolyester
- upper body
- 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
- 239000000853 adhesive Substances 0.000 claims description 70
- 230000001070 adhesive effect Effects 0.000 claims description 69
- 229920005989 resin Polymers 0.000 claims description 54
- 239000011347 resin Substances 0.000 claims description 54
- 238000000576 coating method Methods 0.000 claims description 53
- 239000011248 coating agent Substances 0.000 claims description 50
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 49
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- 229920001634 Copolyester Polymers 0.000 claims description 37
- 239000007769 metal material Substances 0.000 claims description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 230000009477 glass transition Effects 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 25
- 239000003973 paint Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 16
- -1 polyethylene terephthalate Polymers 0.000 description 15
- 229910000831 Steel Inorganic materials 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 11
- 239000012790 adhesive layer Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000011049 filling Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000010409 ironing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000005304 joining Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000002987 primer (paints) Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 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
- 235000013405 beer Nutrition 0.000 description 4
- 235000014171 carbonated beverage Nutrition 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 238000004826 seaming Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 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 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 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 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000013615 primer Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- XFNGYPLLARFULH-UHFFFAOYSA-N 1,2,4-oxadiazetidin-3-one Chemical compound O=C1NON1 XFNGYPLLARFULH-UHFFFAOYSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920003946 DuPont™ Surlyn® 1706 Polymers 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
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HMVUSAGAXUYVQN-UHFFFAOYSA-N chloroethene;ethenyl acetate;2-methylprop-2-enoic acid Chemical compound ClC=C.CC(=O)OC=C.CC(=C)C(O)=O HMVUSAGAXUYVQN-UHFFFAOYSA-N 0.000 description 1
- OAWKUMDOADACKG-UHFFFAOYSA-N chloroethene;ethenyl acetate;prop-2-enoic acid Chemical compound ClC=C.OC(=O)C=C.CC(=O)OC=C OAWKUMDOADACKG-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 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 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
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Description
本発明は、周状側面継目を有する金属製容器に
関するもので、より詳細には継目の接着性、密封
性及び耐腐食性の顕著に改善されたびんの形状の
容器に関する。
金属素材の絞り加工或いは絞り−しごき加工で
形成されたカツプ状成形体から成る上部体と下部
体とを、円周状の開放端部においてラツプ（重ね
合せ）接合し、周状の側面継目を形成させたビン
状の金属製容器は、所謂罐の形の金属製容器に比
して多くの利点を有している。
従来の包装用金属製容器の内、スリーピース罐
と呼ばれるものでは、側面継目を有する罐胴の天
地に夫々罐蓋を二重巻締して密封部を形成させて
おり、またツーピース罐と呼ばれるものでは、金
属素材の絞り加工或いは絞り−しごき加工で形成
されたカツプ状罐胴の開放端部と罐蓋との間で二
重巻締をして密封部を形成させている。
しかしながら、このような二重巻締構造の金属
製容器では、密封部の耐圧性の点で、また金属素
材の材料節約の点で大きな制約を受ける。即ち、
二重巻締による継目においては、継目に加わる荷
重によつて継目を構成する素材が先に変形し、こ
の変形によつて継目での漏洩や継目の破壊が比較
的小さな荷重で生ずるようになる。これを防止す
るためには素材自体の厚みをかなり大きくとらな
ければならない。また、包装容器においては、経
済性の見地からも、容器軽量化の見地からも、用
いる金属素材を薄肉化することが常に要求されて
いるが、容器胴壁を薄肉化する場合には、二重巻
締工程或いはフランジ加工等の準備工程におい
て、容器軸方向に加わる荷重によつて座屈を生じ
やすいという問題がある。
夫々がカツプ状成形体から成る上部体と下部体
とをその開放端部においてラツプ接合して成る金
属製ビンは、継目を形成する素材が著しく薄い場
合にも、素材の厚みに無関係な継目の剪断強度迄
耐えることが可能であり、また巻締工程が不要で
あるため、座屈の恐れなしに容器側壁を薄肉化で
きるという利点を有している。
しかしながら、下部体と上部体とをそれらの周
状開放端部においてラツプ接合して周状の側面継
目を形成する場合には、用いる接着剤及び接着プ
ライマー兼保護塗膜に関して多くの制約が存在す
る。
即ち、罐胴のストレートなラツプ接合の場合に
は、この継目の両端部が罐蓋との巻締により機械
的に固定されるが、前述した周状の側面継目の場
合には、全周にわたつて機械的な固定がなく、継
目自体の寸法変形が容易に生じやすい。また温度
変化により開放端部の径が変化しようとするため
接着層に応力が生じ易い。更に継目を形成する開
放端部が薄肉化されている場合が多く、外力によ
り継目が容易に変形する傾向がある。これらの理
由により、用いる接着剤は、金属素材表面の塗膜
に対して強固な接着力を示すものでなければなら
ないだけでなく、この接着剤層そのものの機械的
強度、寸法安定性が大であり、更に諸物性が熱的
にも経時的にも安定したものでなければならな
い。
更に、用いるプライマー塗膜も前述した苛酷な
条件下でも金属素材及び接着剤層の両者に対して
強い密着性乃至は接着性を示すものでなければな
い。しかも、下部体及び上部体は高度の絞り加工
や絞り−しごき加工で形成されることから、接着
用プライマー兼保護層としての塗膜もこれらの成
形加工に耐え、しかも耐腐食性に優れたものでな
ければならない。
本発明によれば、下部体及び上部体の各々が塗
装金属カツプ状成形体から成り且つ該下部体と上
部体とはそれらの開放端部同志が接着剤を介して
重ね合せ接合されて周状側面継目を形成している
金属製容器であつて、
前記塗装金属カツプ状成形体は、全体当りの塩
化ビニル単位の含有量が30乃至97重量％であり且
つカルボキシル基及び／又は水酸基を10乃至500
ミリモル／100ｇ樹脂の濃度で含有するガラス転
移温度が40℃以上の塩化ビニル系樹脂塗膜を備え
た金属素材で形成され、前記接着剤は酸成分とし
てテレフタル酸成分を50モル％以上、アルコール
成分として１，４−ブタンジオール成分を50モル
％以上で且つ上記以外の酸成分及びアルコール成
分の少なくとも１種を１モル％以上の量で主鎖中
に含有するコポリエステルを主体とする接着剤で
あり、且つ該下部体及び上部体は前記塩化ビニル
系樹脂塗膜及びコポリエステル系接着剤を介して
接合されていることを特徴とする金属製容器が提
供される。
本発明を以下に詳細に説明する。
ビン状の金属製容器の一例を示す第１乃至３図
においてこのビンは、例えば塗装金属製の無継目
カツプ状成形体から成る下部体１と、塗装金属製
の無継目カツプ状成形体から成る上部体２とから
成つており、これらのカツプ状成形体は、開放端
部３と開放端部４とが重ね合せ接合されて、周状
の側面継目５を形成することにより容器の形に一
体化されている。
この具体例において、下部体１は塗装金属素材
の絞り加工で形成された側壁部６と底部７とから
成るカツプであり、上部体２も塗装金属素材の絞
り成形で形成された側壁部８と上壁９とから成る
カツプである。下部体１の側壁６と上部体２の側
壁８とはほぼ同じ径を有しており、この具体例で
は、それらの高さもほぼ同じであつて、継目５は
容器のほぼ中間の高さに位置している。また上部
体２の上壁９は上に凸のテーパー面をなしてお
り、その中央には内容物の充填用乃至は取出し用
の注ぎ口１０が形成されている。かくして、上部
体２は所謂ビンの肩、首及び胴の半分の形で下部
体上に接合されていることが明らかであろう。
第１図に示す具体例では、下部体１の開放端部
３はそれに近接した部分でのネツクイン加工によ
り、それ以外の胴壁部に比して小径となるように
絞られており、より大径の上部体開放端部４内に
嵌挿される。第３図に拡大して示す通り、下部体
及び上部体を構成する塗装金属素材は、表面処理
アルミニウム等の金属基質１１とその表面に施さ
れた接着プライマー兼保護層としての塗膜１２
ａ，１２ｂとから成つている。下部体開放端部３
の外面と上部体開放端部４の内面との間には接着
剤層１３が設けられ、下部体と上部体との接合、
固着が行われている。接着剤１３の一部は継目５
からはみ出して、継目の内側に位置する金属素材
切断端縁１４に対する被覆層１５を形成している
ことが、耐腐食性の点で望ましい。
本発明は、塗膜１２ａ，１２ｂとして、全体当
りの塩化ビニル単位の含有量が30乃至97重量％、
特に好適には50乃至95重量％であり且つカルボキ
シル基及び／又は水酸基を10乃至500ミリモル／
100ｇ樹脂、特に好適には20乃至400ミリモル／
100ｇ樹脂の濃度で含有するガラス転移温度が40
℃以上、特に望ましくは60℃以上の塩化ビニル系
樹脂及び接着剤層１３として、酸成分としてテレ
フタル酸成分を50モル％以上、特に好適には70モ
ル％以上の量で、アルコール成分として１，４−
ブタンジオール成分を50モル％以上、特に好適に
は60モル％以上の量で、しかも上記以外の酸成分
及びアルコール成分の少なくとも１種を１モル％
以上、特に好適には３モル％以上の量で主鎖中に
含有するコポリエステルを主体とする接着剤を組
合せで用い、下部体１及び上部体２を、金属基質
１１、塗膜１２ａ、接着剤１３、塗膜１２ｂ、金
属基板１１の順で接合させることに重要な特徴を
有するものである。
先ず、本発明は、上述した特定の塩化ビニル系
樹脂塗膜と特定のコポリエステル系接着剤とは加
熱により強固な接着結合を生じるという現象を利
用するものである。即ち、本発明者等の研究によ
ると、塩化ビニル系樹脂塗膜にコポリエステル系
接着剤を熱融着させると、両者の接着界面におい
て両樹脂の混じり合いが極めて良好に行われてお
り、これが強固な接着が可能となる原因と考えら
れる。これら両樹脂の化学構造が全く異なるにも
かかわらず、熱融着条件下で両樹脂の混じり合い
が良好に行われるのは、両樹脂の溶解度指数がか
なり接近しているという事実と関連するものと認
められる。
溶解度指数（Solubility Parameter Sp値）と
は、例えばJ.BRANDRUPら編“Polymer
Hondbook”第４章（Johm Wiley ＆ Soons、
Inc.発行、1967年）に定義されているように、凝
集エネルギー密度（cal／c.c.）の1/2乗値として定
義される。この溶解度指数は、熱可塑性樹脂の水
素結合の強さとも密接に関連しており、水酸基、
アミド基、エステル基、ニトリル基或いは塩素原
子等の極性基を重合体主鎖または側鎖に含有する
熱可塑性重合体は、これらの極性基の含有量や分
布状態にも関連し、一般に９以上の高い溶解度指
数を示す。
下記第Ａ表は、ポリ塩化ビニル、ポリエチレン
テレフタレート、ポリブチレンテレフタレートの
Sp値を示す。
第Ａ表 樹 脂 Sp値〔（Cal／c.c.）1/2〕
ポリ塩化ビニル 9.53
ポリエチレンテレフタレート 10.7
ポリブチレンテレフタレート 9.8
共重合体の溶解度指数（Sp値）は共重合体を
構成する各単量体のホモ重合体のSp値から算術
平均値として近似的に求めることもできる。例え
ば、ポリブチレン／エチレン・テレフタレールの
Sp値は下記式
Sp＝Bsp・BM＋Esp・EM ……(1)
式中、BspはポリブチレンテレフタレートのSp
値であり、BMはコポリエステル中のブチレンテ
レフタレート単位のモル分率であり、Espはポリ
エチレンテレフタレートのSp値であり、EMはコ
ポリエステル中のエチレンテレフタレート単位の
モル分率である
によつて近似的に求めることできる。これは共重
合タイプの塩化ビニル系樹脂についても同様であ
る。
塩化ビニル系樹脂塗膜に、通常のポリエチレン
テレフタレートを融着させても殆んど接着は認め
られない。これに対して、エステル連鎖中にブチ
レンテレフタレート単位を導入することにより、
両者の接着強度が顕著に向上するのであつて、こ
の事実は、コポリエステルとすることによる熱接
着性の一般的な増加の他に、両樹脂層の溶解度指
数が接近することにより接着界面での樹脂混和性
の向上が重大な要因となつていることを示唆して
いる。本発明に用いる塗料樹脂とコポリエステル
系接着剤とはSp値の差が1.0（（Cal／c.c.）1/2）以内
、
特に0.8（（Cal／c.c.）1/2）以内にあることが望まし
い。
更に、塩化ビニル系樹脂塗膜を用いることは、
コポリエステル接着剤との強固な接着を可能にす
るという以外は、塗膜の加工性や保護塗膜として
の耐腐食性の点で顕著な利点をもたらす。後に詳
述する如く、塩化ビニル系樹脂は機械的特性と加
工性とに優れた熱可塑性樹脂であり、この塗膜を
備えた金属素材は高度の絞り加工、例えば絞り−
再絞り加工等に賦した場合にも、クラツク、ピン
ホール、シワ等の塗膜欠陥を生じることがない。
しかも、塩化ビニル系樹脂は比較的強い極性を有
する樹脂でありながら耐水性に優れており、しか
も容器内容物中に含まれる金属腐食性成分に対し
ても優れたバリヤー性を示す。
本発明に用いる塩化ビニル系樹脂塗料は、前述
した範囲の塩化ビニル単位を有することも極めて
重要である。塗膜中の塩化ビニル単位の量は、コ
ポリエステルとの接着性と金属基質の耐腐食性と
の両方に関連している。即ち、塗膜中に含まれる
全塩化ビニル単位の量が30重量％よりも少ない場
合には、コポリエステルに対する接着力が低下
し、また腐食性成分に対するバリヤー性も低下す
る。一方塩化ビニル単位の含有量が97％を越える
と、塗膜が硬くなり加工性や金属素材との密着性
が低下することになる。
更に、本発明に用いる塩化ビニル系樹脂塗膜
は、金属基体に対する密着性の見地からは、カル
ボキシル基及び水酸基から成る群より選ばれた少
なくとも１種の極性基を前述した範囲の濃度で含
有することも重要であり、この濃度が10ｍ−
mol／100ｇ樹脂よりも低い場合には、金属基体
−塗膜間で剥離を生じる傾向があり、一方この濃
度が500ｍ−mol／100ｇ樹脂よりも高いと塗膜の
耐水性が低下し、耐腐食性も失われるようにな
る。
更にまた、この塩化ビニル系樹脂塗膜は40℃以
上、特に60℃以上のガラス転移温度（Tg）を有
することも重要である。即ち、本発明が対象とす
る周状の側面継目を有する金属製容器において
は、加熱殺菌時、保存時或いは輸送時等において
容器に加わる荷重は殆んどの場合接着剤及び塗膜
に対する剪断力として作用する。可塑剤を20乃至
30重量％程度の比較的多い量で含有する通常の塩
化ビニル系樹脂塗膜においては、ガラス転移温度
が室温附近であり、このような塗膜は前述した剪
断力に耐えられず、金属或いは接着剤層との間で
剥離を生じやすいが、本発明の塗膜は、上述した
ガラス転移温度を有するため、継目に加わる剪断
力に耐え、接着劣化や気密低下を防止し得る。
本発明においては、種々の熱融着型の熱可塑性
接着剤の内でも、前述したコポリエステル系接着
剤を用いることが重要となる。先ず、このコポリ
エステル系接着剤は、既に指摘した通り、塩化ビ
ニル系樹脂塗膜に対して優れた接着力を示すばか
りではなく、他の樹脂から成る接着剤に比して引
張り強度、曲げ強度等の機械的強度が大であり、
継目の接着剤層に加わる剪断力に耐え、苛酷な条
件下においても、接着劣化、気密性低下等を防止
することができる。しかもこのコポリエステル
は、強靭性、可撓性等の性質をも有しているた
め、接着剤層に応力による歪が生じ、継目に変形
が生じた場合にも、継目の破壊や漏洩が防止され
る。更に、このコポリエステル系接着剤は、耐熱
性に優れていると共に、熱接着温度が好都合な範
囲内にあり、またポリアミド系熱接着剤に比して
吸水率が小さく、耐水性、耐熱水性等にも優れて
いる。
このコポリエステル接着剤において、テレフタ
ル酸成分、１，４−ブタンジオール成分及びそれ
以外の酸成分及び／又はジオール成分を、前述し
た量比で含有することも重要である。テレフタル
酸成分は、主としてコポリエステルの耐クリープ
性等の機械的や耐熱性に関連しており、この量が
前記範囲よりも低いとこれらの特性が低下する。
１，４−ブタンジオール成分は主としてコポリエ
ステルの融点以下による接着作業性の向上とコポ
リエステルの可撓性等の性質に関連しており、こ
の量が上記範囲よりも少ないとやはりこれらの特
性が低下する。また、これら以外の酸及び／又は
アルコール成分も融点低下による接着性の向上及
び接着作業性の向上と関連しており、前記範囲よ
りも低いと上記特性に関して満足すべき結果は得
られない。
無継目カツプを構成する金属素材としては、未
処理の鋼板（ブラツクプレート）、各種表面処理
鋼板、例えば錫メツキ鋼板（ブリキ）、亜鉛メツ
キ鋼板、アルミメツキ鋼板、ニツケルメツキ鋼
板、クロムメツキ鋼板等のメツキ鋼板；電解クロ
ム酸処理鋼板等の電解処理鋼板；リン酸及び／又
はクロム酸処理鋼板等の化学処理鋼板や、アルミ
ニウム等の軽金属板或いはこれらの複合材等が使
用される。
金属素材の塗装に用いる塩化ビニル系樹脂とし
ては、前述した要件を満足するものであれば、特
に制限なしに使用し得る。先ず、この塗料は、塩
化ビニル単位を30乃至90重量％の量で含有する
が、この塩化ビニル単位は、後述する他の単量体
との共重合体の形で、或いは一部が該共重合体の
形で、残りの他の一部がストレートな樹脂、即ち
ホモ重合体の形で存在する。一方、塗料中のカル
ボキシル基及び／又は水酸基は、このような極性
基を有するエチレン系不飽和単量体単位と塩化ビ
ニル単位との共重合体の形で塗膜中に存在しても
よいし、また前述した極性基を有する樹脂と塩化
ビニル系樹脂とのブレンド物の形で存在してもよ
い。要するに、本発明においては、塗膜中に共重
合体或いはブレンド物の形であれ、塩化ビニル単
位とカルボキシル基及び／又は水酸基とが前述し
た量及び濃度で含有されればよい。更に、塗膜の
加工性や密着性の点では、塩化ビニル系樹脂は、
その主鎖中に酢酸ビニル単位を含有することが望
ましく、酢酸ビニル単位は塗料当り30重量％以下
の量で存在することができる。
カルボキシル基を与えるエチレン系不飽和単量
体の適当な例は、アクリル酸、メタクリル酸、フ
マル酸、無水マレイン酸、クロトン酸、イタコン
酸、シトラコン酸、テトラヒドロ無水フタル酸等
であり、水酸基を与える単量体の適当な例は、ビ
ニルアルコール（即ち酢酸ビニルケン化物）、ヒ
ドロキシエチルアクリレート、ヒドロキシエチル
メタクリレート、ヒドロキシプロピルアクリレー
ト、ヒドロキシプロピルメタクリレート等であ
る。
塩化ビニル系樹脂の適当な例は、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−酢酸ビニル共重合体部分ケン化物、塩化ビニ
ル−酢酸ビニル−アクリル酸共重合体、塩化ビニ
ル−酢酸ビニル共重合体部分ケン化・部分ブチラ
ール化物、塩化ビニル−酢酸ビニル−メタクリル
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、塩化ビニル−酢酸ビニル−ヒド
ロキシエチルアクリレート共重合体、塩化ビニル
−酢酸ビニル−ヒドロキシエチルメタクリレート
共重合体等である。一般にポリ塩化ビニル、塩化
ビニル−酢酸ビニル共重合体のようにカルボキシ
ル基及び／又は水酸基を有さない樹脂は、カルボ
キシル基及び／又は水酸基を有する塩化ビニル共
重合体とのブレンド物の形で使用するのが望まし
い。
これらの塩化ビニル系樹脂は、熱硬化性樹脂、
特に水酸基を有する熱硬化性樹脂、例えばレゾー
ル型及び／又はノボラツク型のフエノール・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、エポキシ樹脂、アルキド樹脂等
の１種又は２種以上と組合せて用いることができ
る。
これらの塩化ビニル系樹脂塗料は、トルエン、
キシレン等の芳香族炭化水素系溶媒；アセトン、
メチルエチルケトン、メチルイソブチルケトン、
シクロヘキサノン等のケトン系溶媒；エタノー
ル、プロパノール、ブタノール等のアルコール系
溶媒；エチルセロソルブ、ブチルセロソルブ等の
セロソルブ系溶媒；酢酸エチル、酢酸ブチル等の
エステル系溶媒等の１種又は２種以上に溶解させ
た有機溶媒溶液塗料の形で用いることができ、更
にこれらの有機溶媒溶液塗料に、塩化ビニル重合
体粒子を懸濁させた所謂オルガノゾル塗料の形で
用いることができる。この塗料は、固形分濃度が
10乃至50重量％の範囲内で、塗装に適した粘度で
金属素材への塗布に用いられる。塗装は、ローラ
塗布、ブラシ塗布、ドクターコータ、スプレー塗
布、静電塗装、浸漬塗布等の任意の手段で行うこ
とができる。金属素材への塗工量は、乾燥基準で
0.5乃至30ｇ／m2、特に１乃至20ｇ／m2の範囲と
することが、本発明の目的に好都合である。塗装
後の金属素材は、熱風炉、赤外線加熱炉等におい
て、150乃至350℃で５秒乃至30分間焼付けて所望
の塗膜とする。
既に詳述した通り、本発明において、塩化ビニ
ル系樹脂塗膜は、40℃以上のガラス転移温度を有
することが重要である。この点に関して、本発明
の塩化ビニル系樹脂塗膜は、可塑剤を全く含有し
ないか、或いは含有するとしても、ガラス転移温
度が40℃よりも低くならない範囲の比較的少量で
含有すべきである。また、塩化ビニル系樹脂中に
組込まれた酢酸ビニル単位もガラス転移温度を低
下させる傾向があるので、ガラス転移温度が上記
範囲内となる範囲で酢酸ビニル単位を組込むべき
である。
この塩化ビニル系樹脂には、それ自体公知の配
合剤を配合し得る。例えば、ジオクチルフタレー
ト、エポキシ化大豆油等の可塑剤は上記制限内で
使用でき、またステアリン酸カルシウム、ステア
リン酸亜鉛、有機錫化合物、有機リン酸エステル
等の熱安定剤や、ミクロクリスタリンワツクス、
高級脂肪酸アミド等の滑剤や、炭酸カルシウム、
焼成クレイ等の充填剤をそれ自体公知の処方で配
合し得る。
無継目カツプを得るために、上述した塗装金属
素材を円板等の形状に打抜き、絞りポンチと絞り
ダイスとの間で、１段或いは多段の絞り加工に付
し、所望により絞りカツプをしごきポンチとしご
きダイスとの間で多段のしごき加工に賦す。これ
らの絞り加工やしごき加工の操作や条件は、それ
自体公知のものであり、それ自体公知の条件で行
うことができる。
加工に対する塗装金属素材の素板厚は、容器の
最終寸法や素材の種類によつても相違するが、一
般に0.10乃至0.5mm、特に0.2乃至0.35mmの範囲に
あるのが望ましく、一方しごき加工を行う場合に
はその側壁部の厚みは0.05乃至0.20mm、特に0.06
乃至0.17mmとなるようにするのがよい。
本発明においては、塗装金属素材に絞り成形、
或いは絞り−再絞り（深絞り）成形を行つて、カ
ツプ状成形体を製造することが望ましいが、未塗
装の金属素材に絞り−しごき加工を行つてカツプ
状成形体を製造し、このカツプ状成形体に前記塩
化ビニル系樹脂塗料を塗装することも勿論可能で
ある。
本発明に用いるコポリエステル系接着剤も、主
鎖中に、テレフタル酸成分を酸成分として50モル
％以上、１，４−ブタンジオール成分をアルコー
ル成分として50モル％以上含有し且つ上記以外の
酸成分及びアルコール成分の少なくとも１種を１
モル％以上含有するコポリエステルを主体とする
という条件下で、コポリエステル単独、コポリエ
ステル同志あるいはコポリエステルとホモポリエ
ステルとのブレンド物或いはコポリエステル或い
は上記ブレンド物と他の熱可塑性樹脂とのブレン
ド物であり得る。
テレフタル酸以外の酸成分としては、イソフタ
ル酸、ナフタレンジカルボン酸、ジフエニルジカ
ルボン酸、ジフエニルメタンジカルボン酸、アジ
ピン酸、セバチン酸、マレイン酸、フマール酸、
コハク酸、ヘキシヒドロテレフタル酸等を挙げる
ことができ、また１，４−ブタンジオール以外の
アルコール成分としては、エチレングリコール、
プロピレングリコール、ネオペンチルグリコー
ル、ジエチレングリコール、トリエチレングリコ
ール、シクロヘキサンジオール、キシレングリコ
ール等を挙げることができる。
このコポリエステルは、機械的特性の点から
は、十分に高い分子量を有するべきであり、一般
に6000以上、特に9000乃至500000の数平均分子量
を有することが望ましい。更に、このコポリエス
テルは、前述した耐クリープ性の見地から、密度
法で測定して、３乃至45％、５乃至40％の結晶化
度を有することが好ましい。更に、このコポリエ
ステルは、熱接着作業性の見地から、80乃至280
℃、特に90乃至240℃の融点を有することが望ま
しい。
上述したコポリエステルは単独でも、或いは２
種以上のブレンド物でも使用し得る他、他の熱可
塑性樹脂、例えばポリエチレン、ポリプロピレ
ン、エチレン−プロピレン共重合体、エチレン−
ブテン−１共重合体、イオン架橋オレフイン共重
合体（アイオノマー）、エチレン−酢酸ビニル共
重合体、エチレン−アクリル酸共重合体、酸変性
ポリエチレン、酸変性ポリプロピレン等のオレフ
イン系樹脂等のブレンド物の形でも使用し得る。
勿論、これらのオレフイン系樹脂は接着剤全体の
50重量％を越えない範囲、特に30重量％以下の量
で使用される。
本発明において接着剤は、カツプの接合すべき
開放端縁部に、カツプ相互の嵌合に先立つて施こ
す。この接着剤層は、樹脂層の厚みが10乃至
200μｍ、特に20乃至150μｍとなるように施こす
のがよく、且つ重ね合せ接合部の巾、即ちラツプ
巾が１乃至30mm、特に２乃至20mmとなるように施
すのがよい。
接着剤樹脂は、種々の形態、例えばフイルム、
粉体、スラリー、溶液、プラスチゾル乃至はエマ
ルジヨンの形で所望とするカツプの部分に施こす
ことができ、特に上記接着剤は、取扱い及び塗布
操作が容易で、乾燥等の操作が容易なフイルムの
形で施用することも有利な点である。
接着剤の施用は、接着剤の形態に応じて、ラミ
ネート、押出（エクストルード）、静電粉体塗装、
電着塗装、スプレーコート、ノズル吐出、デイツ
プコート、ロールコート、ブラツシング（刷毛塗
り）等の塗布方式を採用できる。
金属素材の接合すべき部分に前記塗料が施され
ているので、この塗料は接着剤に対してプライマ
ーとして作用し、望ましい接着性が得られる。
カツプの円周状開放端部を重ね合せ接合する場
合には、継目の内側に必然的に金属素材のカツト
エツジが露出する。このカツトエツジを、カツプ
の嵌合に先立つて、接着剤テープで包み込む或い
は接着剤の粉末、スラリー、溶液をこのカツトエ
ツジに施こして、カツトエツジの保護を行うこと
もできる。
接着剤は、継目の内側或いは外側となるカツプ
開放端縁部の外面或いは内面に施こすことがで
き、また両面に施こすこともできる。
接着剤を施したカツプに他方のカツプを嵌合さ
せ、次いで重ね合せ部に存在する接着剤を溶融さ
せ、必要により継目を冷却して継目を形成させ
る。重ね合せ部の加熱は、高周波誘導加熱、赤外
線加熱、熱風加熱、加熱体からの伝熱加熱等によ
ることができ、また継目の冷却は放冷、空冷、水
冷等の任意の操作によることができる。
この際、継目の外方となる開放端部と継目の内
方となる開放端部との間で接着剤層が圧接挾持さ
れる状態で接着剤の溶融を行うことが、気密性及
び接着力に優れた継目を形成させる上で有利であ
り、一般に、周状の重ね合せ接合を形成する両開
放端部の内、内側に位置するものの外径をDI、
外側に位置するものの内径をDO、両者の間に介
在させる接着剤層の厚みをdAとしたとき、下記不
等式
DO−DI＜2dA
が成立するようにこれらの諸寸法を選び且つ接着
後の接着剤の厚みが10乃至150μｍ特に10乃至
100μｍとなるようにするのが望ましい。
また、カツプの嵌合に際しては、外側に位置す
る開放端部を加熱による膨脹させておくと嵌込み
が容易である。
本発明による周状側面継目を有するビン状金属
製容器は、炭酸飲料、ビール、発泡酒等の自生圧
力を有する内容物に対する容器として、また窒素
ガス、液体窒素等を内容物と共に充填する内圧容
器等として特に有用である。
本発明を次の例で説明する。
（参照）
〔塗料の調整〕
以下の実施例に使用する塗料は、下記(1)〜(6)の
成分をそれぞれ表１に記した割合に混合し、不揮
発分が25重量％となるように溶剤に溶解及び／又
は分散したものである。
(1) 塩化ビニル樹脂：QYNV−２（U.C.C.社製ビ
ニル樹脂、商品名）
(2) 塩化ビニル系共重合樹脂：
オートクレーブ中に、加水分解率80％のポリ
ビニルアルコール0.6ｇを溶解した水300ml、ア
ゾビスイソブチニトリル0.15ｇ及び酢酸ビニル
モノマー10ｇを加え、ドライアイス−メタノー
ル浴中で−20℃に冷却した。次いで液状の塩化
ビニルモノマー90ｇをすばやく加えた。温度を
58℃に上げ、かく拌しながら３時間重合を行な
つた。得られたポリマーは、重合度325、塩化
ビニル／酢酸ビニル＝91／９（重量％）の組成
であつた（これをＶ−１とする）。
同様にして、重合度310、塩化ビニル／酢酸
ビニル＝87／13（重量％）（Ｖ−２）；重合度
290、塩化ビニル／酢酸ビニル＝80／20（重量
％）（Ｖ−３）、の塩化ビニル−酢酸ビニル共重
合体を合成した。
また、重合度295、塩化ビニル／酢酸ビニ
ル／無水マレイン酸＝86／10／３（重量％）（Ｖ
−４）の３元共重合体も同様の方法で合成し
た。
また、前記塩化ビニル−酢酸ビニル共重合体
Ｖ−１、Ｖ−３をアルカリで部分ケン化するこ
とにより、塩化ビニル−酢酸ビニル−ビニルア
ルコール共重合体を得た。それぞれ、重合度
325、塩化ビニル／酢酸ビニル／ビニルアルコ
ール＝91／３／６（重量％）（Ｖ−５）；重合度
290、塩化ビニル／酢酸ビニル／ビニルアルコ
ール＝80／５／15（重量％）（Ｖ−６）の組成で
あつた。
(3) エポキシ樹脂：Epon828（シエル化学社製品、
商品名、ビスフエノールＡ型エポキシ樹脂、平
均分子量380、エポキシ当量184〜194）
(4) アミノ樹脂：ベツカミンＰ−138（大日本イン
キ社製品、商品名、ブチルエーテル化ユリア樹
脂）
(5) フエノール樹脂：
石炭酸0.5モルとｐ−クレゾール0.5モルを37
％ホルムアルデヒド水溶液1.5モルに溶かし、
触媒としてアンモニア0.15モルを加えて95℃で
３時間反応させた。反応生成物はケトン、アル
コール、炭化水素などから成る混合溶剤で抽出
し、水で洗滌した後水層を取り除き、更に共沸
法で残つた少量の水分を除去し、冷却してレゾ
ール型フエノール樹脂の30％溶液を得た。
(6) 可塑剤：エポキシ化大豆油
また、各塗料の最終的塩化ビニル単位含有
量、及びカルボキシル基と水酸基の赤外スペク
トル特性吸収から検量線法を用いて求めたカル
ボキシル基及び／又は水酸基の濃度、また昇温
速度５℃／分でTMAを用いて測定したガラス
転移温度を表３に示す。
The present invention relates to a metal container having a circumferential side seam, and more particularly to a bottle-shaped container having significantly improved seam adhesion, sealing and corrosion resistance. An upper body and a lower body, which are cup-shaped molded bodies formed by drawing or drawing and ironing of metal materials, are lap-joined at the circumferential open ends, and the circumferential side seams are joined. The formed bottle-shaped metal containers have many advantages over so-called can-shaped metal containers. Among conventional metal containers for packaging, those called three-piece cans have a can lid double-sealed to the top and bottom of the can body, which has side seams, to form a sealed part, and those called two-piece cans In this case, a sealed portion is formed by double seaming between the open end of a cup-shaped can body formed by drawing or drawing-ironing a metal material and the can lid. However, such a double-sealed metal container is subject to major limitations in terms of pressure resistance of the sealed portion and in terms of saving the metal material. That is,
In double-sealed joints, the material that makes up the joint deforms first due to the load applied to the joint, and this deformation causes joint leakage and joint failure to occur with relatively small loads. . In order to prevent this, the material itself must be considerably thicker. In addition, in packaging containers, it is always required to make the metal material used thinner, both from the standpoint of economy and from the standpoint of reducing the weight of the container, but when making the container body wall thinner, there are two There is a problem in that buckling is likely to occur due to loads applied in the axial direction of the container during heavy seaming processes or preparatory processes such as flange processing. A metal bottle made by lap-joining an upper body and a lower body, each made of a cup-shaped molded body, at their open ends, can be used to seal the seam regardless of the thickness of the material, even when the material forming the seam is extremely thin. Since it can withstand up to shear strength and does not require a seaming process, it has the advantage that the side wall of the container can be made thinner without fear of buckling. However, when the lower body and the upper body are lap-joined at their circumferential open ends to form a circumferential side seam, there are many restrictions regarding the adhesive and adhesive primer/protective coating used. . In other words, in the case of a straight lap joint of the can body, both ends of the joint are mechanically fixed by seaming to the can lid, but in the case of the circumferential side joint described above, the joint is secured all around the entire circumference. Since there is no mechanical fixation across the joint, dimensional deformation of the seam itself is likely to occur easily. Furthermore, since the diameter of the open end tends to change due to temperature changes, stress is likely to occur in the adhesive layer. Furthermore, the open ends forming the joints are often thinned, and the joints tend to be easily deformed by external forces. For these reasons, the adhesive used must not only exhibit strong adhesion to the coating film on the surface of the metal material, but also the adhesive layer itself must have high mechanical strength and dimensional stability. Furthermore, the physical properties must be stable both thermally and over time. Furthermore, the primer coating film used must also exhibit strong adhesion or adhesion to both the metal material and the adhesive layer even under the above-mentioned severe conditions. Moreover, since the lower body and upper body are formed by advanced drawing or drawing-iron processing, the coating film that serves as an adhesive primer and protective layer must withstand these forming processes and have excellent corrosion resistance. Must. According to the present invention, each of the lower body and the upper body is made of a painted metal cup-shaped molded body, and the open ends of the lower body and the upper body are overlapped and joined together via an adhesive to form a circumferential shape. It is a metal container forming a side seam, and the coated metal cup-shaped molded product has a vinyl chloride unit content of 30 to 97% by weight per whole, and a carboxyl group and/or hydroxyl group content of 10 to 97% by weight. 500
The adhesive is made of a metal material with a vinyl chloride resin coating having a glass transition temperature of 40°C or more at a concentration of mmol/100g resin, and the adhesive contains 50 mol% or more of a terephthalic acid component as an acid component and an alcohol component. An adhesive mainly composed of a copolyester containing 50 mol% or more of a 1,4-butanediol component and 1 mol% or more of at least one of an acid component and an alcohol component other than the above in the main chain. There is provided a metal container characterized in that the lower body and the upper body are joined via the vinyl chloride resin coating film and the copolyester adhesive. The invention will be explained in detail below. In FIGS. 1 to 3 showing an example of a bottle-shaped metal container, this bottle is composed of a lower body 1 made of a seamless cup-shaped molded body made of, for example, painted metal, and a seamless cup-shaped molded body made of painted metal. These cup-shaped molded bodies are integrally formed into a container shape by overlapping and joining open ends 3 and 4 to form a circumferential side seam 5. has been made into In this specific example, the lower body 1 is a cup consisting of a side wall portion 6 and a bottom portion 7 formed by drawing a painted metal material, and the upper body 2 also has a side wall portion 8 formed by drawing a painted metal material. It is a cup consisting of an upper wall 9. The side walls 6 of the lower body 1 and the side walls 8 of the upper body 2 have approximately the same diameter and, in this embodiment, their heights are also approximately the same, with the seam 5 at approximately the mid-height of the container. positioned. The upper wall 9 of the upper body 2 has an upwardly convex tapered surface, and a spout 10 for filling or taking out the contents is formed in the center thereof. It will thus be clear that the upper body 2 is joined onto the lower body in the form of a so-called shoulder, neck and torso half of a bottle. In the specific example shown in FIG. 1, the open end 3 of the lower body 1 is narrowed to a smaller diameter than the rest of the body wall by neck-in processing in the vicinity of the open end 3. The upper body open end 4 of the diameter is inserted into the upper body open end 4 of the diameter. As shown in an enlarged view in FIG. 3, the painted metal materials constituting the lower body and the upper body include a metal substrate 11 such as surface-treated aluminum and a coating film 12 applied to the surface as an adhesive primer and protective layer.
a, 12b. Lower body open end 3
An adhesive layer 13 is provided between the outer surface of the upper body and the inner surface of the open end 4 of the upper body, and the bonding between the lower body and the upper body,
Fixation is taking place. A portion of the adhesive 13 is attached to the seam 5
From the viewpoint of corrosion resistance, it is desirable to form a coating layer 15 on the cut edge 14 of the metal material located inside the seam so as to protrude from the seam. In the present invention, the coating films 12a and 12b have a vinyl chloride unit content of 30 to 97% by weight,
Particularly preferably 50 to 95% by weight and 10 to 500 mmol/carboxyl group and/or hydroxyl group.
100 g resin, particularly preferably 20 to 400 mmol/
The glass transition temperature contained in the concentration of 100g resin is 40
℃ or higher, preferably 60℃ or higher, and the adhesive layer 13 contains a terephthalic acid component as an acid component in an amount of 50 mol% or more, particularly preferably 70 mol% or more, and an alcohol component of 1, 4-
The amount of butanediol component is 50 mol% or more, particularly preferably 60 mol% or more, and at least one of the acid component and alcohol component other than the above is 1 mol%.
As described above, the lower body 1 and the upper body 2 are bonded to the metal substrate 11, the coating film 12a, and the adhesive using a combination of an adhesive mainly composed of a copolyester that is particularly preferably contained in the main chain in an amount of 3 mol% or more. It has an important feature in that the agent 13, the coating film 12b, and the metal substrate 11 are joined in this order. First, the present invention utilizes the phenomenon that a specific vinyl chloride resin coating film and a specific copolyester adhesive described above form a strong adhesive bond when heated. That is, according to the research conducted by the present inventors, when a copolyester adhesive is heat-sealed to a vinyl chloride resin coating, the two resins are mixed extremely well at the bonding interface between the two. This is thought to be the reason why strong adhesion is possible. Despite the fact that these two resins have completely different chemical structures, their good mixing under heat fusion conditions is related to the fact that the solubility indices of both resins are quite close. It is recognized that For example, the solubility index (Solubility Parameter Sp value) is described in “Polymer
Hondbook” Chapter 4 (Johm Wiley & Soons,
Inc., 1967), it is defined as the 1/2 power of the cohesive energy density (cal/cc). This solubility index is closely related to the strength of hydrogen bonds in thermoplastic resins, and
Thermoplastic polymers containing polar groups such as amide groups, ester groups, nitrile groups, or chlorine atoms in the polymer main chain or side chain generally have a polar group of 9 or more, depending on the content and distribution state of these polar groups. shows a high solubility index. Table A below shows polyvinyl chloride, polyethylene terephthalate, and polybutylene terephthalate.
Indicates Sp value. Table A Resin Sp value [(Cal/cc) 1/2 ] Polyvinyl chloride 9.53 Polyethylene terephthalate 10.7 Polybutylene terephthalate 9.8 The solubility index (Sp value) of the copolymer is It can also be determined approximately from the Sp value of the homopolymer as an arithmetic mean value. For example, polybutylene/ethylene terephthalyl
The Sp value is calculated using the following formula: Sp=Bsp・B M +Esp・E M ...(1) In the formula, Bsp is the Sp of polybutylene terephthalate.
where B M is the mole fraction of butylene terephthalate units in the copolyester, Esp is the Sp value of polyethylene terephthalate, and E M is the mole fraction of ethylene terephthalate units in the copolyester. It can be obtained approximately. This also applies to copolymer type vinyl chloride resins. Even when ordinary polyethylene terephthalate is fused to a vinyl chloride resin coating, almost no adhesion is observed. On the other hand, by introducing a butylene terephthalate unit into the ester chain,
The adhesive strength between the two is significantly improved, and this fact is due to the fact that in addition to the general increase in thermal adhesion due to the use of copolyester, the solubility indices of both resin layers are close to each other, which increases the adhesive strength at the adhesive interface. This suggests that improved resin miscibility is an important factor. The difference in Sp value between the paint resin and copolyester adhesive used in the present invention is within 1.0 ((Cal/cc) 1/2 ),
In particular, it is desirable that it be within 0.8 ((Cal/cc) 1/2 ). Furthermore, using a vinyl chloride resin coating,
In addition to enabling strong adhesion with copolyester adhesives, it offers significant advantages in terms of processability of the coating and corrosion resistance as a protective coating. As will be explained in detail later, vinyl chloride resin is a thermoplastic resin with excellent mechanical properties and processability, and metal materials with this coating are subjected to advanced drawing processing, such as drawing.
Even when subjected to re-drawing, etc., coating film defects such as cracks, pinholes, and wrinkles do not occur.
In addition, vinyl chloride resin has excellent water resistance even though it has relatively strong polarity, and also exhibits excellent barrier properties against metal corrosive components contained in the contents of the container. It is also extremely important that the vinyl chloride resin paint used in the present invention has vinyl chloride units within the range described above. The amount of vinyl chloride units in the coating is related to both the adhesion with the copolyester and the corrosion resistance of the metal substrate. That is, if the amount of total vinyl chloride units contained in the coating film is less than 30% by weight, the adhesion to the copolyester will be reduced and the barrier properties against corrosive components will also be reduced. On the other hand, if the content of vinyl chloride units exceeds 97%, the coating film becomes hard and processability and adhesion to metal materials decrease. Furthermore, from the viewpoint of adhesion to the metal substrate, the vinyl chloride resin coating film used in the present invention contains at least one polar group selected from the group consisting of carboxyl groups and hydroxyl groups in a concentration within the above-mentioned range. It is also important that this concentration is 10m-
If this concentration is lower than 500 mmol/100g resin, there is a tendency for peeling between the metal substrate and the coating film, while if this concentration is higher than 500mmol/100g resin, the water resistance of the coating film will decrease and the corrosion resistance will decrease. Gender is also lost. Furthermore, it is also important that this vinyl chloride resin coating film has a glass transition temperature (Tg) of 40°C or higher, particularly 60°C or higher. That is, in the case of a metal container having a circumferential side seam, which is the object of the present invention, the load applied to the container during heat sterilization, storage, transportation, etc. is almost always a shearing force on the adhesive and coating. act. Plasticizer from 20 to
In ordinary vinyl chloride resin coatings containing a relatively large amount of about 30% by weight, the glass transition temperature is around room temperature, and such coatings cannot withstand the shearing force mentioned above, Although peeling is likely to occur between the coating film and the adhesive layer, the coating film of the present invention has the above-mentioned glass transition temperature, so it can withstand shearing force applied to the joint and can prevent adhesive deterioration and airtightness. In the present invention, it is important to use the above-mentioned copolyester adhesive among various heat-sealable thermoplastic adhesives. First of all, as already pointed out, this copolyester adhesive not only exhibits excellent adhesion to vinyl chloride resin coatings, but also has higher tensile strength and bending strength than adhesives made of other resins. etc. have high mechanical strength,
It can withstand the shearing force applied to the adhesive layer at the seam, and can prevent adhesive deterioration, airtightness, etc. even under severe conditions. Moreover, this copolyester also has properties such as toughness and flexibility, so even if the adhesive layer is strained due to stress and the joint is deformed, it will prevent the joint from breaking or leaking. be done. Furthermore, this copolyester adhesive has excellent heat resistance, has a thermal bonding temperature within a convenient range, has a lower water absorption rate than polyamide thermal adhesives, and has excellent water resistance, hot water resistance, etc. It is also excellent. It is also important that this copolyester adhesive contains a terephthalic acid component, a 1,4-butanediol component, and other acid components and/or diol components in the above-mentioned quantitative ratios. The terephthalic acid component is mainly related to the mechanical and heat resistance of the copolyester, such as creep resistance, and if the amount is lower than the above range, these properties will deteriorate.
The 1,4-butanediol component is mainly related to the improvement of adhesive workability by lowering the melting point of the copolyester and the flexibility of the copolyester, and if this amount is less than the above range, these properties will be impaired. descend. In addition, acid and/or alcohol components other than these are also associated with improved adhesion and adhesive workability by lowering the melting point, and if the content is lower than the above range, satisfactory results regarding the above properties cannot be obtained. Metal materials constituting the seamless cup include untreated steel plates (black plates), various surface-treated steel plates, such as tin-plated steel plates (tin plate), galvanized steel plates, aluminum-plated steel plates, nickel-plated steel plates, chrome-plated steel plates, and other plated steel plates; Electrolytically treated steel plates such as electrolytic chromic acid treated steel plates; chemically treated steel plates such as phosphoric acid and/or chromic acid treated steel plates, light metal plates such as aluminum, or composites thereof, etc. are used. The vinyl chloride resin used for coating metal materials may be used without any particular restrictions as long as it satisfies the above-mentioned requirements. First, this paint contains vinyl chloride units in an amount of 30 to 90% by weight, and these vinyl chloride units are in the form of a copolymer with other monomers, which will be described later, or partially in the form of a copolymer. In the form of polymers, the remaining part is present in the form of straight resins, ie homopolymers. On the other hand, carboxyl groups and/or hydroxyl groups in the paint may be present in the paint film in the form of a copolymer of ethylenically unsaturated monomer units having such polar groups and vinyl chloride units. , or may exist in the form of a blend of the above-mentioned polar group-containing resin and vinyl chloride resin. In short, in the present invention, vinyl chloride units and carboxyl groups and/or hydroxyl groups may be contained in the coating film in the above-mentioned amounts and concentrations, whether in the form of a copolymer or a blend. Furthermore, in terms of processability and adhesion of coating films, vinyl chloride resins are
It is desirable to contain vinyl acetate units in the backbone, which may be present in amounts up to 30% by weight per paint. Suitable examples of ethylenically unsaturated monomers that provide carboxyl groups are acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, crotonic acid, itaconic acid, citraconic acid, tetrahydrophthalic anhydride, etc., which provide hydroxyl groups. Suitable examples of monomers are vinyl alcohol (ie saponified vinyl acetate), hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and the like. Suitable examples of the vinyl chloride resin include polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, partially saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-acrylic acid copolymer, and vinyl chloride-vinyl acetate copolymer. Partially saponified/partially butyralized vinyl acetate copolymer, vinyl chloride-vinyl acetate-methacrylic acid copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, vinyl chloride-vinyl acetate-hydroxyethyl acrylate copolymer , vinyl chloride-vinyl acetate-hydroxyethyl methacrylate copolymer, and the like. Generally, resins that do not have carboxyl groups and/or hydroxyl groups, such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymers, are used in the form of a blend with vinyl chloride copolymers that have carboxyl groups and/or hydroxyl groups. It is desirable to do so. These vinyl chloride resins are thermosetting resins,
In particular, thermosetting resins having hydroxyl groups, such as resol type and/or novolac type phenol-aldehyde resins, urea-aldehyde resins, melamine-aldehyde resins,
It can be used alone or in combination with two or more of aldehyde resins, epoxy resins, alkyd resins, etc. These vinyl chloride resin paints contain toluene,
Aromatic hydrocarbon solvents such as xylene; acetone,
Methyl ethyl ketone, methyl isobutyl ketone,
Dissolved in one or more of the following: ketone solvents such as cyclohexanone; alcohol solvents such as ethanol, propanol, butanol; cellosolve solvents such as ethyl cellosolve and butyl cellosolve; and ester solvents such as ethyl acetate and butyl acetate. It can be used in the form of an organic solvent solution paint, and furthermore, it can be used in the form of a so-called organosol paint in which vinyl chloride polymer particles are suspended in these organic solvent solution paints. This paint has a solid content concentration of
It is used for coating metal materials with a viscosity suitable for painting within the range of 10 to 50% by weight. Coating can be performed by any means such as roller coating, brush coating, doctor coater, spray coating, electrostatic coating, and dip coating. The amount of coating on metal materials is on a dry basis.
A range of 0.5 to 30 g/m 2 , especially 1 to 20 g/m 2 is advantageous for the purposes of the invention. The coated metal material is baked in a hot air oven, infrared heating furnace, etc. at 150 to 350°C for 5 seconds to 30 minutes to form the desired coating film. As already detailed, in the present invention, it is important that the vinyl chloride resin coating film has a glass transition temperature of 40° C. or higher. In this regard, the vinyl chloride resin coating of the present invention should contain no plasticizer at all, or if it does contain it, it should be contained in a relatively small amount such that the glass transition temperature does not fall below 40°C. . Furthermore, since vinyl acetate units incorporated into vinyl chloride resins also tend to lower the glass transition temperature, the vinyl acetate units should be incorporated within a range where the glass transition temperature is within the above range. This vinyl chloride resin may be blended with compounding agents known per se. For example, plasticizers such as dioctyl phthalate and epoxidized soybean oil can be used within the above limits, as well as heat stabilizers such as calcium stearate, zinc stearate, organotin compounds, organophosphate esters, microcrystalline wax,
Lubricants such as higher fatty acid amides, calcium carbonate,
Fillers such as calcined clay may be incorporated in per se known formulations. In order to obtain a seamless cup, the above-mentioned painted metal material is punched into a shape such as a disk, subjected to one-stage or multi-stage drawing processing between a drawing punch and a drawing die, and if desired, the drawn cup is ironed and punched. It is subjected to multi-stage ironing processing between the ironing die and the ironing die. The operations and conditions for these drawing and ironing processes are known per se, and can be performed under conditions known per se. The thickness of the painted metal material for processing varies depending on the final dimensions of the container and the type of material, but it is generally desirable to be in the range of 0.10 to 0.5 mm, especially 0.2 to 0.35 mm. If the thickness of the side wall is 0.05 to 0.20 mm, especially 0.06
It is preferable that the thickness be between 0.17 mm and 0.17 mm. In the present invention, the painted metal material is drawn and formed.
Alternatively, it is preferable to perform drawing-re-drawing (deep drawing) to produce a cup-shaped molded object. Of course, it is also possible to coat the molded body with the vinyl chloride resin paint. The copolyester adhesive used in the present invention also contains, in the main chain, 50 mol% or more of a terephthalic acid component as an acid component, 50 mol% or more of a 1,4-butanediol component as an alcohol component, and other acids other than the above. At least one of the ingredients and the alcohol ingredient is 1
A copolyester alone, a copolyester or a blend of a copolyester and a homopolyester, or a blend of a copolyester or the above blend with another thermoplastic resin, provided that the main component is a copolyester containing mol% or more. It can be. Acid components other than terephthalic acid include isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylmethanedicarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid,
Succinic acid, hexyhydroterephthalic acid, etc. can be mentioned, and alcohol components other than 1,4-butanediol include ethylene glycol,
Examples include propylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, cyclohexanediol, xylene glycol, and the like. From the point of view of mechanical properties, this copolyester should have a sufficiently high molecular weight, and it is generally desirable to have a number average molecular weight of 6,000 or more, particularly from 9,000 to 500,000. Furthermore, from the viewpoint of the creep resistance mentioned above, it is preferable that this copolyester has a crystallinity of 3 to 45% and 5 to 40% as measured by the density method. Furthermore, from the viewpoint of thermal bonding workability, this copolyester has a molecular weight of 80 to 280.
It is desirable to have a melting point of 90 to 240°C, particularly 90 to 240°C. The copolyesters mentioned above may be used alone or in combination.
Blends of more than one species can also be used, as well as other thermoplastic resins such as polyethylene, polypropylene, ethylene-propylene copolymers, ethylene-
Blends of olefin resins such as butene-1 copolymer, ionically crosslinked olefin copolymer (ionomer), ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, acid-modified polyethylene, acid-modified polypropylene, etc. It can also be used in the form
Of course, these olefin resins
It is used in an amount not exceeding 50% by weight, especially not more than 30% by weight. In the present invention, the adhesive is applied to the open end edges of the cups to be joined prior to fitting the cups together. This adhesive layer has a resin layer thickness of 10 to 10 mm.
The thickness is preferably 200 μm, particularly 20 to 150 μm, and the width of the overlapping joint, that is, the lap width is preferably 1 to 30 mm, particularly 2 to 20 mm. Adhesive resins can be used in various forms, such as films,
The adhesive can be applied to the desired part of the cup in the form of a powder, slurry, solution, plastisol or emulsion.In particular, the above-mentioned adhesive can be applied in the form of a film that is easy to handle, apply, and dry. Application in the form is also advantageous. Depending on the form of the adhesive, adhesive application may include lamination, extrusion, electrostatic powder coating,
Application methods such as electrodeposition coating, spray coating, nozzle discharge, dip coating, roll coating, and brushing can be adopted. Since the paint is applied to the parts of the metal materials to be joined, the paint acts as a primer for the adhesive and provides desired adhesion. When the circumferential open ends of the cups are overlapped and joined together, the cut edge of the metal material is inevitably exposed inside the seam. The cut edge may also be protected by wrapping it with adhesive tape or by applying an adhesive powder, slurry or solution to the cut edge prior to mating the cup. The adhesive can be applied to the outside or inside surface of the open end of the cup, which is the inside or outside of the seam, or can be applied to both sides. The cup coated with adhesive is fitted onto the other cup, and then the adhesive present in the overlapping portion is melted and the seam is cooled if necessary to form a seam. Heating of the overlapping part can be done by high frequency induction heating, infrared heating, hot air heating, heat transfer heating from a heating element, etc., and cooling of the joint can be done by any operation such as air cooling, air cooling, water cooling, etc. . At this time, it is important to melt the adhesive while the adhesive layer is pressed and clamped between the open end on the outside of the seam and the open end on the inside of the seam to ensure airtightness and adhesive strength. Generally speaking, the outer diameter of the inner side of both open ends forming a circumferential overlapping joint is D I ,
When the inner diameter of the outer one is D O and the thickness of the adhesive layer interposed between the two is d A , these dimensions are selected so that the following inequality D O − D I <2d A holds, and The thickness of the adhesive after bonding is 10 to 150μm, especially 10 to 150μm.
It is desirable that the thickness be 100 μm. Further, when fitting the cup, it is easier to fit the cup if the open end located on the outside is expanded by heating. The bottle-shaped metal container having a circumferential side seam according to the present invention can be used as a container for contents having autogenous pressure such as carbonated drinks, beer, and low-malt beer, and as an internal pressure container for filling nitrogen gas, liquid nitrogen, etc. together with the contents. It is particularly useful as The invention is illustrated by the following example. (Reference) [Adjustment of paint] The paint used in the following examples was prepared by mixing the following components (1) to (6) in the proportions shown in Table 1 so that the nonvolatile content was 25% by weight. It is dissolved and/or dispersed in a solvent. (1) Vinyl chloride resin: QYNV-2 (vinyl resin manufactured by UCC, trade name) (2) Vinyl chloride copolymer resin: 300 ml of water in which 0.6 g of polyvinyl alcohol with a hydrolysis rate of 80% was dissolved in an autoclave, 0.15 g of azobisisobutynitrile and 10 g of vinyl acetate monomer were added, and the mixture was cooled to -20°C in a dry ice-methanol bath. Then 90 g of liquid vinyl chloride monomer was quickly added. temperature
The temperature was raised to 58°C, and polymerization was carried out for 3 hours while stirring. The obtained polymer had a degree of polymerization of 325 and a composition of vinyl chloride/vinyl acetate=91/9 (wt%) (this is designated as V-1). Similarly, polymerization degree 310, vinyl chloride/vinyl acetate = 87/13 (wt%) (V-2); polymerization degree
290, vinyl chloride/vinyl acetate = 80/20 (wt%) (V-3), a vinyl chloride-vinyl acetate copolymer was synthesized. In addition, the degree of polymerization is 295, vinyl chloride/vinyl acetate/maleic anhydride = 86/10/3 (wt%) (V
-4) The terpolymer was also synthesized in the same manner. Furthermore, vinyl chloride-vinyl acetate-vinyl alcohol copolymers were obtained by partially saponifying the vinyl chloride-vinyl acetate copolymers V-1 and V-3 with an alkali. respectively, degree of polymerization
325, vinyl chloride/vinyl acetate/vinyl alcohol = 91/3/6 (wt%) (V-5); degree of polymerization
290, the composition was vinyl chloride/vinyl acetate/vinyl alcohol=80/5/15 (wt%) (V-6). (3) Epoxy resin: Epon828 (Ciel Chemical Co., Ltd. product,
Product name, bisphenol A type epoxy resin, average molecular weight 380, epoxy equivalent 184-194) (4) Amino resin: Betsukamine P-138 (product of Dainippon Ink Co., Ltd., product name, butyl etherified urea resin) (5) Phenol resin : 0.5 mol of carbolic acid and 0.5 mol of p-cresol at 37
% formaldehyde aqueous solution 1.5 mol,
0.15 mol of ammonia was added as a catalyst, and the mixture was reacted at 95°C for 3 hours. The reaction product is extracted with a mixed solvent consisting of ketones, alcohols, hydrocarbons, etc., washed with water, the aqueous layer is removed, a small amount of remaining water is removed by an azeotropic method, and the product is cooled to obtain a resol type phenolic resin. A 30% solution of was obtained. (6) Plasticizer: Epoxidized soybean oil In addition, the final vinyl chloride unit content of each paint and the carboxyl group and/or hydroxyl group content determined using the calibration curve method from the infrared spectral characteristic absorption of carboxyl group and hydroxyl group. The concentrations and glass transition temperatures measured using TMA at a heating rate of 5° C./min are shown in Table 3.
以下に実施例に使用するコポリエステルあるい
はそれを主体とする接着剤試料等は次に述べる方
法に従つて作成した。はじめに各々あらかじめ所
定の、相当する酸成分、アルコール成分を約
0.04wt％に相当するテトラ−ｎ−ブチルチタネー
ト等の触媒とともにガラス製反応装置に仕込み、
撹拌しつつ200℃に加熱し、発生するメタノール
を除去しつつ約100分間反応を続け、次いで約260
℃に昇温し0.1〜0.5mmHgの減圧下で約２時間重合
を行つた。得られた重合物はペレツト化した後２
枚のテフロンシートにはさみ、各々の樹脂の融点
もしくは軟化点以上20〜30℃の温度下でホツトプ
レスにより成形して厚さ約80μｍのフイルム状シ
ートを作成した。各試料の最終的な組成はプロト
ンNMR、ガスクロマトグラフイーにより分析し
た。表２にはその分析結果に従つた組成比をモル
％で示した。この重合条件によると、その重合度
は組成とも関連して変化するが、数平均分子量と
して約15000〜35000の範囲のものが得られた。な
お、ブレンド試料Ｂ−１、Ｂ−２についてはそれ
ぞれアイオノマーとしてサーリン1706、別途に重
合したポリエチレンテレフタレート（数平均分子
量約18000）ポリエチレンテレフタレート／イソ
フタレート（組成比70／30）（同約16000）を使用
し、高温型ニーダーを用いそれぞれ約240℃、270
℃窒素雰囲気内でブレンドした後ペレツト化し
た。
Copolyester or adhesive samples mainly composed of copolyester used in the examples below were prepared in accordance with the following method. First, add the corresponding acid components and alcohol components to approx.
It is charged into a glass reactor together with a catalyst such as tetra-n-butyl titanate equivalent to 0.04wt%,
Heat to 200°C with stirring, continue reaction for about 100 minutes while removing generated methanol, then heat to about 260°C.
The temperature was raised to .degree. C., and polymerization was carried out for about 2 hours under reduced pressure of 0.1 to 0.5 mmHg. After pelletizing the obtained polymer, 2
The mixture was sandwiched between two Teflon sheets and molded by hot pressing at a temperature of 20 to 30° C. above the melting point or softening point of each resin to produce a film-like sheet with a thickness of about 80 μm. The final composition of each sample was analyzed by proton NMR and gas chromatography. Table 2 shows the composition ratios in mol% according to the analysis results. According to these polymerization conditions, a number average molecular weight of about 15,000 to 35,000 was obtained, although the degree of polymerization varied depending on the composition. For blend samples B-1 and B-2, Surlyn 1706 and separately polymerized polyethylene terephthalate (number average molecular weight approximately 18,000) and polyethylene terephthalate/isophthalate (composition ratio 70/30) (approximately 16,000) were used as the ionomers for blend samples B-1 and B-2, respectively. approximately 240℃ and 270℃ using a high-temperature kneader, respectively.
℃ in a nitrogen atmosphere and then pelletized.
(イ) 接合部せん断強度の測定
接合後の金属製容器、そして、これに水を充
填して70℃にて10時間経時させたものについ
て、それぞれ高さ方向７cm、円周方向２cmの接
合部を含む試料片を切り出し、テンシロンを用
いて引張り速度100mm／min、室温下でせん断
破壊試験を行い、ラツプ接合部の接着面積を考
慮してせん断強度として表記した。各々３個の
容器について測定し、それらの算術平均値を持
つて測定値とした。なお、ここで54〜57Kg／cm2
以上と表記されているものは、板の破断が生じ
たもので、実際の強度はこれ以上の値である事
を表わしている。
(ロ) 接合部はく離強度の測定
接合後の金属製容器、そして、これに水を充
填して70℃にて10時間経時させたものについ
て、それぞれ接合部を円周状に切り出し、テン
シロンを用いて引張り速度200mm／min、室温
下でＴピール破壊強度を行つた。ラツプ接合部
の幅を考慮した上で各々３個の容器ついて平均
のはくり強度を求め主要な破壊形式を．塗膜
−板間、．塗膜−接着剤、．接着剤、．
塗膜に分類し、目視観察の上表に示した。
(ハ) デンテイングテスト
金属製容器にそれぞれの所定の内容品を充填
した後、図４に示すような、重さ４Kgの錘Ａを
一定高さ（６mm）より水平方向に対して22.5゜
の角度で傾斜した金属製容器Ｂ接合部の外部体
端縁より0.3mmの位置へ垂直に自然落下させる。
この試験で、上部体と底部体とが離別したり
接合部にすき間が発生したものを破胴、23℃で
48時間放置後に内圧を測定した充填直後に比べ
て５％以上の低下が見られるもの、そして接合
部近傍に内容品のにじみ出しが観察されるもの
を漏洩と見なした。表には、上記漏洩と破胴の
総和を漏洩率（％）として示し、カツコ内には
そのうちの破胴率（％）を示した。
なお、試験条件として０℃と25℃を選び試験
体全体が十分その温度に到達しているのを確認
した上で、それぞれ50個の試験を行つた。
(ニ) 落下テスト
金属製容器にそれぞれの所定の内容品を充填
した後、室温下で高さ90cmより(i)底部が下方に
来る向き、(ii)接合部が下方に来る向きの２方向
で各々25本ずつ落下させ、破胴の有無、更に48
時間経過後に漏洩の有無を調べた。表には各々
の場合について、上記漏洩と破胴の総和を漏洩
率（％）として示し、カツコ内にはそのうちの
破胴率（％）を示した。
(ホ) 50℃３ケ月の経時試験
Γ容積変化
あらかじめ充填前の容器の全容積を測定し
たものに、内容物を充填し、経時した後、漏
洩の全く無いものについて再び全容積を測定
して、その差を容積変化△Ｖとした。各々10
個ずつ測定し、それらの算術平均値を結果と
して採用した。
Γ漏洩および破胴率
上部体と底部体が離別したり、あるいはど
ちらかが変形して接合部にすき間の見られる
ものを破胴とした。また；25℃での内圧が、
充填直後に比べて５％以上低下しているも
の、そして、接合部近傍に何らかの内容品の
にじみ出しが観察されるものを漏洩と見なし
た。時には、50個中の漏洩数と破胴数の総和
を漏洩率（％）として示し、カツコ内にはそ
のうちの破胴率（％）を示した。
Γ金属溶出
金属製容器に合成炭酸飲料を充填し、所定
の温度、時間で経時した後、原子吸光法によ
り溶出金属量を測定した。各々10個ずつ測定
し、それらの算術平均値を結果として採用し
た。
実施例１〜８、比較例１〜５
素材厚0.23mmのアルミ板（3004材H19、クロメ
ート処理）の内外面に表１に示した組成から成る
塗料をそれぞれ全体の塗膜量が180mg／ｄm2、80
mg／ｄm2となるように塗布、焼付を行つた後に
250mmの径の円板に打抜き、通常のプレス加工に
より成形を施し、接合部端縁の内径が110.6mmで
中心部に直径30mmの注ぎ口を有する上部体を作製
した。
一方、同じ塗装板より250mmの径の円板を打抜
き、プレス加工により成形を行つて接合部端縁の
外径が110.6mmの下部体を作製した。
この下部体の端縁全周にわたつて、その外面側
約5.5mm巾、内面側約1.5mm巾で以下のように接着
剤を塗布した。すなわち、表２に示したコポリエ
ステル（C1、酸成分中のテレフタル酸含有量80
モル％、グリコール成分中の１，４−ブタンジオ
ール90モル％）から成るフイルムで膜厚80μｍ、
巾７mmのものを、あらかじめ高周波加熱した下部
体外面端縁全周にわたり約1.5mmはみ出るように
貼着し、しかる後、再度端縁を高周波加熱しなが
らこのはみ出し部分をロールにより折り返して内
面側に貼着させ端縁が接着剤ににより被覆された
下部体を作製した。
この様に得られた、上部体と接着剤を塗布した
下部体とを嵌合し、嵌合部を高周波加熱して接着
剤を溶融した後冷却固化させて上部体と下部体を
接合した容量約２の金属製容器を作製した。
これら金属製容器の接合部強度を評価する一方
で、ビールを充填した後注ぎ口を密栓し、65℃30
分の殺菌を施した上で50℃で経時させ、内容積の
変化や漏洩、破胴の有無を観察した。また、炭酸
飲料を充填したものについては、アルミ溶出量を
測定した。さらに、デンテイングテスト、落下テ
ストを行なつて、漏洩、破胴の有無を観察した。
表３にこれらの結果を示す。
(b) Measurement of shear strength of joints For the metal containers after joining, and for those filled with water and aged at 70°C for 10 hours, the joints were measured at 7 cm in the height direction and 2 cm in the circumferential direction, respectively. A sample piece containing the material was cut out, and a shear fracture test was performed using Tensilon at a tensile speed of 100 mm/min at room temperature, and the shear strength was expressed in consideration of the adhesive area of the lap joint. Measurements were made for each of three containers, and the arithmetic mean value was taken as the measured value. In addition, here 54-57Kg/cm 2
Items marked as above indicate that the plate has broken, and the actual strength is greater than this value. (b) Measurement of peel strength of joints The joints of the metal containers after joining and those filled with water and aged at 70°C for 10 hours were cut out in a circumferential shape and measured using Tensilon. T-peel fracture strength was measured at room temperature and a tensile speed of 200 mm/min. After considering the width of the lap joint, calculate the average peel strength for each of the three containers and determine the main failure types. Between the coating film and the plate. Paint film-adhesive, . glue,.
The coating film was classified and visually observed as shown in the table above. (c) Denting test After filling each metal container with the specified contents, a weight A weighing 4 kg is placed at an angle of 22.5° horizontally from a certain height (6 mm) as shown in Figure 4. Let it fall naturally vertically to a position 0.3 mm from the edge of the external body of the metal container B joint part that is inclined at an angle. In this test, if the upper body and bottom body have separated or a gap has occurred at the joint, the body will be broken and heated at 23℃.
If the internal pressure was measured after being left for 48 hours and showed a decrease of 5% or more compared to immediately after filling, or if the content oozed out near the joint, it was considered to be a leak. In the table, the sum of the leakage and shell breakage is shown as a leakage rate (%), and the shell breakage rate (%) is shown in the box. Note that 0°C and 25°C were selected as the test conditions, and after confirming that the entire test specimen had sufficiently reached that temperature, 50 tests were conducted for each. (d) Drop test After filling a metal container with the specified contents, drop the container at room temperature from a height of 90 cm in two directions: (i) with the bottom facing downwards, and (ii) with the joint facing downwards. Drop 25 pieces each, check whether there is a broken shell or not, and then drop 48 pieces each.
After a period of time, the presence or absence of leakage was examined. For each case, the table shows the sum of the leakage and shell breakage as a leakage rate (%), and the shell breakage rate (%) is shown in the box. (e) Aging test for 3 months at 50℃ Γ Volume change The total volume of the container before filling was measured in advance, and the contents were filled with the contents, and after aging, the total volume was measured again for containers with no leakage. , the difference was defined as volume change ΔV. 10 each
They were measured one by one, and their arithmetic mean value was used as the result. Γ leakage and shell fracture rate A shell was defined as a shell in which the upper body and the bottom body were separated, or one of them was deformed and there was a gap at the joint. Also; the internal pressure at 25℃ is
A leak was considered to be a decrease of 5% or more compared to immediately after filling, and a case where some content was observed to ooze out near the joint. Sometimes, the sum of the number of leaks and the number of broken shells out of 50 is shown as the leakage rate (%), and the broken shell rate (%) is shown in the box. Γ Metal Elution A synthetic carbonated beverage was filled into a metal container, and after aging at a predetermined temperature and time, the amount of eluted metal was measured by atomic absorption spectrometry. Ten pieces of each were measured, and their arithmetic mean value was used as the result. Examples 1 to 8, Comparative Examples 1 to 5 A coating having the composition shown in Table 1 was applied to the inner and outer surfaces of an aluminum plate (3004 material H19, chromate treated) with a material thickness of 0.23 mm, with a total coating amount of 180 mg/dm. 2 , 80
After coating and baking to achieve mg/dm 2
A disk with a diameter of 250 mm was punched out and formed by normal press working to produce an upper body having an inner diameter of 110.6 mm at the edge of the joint and a spout with a diameter of 30 mm in the center. On the other hand, a disk with a diameter of 250 mm was punched out from the same painted plate and formed by press working to produce a lower body with an outer diameter of 110.6 mm at the edge of the joint. Adhesive was applied as follows over the entire edge of this lower body to a width of about 5.5 mm on the outer surface and a width of about 1.5 mm on the inner surface. That is, the copolyester shown in Table 2 (C1, terephthalic acid content in the acid component 80
1,4-butanediol (90 mol% in glycol component) with a film thickness of 80 μm.
A piece with a width of 7 mm is pasted so that about 1.5 mm protrudes around the entire circumference of the outer edge of the lower body, which has been previously heated with high frequency. After that, while the edge is heated with high frequency again, this protruding part is folded back with a roll to the inner side. A lower body was prepared by attaching the lower body and having the edges covered with an adhesive. The capacity obtained by fitting the upper body and the lower body coated with adhesive, then heating the fitted part with high frequency to melt the adhesive, and then cooling and solidifying it to join the upper body and the lower body. Approximately 2 metal containers were made. While evaluating the joint strength of these metal containers, after filling with beer, the spout was tightly closed and
After being sterilized for several minutes, it was kept at 50°C and observed for changes in internal volume, leakage, and broken shells. In addition, for those filled with carbonated drinks, the amount of aluminum eluted was measured. Furthermore, a denting test and a drop test were conducted to observe the presence or absence of leakage and shell damage.
Table 3 shows these results.
【表】
実施例９〜18、比較例６〜10
素材厚0.23mmのアルミ板（3004材H19クロメー
ト処理）の内外面に変性ビニル系塗料E1（塩化ビ
ニル単位含有量70.8wt％、水酸基濃度191.1ｍモ
ル／100ｇ樹脂、Tg88℃；表１参照）をそれぞれ
全体の塗膜量が180mg／ｄm2、80mg／ｄm2となな
るように塗布、焼付を行つた後に250mmの径の円
板に打抜き、通常のプレス加工により成形を施
し、接合部端縁の内径が110.6mmで中心部に直径
30mmの注ぎ口を有する上部体を作製した。
一方、同じ塗装板より250mmの径の円板を打抜
き、プレス加工により成形を行つて接合部端縁の
外径が110.6mmの下部体を作製した。
この下部体の端縁全周にわたつて、その外面側
約5.5mm巾、内面側約1.5mm巾で以下のように接着
剤を塗布した。すなわち、表２に各々示した組成
から成るフイルムで膜厚80μｍ、巾７mmのもの
を、あらかじめ高周波加熱した下部体外面端縁全
周にわたり約1.5mmはみ出るように貼着し、しか
る後、このはみ出し部分をロールにより折り返し
再度端縁を高周波加熱しながら内面側に貼着させ
端縁が接着剤により被覆された下部体を作製し
た。
この様に得られた、上部体と接着剤を塗布した
下部体とを嵌合し、嵌合部を高周波加熱して接着
剤を溶融した後冷却固化させて上部体と下部体を
接合した容量約２の金属製容器を作製した。
これら金属製容器の接合部強度を評価する一方
でビールを充填した後注ぎ口を密栓し、65℃30分
の殺菌を施した上で50℃で経時させ、内容積の変
化や漏洩、破胴の有無を観察した。また、デンテ
イングテスト、落下テストを行つて漏洩、破胴の
有無を観察した。表４には、これらの結果を各接
着剤の組成として、酸成分中に占めるテレフタル
酸、グリコール成分中に占める１，４−ブタンジ
オールのそれぞれの含有量とともに示した。[Table] Examples 9 to 18, Comparative Examples 6 to 10 Modified vinyl paint E1 (vinyl chloride unit content 70.8 wt%, hydroxyl group concentration 191.1 mmol/100g resin, Tg 88℃; see Table 1) was applied so that the total coating amount was 180mg/dm 2 and 80mg/dm 2 respectively, and after baking, it was punched into a disc with a diameter of 250mm. , molded using normal press processing, the inner diameter of the joint edge is 110.6 mm, and the diameter in the center is 110.6 mm.
An upper body with a 30 mm spout was fabricated. On the other hand, a disk with a diameter of 250 mm was punched out from the same painted plate and formed by press working to produce a lower body with an outer diameter of 110.6 mm at the edge of the joint. Adhesive was applied as follows over the entire edge of this lower body to a width of about 5.5 mm on the outer surface and a width of about 1.5 mm on the inner surface. That is, a film having a composition shown in Table 2 with a thickness of 80 μm and a width of 7 mm is pasted so as to protrude by approximately 1.5 mm over the entire circumference of the outer edge of the lower body, which has been preheated by high frequency. The portion was folded back with a roll and the edges were again attached to the inner surface while being heated with high frequency to produce a lower body whose edges were coated with adhesive. The capacity obtained by fitting the upper body and the lower body coated with adhesive, then heating the fitted part with high frequency to melt the adhesive, and then cooling and solidifying it to join the upper body and the lower body. Approximately 2 metal containers were made. While evaluating the joint strength of these metal containers, after filling with beer, the spout was sealed, sterilized at 65℃ for 30 minutes, and then aged at 50℃. The presence or absence of was observed. In addition, a denting test and a drop test were conducted to observe the presence or absence of leakage and shell damage. Table 4 shows these results as the composition of each adhesive, together with the respective contents of terephthalic acid in the acid component and 1,4-butanediol in the glycol component.
【表】
実施例 19
素材厚0.23mmのブライト錫メツキ鋼板（Ｔ−１
材、めつき量＃50／50）の内外面に塗料E3（組成
は表１参照）をそれぞれ全体の塗膜量が150mg／
ｄm2、60mg／ｄm2となるように塗布、焼付を行つ
た後に94mmの円板に打抜き、通常のプレス加工に
より成形を施し、接合部端縁の内径が64.48mmで
中心部に直径25mmの注ぎ口を有する上部体を作製
した。
一方、素材厚0.30mmの錫メツキ鋼板を約142mm
の径に打抜き、絞りポンチと絞りダイスとの間で
内径が約85mmのコツプ状に成形する。次いで、こ
のコツプ状成形物を再絞り工程に賦した後、直径
約66.1mmのしごきポンチとダイスによりしごき加
工を施した。この外面に上部体と同一の試料E3
を塗膜量が60mg／ｄm2になるようにマンドレルコ
ーターで塗布後焼付し、更に内面には、エポキシ
ユリア系塗料を塗膜量150mg／ｄm2になるように
スプレーコートし、焼付を行つた後に、ネツクイ
ン加工を行つてその内周端縁の外径が64.40mmの
下部体を作製した。
次いでこの下部体の端縁全周にわたつて、その
外面側約４mm巾、内面側約２mm巾で以下のように
接着剤を塗布した。すなわちコポリエステル接着
剤C4（組成は表２参照）のフイルム、膜厚80μｍ
巾６mmのもの、をあらかじめ高周波加熱した下部
体外面端縁に全周にわたり約２mmはみ出るように
貼着し、しかる後、再度端縁を高周波加熱しなが
らこのはみ出し部分をロールで折り返して内面側
に貼着させ端縁が接着剤により被覆された下部体
を作製した。
このように得られた上部体と接着剤を塗布した
下部体とを嵌合し、嵌合部を高周波加熱して接着
剤を溶融した後冷却固化させて上部体と下部体を
接合した容量約500mlのビン状の金属製容器を作
成した。
これらの金属製容器に合成炭酸飲料を充填した
後注ぎ口を密栓し、キヤンウオーマーにより42℃
で殺菌を施し50℃での経時試験を行うとともに、
落下テスト、０℃と25℃でのデンデイングテスト
を行つて容器の強度を評価したところ、実用上十
分満足できる性能が得られた。[Table] Example 19 Bright tin-plated steel plate with a material thickness of 0.23 mm (T-1
Paint E3 (see Table 1 for composition) was applied to the inner and outer surfaces of the material, plating amount #50/50), with a total coating amount of 150 mg/each.
dm 2 , 60mg/dm 2 , and then punched into a 94mm disk and formed by normal press working, with an inner diameter of 64.48mm at the joint edge and a 25mm diameter in the center. An upper body having a spout was manufactured. On the other hand, a tin-plated steel plate with a material thickness of 0.30 mm is approximately 142 mm thick.
It is punched out to a diameter of , and then formed into a tip shape with an inner diameter of approximately 85 mm between a drawing punch and a drawing die. Next, this pot-shaped molded product was subjected to a re-drawing process, and then ironed using an ironing punch and die having a diameter of about 66.1 mm. Sample E3, which is the same as the upper body, is attached to this outer surface.
was coated with a mandrel coater to a coating amount of 60 mg/dm 2 and then baked. Furthermore, the inner surface was spray-coated with epoxy urea paint to a coating amount of 150 mg/dm 2 and baked. Later, a net-in process was performed to produce a lower body with an outer diameter of 64.40 mm at the inner peripheral edge. Next, adhesive was applied around the entire edge of the lower body to a width of about 4 mm on the outer surface and a width of about 2 mm on the inner surface as described below. That is, a film of copolyester adhesive C4 (see Table 2 for composition), film thickness 80 μm.
A piece with a width of 6 mm is pasted on the edge of the outer surface of the lower body, which has been previously heated with high frequency, so that about 2 mm protrudes from the entire circumference, and then, while the edge is heated with high frequency again, this protruding part is folded back with a roll to the inner side. A lower body was prepared by attaching the lower body and having the edges covered with an adhesive. The upper body thus obtained and the lower body coated with adhesive are fitted together, the fitted part is heated with high frequency to melt the adhesive, and then cooled and solidified to form a bonded capacity of approximately A 500ml bottle-shaped metal container was created. After filling these metal containers with synthetic carbonated beverages, the spouts are tightly closed, and the temperature is heated to 42℃ using a can warmer.
In addition to sterilizing the product and conducting a time-lapse test at 50℃,
When the strength of the container was evaluated by performing a drop test and a dending test at 0°C and 25°C, it was found that the performance was sufficiently satisfactory for practical use.
第１図は、本発明の金属製容器の上部体と下部
体とを夫々別個に示す断面図、第２図は、上部体
と下部体とを重ね合わせ接合して成る本発明の金
属製容器の断面図、第３図は、第２図における接
合部断面の拡大図、第４図は、デンテングテスト
の概略を示す図であつて、
引照数字はそれぞれ、１は下部体、２は上部
体、３及び４は開放端部、５は側面継目、６は薄
肉側壁部、７は底部、９は上壁、１０は注ぎ口、
１１は金属基質、１２ａ，ｂは塗膜、１３は接着
剤、１４は金属素材切断端縁、１５は被覆層を示
す。
FIG. 1 is a sectional view showing separately an upper body and a lower body of a metal container of the present invention, and FIG. 2 is a metal container of the present invention formed by overlapping and joining the upper body and the lower body. 3 is an enlarged view of the cross section of the joint in FIG. 2, and FIG. 4 is a diagram schematically showing the denting test, where 1 is for the lower body and 2 is for the upper body. body, 3 and 4 are open ends, 5 is a side seam, 6 is a thin side wall, 7 is a bottom, 9 is a top wall, 10 is a spout;
11 is a metal substrate, 12a and b are coating films, 13 is an adhesive, 14 is a cut edge of a metal material, and 15 is a coating layer.
Claims (1)
成形体から成り且つ該下部体と上部体とはそれら
の開放端部同志が接着剤を介して重ね合せ接合さ
れて周状側面継目を形成している金属製容器であ
つて、 前記塗装金属カツプ状成形体は、全体当りの塩
化ビニル単位の含有量が30乃至97重量％であり、
カルボキシル基及び／又は水酸基を10乃至500ミ
リモル／100ｇ樹脂の濃度で含有するガラス転移
温度が40℃以上の塩化ビニル系樹脂塗膜を備えた
金属素材で形成され、前記接着剤は酸成分として
テレフタル酸成分を50モル％以上、アルコール成
分として１，４−ブタンジオール成分を50モル％
以上で且つ上記以外の酸成分及びアルコール成分
の少なくとも１種を１モル％以上の量で主鎖中に
含有するコポリエステルを主体とする接着剤であ
り、且つ該下部体及び上部体は前記塩化ビニル系
樹脂塗膜及びコポリエステル系接着剤を介して接
合されていることを特徴とする金属製容器。[Scope of Claims] 1. Each of the lower body and the upper body is made of a coated metal cup-shaped molded body, and the open ends of the lower body and the upper body are overlapped and joined together via an adhesive, and the circumference of the lower body and the upper body is A metal container forming a side seam, the coated metal cup-shaped molded body having a vinyl chloride unit content of 30 to 97% by weight per whole,
It is formed of a metal material with a vinyl chloride resin coating film containing carboxyl groups and/or hydroxyl groups at a concentration of 10 to 500 mmol/100 g of resin and having a glass transition temperature of 40°C or higher, and the adhesive contains terephthalic acid as an acid component. 50 mol% or more of acid component and 50 mol% of 1,4-butanediol component as alcohol component
An adhesive mainly composed of a copolyester having the above and containing at least one of an acid component and an alcohol component other than the above in an amount of 1 mol% or more in the main chain, and the lower body and the upper body are made of the chloride. A metal container characterized by being joined via a vinyl resin coating and a copolyester adhesive.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18611082A JPS5984742A (en) | 1982-10-25 | 1982-10-25 | Vessel made of metal with circumferential side-surface joint |
| US06/544,266 US4556151A (en) | 1982-10-25 | 1983-10-21 | Metal vessel having circumferential side seam and adhesive primer for use in production thereof |
| AU20517/83A AU2051783A (en) | 1982-10-25 | 1983-10-24 | Pvc copolymer blends and their use as adhesive primers for metals |
| GB08328460A GB2132977B (en) | 1982-10-25 | 1983-10-25 | Metal vessel having circumferential side seam and adhesive primer for use in production thereof |
| FR8316953A FR2534881A1 (en) | 1982-10-25 | 1983-10-25 | METAL RECIPIENT WITH PERIPHERAL SIDE SEAL AND ADHESIVE BASE LAYER FOR MANUFACTURING |
| US06/731,384 US4683263A (en) | 1982-10-25 | 1985-05-07 | Metal vessel having circumferential side seam and adhesive primer for use in production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18611082A JPS5984742A (en) | 1982-10-25 | 1982-10-25 | Vessel made of metal with circumferential side-surface joint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5984742A JPS5984742A (en) | 1984-05-16 |
| JPS6330216B2 true JPS6330216B2 (en) | 1988-06-16 |
Family
ID=16182530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18611082A Granted JPS5984742A (en) | 1982-10-25 | 1982-10-25 | Vessel made of metal with circumferential side-surface joint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5984742A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6276135U (en) * | 1985-10-31 | 1987-05-15 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4988685A (en) * | 1972-12-29 | 1974-08-24 | ||
| JPS54143387A (en) * | 1978-04-25 | 1979-11-08 | Toray Industries | Coating metal container |
| JPS57125142A (en) * | 1981-01-23 | 1982-08-04 | Toyo Seikan Kaisha Ltd | Metallic can |
-
1982
- 1982-10-25 JP JP18611082A patent/JPS5984742A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4988685A (en) * | 1972-12-29 | 1974-08-24 | ||
| JPS54143387A (en) * | 1978-04-25 | 1979-11-08 | Toray Industries | Coating metal container |
| JPS57125142A (en) * | 1981-01-23 | 1982-08-04 | Toyo Seikan Kaisha Ltd | Metallic can |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5984742A (en) | 1984-05-16 |
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