JPH01313552A - Food packaging material - Google Patents
Food packaging materialInfo
- Publication number
- JPH01313552A JPH01313552A JP63146044A JP14604488A JPH01313552A JP H01313552 A JPH01313552 A JP H01313552A JP 63146044 A JP63146044 A JP 63146044A JP 14604488 A JP14604488 A JP 14604488A JP H01313552 A JPH01313552 A JP H01313552A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- copolymer
- ethylene
- flavor
- olefin
- 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.)
- Pending
Links
- 239000005003 food packaging material Substances 0.000 title claims description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 229920001400 block copolymer Polymers 0.000 claims abstract description 11
- 229920000098 polyolefin Polymers 0.000 claims abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 8
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims abstract description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001993 dienes Chemical class 0.000 claims abstract description 5
- 238000007127 saponification reaction Methods 0.000 claims abstract description 5
- 150000001336 alkenes Chemical class 0.000 claims abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 3
- -1 vinyl aromatic compound Chemical class 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 229920006026 co-polymeric resin Polymers 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims 1
- 239000000796 flavoring agent Substances 0.000 abstract description 33
- 235000019634 flavors Nutrition 0.000 abstract description 33
- 239000000463 material Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract 1
- 230000004888 barrier function Effects 0.000 description 22
- 239000010410 layer Substances 0.000 description 22
- 235000013305 food Nutrition 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 229920005672 polyolefin resin Polymers 0.000 description 12
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 10
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 9
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000728 polyester 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
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-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
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XHALKWMTKWHQLO-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=CC=2)C(C)(C)C)=C1 XHALKWMTKWHQLO-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- PRQREXSTQVWUGV-UHFFFAOYSA-N 6-ethenoxy-6-oxohexanoic acid Chemical compound OC(=O)CCCCC(=O)OC=C PRQREXSTQVWUGV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 101100084634 Arabidopsis thaliana PBE1 gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000283725 Bos Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate 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
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000000071 blow moulding Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-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
- 229940043350 citral Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000021438 curry Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- DWLAVVBOGOXHNH-UHFFFAOYSA-L magnesium;prop-2-enoate Chemical compound [Mg+2].[O-]C(=O)C=C.[O-]C(=O)C=C DWLAVVBOGOXHNH-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 235000021586 packaging of beverage Nutrition 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- QKNZNUNCDJZTCH-UHFFFAOYSA-N pentyl benzoate Chemical compound CCCCCOC(=O)C1=CC=CC=C1 QKNZNUNCDJZTCH-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- MBDOYVRWFFCFHM-UHFFFAOYSA-N trans-2-hexenal Natural products CCCC=CC=O MBDOYVRWFFCFHM-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical compound C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ジュースやコーヒーなどの飲料、カレーやス
ープなどのレトルト食品などの包装材に適する材料に関
する。特に食品の重要な商品価値の−っである、香気に
ついてその保存性を向上し、且つヒートシール可能な食
品包装用材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a material suitable for packaging of beverages such as juice and coffee, retort foods such as curry and soup, and the like. In particular, the present invention relates to food packaging materials that improve the preservability of aroma, which is an important commercial value of foods, and are heat-sealable.
食品の香気（以下フレーバーと略す）は種々の炭素数の
有機化合物より成っている。例えばテルペン系炭化水素
類（ｄ−リモネン、ミルセンなど）、テルペンアルコー
ル類（α−テルピネオール、リナルール、ゲラニオール
など）、アルコール類（オクタツール、イソアミルアル
コールなど）、アルデヒド類（オクタナール、シトラー
ル、トランス−２−ヘキサナールなど）やエステル類（
エチルカブレイト、アミルベンゾエイト、エチルシナメ
イトなど）等が挙げられる。Food aromas (hereinafter referred to as flavors) are composed of organic compounds with various carbon numbers. For example, terpene hydrocarbons (d-limonene, myrcene, etc.), terpene alcohols (α-terpineol, linalool, geraniol, etc.), alcohols (octatool, isoamyl alcohol, etc.), aldehydes (octanal, citral, trans-2 - hexanal, etc.) and esters (
ethyl cabrate, amylbenzoate, ethylcinnamate, etc.).
これらの香気を保存すべき食品包装用のガスバリヤ−性
（あるいはフレーバーバリヤー性）多層積層体の一般的
な構成はヒートシール可能なポリオレフィン樹脂層、中
間にガスバリヤ−層としてエチレン−ビニルアルコール
共重合体（以下ＥＶＯＨと略す）、ポリ塩化ビニリデン
樹脂、ポリアミド樹脂の様なガスバリヤ−性樹脂やアル
ミニウムなどの金属箔、そしてその外側に支持層或いは
保護層としてのポリオレフィン樹脂やポリエステル樹脂
、塩化ビニル樹脂、ポリスチレン樹脂などの合成樹脂層
より成っている。そしてこれらの各層は、接着剤層によ
って積層されているのか一般的である。The general structure of gas barrier (or flavor barrier) multilayer laminates for food packaging that preserves aroma is a heat-sealable polyolefin resin layer, and an ethylene-vinyl alcohol copolymer as a gas barrier layer in the middle. (hereinafter abbreviated as EVOH), polyvinylidene chloride resin, gas barrier resin such as polyamide resin, metal foil such as aluminum, and on the outside as a support layer or protective layer polyolefin resin, polyester resin, vinyl chloride resin, polystyrene. It is made of a synthetic resin layer such as resin. Each of these layers is generally laminated with an adhesive layer.
特に、内面側のヒートシーラント層としてのポリオレフ
ィン樹脂とガスバリヤ−樹脂や金属箔は互いに親和性か
ない。この事はポリエチレンやポリプロピレンで代表さ
れるポリオレフィン樹脂か無極性である事から容易に想
像できる。従って一般的にはポリエステル系やアクリル
系やポリウレタン系などの接着剤を介して積層するラミ
ネート法やポリオレフィン樹脂を有機過酸化物と不飽和
カルボン酸無水物を押出溶融クラフトしたものや熱キシ
レンにポリオレフィン樹脂を溶解し有機過酸化物でカル
ボン酸無水物をクラフトする方法などによって得られる
いわゆる変性ポリオレフィンを接着剤層とした多層共押
出法によって積層体を得る方法は良く知られており公知
である。In particular, the polyolefin resin used as the inner heat sealant layer and the gas barrier resin or metal foil have no affinity with each other. This can be easily imagined from the fact that polyolefin resins such as polyethylene and polypropylene are nonpolar. Therefore, in general, lamination methods are used in which adhesives such as polyester, acrylic, or polyurethane are used, extrusion melt crafting of polyolefin resin with organic peroxide and unsaturated carboxylic acid anhydride, or polyolefin with hot xylene. A method of obtaining a laminate by a multilayer coextrusion method using a so-called modified polyolefin obtained by dissolving a resin and crafting a carboxylic acid anhydride with an organic peroxide as an adhesive layer is well known. .
ところて、包装される食品の改要な商品価値の一つにそ
のフレーバーかある。これは食品の風味の一要素であり
、フレーバー劣化それ自体か商品としての食品の劣化と
言っても過言てはない。このフレーバーは食品中に含ま
れる多数の微量有機成分によってつくられており、その
食品独自の香気は、それら重量有機成分の蒸気濃度のバ
ランスによって形成されている。ところか食品と直接接
するヒートシーラント層としてのポリオレフィン樹脂は
食品中のフレーバーを少なからず収着してしまうので、
ヒートシーラント層を薄くしなければならず、これに伴
うヒートシーラント層ての破れなどがあった。フレーバ
ーの保香性とポリマーとの関係及びフレーバー収着に関
しては渡辺渉ら、日本食品工業学会誌、１０． Ｎｏ
、４．１１８（１９６３）や食品工業別冊、食品の包装
と材料、光群（８５４年）や榛田滋行：ジャパンフード
サイエンス３月号、４９ （１９８７） 、 ＰＲＣＥ
ＥＤｒＮＧＳ ０ＦＦＵＴＵＲＥ−ＰＡＫ’８７ （
ＲＹＤＥＲＡＳＳＯＣＩＡＴＥＳ ＩＮｃ、 ）ＮＯ
ＶＥＭＶＥＲ９−１１，１９８７等に述べられテイル。However, one of the important commercial values of packaged food is its flavor. This is one element of the flavor of food, and it is no exaggeration to say that it is the flavor deterioration itself or the deterioration of the food as a product. This flavor is created by a large number of trace organic components contained in food, and the unique aroma of that food is formed by the balance of the vapor concentration of these heavy organic components. However, the polyolefin resin used as a heat sealant layer that comes into direct contact with food absorbs a considerable amount of the flavor in the food.
The heat sealant layer had to be made thinner, which caused the heat sealant layer to tear. Regarding the relationship between flavor retention and polymers and flavor sorption, see Wataru Watanabe et al., Journal of Japan Food Industry Association, 10. No
, 4.118 (1963), Food Industry Special Edition, Food Packaging and Materials, Hikaru Gun (854), Shigeyuki Shinta: Japan Food Science March Issue, 49 (1987), PRCE
EDrNGS 0FFUTURE-PAK'87 (
RYDERASSOCIATES INc, )NO
The story is described in VEMVER9-11, 1987, etc.
これらによるとガスバリヤ−性とフレーバー保持性の関
係は一次的な関係にある事かわかる。According to these results, it can be seen that the relationship between gas barrier properties and flavor retention is linear.
これらフレーバーの保香性に関する従来技術としてはポ
リエチレンテレフタレート、ＥＶＯＨ。Conventional technologies related to the aroma retention properties of these flavors include polyethylene terephthalate and EVOH.
ナ・イロンのうち１種あるいは２種以上のものを内容物
と接する最内層とする方法（特開昭５７−１６３６５４
および特開昭６Ｏ−４８３４４） 、最内層をポリエス
テルとポリアミドとの混合物とする方法（特開昭６ｌ−
６４４４９） 、最内層を形成する樹脂に食品香料を練
り込む方法（特開昭５９−１７４：１４８，１７４４７
０）、分子量の異なるポリエステルの混合物を内面材と
して用いる方法（特開昭５７−１６３６５４ ）等が知
られている。しかしこれらの方法はいずれもポリオレフ
ィンより融点が高く、ヒートシール性か悪いという問題
かあり、また混錬温度が高いため食品香料を最内層樹脂
に練り込む時熱劣化を起すという問題かあった。A method in which one or more types of Na-Iron are used as the innermost layer in contact with the contents (Japanese Patent Application Laid-Open No. 57-163654
and JP-A-6O-48344), a method in which the innermost layer is a mixture of polyester and polyamide (JP-A-6O-48344);
64449), Method of kneading food flavoring into resin forming innermost layer (JP-A-59-174:148, 17447)
0), a method using a mixture of polyesters having different molecular weights as an inner material (Japanese Patent Application Laid-Open No. 163654/1983), and the like are known. However, all of these methods have a problem that their melting point is higher than that of polyolefin, resulting in poor heat-sealing properties, and the kneading temperature is high, resulting in thermal deterioration when kneading the food flavoring into the innermost layer resin.
本発明の目的は、ポリオレフィン樹脂とＥＶＯＨ及び不
飽和カルボン酸変性スチレン−共役ジエンブロック共重
合体の水素添加誘導体混合物をヒートシール層とする事
によりフレーバーバリヤー性と良ヒートシール性を兼ね
備えた食品包装用材料を提供することにある。The object of the present invention is to provide food packaging that has both flavor barrier properties and good heat sealability by using a heat seal layer of a hydrogenated derivative mixture of polyolefin resin, EVOH, and unsaturated carboxylic acid modified styrene-conjugated diene block copolymer. The aim is to provide materials for
従来の技術はフレーバーバリヤー性はポリオレフィン樹
脂より優れているもののヒートシール性がポリオレフィ
ン樹脂よりも悪いという欠点があった。フレーバーバリ
ヤー性についてはＥＶＯＨか最も優れているもののヒー
トシール性が悪いなどの問題かあり、ＥＶＯＨとポリオ
レフィンの混合物を最内層とする事によりヒートシール
性とフレーバーバリヤー性に優れる包装体にするバがで
きる。ＥＶＯＨとポリオレフィンの混合物に関しては特
公昭５１−３０１０４や特公昭５１−４３４２３、特開
昭５（１（］−６５５４４などの方法か知られていた。Although the conventional technology has better flavor barrier properties than polyolefin resins, it has the disadvantage that heat sealability is worse than polyolefin resins. Regarding flavor barrier properties, EVOH is the best, but there are problems such as poor heat sealing properties, so it is possible to create a package with excellent heat sealing properties and flavor barrier properties by using a mixture of EVOH and polyolefin as the innermost layer. can. Regarding mixtures of EVOH and polyolefin, methods such as Japanese Patent Publication No. 51-30104, Japanese Patent Publication No. 51-43423, and Japanese Unexamined Patent Publication No. 51-1(1)-65544 are known.
しかし、これらの方法はいずれもＥＶＯＨとポリオレフ
ィン樹脂の相溶性か未た不充分て成形物にブツか発生し
成形しずら〈機械的強度の劣るものてあった。従って本
発明の目的はＥＶＯＨとポリオレフィン樹脂との相溶性
を高め、機械的強度に優れしかもヒートシール性、フレ
ーバーバリヤー、成形性に優れた食品包装用材料を得る
ことである。However, in all of these methods, the compatibility between the EVOH and the polyolefin resin was still insufficient, resulting in the formation of bumps in the molded products and poor molding (some had poor mechanical strength). Therefore, an object of the present invention is to improve the compatibility between EVOH and polyolefin resin, and to obtain a food packaging material that has excellent mechanical strength, heat sealability, flavor barrier, and moldability.
（課題を解決するための手段）
本発明は上記の目的を達成すべくなされたものて、その
要旨は、ポリオレフィン系熱可塑性樹脂を５〜７０重量
％、オレフィン−ビニルアルコール樹脂を３０〜９０重
量％及びビニル芳香族化合物重合体ブロックＡと共役ジ
エン重合体ブロックＢとからなる重合体を水素添加した
ブロック共重合体１００重量部に対し不飽和カルボン酸
もしくはその誘導体をクラフト重合した変性共重合体を
２〜２０重量％配合してなる食品包装用材料を用いるこ
とにより解決することか判明した。(Means for Solving the Problems) The present invention has been made to achieve the above object, and its gist is that 5 to 70% by weight of polyolefin thermoplastic resin and 30 to 90% by weight of olefin-vinyl alcohol resin. % and a modified copolymer obtained by craft polymerizing an unsaturated carboxylic acid or a derivative thereof to 100 parts by weight of a block copolymer obtained by hydrogenating a polymer consisting of a vinyl aromatic compound polymer block A and a conjugated diene polymer block B. It has been found that the problem can be solved by using a food packaging material containing 2 to 20% by weight of
本発明に使用するオレフィンビニルアルコール樹脂はエ
チレン−酢酸ビニル共重合体ケン化物、プロピレン−酢
酸ビニルケン化合物等をいい、とりわけ重合か容易な点
てエチレン−酢酸ビニル共重合体ケン化物か良い。ＥＶ
ＯＨとしてはエチレン含罎１５〜６０モル％、酢酸ビニ
ル成分のケン化度９（）モル％以北の組成を有するもの
か好適であり、エチレン含量か１５モル％未満ては溶融
成形性が低下し６０モル％を越えるときはガスバリヤ−
性か低下し、又酢酸ビニル成分のケン化度か９０モル％
未満のときもガスバリヤ−性か低下する。好ましくはヒ
ートシール性、ガスバリヤ−性の点からエチレン含有ｂ
ｋ２５〜４８モル％、ケン化度９６％以上のＥＶＯＨか
良い。なお、エチレンと酢酸ビニル（又はそれをケン化
したビニルアルコール）以外に、アクリル酸、メタクリ
ル酸、クロトン酸、マレイン酸などの不飽和酸或いはそ
のアルキルエステル、プロピレン、ブテン、α−デセン
、α−オクタデセンなどのα−オレフィン等をコモノマ
ーとして少星含んていても差支えない。The olefin vinyl alcohol resin used in the present invention includes a saponified ethylene-vinyl acetate copolymer, a propylene-vinyl acetate compound, and a saponified ethylene-vinyl acetate copolymer is particularly preferred since it is easy to polymerize. EV
It is preferable that the OH has an ethylene content of 15 to 60 mol% and a degree of saponification of the vinyl acetate component of 9 () mol% or more.If the ethylene content is less than 15 mol%, melt moldability will deteriorate. If it exceeds 60 mol%, use a gas barrier.
The saponification degree of vinyl acetate component decreased to 90 mol%.
Gas barrier properties also decrease when it is less than 20%. Preferably ethylene-containing b from the viewpoint of heat sealability and gas barrier properties.
EVOH with k25 to 48 mol% and saponification degree of 96% or more is good. In addition to ethylene and vinyl acetate (or saponified vinyl alcohol), unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and maleic acid, or their alkyl esters, propylene, butene, α-decene, α- There is no problem even if α-olefin such as octadecene is included as a comonomer.
また、ポリオレフィン系樹脂としてはヒートシール性を
加味してポリエチレン、ポリプロピレン、エチレンと炭
素数３〜１２のα−オレフィン共重合体か用いられる。Further, as the polyolefin resin, polyethylene, polypropylene, or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms may be used in consideration of heat sealability.
エチレンと炭素数３〜１２のα−オレフィン共重合体と
しては例えばエチレン−プロピレン共重合体、エチレン
−ブテン−１共重合体、エチレンー４−メチルペンテン
−１共重合体、エチレンーヘキセンー１共重合体等があ
げられる。Examples of copolymers of ethylene and α-olefin having 3 to 12 carbon atoms include ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methylpentene-1 copolymer, and ethylene-hexene-1 copolymer. Examples include polymers.
一方、ビニル芳香族化合物重合体ブロックＡと共役ジエ
ン重合体Ｂとからなる重合体を水素添加したブロック共
重合体１００重合体に対し不飽和カルホン酸もしくはそ
の誘導体をグラフト重合した変性共重合体とは、例えば
スチレン−ツタジエンブロックポリマー（ＳＢＳ）のよ
うなポリスチレン系熱可・Ｗ性エラストマーの分子内二
重結合を水素添加したスチレンーエチレンーフチレンブ
ロック共重合体（以下５ＥＢＳと略す）を、不飽和カル
ホン酸もしくはこれらの誘導体でクラフト変性しその成
分濃度が好ましくは０．旧〜２０玉驕％の変性重合体を
いう。On the other hand, a modified copolymer obtained by graft polymerizing an unsaturated carbonic acid or a derivative thereof to a block copolymer 100 obtained by hydrogenating a polymer consisting of a vinyl aromatic compound polymer block A and a conjugated diene polymer B; is a styrene-ethylene-phthylene block copolymer (hereinafter abbreviated as 5EBS) obtained by hydrogenating the intramolecular double bonds of a polystyrene-based thermoplastic/W-based elastomer such as a styrene-tutadiene block polymer (SBS). , unsaturated carbonic acid or a derivative thereof, and the component concentration is preferably 0. It refers to a modified polymer with a content of 20 to 20%.
５ＥＢＳの製造方法については公知である。例えば特公
昭４２−８７０４号、特公昭４：１−６６：１６号、特
公昭４５−２ ＋１５０４号、特公昭４８−３５５５号
等の各明細書に記載されている。代表的な方法としては
特公昭４０−２３７９８号明細書に記載された方法によ
り、リチウム触媒またはチーグラー型触媒を用い不活性
溶媒中てブロック重合させて得ることかできる。The method for producing 5EBS is known. For example, they are described in the specifications of Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 4:1-66:16, Japanese Patent Publication No. 45-2 +1504, Japanese Patent Publication No. 3555 of 1977, and the like. As a typical method, it can be obtained by block polymerization in an inert solvent using a lithium catalyst or Ziegler type catalyst according to the method described in Japanese Patent Publication No. 40-23798.
これらの水素添加処理は例えば特公昭４２−８７０４号
、特公昭４：１−６６：１６号、特公昭４６−２０８１
４号の各明細書、米国特許明細書再発行２７１４５ ＄
に記載されている方法により、不活性溶媒中て水素添加
触媒の存在Ｆに水素添加される。この水素添加では、重
合体ソロツク中のオレフィン型二重結合の少なくとも５
０％、好ましくは８０％以上か水素添加される。These hydrogenation treatments are described, for example, in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 4:1-66:16, and Japanese Patent Publication No. 46-2081.
Each specification of No. 4, U.S. patent specification reissue 27145 $
The hydrogenation catalyst present F in an inert solvent is hydrogenated by the method described in . This hydrogenation involves at least 5 of the olefinic double bonds in the polymer
0%, preferably 80% or more hydrogenation.
一方、不飽和カルホン酸又はその誘導体としての好まし
い変性田七ツマ−は、好ましくは少なくとも１個のオレ
フィン不飽和を有する不飽和のモノカルボン酸およびポ
リカルボン酸含有酸（Ｃ〜Ｃｌ０）、該醜からの無水物
、塩、エステル、エーテル、アミド、ニトリル、チオー
ル、チオ酸、グリシジル、シアノ、ヒドロキシ、クリコ
ールおよび他の置換誘導体である。On the other hand, preferred modified Tanatsumers as unsaturated carbonic acids or derivatives thereof are preferably unsaturated monocarboxylic and polycarboxylic acids containing at least one olefinic unsaturation (C to Cl0), anhydrides, salts, esters, ethers, amides, nitriles, thiols, thio acids, glycidyl, cyano, hydroxy, glycols and other substituted derivatives from.
このような酸、無水物、およびその誘導体の例には、次
のものかある：マレイン酸、フマル酸、イタコン酸、シ
トラコン酸、アクリル酸、グリシジルアクリレート、シ
アノアクリレート、ヒドロキシＣ１〜Ｃ２ｏアルキルメ
タアクリレートアクリルポリエーテル、無水アクリル酸
、メタクリル酸、クロトン酸、インクロトン酸、メサコ
ン酸、アケリカ酸、無水マレイン酸、無水イタコン酸、
無水シトラコン酸、アクリロニトリル、メタクロロニト
リル、アクリル酸ナトリウム、アクリル醜カルシウムお
よびアクリル酸マクネシウム。Examples of such acids, anhydrides, and derivatives thereof include: maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, glycidyl acrylate, cyanoacrylate, hydroxy C1-C2o alkyl methacrylate. Acrylic polyether, acrylic anhydride, methacrylic acid, crotonic acid, incrotonic acid, mesaconic acid, achelic acid, maleic anhydride, itaconic anhydride,
Citraconic anhydride, acrylonitrile, methachloronitrile, sodium acrylate, acrylic calcium and magnesium acrylate.
中独て、または１種またはそれ以上のカルボン酸あるい
はその誘導体との組合せて用いられ得る他の七ツマ−に
は、Ｃ〜Ｃ５ｏビニルモノマーたとえばアクリルアミド
、アクリロニトリルおよびモノビニル芳香族化合物すな
わちスチレン、クロロスチレン、ブロモスチレン、α−
メチルスチレン、ビニルピリジンなどがある。Other polymers that may be used alone or in combination with one or more carboxylic acids or derivatives thereof include C-C5o vinyl monomers such as acrylamide, acrylonitrile and monovinyl aromatics such as styrene, chlorostyrene. , bromostyrene, α-
Examples include methylstyrene and vinylpyridine.
使用され得る他の七ツマ−は、Ｃ４ないしＣ５゜ビニル
エステル、ビニルエーテルおよびアリルエステルたとえ
ばビニルブチレート、ビニルラウレート、ビニルステア
レート、ビニルアジペートなど、および２個以上のビニ
ル基を有する千ツマ−たとえばジビニルベンゼン、エチ
レンジメタアクリレート、トリアリルホスフィツト、ジ
アルキルシアヌレートおよびトリアリルシアヌレートで
ある。Other polymers that may be used are C4 to C5 vinyl esters, vinyl ethers and allyl esters such as vinyl butyrate, vinyl laurate, vinyl stearate, vinyl adipate, etc., and polymers having two or more vinyl groups. Examples are divinylbenzene, ethylene dimethacrylate, triallylphosphite, dialkyl cyanurate and triallyl cyanurate.
本発明に従い、ブロックコポリマーにグラフトされるべ
き好ましい七ツマ−は、無水マレイン酸、マレイン酸、
フマル酸およびこれらの誘導体である。本分野では、こ
れらの千ツマ−か容易には重合しないことか公知である
。酸化合物は、スルホン酸てあってもよい。Preferred heptamers to be grafted to the block copolymer according to the invention are maleic anhydride, maleic acid,
fumaric acid and their derivatives. It is known in the art that these polymers do not readily polymerize. The acid compound may be a sulfonic acid.
クラフト鎖か少なくとも２種のモノマー（基本ポリマー
モノマーに対し追加的なモノマー）を含むクラフトコポ
リマーを達成するため千ツマ−の混合物を加えてよいの
は当然である。Of course, mixtures of thousands of monomers may be added to achieve kraft copolymers containing kraft chains or at least two monomers (monomers additional to the base polymer monomers).
これらグラフトモノマーの５ＥＢＳへのクラフト重合方
法は公知の方法により得る事かできる。Craft polymerization of these graft monomers to 5EBS can be carried out by known methods.
例えば特開昭６１−７６５１８号、特開昭５７−２０５
４４０号、特開昭５５−１３７１９号、特開昭５５−１
３７２０号等に記載された方法で得る事かできる。For example, JP-A-61-76518, JP-A-57-205
No. 440, JP-A-55-13719, JP-A-55-1
It can be obtained by the method described in No. 3720.
本発明に於いてポリオレフィン系熱可塑性樹脂とオレフ
ィン−ビニルアルコール樹脂の比率についてはポリオレ
フィン系熱可塑性樹脂の割合か５重量％以下になるとヒ
ートシール性か悪くなり。In the present invention, when the ratio of the polyolefin thermoplastic resin to the olefin-vinyl alcohol resin is less than 5% by weight, the heat sealability deteriorates.
一方、７０重量％を越えるとフレーバーバリヤー性か著
しく低下する。好ましくは１５〜６０重量％の範囲にす
るのか良い。またオレフィン−ビニルアルコール樹脂の
割合についても同様でオレフィン−ビニルアルコール共
重合体樹脂の割合が９０重量％以上になるとフレーバー
バリヤー性が良くなるもののヒートシール性が極端に悪
化する。一方、３０重量％以下になるとヒートシール性
か良くなるものの逆にフレーバーバリヤー性か悪くなる
。好ましくは８０〜４０重量％か良い。On the other hand, if it exceeds 70% by weight, the flavor barrier properties will be significantly reduced. Preferably, it is in the range of 15 to 60% by weight. The same applies to the proportion of the olefin-vinyl alcohol resin, and when the proportion of the olefin-vinyl alcohol copolymer resin exceeds 90% by weight, the flavor barrier property is improved, but the heat sealability is extremely deteriorated. On the other hand, if it is less than 30% by weight, the heat sealability will improve, but the flavor barrier property will deteriorate. Preferably it is 80 to 40% by weight.
変性グラフト共重合体の割合は２〜２０重量部の割合に
する必要かある。なぜなら２重量部以下だとポリオレフ
ィン系熱可塑性樹脂とオレフィン−ビニルアルコール樹
脂の均一性か悪くなり、きわめて外観及び機械的強度の
劣る樹脂組成物となる。また２０重量部以上になると外
観はさらに良くなるものの剛性、フレーバーバリヤー性
が低下する。従って好ましくは４〜１５重量部の範囲で
用いると良い。The proportion of the modified graft copolymer needs to be 2 to 20 parts by weight. This is because if it is less than 2 parts by weight, the polyolefin thermoplastic resin and olefin-vinyl alcohol resin will have poor uniformity, resulting in a resin composition with extremely poor appearance and mechanical strength. Moreover, when the amount exceeds 20 parts by weight, the appearance becomes better, but the rigidity and flavor barrier properties decrease. Therefore, it is preferably used in a range of 4 to 15 parts by weight.
本発明の食品包装用材料にたいしては熱可塑性樹脂に慣
用される他の添加剤を配合することかてきる。このよう
な添加剤の例としては、酸化防ＩＥ剤、紫外線吸収剤、
可塑剤、帯電防止剤、滑剤。The food packaging material of the present invention may contain other additives commonly used in thermoplastic resins. Examples of such additives include antioxidant IE agents, ultraviolet absorbers,
Plasticizer, antistatic agent, lubricant.
充填剤を挙げる事かでき、これらを本発明の作用効果か
阻害されない範囲内でツレントすることかできる。添加
剤の具体的な例としては次の様なものが挙げられる。酸
化防止剤：２，５−シー Ｌ−ブチルハイドロキノン、
２．６−ジーｔ−ツチルー ｐ−クレゾール、４，４′
−チオビス−（６−ｔ−ブチルフェノール） 、 ２．
２’メチレン−ビス（４−メチル−６−シーツチルフェ
ノール）、テトラキスー［メチレン−３−Ｈ’、５’
−ジー ｔ−フチルー４゜−ヒドロキシフェニル）プロ
ピオネートコメタン、オクタデシル−３−Ｎ’、５−ジ
−ｔ−ブチル−４゛−ヒドロキシフェニル）プロピオネ
ート、４．４°−チオビス−（６−ｔ−ブチルフェノー
ル）等。紫外線吸収剤：エチル−２−シアノ−３，３−
ジフェニルアクリレート、 ２−（２’−ヒドロキシ−
５°−メチルフェニル）−５−クロロベンゾトリアゾー
ル、２−（２°−ヒドロキシ−３°−１−ブチル−５゛
−メチルフェニル）−５−クロロベンゾトリアゾール、
２−ヒドロキシ−４−メトキシベンツフェノン、２，２
′−ジヒドロキシ−４−メトキシベンツフェノン、２−
ヒドロキシ−４−オクトキシベンツフェノン等。可塑剤
：フタル酸ジメチル、フタル酸ジエチル、フタル酸ジオ
クチル、ワックス、流動パラフィン、リン酸エステル等
。Fillers can be mentioned, and these can be used within a range that does not impede the effects of the present invention. Specific examples of additives include the following. Antioxidant: 2,5-C-L-butylhydroquinone,
2.6-di-t-tutyl-p-cresol, 4,4'
-thiobis-(6-t-butylphenol), 2.
2'methylene-bis(4-methyl-6-sheettylphenol), tetrakis-[methylene-3-H', 5'
-di-t-phthyl-4゜-hydroxyphenyl)propionate comethane, octadecyl-3-N', 5-di-t-butyl-4゛-hydroxyphenyl)propionate, 4.4°-thiobis-(6-t -butylphenol) etc. Ultraviolet absorber: ethyl-2-cyano-3,3-
diphenyl acrylate, 2-(2'-hydroxy-
5°-methylphenyl)-5-chlorobenzotriazole, 2-(2°-hydroxy-3°-1-butyl-5′-methylphenyl)-5-chlorobenzotriazole,
2-Hydroxy-4-methoxybenzophenone, 2,2
'-dihydroxy-4-methoxybenzophenone, 2-
Hydroxy-4-octoxybenzophenone and the like. Plasticizer: dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester, etc.
帯電防止剤：ペンタエリスリットモノステアレート、ソ
ルビタンモノパルミテート。Antistatic agents: pentaerythritol monostearate, sorbitan monopalmitate.
（実施例）
（変性ブロック共重合体の調製）
ベースポリマーとなる５ＥＢＳはＫｒａｔｏｎ＠ＧＩ６
５２ （平均分子量７５００−３７５００−７５００
を有する市販の５ＥＢＳツロック共重合体、シェル化学
■製）を用いた。(Example) (Preparation of modified block copolymer) 5EBS as the base polymer is Kraton@GI6
52 (average molecular weight 7500-37500-7500
A commercially available 5EBS Turok copolymer (manufactured by Shell Kagaku ■) was used.
このポリマーを中容機械■製二軸３０■φ異方向回転式
押出機を用い押出温度２４０℃とし、ジクミルパーオキ
サイド及び無水マレイン酸の添加量を変化させることに
より、グラフト量か０．８重量、２．８重陽部のものを
得た。クラフト量については赤外分光光度計を用い定量
した。This polymer was extruded at a temperature of 240°C using a two-screw 30-diameter counter-rotating extruder made by Nakayo Machinery Co., Ltd., and by varying the amounts of dicumyl peroxide and maleic anhydride, the amount of grafting was reduced to 0.8. A product weighing 2.8 parts was obtained. The amount of craft was determined using an infrared spectrophotometer.
（配合及びフィルム成形）
前述の変性ブロック共重合体を用い表−１の如き配合比
で混合し、変性ブロック共重合体の調製で用いたものと
同じ押出機及び押出条件で樹脂組Ｊ＆物をベレット化し
た。(Blending and film forming) The modified block copolymers described above were mixed at the blending ratio as shown in Table 1, and the resin assembly J&M was produced using the same extruder and extrusion conditions as those used in the preparation of the modified block copolymers. Made into a beret.
次にこのベレットを用い吉井鉄工■製４０１ｍφＴダイ
成形機で３０４ｍ 、６０ｐｍの厚みを有するフィルム
を得た。Next, using this pellet, a film having a thickness of 304 m and 60 pm was obtained using a 401 mφ T-die molding machine manufactured by Yoshii Iron Works.
この際の成形性のレベルを表＝１に示した。The moldability level at this time is shown in Table 1.
（◎非常に良好、○良好 、△やや不良、×不良）
（ヒートシール強度の評価）
テスター産業■製ヒートシールテスターＴＰ７０１を用
い６０ｇａ＋のフィルムについて圧力２ ［ｋｇ／ｃｍ
’］、シール時間１．０秒とし夫々ヒートシール温度を
変化させ幅１５＋ｕ＋を有するヒートシール評価用試料
を得た。(◎Very good, ○Good, △Slightly poor, ×Poor) (Evaluation of heat seal strength) Pressure 2 [kg/cm
'], the sealing time was 1.0 seconds, and the heat sealing temperature was varied to obtain samples for heat seal evaluation having a width of 15+u+.
次にこのヒートシール強度を東洋精器■製テンシロンを
用い剥離速度：１００■／ ＩｉｎでＴ型剥離し、ヒー
トシール強度を求めた。これらの測定結果をヒートシー
ル強度が４００ｇ／１５ｍｍ以上になる温度をもって表
＝１に示す。Next, this heat seal strength was determined by T-peeling at a peeling rate of 100 mm/Iin using Tensilon manufactured by Toyo Seiki ■. These measurement results are shown in Table 1 with the temperature at which the heat seal strength is 400 g/15 mm or more.
（フレーバーの収着の評価）
表−１の配合比の厚み３０ｇｍの本発明のフィルム及び
厚さ９４ｔｘのアルミニルム箔および厚さ１２ｇ １ｍ
のポリエチレンテレフタレートフィルムをドライラミネ
ートし多層積層体を得た。ドライラミネートは東洋モー
トン−製の接着剤ＡＤ９５０Ａ／ Ｂを用い、塗布量は
乾燥時４ｇ／ｒｒｆどなる株制製し、その後４０°Ｃの
恒温室て４日間エージングを行った。多層積層体を用い
本発明の樹脂組成物か内面となるようにヒートシールを
行い、１８ｃｍＸ ｌ０ｃＩ！１のパウチを作成した。(Evaluation of flavor sorption) Film of the present invention with a thickness of 30 gm and aluminum foil with a thickness of 94 tx and a thickness of 12 g 1 m with the blending ratio shown in Table 1
Polyethylene terephthalate films were dry laminated to obtain a multilayer laminate. The dry laminate was made using adhesive AD950A/B manufactured by Toyo Morton Co., Ltd., with a coating amount of 4 g/rrf when dry, and then aged in a constant temperature room at 40°C for 4 days. A multilayer laminate was heat-sealed so that the inner surface was coated with the resin composition of the present invention, and the size was 18cm x 10cI! 1 pouch was created.
このパウチの中に各種フレーバー成分を溶解させた界面
活性剤水溶液（リョートシュガーエステル３１１７０
０．５％水溶液、三菱化成食品■製）を３００Ｉ１文封
入し、２３℃の恒温で５０日間保持した。その後、パウ
チを開封し、パウチ内面のフィルムか収着したフレーバ
ー成分ヲエーテルにより抽出し、また水溶液中に残存す
るフレーバー成分もエーテル抽出を行った。次にそれぞ
れについてガスクロマトグラフィーを利用して、元の水
溶液濃度に換算した収着量及び残存丑を各フレーバー成
分について定量した。得られた結果より、次式に従って
フレーバー収着の分配比を計算した。ここで分配比とは
下記（１）式のように定義される。This pouch contains a surfactant aqueous solution (Ryoto Sugar Ester 31170) in which various flavor components are dissolved.
A 0.5% aqueous solution (manufactured by Mitsubishi Kasei Foods Co., Ltd.) was sealed in one container of 300I and kept at a constant temperature of 23° C. for 50 days. Thereafter, the pouch was opened, and the flavor components adsorbed on the film on the inner surface of the pouch were extracted with ether, and the flavor components remaining in the aqueous solution were also extracted with ether. Next, using gas chromatography, the sorption amount and residual oxen converted to the original aqueous solution concentration were determined for each flavor component. From the obtained results, the distribution ratio of flavor sorption was calculated according to the following formula. Here, the distribution ratio is defined as shown in equation (1) below.
即ち、分配比か大きい程フレーバー収着は強く、分配比
１のときは封入前に水溶液中に含まれていたフレーバー
の半分かパウチの内面層側に収着されており、分配比が
１よりも大きくなるに従って水溶液中に残るフレーバー
の濁度は少なくなっていく。この様に評価したフレーバ
ー収着の結果を表−２に示す。In other words, the larger the distribution ratio, the stronger the flavor sorption; when the distribution ratio is 1, half of the flavor contained in the aqueous solution before encapsulation is sorbed to the inner layer of the pouch; As the amount increases, the turbidity of the flavor remaining in the aqueous solution decreases. The results of flavor sorption evaluated in this manner are shown in Table 2.
（以下余白）
こうして本発明の材料て得られた成形物は均一て外観か
美しいたけでなく、均一混合性が良好であると共にガス
バリヤ−性、フレーバーバリヤー性、ヒートシール性、
機械的強度など多くの優れた特性のバランスを有してお
り、その工業的意義は誠に大きい。(Left below) The molded product thus obtained using the material of the present invention not only has a uniform and beautiful appearance, but also has good uniform mixing properties, as well as gas barrier properties, flavor barrier properties, heat sealability, and
It has a good balance of many excellent properties such as mechanical strength, and its industrial significance is truly great.
（効果）
本発明の食品包装用材料は多層構造体の一層として使用
てきるか、疎水性熱可塑性樹脂層をＰ。(Effects) The food packaging material of the present invention can be used as one layer of a multilayer structure, or can be used as a hydrophobic thermoplastic resin layer.
ガスバリヤ−層をＧ、接着性樹脂層をＡ、本発明の食品
包装用材料の層をＭとする時、Ｍ／Ｇ／Ｍ、Ｍ／Ａ／Ｇ
、Ｍ／Ａ／Ｇ／Ａ／Ｍ、Ｐ／Ａ／Ｇ／Ａ／Ｍ、Ｐ／Ｇ／
Ｐ／Ｍ、Ｐ／Ｍ／Ａ／Ｇ／Ａ／Ｍ／Ｐ、Ｐ／Ｍ／Ａ／Ｇ
／Ａ／Ｐ等の層構成をとる時、フレーバーバリヤー性、
ヒートシール性、機械的強度にすぐれた成形物を得るこ
とができる。When the gas barrier layer is G, the adhesive resin layer is A, and the food packaging material layer of the present invention is M, M/G/M, M/A/G
, M/A/G/A/M, P/A/G/A/M, P/G/
P/M, P/M/A/G/A/M/P, P/M/A/G
/A/P etc. layer structure, flavor barrier property,
A molded product with excellent heat sealability and mechanical strength can be obtained.
また本発明の材料の単独成形品、あるいは本発明の組成
物を含む多層成形物を一軸あるいは二軸延伸、深絞り、
ブロー成形等の工程を経る事によってより有用な物とす
る事かできる。また本発明て得られた積層体を更に合成
樹脂フィルム、金属、紙等とラミネートすることもでき
る。In addition, a single molded product of the material of the present invention or a multilayer molded product containing the composition of the present invention may be uniaxially or biaxially stretched, deep drawn,
By going through processes such as blow molding, it can be made into more useful products. Further, the laminate obtained by the present invention can be further laminated with a synthetic resin film, metal, paper, etc.
Claims (2)
重量％、 （Ｂ）オレフィン−ビニルアルコール樹脂を３０〜９０
重量％、および （Ｃ）ビニル芳香族化合物重合体ブロックＡと共役ジエ
ン重合体ブロックＢとからなる重合体を水素添加したブ
ロック共重合体１００重量部に対し不飽和カルボン酸も
しくはそ の誘導体をグラフト重合した変性共重合体 を２〜２０重量％配合してなる食品包装用材料。(1) (A) 5 to 70 polyolefin thermoplastic resin
Weight%, (B) olefin-vinyl alcohol resin 30-90
and (C) graft polymerization of an unsaturated carboxylic acid or its derivative to 100 parts by weight of a block copolymer obtained by hydrogenating a polymer consisting of a vinyl aromatic compound polymer block A and a conjugated diene polymer block B. A food packaging material containing 2 to 20% by weight of a modified copolymer.
量１５〜６０モル％、ケン化度９０％以上のエチレン−
酢酸ビニル共重合体ケン化物樹脂である請求項（１）記
載の食品包装用材料。(2) Olefin - Ethylene containing vinyl alcohol resin with an ethylene content of 15 to 60 mol% and a degree of saponification of 90% or more
The food packaging material according to claim 1, which is a saponified vinyl acetate copolymer resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63146044A JPH01313552A (en) | 1988-06-13 | 1988-06-13 | Food packaging material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63146044A JPH01313552A (en) | 1988-06-13 | 1988-06-13 | Food packaging material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01313552A true JPH01313552A (en) | 1989-12-19 |
Family
ID=15398834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63146044A Pending JPH01313552A (en) | 1988-06-13 | 1988-06-13 | Food packaging material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01313552A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5091467A (en) * | 1991-03-29 | 1992-02-25 | The Goodyear Tire & Rubber Company | Controlled morphology barrier elastomers made from blends of syndiotactic 1,2-polybutadiene and ethylene-vinyl acetate-vinyl alcohol terpolymers |
| US5153262A (en) * | 1991-03-29 | 1992-10-06 | The Goodyear Tire & Rubber Company | Controlled morphology barrier elastomers made from blends of syndiotactic 1,2-polybutadiene and ethylene-vinyl acetate-vinyl alcohol terpolymers |
| JPH10195252A (en) * | 1997-01-10 | 1998-07-28 | Kuraray Co Ltd | Resin composition and its molding product |
| JPH10195270A (en) * | 1997-01-10 | 1998-07-28 | Kuraray Co Ltd | Molding material for closing tool or sealing element |
| US6410109B1 (en) | 1997-01-10 | 2002-06-25 | Kuraray Co., Ltd. | Resin composition and usage thereof |
| EP1431342A2 (en) * | 2002-12-12 | 2004-06-23 | Kuraray Co., Ltd. | Thermoplastic polymer composition, molded product, and multilayer structure |
| KR100575467B1 (en) * | 1999-12-30 | 2006-05-03 | 삼성토탈 주식회사 | Self-adhesive resin composition for protection film |
-
1988
- 1988-06-13 JP JP63146044A patent/JPH01313552A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5091467A (en) * | 1991-03-29 | 1992-02-25 | The Goodyear Tire & Rubber Company | Controlled morphology barrier elastomers made from blends of syndiotactic 1,2-polybutadiene and ethylene-vinyl acetate-vinyl alcohol terpolymers |
| US5153262A (en) * | 1991-03-29 | 1992-10-06 | The Goodyear Tire & Rubber Company | Controlled morphology barrier elastomers made from blends of syndiotactic 1,2-polybutadiene and ethylene-vinyl acetate-vinyl alcohol terpolymers |
| JPH10195252A (en) * | 1997-01-10 | 1998-07-28 | Kuraray Co Ltd | Resin composition and its molding product |
| JPH10195270A (en) * | 1997-01-10 | 1998-07-28 | Kuraray Co Ltd | Molding material for closing tool or sealing element |
| US6410109B1 (en) | 1997-01-10 | 2002-06-25 | Kuraray Co., Ltd. | Resin composition and usage thereof |
| KR100575467B1 (en) * | 1999-12-30 | 2006-05-03 | 삼성토탈 주식회사 | Self-adhesive resin composition for protection film |
| EP1431342A2 (en) * | 2002-12-12 | 2004-06-23 | Kuraray Co., Ltd. | Thermoplastic polymer composition, molded product, and multilayer structure |
| EP1431342A3 (en) * | 2002-12-12 | 2004-07-14 | Kuraray Co., Ltd. | Thermoplastic polymer composition, molded product, and multilayer structure |
| US7354654B2 (en) | 2002-12-12 | 2008-04-08 | Kuraray Co., Ltd | Thermoplastic polymer composition, molded product, and multilayer structure |
| KR101007533B1 (en) * | 2002-12-12 | 2011-01-14 | 가부시키가이샤 구라레 | Thermoplastic polymer composition, molded product, and multilayer structure |
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