JP2002200725A - Biodegradable resin laminate, container and container cover - Google Patents
Biodegradable resin laminate, container and container coverInfo
- Publication number
- JP2002200725A JP2002200725A JP2000403346A JP2000403346A JP2002200725A JP 2002200725 A JP2002200725 A JP 2002200725A JP 2000403346 A JP2000403346 A JP 2000403346A JP 2000403346 A JP2000403346 A JP 2000403346A JP 2002200725 A JP2002200725 A JP 2002200725A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- layer
- container
- oxygen
- acid
- 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.)
- Granted
Links
- 229920006167 biodegradable resin Polymers 0.000 title claims description 8
- 229920005989 resin Polymers 0.000 claims abstract description 85
- 239000011347 resin Substances 0.000 claims abstract description 85
- 229920001225 polyester resin Polymers 0.000 claims abstract description 35
- 239000004645 polyester resin Substances 0.000 claims abstract description 35
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 31
- 230000004888 barrier function Effects 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims description 25
- -1 transition metal salt Chemical class 0.000 claims description 25
- 239000011342 resin composition Substances 0.000 claims description 12
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 11
- 239000002304 perfume Substances 0.000 abstract 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 35
- 239000004626 polylactic acid Substances 0.000 description 35
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 150000004696 coordination complex Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002961 polybutylene succinate Polymers 0.000 description 3
- 239000004631 polybutylene succinate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003303 reheating Methods 0.000 description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- MHPUGCYGQWGLJL-UHFFFAOYSA-N 5-methyl-hexanoic acid Chemical compound CC(C)CCCC(O)=O MHPUGCYGQWGLJL-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- CNVZJPUDSLNTQU-SEYXRHQNSA-N petroselinic acid Chemical compound CCCCCCCCCCC\C=C/CCCCC(O)=O CNVZJPUDSLNTQU-SEYXRHQNSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
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- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 235000013310 margarine Nutrition 0.000 description 1
- 239000003264 margarine Substances 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【0001】[0001]
【発明が属する技術分野】本発明は、生分解性樹脂積層
体、及びこの樹脂積層体から成る容器及び容器蓋に関
し、より詳細には、ヒドロキシアルカノエート単位を主
体とする飽和ポリエステル樹脂を樹脂成分とし、酸素吸
収性、ガスバリヤー性を兼ね備えた樹脂積層体、及びこ
の樹脂積層体から成る容器及び容器蓋に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biodegradable resin laminate, a container and a container lid made of the resin laminate, and more particularly, to a resin composition comprising a saturated polyester resin mainly composed of hydroxyalkanoate units. The present invention also relates to a resin laminate having both oxygen absorption and gas barrier properties, and a container and a container lid made of the resin laminate.
【0002】[0002]
【従来の技術】従来、包装容器としては、金属缶、ガラ
スビン、各種プラスチック容器等が使用されているが、
容器内に残留する酸素や容器壁を透過する酸素による内
容物の変質やフレーバー低下が問題となっている。2. Description of the Related Art Conventionally, metal cans, glass bottles, various plastic containers and the like have been used as packaging containers.
Deterioration of contents and reduction in flavor due to oxygen remaining in the container and oxygen permeating the container wall have become problems.
【0003】特に、金属缶やガラスビンでは容器壁を通
しての酸素透過がゼロであり、容器内に残留する酸素の
みが問題であるのに対して、プラスチック容器の場合に
は器壁を通しての酸素透過が無視し得ないオーダーで生
じ、内容品の保存性の点で問題となっている。[0003] In particular, in a metal can or a glass bottle, oxygen permeation through the container wall is zero, and only oxygen remaining in the container is a problem, whereas in a plastic container, oxygen permeation through the container wall is zero. It occurs in orders that cannot be ignored and poses a problem in the preservability of the contents.
【0004】これを防止するために、プラスチック容器
では容器壁を多層構造とし、その内の少なくとも一層と
して、エチレン−ビニルアルコール共重合体等の耐酸素
透過性を有する樹脂を用いることが行われている。In order to prevent this, in a plastic container, the container wall has a multilayer structure, and at least one of the layers is made of an oxygen-permeable resin such as an ethylene-vinyl alcohol copolymer. I have.
【0005】容器内の酸素を除去するために、脱酸素剤
の使用も古くから行われており、これを容器壁に適用し
た例としては、特公昭62−1824号公報の発明があ
り、これによると、酸素透過性を有する樹脂に鉄粉など
の還元性物質を主剤とする脱酸素剤を配合して成る層
と、酸素ガス遮断性を有する層とを積層して、包装用多
層構造物とすることが記載されている。[0005] An oxygen absorber has been used for a long time to remove oxygen in a container. An example of applying the oxygen absorber to the container wall is disclosed in Japanese Patent Publication No. 62-1824. According to the above, a layer formed by mixing a deoxygenating agent mainly composed of a reducing substance such as iron powder with an oxygen-permeable resin and a layer having an oxygen gas barrier property are laminated to form a multilayer structure for packaging. Is described.
【0006】一方、プラスチック廃棄物の理想的な解決
方法として、自然環境で消滅する分解性プラスチックが
注目されており、かかる分解性プラスチックを用いて、
内容物の保存性に優れた容器を提供することが望まれて
いる。On the other hand, as an ideal solution for plastic waste, degradable plastics that disappear in the natural environment are attracting attention.
It is desired to provide a container having excellent preservability of the contents.
【0007】[0007]
【発明が解決しようとする課題】分解性プラスチックの
うち、バクテリアや真菌類が体外に放出する酵素の作用
で崩壊する生分解性プラスチックにおいては、遷移金属
触媒を添加することにより、酸素吸収性が得られること
が知られているが、ガスバリヤー性が低いことから、容
器に適用した場合、内容物に対する酸素吸収速度が不十
分であるという問題を有している。Among biodegradable plastics, among biodegradable plastics, bacteria and fungi are degraded by the action of enzymes released outside the body. By adding a transition metal catalyst, oxygen absorption is reduced. Although it is known that it can be obtained, it has a problem that when it is applied to a container, the oxygen absorption rate to the contents is insufficient because of its low gas barrier property.
【0008】また、遷移金属系触媒を含有する酸素吸収
性樹脂組成物は、実質上透明である包装容器にも適用で
きるという利点を有しているが、酸素の吸収速度が未だ
十分でなく、しかも容器内の酸素或いは容器の器壁を通
して透過する酸素を有効に吸収すると共に、容器の保存
中には容器に必要な機械的特性も十分に保持されるとい
うバランスにも未だ問題を有している。The oxygen-absorbing resin composition containing a transition metal-based catalyst has the advantage that it can be applied to packaging containers that are substantially transparent, but the oxygen absorption rate is still insufficient. Moreover, there is still a problem in the balance that the oxygen in the container or the oxygen permeating through the container wall is effectively absorbed and the mechanical properties required for the container are sufficiently maintained during the storage of the container. I have.
【0009】従って、本発明の目的は、生分解性を有す
ると共に、酸素吸収性、ガスバリヤー性、及び透明性に
優れており、内容物の香味保持性や、内容物の保存性に
も優れている樹脂積層体、容器及び容器蓋を提供するこ
とである。Accordingly, an object of the present invention is to have biodegradability, excellent oxygen absorption, gas barrier properties, and transparency, and excellent flavor retention of contents and preservation of contents. To provide a resin laminate, a container, and a container lid.
【0010】[0010]
【課題を解決するための手段】本発明によれば、ヒドロ
キシアルカノエート単位を主体とする飽和ポリエステル
樹脂を樹脂成分として含有する樹脂積層体であって、酸
素吸収性を有する樹脂層を少なくとも一層及びガスバリ
ヤー性被覆を少なくとも一層含んで成ることを特徴とす
る樹脂積層体が提供される。本発明の樹脂積層体におい
ては、 1. 酸素吸収性樹脂層がヒドロキシアルカノエート単
位を主体とする飽和ポリエステル樹脂を樹脂成分として
含有する生分解性樹脂及び有機遷移金属塩或いは更に不
飽和炭化水素を含有する樹脂組成物から成ること、 2.ガスバリヤー性被覆が無機蒸着被膜であること、 3. 内面側にヒドロキシアルカノエート単位を主体と
する飽和ポリエステル樹脂を樹脂成分として含有する生
分解性樹脂層を有すること、 が好ましい。また、本発明によれば、上記樹脂積層体か
ら成る容器或いは容器蓋が提供される。According to the present invention, there is provided a resin laminate containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component, wherein at least one resin layer having oxygen absorbability is provided. A resin laminate comprising at least one gas barrier coating is provided. In the resin laminate of the present invention, 1. The oxygen-absorbing resin layer is composed of a biodegradable resin containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component and a resin composition containing an organic transition metal salt or further unsaturated hydrocarbon. 2. the gas barrier coating is an inorganic vapor-deposited coating; It is preferable to have a biodegradable resin layer containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component on the inner surface side. Further, according to the present invention, there is provided a container or a container lid made of the above resin laminate.
【0011】[0011]
【発明の実施形態】本発明においては、ヒドロキシアル
カノエート単位を主体とする飽和ポリエステル樹脂を樹
脂成分として含有する樹脂積層体であって、酸素吸収性
を有する樹脂層を少なくとも一層及びガスバリヤー性被
覆を少なくとも一層含んで成ることが重要な特徴であ
る。すなわち、本発明の積層体においては、容器等に成
形した場合に、容器内の残存酸素等を酸素吸収性を有す
る樹脂層によって吸収すると共に、ガスバリヤー性被覆
によって、外部からの酸素等の透過を有効に防止するこ
とが可能となり、内容物の保存性に優れた容器等を提供
することが可能となる。しかも積層体の樹脂成分はヒド
ロキシアルカノエート単位を主体とする飽和ポリエステ
ル樹脂からなっているので、かかる積層体から成る容器
は、生分解性をも具備しているのである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin laminate containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component, comprising at least one oxygen-absorbing resin layer and a gas barrier coating. It is an important feature that it comprises at least one layer. That is, in the laminate of the present invention, when molded into a container or the like, the residual oxygen and the like in the container are absorbed by the resin layer having an oxygen-absorbing property, and the gas barrier coating allows transmission of oxygen and the like from the outside. Can be effectively prevented, and a container or the like excellent in preservation of the contents can be provided. Moreover, since the resin component of the laminate is made of a saturated polyester resin mainly composed of hydroxyalkanoate units, the container made of such a laminate also has biodegradability.
【0012】本発明においては、酸素吸収性樹脂層が、
ヒドロキシアルカノエート単位を主体とする飽和ポリエ
ステル樹脂を樹脂成分として含有する生分解性樹脂及び
有機遷移金属塩或いは更に不飽和炭化水素を含有する樹
脂組成物から成ることが望ましい。すなわち、ヒドロキ
シアルカノエート単位を主体とする飽和ポリエステル樹
脂に有機遷移金属塩を含有させた樹脂組成物において
は、遷移金属によるヒドロキシアルカノエート単位を
主体とする飽和ポリエステル樹脂の3級炭素やαメチレ
ン部位の水素原子の引き抜きによるラジカルの発生、
このラジカルへの酸素分子の付加によるパーオキシラジ
カルの発生、パーオキシラジカルによる水素原子の引
き抜き、の各素反応を通して酸素吸収性を生じると考え
られる。In the present invention, the oxygen-absorbing resin layer comprises
It is desirable that the resin composition comprises a biodegradable resin containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component and a resin composition containing an organic transition metal salt or further unsaturated hydrocarbon. That is, in a resin composition in which an organic transition metal salt is contained in a saturated polyester resin mainly composed of hydroxyalkanoate units, the tertiary carbon or α-methylene moiety of the saturated polyester resin mainly composed of hydroxyalkanoate units composed of transition metal is used. Generation of radicals by abstraction of hydrogen atoms of
It is considered that oxygen absorption is generated through each elementary reaction of generation of a peroxy radical by addition of an oxygen molecule to this radical and abstraction of a hydrogen atom by the peroxy radical.
【0013】ところが、常態での樹脂の劣化を生じない
遷移金属の共存下では、上記ラジカルの発生や、酸素の
付加に誘導期があり、これらの素反応が必ずしも有効に
行われていないと考えられる。本発明においては、ヒド
ロキシアルカノエート単位を主体とする飽和ポリエステ
ル樹脂及び有機遷移金属塩を含有する樹脂組成物に、不
飽和炭化水素を更に含有させることによって、上記素反
応を有効に行わせ、酸素吸収能を高めているのである。
すなわち、本発明において使用する不飽和炭化水素にお
いては、炭素−炭素二重結合に隣接する炭素原子の位置
で水素原子の引き抜きが容易に行われ、これによりラジ
カルが発生して上記素反応が迅速且つ有効に行われ、酸
素吸収能を高めることが可能になるのである。However, under the coexistence of a transition metal which does not cause deterioration of the resin under normal conditions, there is an induction period in the generation of the above radicals and addition of oxygen, and it is considered that these elementary reactions are not necessarily carried out effectively. Can be In the present invention, the unsaturated polyester is further contained in a resin composition containing a saturated polyester resin mainly composed of hydroxyalkanoate units and an organic transition metal salt, so that the elementary reaction is effectively performed, and oxygen is added. It increases the absorption capacity.
That is, in the unsaturated hydrocarbon used in the present invention, the hydrogen atom can be easily extracted at the position of the carbon atom adjacent to the carbon-carbon double bond, whereby a radical is generated and the elementary reaction is rapidly performed. In addition, it is performed effectively, and the oxygen absorbing ability can be increased.
【0014】(ヒドロキシアルカノエート単位を主体と
する飽和ポリエステル樹脂)樹脂積層体の樹脂成分とし
て使用するヒドロキシアルカノエート単位を主体とする
飽和ポリエステル樹脂としては、生分解性プラスチック
として従来から公知のポリヒドロキシブチレート(PH
B)、3−ヒドロキシブチレート(3HB)と3−ヒド
ロキシバリレート(3HV)とのランダムコポリマー、
ポリ(ε−カプロラクトン)(PCL)、ポリブチレン
サクシネート(PBS)、ポリブチレンサクシネート・
アジペート(PBAS)、ポリ乳酸(PLLA)等の脂
肪族ポリステルを一種又は二種以上を組み合わせて好適
に使用することができる。(Saturated polyester resin mainly composed of hydroxyalkanoate units) As the saturated polyester resin mainly composed of hydroxyalkanoate units used as a resin component of the resin laminate, a polyhydroxy resin conventionally known as a biodegradable plastic is used. Butyrate (PH
B), a random copolymer of 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV),
Poly (ε-caprolactone) (PCL), polybutylene succinate (PBS), polybutylene succinate
Aliphatic polyesters such as adipate (PBAS) and polylactic acid (PLLA) can be suitably used alone or in combination of two or more.
【0015】本発明で特に好適に用いることができるポ
リ乳酸(以下、PLLAと表すことがある)は、下記式
(1)Polylactic acid (hereinafter sometimes referred to as PLLA) which can be particularly preferably used in the present invention is represented by the following formula (1)
【化1】 で表される反復単位から成り、工業的に量産され入手が
容易で、環境にも優しい脂肪族ポリエステルであり、自
然界に存在する微生物により、水と炭酸ガスにより分解
され、完全リサイクルシステム型の樹脂としても着目さ
れている。またそのガラス転移点(Tg)も約58℃と
ポリエチレンテレフタレートのTgに近いという利点を
有している。Embedded image Is an aliphatic polyester that is industrially mass-produced, easily available, and environmentally friendly. It is decomposed by water and carbon dioxide by natural microorganisms, and is a complete recycling system type resin. Has also attracted attention. The glass transition point (Tg) is also about 58 ° C., which is close to the Tg of polyethylene terephthalate.
【0016】本発明に用いるヒドロキシアルカノエート
単位を主体とする飽和ポリエステル樹脂は、勿論これに
限定されないが、10000〜300000、特に20
000〜200000の範囲の重量平均分子量を有する
ことが好ましい。また密度1.20〜1.26g/cm
3、融点165〜200℃、メルトフローレート(AS
TM D1238,190℃)2〜20g/10分の範
囲にあることが好ましい。The saturated polyester resin mainly comprising hydroxyalkanoate units used in the present invention is, of course, not limited to, but 10,000 to 300,000, particularly 20
It preferably has a weight average molecular weight in the range of 000 to 200,000. The density is 1.20 to 1.26 g / cm
3 , melting point 165 to 200 ° C, melt flow rate (AS
(TMD1238, 190 ° C.) 2-20 g / 10 min.
【0017】(有機遷移金属塩)遷移金属としては、
鉄、コバルト、ニッケル等の周期律表第VIII族金属成分
が特に好ましいが、他に銅、銀等の第I族金属、錫、チ
タン、ジルコニウム等の第IV族金属、バナジウム等の第
V族、クロム等の第VI族、マンガン等の第VII族の金属成
分を挙げることができる。これら金属成分の中でもコバ
ルト成分は、酸素吸収速度が大きく、本発明の目的に特
に適したものである。有機酸塩としては、カルボン酸
塩、スルホン酸塩、ホスホン酸塩などが挙げられるが、
カルボン酸塩が本発明の目的に好適であり、その具体例
としては、酢酸、プロピオン酸、イソプロピオン酸、ブ
タン酸、イソブタン酸、ペンタン酸、イソペンタン酸、
ヘキサン酸、ヘプタン酸、イソヘプタン酸、オクタン
酸、2−エチルヘキサン酸、ノナン酸、3,5,5−ト
リメチルヘキサン酸、デカン酸、ネオデカン酸、ウンデ
カン酸、ラウリン酸、ミリスチン酸、パルミチン酸、マ
ーガリン酸、ステアリン酸、アラキン酸、リンデル酸、
ツズ酸、ペトロセリン酸、オレイン酸、リノール酸、リ
ノレン酸、アラキドン酸、ギ酸、シュウ酸、スルファミ
ン酸、ナフテン酸等の遷移金属塩が挙げられる。(Organic Transition Metal Salt) As the transition metal,
Particularly preferred are Group VIII metal components of the periodic table such as iron, cobalt, and nickel.Others are Group I metals such as copper and silver; and Group IV metals such as tin, titanium and zirconium; and vanadium and the like.
Examples of the metal component include Group V metals such as Group V and chromium and Group VII such as manganese. Among these metal components, the cobalt component has a high oxygen absorption rate and is particularly suitable for the purpose of the present invention. Examples of the organic acid salt include carboxylate, sulfonate, phosphonate and the like,
Carboxylates are suitable for the purposes of the present invention, examples of which include acetic acid, propionic acid, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid,
Hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3,5,5-trimethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margarine Acid, stearic acid, arachidic acid, lindelic acid,
Transition metal salts such as tsunic acid, petroselinic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, formic acid, oxalic acid, sulfamic acid, naphthenic acid and the like can be mentioned.
【0018】(不飽和炭化水素)不飽和炭化水素として
は、これに限定されるものではないが、炭素数1〜10
のものを好適に使用することができ、例えばエチレン、
プロピレン、1−ブテン、4-メチル−1− ペンテン、
1−ヘキセン、1−ヘプテン、1−オクテン、1−ノネ
ン、1−デセン、1−ウンデセン、1−ドデセン、1−
トリデセン、1−テトラデセン、1−ペンタデセン、1
−ヘキサデセン、1−ヘプタデセン、1−ノナデセン、
1−エイコセン、9−メチル−1−デセン、11−メチ
ル−1−ドデセン、12−エチル−1−テトラデセン等
のα−オレフィン;イソプレン、ブタジエン等の共役ジ
エン;1,4−ヘキサジエン、3−メチルー1,4−ヘ
キサジエン、4−メチル−1,4−ヘキサジエン、5−
メチル−1,4−ヘキサジエン、4,5−ジメチル−
1,4−ヘキサジエン、7−メチル−1,6−オクタジ
エン等の鎖状非共役ジエン;メチルテトラヒドロインデ
ン、5−エチリデン−2−ノルボルネン、5−メチレン
−2−ノルボルネン、5−イソプロピリデン−2−ノル
ボルネン、5−ビニリデン−2−ノルボルネン、6−ク
ロロメチル−5−イソプロペニル−2−ノルボルネン、
ジシクロペンタジエン等の環状非共役ジエン;2,3−
ジイソプロピリデン−5−ノルボルネン、2−エチリデ
ン−3−イソプロピリデン−5−ノルボルネン、2−プ
ロペニル−2,2−ノルボルナジエン等のトリエン、ク
ロロプレン等が挙げられる。これらの不飽和炭化水素
は、単独で或いは2種以上の組み合わせで、或いはこれ
らの重合体或いは共重合体の形で使用することができ
る。(Unsaturated Hydrocarbon) The unsaturated hydrocarbon is not limited to this, but may have 1 to 10 carbon atoms.
Can be suitably used, for example, ethylene,
Propylene, 1-butene, 4-methyl-1-pentene,
1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-
Tridecene, 1-tetradecene, 1-pentadecene, 1
-Hexadecene, 1-heptadecene, 1-nonadecene,
Α-olefins such as 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene; conjugated dienes such as isoprene and butadiene; 1,4-hexadiene and 3-methyl- 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-
Methyl-1,4-hexadiene, 4,5-dimethyl-
Chain non-conjugated dienes such as 1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2- Norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene,
Cyclic non-conjugated dienes such as dicyclopentadiene; 2,3-
Trienes such as diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, chloroprene and the like can be mentioned. These unsaturated hydrocarbons can be used alone or in combination of two or more, or in the form of a polymer or copolymer thereof.
【0019】(酸素吸収性層)本発明の樹脂積層体にお
いては、有機遷移金属塩は、金属としてヒドロキシアル
カノエート単位を主体とする飽和ポリエステル樹脂当り
10乃至8000ppm、特に50乃至5000ppm
の量で含有されることが好ましい。また本発明において
は、不飽和炭化水素は、ヒドロキシアルカノエート単位
を主体とする飽和ポリエステル樹脂当り0.5乃至20
重量%、特に1乃至5重量%の量で含有されることが好
ましい。(Oxygen-absorbing layer) In the resin laminate of the present invention, the organic transition metal salt is contained in an amount of from 10 to 8,000 ppm, particularly from 50 to 5,000 ppm, based on a saturated polyester resin mainly containing hydroxyalkanoate units as a metal.
Is preferably contained in an amount of Further, in the present invention, the unsaturated hydrocarbon is used in an amount of 0.5 to 20 per saturated polyester resin mainly composed of hydroxyalkanoate units.
It is preferably contained in an amount of from 1 to 5% by weight.
【0020】本発明の樹脂積層体においては、上記各成
分の配合については特に制限はなく、上記二成分或いは
三成分を別個に配合してもよく、また上記三成分のうち
二成分を予め配合し、これと残りの成分を配合してもよ
い。この配合の方式の例としては、ヒドロキシアルカノ
エート単位を主体とする飽和ポリエステル樹脂と不飽和
炭化水素を予め配合し、これに有機遷移金属塩を配合す
る方法や、ヒドロキシアルカノエート単位を主体とする
飽和ポリエステル樹脂と有機遷移金属塩を予め配合し、
これに不飽和炭化水素を配合する方法等が挙げられる。In the resin laminate of the present invention, there is no particular limitation on the blending of each of the above components, and the above two or three components may be separately blended, or two of the above three components may be blended in advance. Then, this and the remaining components may be blended. As an example of the method of this compounding, a method in which a saturated polyester resin mainly containing a hydroxyalkanoate unit and an unsaturated hydrocarbon are preliminarily mixed, and an organic transition metal salt is added thereto, or a method mainly including a hydroxyalkanoate unit Pre-blend saturated polyester resin and organic transition metal salt,
There may be mentioned a method of blending an unsaturated hydrocarbon with the mixture.
【0021】ヒドロキシアルカノエート単位を主体とす
る飽和ポリエステル樹脂に有機遷移金属塩を配合するに
は、種々の手段を用いることができ、例えば、有機遷移
金属塩を樹脂に単に乾式でブレンドすることもできる
が、有機遷移金属塩がヒドロキシアルカノエート単位を
主体とする飽和ポリエステル樹脂に比して少量であるこ
とから、ブレンドを均質にするために、有機遷移金属塩
を有機溶媒に溶解し、この溶液と粉末或いは粒状の樹脂
とを混合し、必要によりこの混合物を不活性雰囲気下に
乾燥することが好ましい。有機遷移金属塩を溶解させる
溶媒としては、メタノール、エタノール、ブタノール等
のアルコール系溶媒、ジメチルエーテル、ジエチルエー
テル、メチルエチルエーテル、テトラヒドロフラン、ジ
オキサン等のエーテル系溶媒、メチルエチルケトン、シ
クロヘキサノン等のケトン系溶媒、n−ヘキサン、シク
ロヘキサン等の炭化水素系溶媒を用いることができ、一
般に有機遷移金属塩の濃度が5乃至90重量%となるよ
うな濃度で用いるのがよい。Various methods can be used for blending the organic transition metal salt with the saturated polyester resin mainly composed of hydroxyalkanoate units. For example, it is also possible to simply blend the organic transition metal salt with the resin by a dry method. Although it is possible, since the organic transition metal salt is in a smaller amount than the saturated polyester resin mainly composed of hydroxyalkanoate units, the organic transition metal salt is dissolved in an organic solvent in order to homogenize the blend, and this solution is used. And a powdery or granular resin, and if necessary, drying the mixture under an inert atmosphere. Examples of the solvent for dissolving the organic transition metal salt include alcohol solvents such as methanol, ethanol and butanol; ether solvents such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran and dioxane; ketone solvents such as methyl ethyl ketone and cyclohexanone; -A hydrocarbon solvent such as hexane and cyclohexane can be used, and it is generally preferable to use a concentration such that the concentration of the organic transition metal salt is 5 to 90% by weight.
【0022】ヒドロキシアルカノエート単位を主体とす
る飽和ポリエステル樹脂と有機遷移金属塩との混合、及
びその後の保存は、組成物の前段階での酸化が生じない
ように、非酸化性雰囲気中で行うのがよい。この目的に
減圧下或いは窒素気流中での混合或いは乾燥が好まし
い。この混合及び乾燥は、ベント式或いは乾燥機付の押
出機や射出機を用いて、成形工程の前段階で行うことが
でき、この場合には、有機遷移金属塩配合樹脂の保存に
格別の配慮が不必要になるという利点が達成される。ま
た、有機遷移金属塩を比較的高い濃度で含有する樹脂の
マスターバッチを調製し、このマスターバッチを未配合
の樹脂と乾式ブレンドして、酸素吸収性樹脂組成物を調
製することもできる。尚、本発明に用いる樹脂組成物
は、一般的な乾燥条件である40乃至160℃の温度
で、0.5乃至2mmHgの減圧下2乃至24時間乾燥
して後述する成形に用いるのがよい。The mixing of the saturated polyester resin mainly composed of hydroxyalkanoate units with the organic transition metal salt and the subsequent storage are performed in a non-oxidizing atmosphere so as to prevent the oxidation of the composition at the previous stage. Is good. For this purpose, mixing or drying under reduced pressure or in a nitrogen stream is preferred. This mixing and drying can be carried out at an earlier stage of the molding process by using an extruder or an injection machine equipped with a vent type or a dryer. In this case, special consideration is given to the preservation of the resin containing the organic transition metal salt. Is achieved. Alternatively, an oxygen-absorbing resin composition can be prepared by preparing a masterbatch of a resin containing a relatively high concentration of an organic transition metal salt and dry-blending the masterbatch with an unblended resin. The resin composition used in the present invention is preferably dried at a temperature of 40 to 160 ° C., which is a general drying condition, under a reduced pressure of 0.5 to 2 mmHg for 2 to 24 hours, and then used for molding described below.
【0023】本発明の積層体における酸素吸収性層に
は、一般に必要ではないが、所望によりそれ自体公知の
活性化剤を配合することができる。活性化剤の適当な例
は、これに限定されないが、ポリエチレングリコール、
ポリプロピレングリコール、エチレンビニルアルコール
共重合体、エチレン・メタクリル酸共重合体、各種アイ
オノマー等の水酸基及び/又はカルボキシル基含有重合
体である。これらの水酸基及び/又はカルボキシル基含
有重合体は、ヒドロキシアルカノエート単位を主体とす
る飽和ポリエステル樹脂100重量部当たり30重量部
以下、特に0.01乃至10重量部の量で配合すること
ができる。本発明に用いる酸素吸収性樹脂組成物には、
充填剤、着色剤、耐熱安定剤、耐候安定剤、老化防止
剤、光安定剤、紫外線吸収剤、帯電防止剤、金属セッケ
ンやワックス等の滑剤、改質用樹脂乃至ゴム、等の公知
の樹脂配合剤を、それ自体公知の処方に従って配合でき
る。The oxygen-absorbing layer in the laminate of the present invention is not generally required, but may optionally contain a known activator. Suitable examples of activators include, but are not limited to, polyethylene glycol,
Hydroxyl and / or carboxyl group-containing polymers such as polypropylene glycol, ethylene vinyl alcohol copolymer, ethylene / methacrylic acid copolymer, and various ionomers. These hydroxyl and / or carboxyl group-containing polymers can be blended in an amount of 30 parts by weight or less, particularly 0.01 to 10 parts by weight, per 100 parts by weight of the saturated polyester resin mainly composed of hydroxyalkanoate units. In the oxygen-absorbing resin composition used in the present invention,
Known resins such as fillers, colorants, heat stabilizers, weather stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants such as metal soaps and waxes, modifying resins and rubbers, etc. The compounding agent can be compounded according to a formulation known per se.
【0024】(ガスバリヤー性被膜)本発明の樹脂積層
体においてガスバリヤー性被膜としては、樹脂成分たる
ヒドロキシアルカノエート単位を主体とする飽和ポリエ
ステル樹脂膜に、エポキシアミンをコーティングしたも
のや、SiOx等のセラミックや炭素を蒸着した無機蒸
着被膜やアルミニウム等の金属を蒸着した金属無機蒸着
被膜等を挙げることができる。好適には無機蒸着被膜で
あることが好ましい。(Gas Barrier Coating) The gas barrier coating in the resin laminate of the present invention may be, for example, a resin obtained by coating a saturated polyester resin film mainly composed of a hydroxyalkanoate unit as a resin component with epoxyamine, or SiOx. And an inorganic vapor-deposited film obtained by evaporating a ceramic or carbon, or a metal-inorganic vapor-deposited film obtained by evaporating a metal such as aluminum. Preferably, it is an inorganic vapor-deposited film.
【0025】(層構成)本発明の樹脂積層体は、ヒドロ
キシアルカノエート単位を主体とする飽和ポリエステル
樹脂を樹脂成分とし、酸素吸収性を有する樹脂層及びガ
スバリヤー性被膜を有する限り、種々の態様を採用する
ことができるが、一般には、外部からの酸素透過を防止
するために外面となる側にガスバリヤー性被膜が位置
し、酸素吸収性層は容器等の内部の残存酸素等を吸収す
るために、ガスバリヤー性被膜よりも内側に位置するこ
とが必要である。また、一般に酸素吸収性層は、容器な
どの外表面に露出しないように容器などの外表面よりも
内側に設けることが好ましく、また、内容物の直接的な
接触を避ける目的で、容器などの内表面よりも外側に設
けることが好ましいので、内表面はヒドロキシアルカノ
エート単位を主体とする飽和ポリエステル樹脂から成る
層を設けることが好ましい。ヒドロキシアルカノエート
単位を主体とする飽和ポリエステル樹脂から成る樹脂層
を(HP)、酸素吸収性層を(OAR)、ガスバリヤー
性被膜を(GB)とすると、以下の例を挙げることがで
きる。 (内面)HP/OAR/HP/GB(外面) (内面)HP/OAR/GB(外面) 各層の厚みは、用途等によっても異なるが、一般にヒド
ロキシアルカノエート単位を主体とする飽和ポリエステ
ル樹脂から成る層は、30乃至1500μm、特に50
乃至500μm、酸素吸収性層は、20乃至500μ
m、特に30乃至100μm、ガスバリヤー性被膜は、
0.005乃至0.5μm、特に0.1乃至0.4μm
の範囲にあることが好ましい。また樹脂積層体全体の厚
みは、100乃至2000μm、特に200乃至100
0μmの範囲にあることが好ましい。(Layer Structure) The resin laminate of the present invention comprises a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component, and has various modes as long as it has a resin layer having an oxygen absorbing property and a gas barrier coating. However, in general, a gas barrier coating is located on the side that will be the outer surface to prevent oxygen transmission from the outside, and the oxygen-absorbing layer absorbs residual oxygen and the like inside the container or the like. Therefore, it is necessary to be located inside the gas barrier coating. In general, the oxygen-absorbing layer is preferably provided inside the outer surface of the container or the like so as not to be exposed on the outer surface of the container or the like. Since the inner surface is preferably provided outside the inner surface, the inner surface is preferably provided with a layer made of a saturated polyester resin mainly composed of hydroxyalkanoate units. When the resin layer composed of a saturated polyester resin mainly composed of hydroxyalkanoate units is (HP), the oxygen absorbing layer is (OAR), and the gas barrier coating is (GB), the following examples can be given. (Inner surface) HP / OAR / HP / GB (Outer surface) (Inner surface) HP / OAR / GB (Outer surface) Although the thickness of each layer varies depending on the use and the like, it generally comprises a saturated polyester resin mainly composed of hydroxyalkanoate units. The layer is between 30 and 1500 μm, especially 50
To 500 μm, and the oxygen-absorbing layer is 20 to 500 μm.
m, especially 30 to 100 μm, gas barrier coating,
0.005 to 0.5 μm, especially 0.1 to 0.4 μm
Is preferably within the range. The thickness of the entire resin laminate is 100 to 2000 μm, particularly 200 to 100 μm.
It is preferably in the range of 0 μm.
【0026】(積層体)本発明の樹脂積層体の製造方法
は、特に限定されるものではなく、上述した層構成の積
層体が作成される限りにおいてそれ自体公知の方法で製
造が可能であるが、例えば、インフレキャスト法、押出
しコート法、共押出し法、サンドイッチラミネーション
等を採用でき、公知の接着剤を用いることができる。ま
た本発明の樹脂積層体は、上記シート形状の他、共射出
成形や共押出し成形により多層プリフォームの形状にす
ることもできるし、或いは直接共射出成形等により目的
とする容器形状とすることも可能である。(Laminate) The method for producing the resin laminate of the present invention is not particularly limited, and the resin laminate can be produced by a method known per se as long as a laminate having the above-described layer structure is produced. However, for example, an inflation casting method, an extrusion coating method, a co-extrusion method, a sandwich lamination and the like can be adopted, and a known adhesive can be used. In addition, the resin laminate of the present invention can be formed into a multilayer preform by co-injection molding or co-extrusion molding in addition to the sheet shape described above, or can be formed into a target container shape by direct co-injection molding or the like. Is also possible.
【0027】ガスバリヤー性被膜は、ヒドロキシアルカ
ノエート単位を主体とする飽和ポリエステル樹脂から成
る基材樹脂層と酸素吸収性樹脂層等を予め積層した後、
最後に蒸着等させて被膜を形成してもよいし、予めヒド
ロキシアルカノエート単位を主体とする飽和ポリエステ
ル樹脂から成る基材樹脂層に蒸着等させて被膜を形成し
た後に積層してもよい。また、ヒドロキシアルカノエー
ト単位を主体とする飽和ポリエステル樹脂から成る基材
樹脂層と酸素吸収性樹脂層等を予め積層したものを目的
とする容器形状に成形し、この外面側にガスバリヤー性
被膜を蒸着させることもできる。The gas barrier film is formed by previously laminating a base resin layer composed of a saturated polyester resin mainly composed of hydroxyalkanoate units, an oxygen-absorbing resin layer, and the like.
Finally, a film may be formed by vapor deposition or the like, or the film may be formed in advance by forming a film on a base resin layer composed of a saturated polyester resin mainly composed of hydroxyalkanoate units, and then laminated. Further, a base resin layer composed of a saturated polyester resin mainly composed of hydroxyalkanoate units, an oxygen-absorbing resin layer, and the like are preliminarily laminated and molded into a target container shape, and a gas barrier coating is formed on the outer surface side. It can also be deposited.
【0028】(容器及び容器蓋)本発明の容器の製造方
法は特に限定されるものではなく、従来公知の製法によ
り成形される。例えば、上記多層プリフォームを延伸ブ
ロー成形してなるブロー成形体であってもよいし、直接
共射出成形によりカップ、トレイ等の形状に成形した容
器であってもよい。また、シート状の樹脂積層体を加熱
溶融した後、真空成形、圧空成形、或いはプラグアシス
ト成形することによって得られる容器であってもよい。
更に積層体の周辺をヒートシールすることによるパウチ
形状容器等任意の形状にすることができる。また容器蓋
は、上述した各種成形法により容器蓋殻体を成形して容
器蓋とすることもできるし、本発明の積層体を適用すべ
き容器の口部形状にしたシール蓋とすることもできる。(Container and Container Lid) The method for producing the container of the present invention is not particularly limited, and is molded by a conventionally known production method. For example, the multilayer preform may be a blow molded article obtained by stretch blow molding, or may be a container molded into a shape such as a cup or a tray by direct co-injection molding. Further, a container obtained by heating and melting a sheet-shaped resin laminate and then performing vacuum forming, pressure forming, or plug assist forming may be used.
Further, the laminate can be formed into an arbitrary shape such as a pouch-shaped container by heat sealing the periphery. Further, the container lid can be formed into a container lid by molding the container lid shell by the above-described various molding methods, or can be a seal lid formed into a mouth shape of a container to which the laminate of the present invention is applied. it can.
【0029】[0029]
【実施例】次に、具体的な実施例をもって本発明を説明
する。尚、本発明は以下の実施例に限定されるものでは
ない。Next, the present invention will be described with reference to specific examples. The present invention is not limited to the following embodiments.
【0030】(酸素ガスバリヤー性の評価)試作ボトル
を真空チャンバー内に入れ、真空減圧した後、高純度窒
素ガスを流入させ、ボトル内気相を窒素ガス置換した。
その後、ゴム栓にて密封した.酸素濃度20.9%の3
0℃−RH80%条件に保存した。21日後、ガスタイ
トシリンジを用い、ボトル内空気を採取し、GC分析
し、BO2に換算した。(Evaluation of Oxygen Gas Barrier Property) A prototype bottle was placed in a vacuum chamber, and after depressurizing under vacuum, high-purity nitrogen gas was introduced, and the gas phase in the bottle was replaced with nitrogen gas.
Then, it was sealed with a rubber stopper.
Stored at 0 ° C.-80% RH. After 21 days, the air in the bottle was collected using a gas tight syringe, analyzed by GC, and converted to BO2.
【0031】(実施例1)島津製作所ポリ乳酸ラクテー
を用いた。最内層と最外層をポリ乳酸とし、中間層に出
光石油化学社製Poly ipを3重量%メルトブレン
ドしたポリ乳酸樹脂層に有機金属錯体(ステアリン酸コ
バルト)をコバルト濃度5000ppmでメルトブレン
ドした樹脂層を用いた。2本の射出成形機を用い、19
0℃〜200℃条件下、内層から外層に至る層構成が、
ポリ乳酸層/有機金属錯体含有ポリ乳酸層/ポリ乳酸層
の2種3層の口径28mmφのプリフォームを共射出成
形した。尚、金型温度は15℃であった。次にプリフォ
ームを赤外線ヒーターにて65℃〜85℃に再加熱後、
500ml容の平均肉厚300μmのボトルにブロー成
形した。次にCVD蒸着装置にて、ボトル形状の電極と
ボトル内部に設置した電極を用い、ボトル外層とボトル
外壁側電極間の空隙を真空減圧後、ボトル外層面に、ヘ
キサン・アルゴン混合ガスを原料ガスとし、製膜圧0.
1torr、高周波電力13.56MHzのPE−CV
D炭素膜を蒸着した。(Example 1) Polylactic acid lactate of Shimadzu Corporation was used. A resin layer in which the innermost layer and the outermost layer are made of polylactic acid, and an intermediate layer is a polylactic acid resin layer in which Polyip manufactured by Idemitsu Petrochemical Co., Ltd. is melt-blended at 3% by weight, and an organic metal complex (cobalt stearate) is melt-blended at a cobalt concentration of 5000 ppm. Was used. Using two injection molding machines, 19
Under the condition of 0 ° C to 200 ° C, the layer structure from the inner layer to the outer layer is
A preform having a diameter of 28 mmφ of two types and three layers of polylactic acid layer / organic metal complex-containing polylactic acid layer / polylactic acid layer was co-injection molded. The mold temperature was 15 ° C. Next, after reheating the preform to 65 ° C to 85 ° C with an infrared heater,
The bottle was blow-molded into a 500-ml bottle having an average thickness of 300 μm. Next, using a bottle-shaped electrode and an electrode placed inside the bottle, the gap between the outer layer of the bottle and the electrode on the outer wall of the bottle is decompressed by a vacuum using a CVD vapor deposition apparatus. And a film forming pressure of 0.
1-torr, 13.56 MHz high frequency power PE-CV
A D carbon film was deposited.
【0032】(実施例2)島津製作所ポリ乳酸ラクテー
を用いた。最内層をポリ乳酸とし、最外層を出光石油化
学社製Poly ipを3重量%メルトブレンドしたポ
リ乳酸樹脂層に有機金属錯体(ステアリン酸コバルト)
をコバルト濃度5000ppmでメルトブレンドした樹
脂層を用いた。2本の射出成形機を用い、190℃〜2
00℃条件下、内層から外層に至る層構成が、ポリ乳酸
層/有機金属錯体含有ポリ乳酸層の2種2層の口径28
mmφのプリフォームを共射出成形した。尚、金型温度
は15℃であった。次にプリフォームを赤外線ヒーター
にて65℃〜85℃に再加熱後、500ml容の平均肉
厚300μmのボトルにブロー成形した。次にCVD蒸
着装置にて、ボトル形状の電極とボトル内部に設置した
電極を用い、ボトル外層とボトル外壁側電極間の空隙を
真空減圧後、ボトル外層面に、ヘキサン・アルゴン混合
ガスを原料ガスとし、製膜圧0.1torr、高周波電
力13.56MHzのPE−CVD炭素膜蒸着をした。Example 2 Shimadzu polylactic acid lactate was used. An organic metal complex (cobalt stearate) is added to a polylactic acid resin layer in which the innermost layer is polylactic acid and the outermost layer is a 3% by weight melt blend of Polyip manufactured by Idemitsu Petrochemical Co., Ltd.
Was melt-blended at a cobalt concentration of 5000 ppm. 190 ° C. to 2 using two injection molding machines
Under the condition of 00 ° C., the layer structure from the inner layer to the outer layer has a diameter of 28 of two kinds of two layers, a polylactic acid layer / an organic metal complex-containing polylactic acid layer.
A mmφ preform was co-injection molded. The mold temperature was 15 ° C. Next, the preform was reheated to 65 ° C. to 85 ° C. using an infrared heater, and then blow-molded into a 500 ml bottle having an average thickness of 300 μm. Next, using a bottle-shaped electrode and an electrode placed inside the bottle, the gap between the outer layer of the bottle and the electrode on the outer wall of the bottle is decompressed by a vacuum using a CVD vapor deposition apparatus. Then, a PE-CVD carbon film was deposited at a film forming pressure of 0.1 torr and a high frequency power of 13.56 MHz.
【0033】(実施例3)島津製作所ポリ乳酸ラクテー
を用いた。最内層をポリ乳酸とし、最外層を出光石油化
学社製Poly ipを3重量%メルトブレンドしたポ
リ乳酸樹脂層に有機金属錯体(ステアリン酸コバルト)
をコバルト濃度5000ppmでメルトブレンドした樹
脂層を用いた。2本の射出成形機を用い、190℃〜2
00℃条件下、内層から外層に至る層構成が、ポリ乳酸
層/有機金属錯体含有ポリ乳酸層の2種2層の肉厚30
0μm、口部外径90mmの500ml容カップを共射
出成形した。次にCVD蒸着装置にて、カップ形状の電
極電極を用い、カップ外層とカップ外壁側電極間を真空
減圧後、カップ外層面に、ヘキサン・アルゴン混合ガス
を原料ガスとし、製膜圧0.1torr、高周波電力1
3.56MHzのPE−CVD炭素膜蒸着をした。Example 3 Shimadzu polylactic acid lactate was used. An organic metal complex (cobalt stearate) is added to a polylactic acid resin layer in which the innermost layer is polylactic acid and the outermost layer is a 3% by weight melt blend of Polyip manufactured by Idemitsu Petrochemical Co., Ltd.
Was melt-blended at a cobalt concentration of 5000 ppm. 190 ° C. to 2 using two injection molding machines
Under the condition of 00 ° C., the layer structure from the inner layer to the outer layer has a thickness of 30% of the two layers of the polylactic acid layer / organic metal complex-containing polylactic acid layer.
A 500 ml cup having a diameter of 0 μm and a mouth outer diameter of 90 mm was co-injection molded. Next, using a cup-shaped electrode electrode, a vacuum pressure was applied between the outer layer of the cup and the outer wall of the cup using a cup-shaped electrode electrode. , High frequency power 1
A 3.56 MHz PE-CVD carbon film was deposited.
【0034】次に、最内層をポリ乳酸とし、最外層を出
光石油化学社製Poly ipを3重量%メルトブレン
ドしたポリ乳酸樹脂層に有機金属錯体(ステアリン酸コ
バルト)をコバルト濃度5000ppmでメルトブレン
ドした樹脂層を用いた。2本の押出成形機を用い、19
0℃〜200℃条件下、共押出し成形を行い、内層から
外層に至る層構成が、ポリ乳酸層/有機金属錯体含有ポ
リ乳酸層の2種2層の100μm厚のシートを作成し
た。更に、CVD蒸着装置にて、真空減圧後、シート外
層側に、ヘキサン・アルゴン混合ガスを原料ガスとし、
製膜圧0.1torr、高周波電力13.56MHzの
PE−CVD炭素膜蒸着をした。Next, an organometallic complex (cobalt stearate) was melt-blended at a cobalt concentration of 5000 ppm to a polylactic acid resin layer in which the innermost layer was made of polylactic acid and the outermost layer was melt-blended with 3% by weight of Polyip manufactured by Idemitsu Petrochemical Co., Ltd. The used resin layer was used. Using two extruders, 19
Co-extrusion was performed under the conditions of 0 ° C. to 200 ° C. to form a 100 μm-thick sheet composed of two layers, a polylactic acid layer / organic metal complex-containing polylactic acid layer, from the inner layer to the outer layer. Further, after reducing the pressure in a vacuum using a CVD deposition apparatus, a mixed gas of hexane and argon is used as a source gas on the outer layer side of the sheet.
A PE-CVD carbon film was deposited at a film forming pressure of 0.1 torr and a high frequency power of 13.56 MHz.
【0035】(比較例1)島津製作所ポリ乳酸ラクテー
を用いた。射出成形機を用い、190℃〜200℃条件
下、口径28mmφのプリフォームを射出成形した。金
型温度は15℃であった。次にプリフォームを赤外線ヒ
ーターにて65℃〜85℃に再加熱後、金型ブロー成形
機を用い、500ml容の平均肉厚300μmのブロー
ボトルに作成した。(Comparative Example 1) Polylactic acid lactate of Shimadzu Corporation was used. Using an injection molding machine, a preform having a diameter of 28 mmφ was injection molded under the conditions of 190 ° C to 200 ° C. The mold temperature was 15 ° C. Next, the preform was reheated to 65 ° C. to 85 ° C. with an infrared heater, and then formed into a 500 ml blow bottle having an average thickness of 300 μm using a mold blow molding machine.
【0036】(比較例2)島津製作所ポリ乳酸ラクテー
を用いた。最内層と最外層をポリ乳酸とし、中間層に出
光石油化学社製Poly ipを3重量%メルトブレン
ドしたポリ乳酸樹脂層に有機金属錯体(ステアリン酸コ
バルト)をコバルト濃度5000ppmでメルトブレン
ドした樹脂層を用いた。2本の射出成形機を用い、19
0℃〜200℃条件下、内層から外層に至る層構成が、
ポリ乳酸層/有機金属錯体含有ポリ乳酸層/ポリ乳酸層
の2種3層の口径28mmφのプリフォームを共射出成
形した。金型温度は15℃であった。次にプリフォーム
を赤外線ヒーターにて65℃〜85℃に再加熱後、50
0ml容の平均肉厚300μmの金型ブローボトルに二
軸延伸成形した。(Comparative Example 2) Polylactic acid lactate of Shimadzu Corporation was used. A resin layer in which the innermost layer and the outermost layer are made of polylactic acid, and an intermediate layer is a polylactic acid resin layer in which Polyip manufactured by Idemitsu Petrochemical Co., Ltd. is melt-blended at 3% by weight, and an organic metal complex (cobalt stearate) is melt-blended at a cobalt concentration of 5000 ppm. Was used. Using two injection molding machines, 19
Under the condition of 0 ° C to 200 ° C, the layer structure from the inner layer to the outer layer is
A preform having a diameter of 28 mmφ of two types and three layers of polylactic acid layer / organic metal complex-containing polylactic acid layer / polylactic acid layer was co-injection molded. The mold temperature was 15 ° C. Next, after reheating the preform to 65 to 85 ° C. with an infrared heater,
It was biaxially stretched and molded into a mold blow bottle having an average thickness of 300 μm having a volume of 0 ml.
【0037】(比較例3)島津製作所ポリ乳酸ラクテー
を用いた。射出成形機を用い、190℃〜200℃条件
下、口径28mmφのプリフォームを射出成形した。金
型温度は15℃であった。次にプリフォームを赤外線ヒ
ーターにて65℃〜85℃に再加熱後、金型ブロー成形
機を用い、500ml容の平均肉厚300μmの金型ブ
ローボトルに二軸延伸成形した。次にCVD蒸着装置に
て、ボトル形状の電極とボトル内部に設置した電極を用
い、ボトル外層とボトル外壁側電極間の空隙を真空減圧
後、ボトル外層面に、ヘキサン・アルゴン混合ガスを原
料ガスとし、製膜圧0.1torr、高周波電力13.
56MHzのPE−CVD炭素膜蒸着をした。(Comparative Example 3) Polylactic acid lactate of Shimadzu Corporation was used. Using an injection molding machine, a preform having a diameter of 28 mmφ was injection molded under the conditions of 190 ° C to 200 ° C. The mold temperature was 15 ° C. Next, the preform was reheated to 65 ° C. to 85 ° C. with an infrared heater, and then biaxially stretch-molded into a 500 ml volume blow mold bottle having an average thickness of 300 μm using a mold blow molding machine. Next, the gap between the outer layer of the bottle and the electrode on the outer wall of the bottle was evacuated using a bottle-shaped electrode and an electrode placed inside the bottle with a CVD vapor deposition apparatus. 12. The film forming pressure is 0.1 torr and the high frequency power is 13.
A 56 MHz PE-CVD carbon film was deposited.
【0038】(比較例4)島津製作所ポリ乳酸ラクテー
を用いた。射出成形機を用い、190℃〜200℃条件
下、射出成形を行い、ポリ乳酸樹脂のみから成る肉厚3
00μm、口部外径90mmの500ml容カップを成
形した。次にプリフォームを赤外線ヒーターにて65℃
〜85℃に再加熱後、金型ブロー成形機を用い、500
ml容の平均肉厚300μmの金型ブローボトルに二軸
延伸成形した。次にCVD蒸着装置にて、カップ形状の
電極を用い、カップ外層とカップ外壁側電極間を真空減
圧後、カップ外層面に、ヘキサン・アルゴン混合ガスを
原料ガスとし、製膜圧0.1torr、高周波電力1
3.56MHzのPE−CVD炭素膜蒸着をした。次に
ポリ乳酸から成る100μm厚のシートを押出し成形し
た。更にCVD蒸着装置にて、真空減圧後、シート外層
側に、ヘキサン・アルゴン混合ガスを原料ガスとし、製
膜圧0.1torr、高周波電力13.56MHzのP
E−CVD炭素膜蒸着をした。(Comparative Example 4) Polylactic acid lactate of Shimadzu Corporation was used. Injection molding is performed using an injection molding machine under the conditions of 190 ° C to 200 ° C, and the thickness is made of only polylactic acid resin.
A 500 ml cup having a diameter of 00 μm and an outer diameter of 90 mm was formed. Next, the preform is heated to 65 ° C with an infrared heater.
After reheating to 85 ° C., using a mold blow molding machine,
It was biaxially stretched and molded into a mold blow bottle having an average thickness of 300 μm and a ml volume. Next, using a cup-shaped electrode, a vacuum pressure was applied between the cup outer layer and the cup outer wall side electrode using a cup-shaped electrode, and then a hexane / argon mixed gas was used as a raw material gas on the cup outer layer surface at a film forming pressure of 0.1 torr. High frequency power 1
A 3.56 MHz PE-CVD carbon film was deposited. Next, a 100 μm-thick sheet made of polylactic acid was extruded. Further, after reducing the pressure in a vacuum by a CVD vapor deposition apparatus, a hexane / argon mixed gas was used as a raw material gas, and a film forming pressure of 0.1 torr and a high frequency power of 13.56 MHz
E-CVD carbon film deposition was performed.
【0039】[0039]
【表1】 [Table 1]
【0040】[0040]
【発明の効果】本発明の樹脂積層体によれば、ヒドロキ
シアルカノエート単位を主体とする飽和ポリエステル樹
脂を樹脂成分として含有する樹脂積層体であって、酸素
吸収性を有する樹脂層を少なくとも一層及びガスバリヤ
ー性被覆を少なくとも一層含んで成ることにより、優れ
た生分解性を有しながら、酸素吸収性及びガスバリヤー
性を有することが可能となった。特に酸素吸収性樹脂層
がヒドロキシアルカノエート単位を主体とする飽和ポリ
エステル樹脂を樹脂成分として含有する生分解性樹脂及
び有機遷移金属塩或いは更に不飽和炭化水素を含有する
樹脂組成物から成り、またガスバリヤー性被覆が無機蒸
着被膜からなることにより、増大した酸素吸収速度を有
すると共に透明性を付与することも可能になった。また
本発明の樹脂積層体から成る容器及び容器蓋によれば、
生分解性を有すると共に、優れた内容物の香味保持性及
び保存性を付与することが可能となった。According to the present invention, there is provided a resin laminate containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component, wherein at least one oxygen-absorbing resin layer is provided. By including at least one gas barrier coating, it is possible to have oxygen absorption and gas barrier properties while having excellent biodegradability. In particular, the oxygen-absorbing resin layer is composed of a biodegradable resin containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component and a resin composition containing an organic transition metal salt or further unsaturated hydrocarbon, and a gas. The fact that the barrier coating comprises an inorganic vapor-deposited coating makes it possible to have an increased oxygen absorption rate and to impart transparency. According to the container and the container lid made of the resin laminate of the present invention,
In addition to having biodegradability, it has become possible to impart excellent flavor retention and preservation of contents.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) // B32B 9/00 B32B 9/00 A Fターム(参考) 3E086 AB01 AD01 AD04 AD05 AD06 BA04 BA15 BA40 BB01 BB05 BB90 4F100 AA01A AA37 AH04B AK02B AK41B AK41C AL05B AR00A BA03 BA04 BA07 BA10A BA10B EH31 EH36 EH66A GB16 GB18 JC00B JD02A JD03B JM02 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI theme coat ゛ (reference) // B32B 9/00 B32B 9/00 A F term (reference) 3E086 AB01 AD01 AD04 AD05 AD06 BA04 BA15 BA40 BB01 BB05 BB90 4F100 AA01A AA37 AH04B AK02B AK41B AK41C AL05B AR00A BA03 BA04 BA07 BA10A BA10B EH31 EH36 EH66A GB16 GB18 JC00B JD02A JD03B JM02
Claims (6)
する飽和ポリエステル樹脂を樹脂成分として含有する樹
脂積層体であって、酸素吸収性を有する樹脂層を少なく
とも一層及びガスバリヤー性被覆を少なくとも一層含ん
で成ることを特徴とする樹脂積層体。1. A resin laminate containing, as a resin component, a saturated polyester resin mainly composed of hydroxyalkanoate units, comprising at least one resin layer having oxygen absorbability and at least one gas barrier coating. A resin laminate characterized by the above-mentioned.
エート単位を主体とする飽和ポリエステル樹脂を樹脂成
分として含有する生分解性樹脂及び有機遷移金属塩或い
は更に不飽和炭化水素を含有する樹脂組成物から成るこ
とを特徴とする請求項1記載の樹脂積層体。2. An oxygen-absorbing resin layer comprising a biodegradable resin containing a saturated polyester resin mainly composed of hydroxyalkanoate units as a resin component and a resin composition containing an organic transition metal salt or further unsaturated hydrocarbon. The resin laminate according to claim 1, wherein:
ることを特徴とする請求項1又は2に記載の樹脂積層
体。3. The resin laminate according to claim 1, wherein the gas barrier coating is an inorganic vapor-deposited coating.
を主体とする飽和ポリエステル樹脂を樹脂成分として含
有する生分解性樹脂層を有することを特徴とする請求項
1乃至3の何れかに記載の樹脂積層体。4. The resin laminate according to claim 1, further comprising a biodegradable resin layer containing, as a resin component, a saturated polyester resin mainly composed of hydroxyalkanoate units on the inner surface side. body.
層体から成ることを特徴とする容器。5. A container comprising the resin laminate according to any one of claims 1 to 4.
層体から成ることを特徴とする容器蓋。6. A container lid comprising the resin laminate according to any one of claims 1 to 4.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000403346A JP4003396B2 (en) | 2000-12-28 | 2000-12-28 | Biodegradable resin laminate, container and container lid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000403346A JP4003396B2 (en) | 2000-12-28 | 2000-12-28 | Biodegradable resin laminate, container and container lid |
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JP2002200725A true JP2002200725A (en) | 2002-07-16 |
JP2002200725A5 JP2002200725A5 (en) | 2005-10-06 |
JP4003396B2 JP4003396B2 (en) | 2007-11-07 |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003070459A1 (en) * | 2002-02-21 | 2003-08-28 | Kao Corporation | Biodegradable film |
JP2003311868A (en) * | 2002-02-21 | 2003-11-06 | Kao Corp | Biodegradable film |
JP2006168733A (en) * | 2004-12-10 | 2006-06-29 | Mikasa Sangyo Kk | Biodegradable resin-made cap |
JP2007029668A (en) * | 2004-08-05 | 2007-02-08 | Bridgestone Sports Co Ltd | Golf ball material, golf ball and method for preparing golf ball material |
JPWO2006046582A1 (en) * | 2004-10-29 | 2008-05-22 | 三笠産業株式会社 | Biodegradable hinge cap |
JP2008155438A (en) * | 2006-12-22 | 2008-07-10 | Dainippon Printing Co Ltd | Heat-sealable film having barrier properties |
JP2008155432A (en) * | 2006-12-22 | 2008-07-10 | Dainippon Printing Co Ltd | Heat-sealable film having barrier properties |
US8106115B2 (en) | 2004-08-05 | 2012-01-31 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
-
2000
- 2000-12-28 JP JP2000403346A patent/JP4003396B2/en not_active Expired - Fee Related
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003070459A1 (en) * | 2002-02-21 | 2003-08-28 | Kao Corporation | Biodegradable film |
JP2003311868A (en) * | 2002-02-21 | 2003-11-06 | Kao Corp | Biodegradable film |
JP2007029668A (en) * | 2004-08-05 | 2007-02-08 | Bridgestone Sports Co Ltd | Golf ball material, golf ball and method for preparing golf ball material |
US8106115B2 (en) | 2004-08-05 | 2012-01-31 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
US8461268B2 (en) | 2004-08-05 | 2013-06-11 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
JPWO2006046582A1 (en) * | 2004-10-29 | 2008-05-22 | 三笠産業株式会社 | Biodegradable hinge cap |
JP2006168733A (en) * | 2004-12-10 | 2006-06-29 | Mikasa Sangyo Kk | Biodegradable resin-made cap |
JP2008155438A (en) * | 2006-12-22 | 2008-07-10 | Dainippon Printing Co Ltd | Heat-sealable film having barrier properties |
JP2008155432A (en) * | 2006-12-22 | 2008-07-10 | Dainippon Printing Co Ltd | Heat-sealable film having barrier properties |
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