TWI762499B - 氧阻障塑料 - Google Patents
氧阻障塑料 Download PDFInfo
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- TWI762499B TWI762499B TW106124937A TW106124937A TWI762499B TW I762499 B TWI762499 B TW I762499B TW 106124937 A TW106124937 A TW 106124937A TW 106124937 A TW106124937 A TW 106124937A TW I762499 B TWI762499 B TW I762499B
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- Prior art keywords
- layer
- esters
- packaging film
- multilayer packaging
- film according
- Prior art date
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 162
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000001301 oxygen Substances 0.000 title claims abstract description 160
- 230000004888 barrier function Effects 0.000 title claims abstract description 113
- 229920003023 plastic Polymers 0.000 title claims abstract description 14
- 239000004033 plastic Substances 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title abstract description 22
- 230000002000 scavenging effect Effects 0.000 claims abstract description 55
- -1 polyacrylonitrils Polymers 0.000 claims abstract description 42
- 239000000654 additive Substances 0.000 claims abstract description 26
- 229920006281 multilayer packaging film Polymers 0.000 claims abstract description 23
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 12
- 239000004793 Polystyrene Substances 0.000 claims abstract description 11
- 229920002223 polystyrene Polymers 0.000 claims abstract description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 10
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims abstract description 9
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 9
- 229920002647 polyamide Polymers 0.000 claims abstract description 8
- 239000004952 Polyamide Substances 0.000 claims abstract description 7
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 4
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 196
- 239000000203 mixture Substances 0.000 claims description 40
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 claims description 31
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 29
- NDTYTMIUWGWIMO-UHFFFAOYSA-N perillyl alcohol Chemical compound CC(=C)C1CCC(CO)=CC1 NDTYTMIUWGWIMO-UHFFFAOYSA-N 0.000 claims description 29
- WONIGEXYPVIKFS-UHFFFAOYSA-N Verbenol Chemical compound CC1=CC(O)C2C(C)(C)C1C2 WONIGEXYPVIKFS-UHFFFAOYSA-N 0.000 claims description 28
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 28
- 150000007860 aryl ester derivatives Chemical class 0.000 claims description 17
- 125000005907 alkyl ester group Chemical group 0.000 claims description 16
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 claims description 16
- 235000000484 citronellol Nutrition 0.000 claims description 16
- 229930007631 (-)-perillyl alcohol Natural products 0.000 claims description 15
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 15
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 claims description 15
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 claims description 15
- 239000005792 Geraniol Substances 0.000 claims description 15
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 claims description 15
- 229940113087 geraniol Drugs 0.000 claims description 15
- 229930007744 linalool Natural products 0.000 claims description 15
- 235000005693 perillyl alcohol Nutrition 0.000 claims description 15
- IRZWAJHUWGZMMT-UHFFFAOYSA-N Chrysanthenol Natural products CC1=CCC2C(C)(C)C1C2O IRZWAJHUWGZMMT-UHFFFAOYSA-N 0.000 claims description 14
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 claims description 10
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 claims description 10
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 claims description 10
- 239000012790 adhesive layer Substances 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- 229930006722 beta-pinene Natural products 0.000 claims description 10
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 claims description 10
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 claims description 10
- 150000003097 polyterpenes Chemical class 0.000 claims description 10
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 claims description 9
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 8
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 8
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- IBVJWOMJGCHRRW-UHFFFAOYSA-N 3,7,7-Trimethylbicyclo[4.1.0]hept-2-ene Chemical compound C1CC(C)=CC2C(C)(C)C12 IBVJWOMJGCHRRW-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 claims description 6
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 claims description 6
- GJWSUKYXUMVMGX-UHFFFAOYSA-N citronellic acid Chemical compound OC(=O)CC(C)CCC=C(C)C GJWSUKYXUMVMGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002098 nerolidol derivatives Chemical class 0.000 claims description 6
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 6
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 claims description 6
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- FUDNBFMOXDUIIE-SNVBAGLBSA-N (S)-3,7-Dimethyl-1,6-octadiene Chemical compound C=C[C@@H](C)CCC=C(C)C FUDNBFMOXDUIIE-SNVBAGLBSA-N 0.000 claims description 4
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims description 4
- UZFLPKAIBPNNCA-UHFFFAOYSA-N alpha-ionone Natural products CC(=O)C=CC1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-UHFFFAOYSA-N 0.000 claims description 4
- UZFLPKAIBPNNCA-BQYQJAHWSA-N alpha-ionone Chemical compound CC(=O)\C=C\C1C(C)=CCCC1(C)C UZFLPKAIBPNNCA-BQYQJAHWSA-N 0.000 claims description 4
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 4
- 229930006739 camphene Natural products 0.000 claims description 4
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims description 4
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 claims description 4
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 4
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 claims description 3
- DCSCXTJOXBUFGB-JGVFFNPUSA-N (R)-(+)-Verbenone Natural products CC1=CC(=O)[C@@H]2C(C)(C)[C@H]1C2 DCSCXTJOXBUFGB-JGVFFNPUSA-N 0.000 claims description 3
- DCSCXTJOXBUFGB-SFYZADRCSA-N (R)-(+)-verbenone Chemical compound CC1=CC(=O)[C@H]2C(C)(C)[C@@H]1C2 DCSCXTJOXBUFGB-SFYZADRCSA-N 0.000 claims description 3
- IBVJWOMJGCHRRW-DTWKUNHWSA-N 2-Carene Natural products C1CC(C)=C[C@H]2C(C)(C)[C@@H]12 IBVJWOMJGCHRRW-DTWKUNHWSA-N 0.000 claims description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 claims description 3
- 229930008398 Citronellate Natural products 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229930006737 car-3-ene Natural products 0.000 claims description 3
- 229930003633 citronellal Natural products 0.000 claims description 3
- 235000000983 citronellal Nutrition 0.000 claims description 3
- KDMCQAXHWIEEDE-UHFFFAOYSA-L cobalt(2+);7,7-dimethyloctanoate Chemical compound [Co+2].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O KDMCQAXHWIEEDE-UHFFFAOYSA-L 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- RUMOYJJNUMEFDD-UHFFFAOYSA-N perillyl aldehyde Chemical compound CC(=C)C1CCC(C=O)=CC1 RUMOYJJNUMEFDD-UHFFFAOYSA-N 0.000 claims description 3
- DCSCXTJOXBUFGB-UHFFFAOYSA-N verbenone Natural products CC1=CC(=O)C2C(C)(C)C1C2 DCSCXTJOXBUFGB-UHFFFAOYSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 239000001169 1-methyl-4-propan-2-ylcyclohexa-1,4-diene Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000005973 Carvone Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001862 citronellol derivatives Chemical class 0.000 claims description 2
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 claims description 2
- TZWGXFOSKIHUPW-UHFFFAOYSA-L cobalt(2+);propanoate Chemical compound [Co+2].CCC([O-])=O.CCC([O-])=O TZWGXFOSKIHUPW-UHFFFAOYSA-L 0.000 claims description 2
- 235000001510 limonene Nutrition 0.000 claims description 2
- 229940087305 limonene Drugs 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229920006280 packaging film Polymers 0.000 claims description 2
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- 150000007875 phellandrene derivatives Chemical class 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 claims 2
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 claims 2
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical compound COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 claims 1
- YXAGIRHBJJLWHW-UHFFFAOYSA-N Ethyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC YXAGIRHBJJLWHW-UHFFFAOYSA-N 0.000 claims 1
- 150000002085 enols Chemical class 0.000 claims 1
- ACXGEQOZKSSXKV-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O.CCCCCCCC(O)=O ACXGEQOZKSSXKV-UHFFFAOYSA-N 0.000 claims 1
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 15
- 230000008569 process Effects 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
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- B32B2307/70—Other properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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Abstract
本發明關於多層包裝膜,其包含至少三不同類型的層(A)、(B)及(C):(A)為至少一外層,(B)為至少一被動氧阻障層,(C)為至少一主動氧清除層,其特徵在於-該至少一外層(A)為熱塑性聚合物;-該至少一被動氧阻障層(B)係選自由下列所組成之群組:乙烯乙烯醇共聚物、聚氯乙烯、聚氯乙烯共聚物、聚乙烯醇、聚偏二氯乙烯、聚偏二氯乙烯共聚物、聚丙烯腈、聚丙烯腈共聚物、聚對酞酸乙二酯、聚萘二甲酸乙二酯、聚喃二甲酸乙二酯、聚矽氧烷和聚醯胺;-該至少一個主動氧清除層(C)包含a)塑料,其為聚烯烴、聚烯烴共聚物或聚苯乙烯;以及添加劑(b)和(c),其中b)為聚萜烯樹脂;及c)為過渡金屬觸媒。
Description
本發明關於包含有機聚合物及聚萜烯樹脂主動氧阻障物之氧阻障塑料,以提高氧敏感性產品在包裝應用中的品質和儲存壽命。本發明亦關於可加工成多層剛性容器或撓性膜之氧阻障塑料,以賦予,與本領域中已知的其他氧阻障組成物相比,提高透明度之氧阻障性質。此外,本發明關於氧阻障組成物於食品、飲料和醫藥包裝之用途以及關於包含該氧阻障組成物之塑料和物件。
就本發明之目的,母料(masterbatch)(MB)為包含聚合物載體(polymeric carrier)或液體媒劑(liquid vehicle)及添加劑之組成物,其中添加劑係以比在最終應用中或在最終物件中更高的濃度存在於母料中,且載體不必需為最終應用或最終物件之有機聚合物。在母料中的添加劑之較佳濃度較佳為0.5至90重量%、更佳為1至80重量%之範圍內,重量%在各例子中係以母料之總重量為基準計。
就本發明之目的,混合物(CO)為包含有機聚合物及添加劑之組成物,其中添加劑係以最終應用或最終物件的所
欲濃度存在於混合物中,且有機聚合物為最終應用或最終物件之有機聚合物,使得化合物僅藉助於物理成型法而成為最終應用或最終物件之所欲形狀。
用於食品和飲料、個人護理、醫療、醫藥、家用和工業產品之包裝需要對氧有高阻障性以保存包裝內容物的鮮度及品質。由傳統材料(如玻璃或金屬)製成的容器對物質自容器離開及物質自環境進入二者提供極佳的阻障性。大部分的情況中,可忽略通過玻璃或金屬容器的氣體滲透。不過,由於與諸如玻璃和金屬之材料相比為可具低成本及功能優勢(諸如熱密封性(thermo-sealability)、可微波性(microwavability)、光學性質、輕量、減少破裂及不受限制的尺寸與形狀),使得近年來越來越多地將塑料用於包裝。常用於包裝應用的聚合物材料為聚烯烴(亦即LDPE、LLDPE、PP)及聚對酞酸乙二酯樹脂(PET)。聚烯烴(從現在起稱為PO)及PET二者具有許多用於包裝應用的有利性質,但是彼等不具有在許多氧敏感性應用中所需或所欲之氣體阻障性質。事實上,有聚合物,例如,為良好的氧阻障物,但為差的水蒸氣阻障物,反之亦然。阻障聚合物往往依賴偶極-偶極交互作用以降低鏈遷移性(chain mobility),且因此降低滲透物的擴散移動(diffusional movement)。不具有偶極-偶極交互作用的聚合物(如PO)溶解極少量的水,但是對非極性分子(如O2和CO2)具有高親
和性且極具可滲透性。另一方面,PET不具有多孔性且與氧的交互作用不佳,儘管水分子容易氫鍵結且滲透過基質。
已提出許多克服與塑料容器相關的阻障問題之解決辦法。
已開發例如包含混合型聚合物層之多層結構的包裝工業。該等層合式包裝容器提供雖不相當但接近於玻璃和鋼者的改良阻障性質。維持可回收性、阻障性質與透明度(clarity)的適當平衡在許多剛性和撓性包裝應用中最為關鍵。
使用含有較高的阻障聚合物材料(與外聚合物層相比)的內層(有時為夾層)之多層膜或瓶是尋常的事。中心層通常為高阻障聚合物,其減慢氧通過容器壁的滲透性。此等系統被歸類為被動阻障。最常見的高阻障聚合物的實例包括乙烯-乙烯醇(EVOH)及聚醯胺。用於此等多層結構的常見構造會包含PO內層和外層與乙烯-乙烯醇(EVOH)中心層或是PET聚合物內層和外層與聚醯胺中心層。
使用聚合物(諸如EVOH)代替賦予氧阻障性質之其他材料(諸如薄的金屬箔片或無機氧化物之蒸氣沈積層)的優點之一在於可利用聚合物加工技術(諸如擠壓、射出模塑(injection moulding)、吹膜(film blowing))而無須任何在製造之後的後處理。然而,EVOH會有水敏感性的缺點,且為了維持其氧阻障性質,通常必需以濕氣阻障材料(諸如聚烯烴)塗佈或層合。EVOH的此缺點意味著塑料改革者
(transformer)及食品、醫藥、個人護理、消費品和電子產品目前所面臨的主要挑戰。事實上,情況是在大於65%(依照ISO 144663-2)之相對濕度(從現在起稱為r.h.)條件下,EVOH會因其羥基的親水性質而緩慢地吸收來自環境的濕氣,直到達到r.h.平衡為止。在此過程期間,EVOH失去其晶體結構且因此失去其對抗氧進入的阻障性質。例如,食品包裝物件容易暴露於各種環境中的此等條件,例如在運輸過潮濕熱帶型氣候的國家期間或更簡單地當包裝具有高水分含量的食品時。高的r.h.不是對使用EVOH之包裝的氧阻障性質具不利效應的唯一情況;低至30℃之溫度亦具有負面效應。在此例子中,阻障性質的損失係隨溫度的增加而呈指數進展,最終導致EVOH完全無效的點。於此點,氧係藉由滲透過包裝壁而自由進入包裝中且因此無可避免地造成加速其敏感內容物的變質過程。此不利效應(由於濕度及/或高溫二者)為持續較長者,且其(在EVOH分子之晶體結構重新建立之前)通常可耗達7天(假如在此期間該包裝可避免上述條件)。對食品製造商的影響極大,因為由於所包裝之產品的性質(亦即熱及/或無菌裝填需要以在高達120℃及更高的溫度下加熱之產品裝填容器),無法在高r.h.及/或高溫條件下提供冷鏈倉儲(cold chain storage)或延遲運輸時間,不可避免地縮短食品的儲存壽命。一些其他重大影響為由於公司不能保證儲存壽命足夠長到能全球配銷其所有產品,而使全世界每年浪費大量的食品。
為了進一步減少氧進入包裝,可將少量的過渡金屬鹽
添加至PO摻合物中以催化且積極地促進添加劑的氧化反應,藉此進一步提高包裝本身的氧阻障特性。使物質以化學或生物方式消耗氧或與氧反應以提供氧阻障性質的此方法是所知的主動氧阻障,且係不同於試圖以物理方式減慢氧滲透過包裝壁的被動氧阻障。
目前可行的解決辦法包含使用相當複雜的系統。這些往往需要有水存在以活化氧清除劑。濕氣必須是例如來自容鈉於包裝內的產品(最常為食品本身)且因此例如乾食便被排除在可應用該等技術之應用範圍之外。另外,在其他的例子中,需要以U.V.-Vis照射以活化阻障成份的清除作用,因此需要使用額外的處理步驟。
除了所包裝之產品的純粹性能及防護以外,外觀亦為產品差異化的關鍵元素。透明材料的趨勢已成為近年來食品包裝工業的關鍵且持續得勢。在那些需要透明度(clarity)的應用,尤其是PO應用中,包裝物件應具有接近於純聚合物(virgin polymer)的那些光學性質。產品能見度在功能上及美觀上皆為有力的工具。其使終端消費者不用打開包裝便能輕易地看見他們購買的產品且檢視其外觀,且使產品製造商能以視覺系統、金屬檢測器和手動視覺檢查容易地檢查包裝之產品。
如所述,在由氧阻障材料與樹脂(諸如PO)之摻合物製成的包裝物件之阻障層中,霧度(haze)可來自於I)阻障材料與基底聚合物的不混溶性,II)無法產生小至足以不干擾光通過之分散相域(disperse-phase domain),及III)阻障材
料對PO之結晶行為的不利影響。使此霧度最小化之一方法為仔細選擇基底樹脂以改進阻障材料的分散且因此降低(但非實質消除)霧度及使不利的結晶效應最小化。此方法可能限制了基底聚合物樹脂的選擇。另一方法為使用充當為相容劑(compatibilizer)以降低霧度之組成物。該等方法增加阻障層的成本且相容劑增加額外的材料,必須評估其與食品接觸的適合性。因此,對改進之塑料有需求,其提供高的氧阻障能力且實質上為透明的。
與例如藉由將阻障材料放在小的高透氧囊內而與食品分開的創作相比,將主動氧阻障添加劑直接包括在最終物件之聚合物基質中的可能性表現出了明顯的優點。此系統的缺點包括需要額外的包裝步驟,還有若囊萬一破裂時之潛在污染風險或萬一被消費者意外吞食之風險。
US-8609744揭示氧清除混合物,其包含可氧化的金屬組份及尤其欲與LDPE混合之電解質組份。此等系統的缺點在於必需要來自食品本身的濕氣以觸發清除作用(scavenging effect),因此無法應用於乾食。
EP-2112201揭示一組成物,其包含聚烯烴、以金屬為基底之氧清除劑、黏土或成核劑以及含有EVOH、奈米黏土和相容劑的以聚醯胺尼龍(polyamide nylon)為基底之母料。
EP-0918818揭示氧清除組成物,其包含可氧化的聚萜烯及有效催化塑料中的氧清除之金屬觸媒。僅說明單層膜的應用。
WO-9625058揭示氧清除系統,其中可氧化的聚萜烯及金屬觸媒必須置於單層膜之兩個別層中。
WO 02/36670揭示硬脂酸鈷與可氧化的樹脂之母料。
總而言之,已進行許多製備氧阻障及/或氧清除物件之嘗試。已有許多涉及使用層合結構之方法及其他涉及併入無機粉末、鹽類及/或犧牲型可氧化化合物之方法。大多數該等系統具有至少一或數個缺點,包括差的加工性質、危及膜機械強度、若暴露於某些相對濕度或溫度時缺乏阻障效果、不足的氧攝取、濕氣或UV-Vis活化要求,以及大多數的該等系統亦有不佳的透明度及缺乏可回收性。
對能滿足所有所述要求的改進之氧阻障組成物、製造該等組成物之方法及使用該等組成物於包裝物件中之方法仍有需求。尤其對具有極佳的阻障及清除能力之多層透明的薄壁物件和容器仍有需求,彼等的性能不依賴於為了保有被動阻障性質而不存在濕氣或高溫或者為了活化清除效應而存在水或UV光。
特別是,想要獲得改進之氣體阻障PO組成物,其可經吹塑或鑄成膜或片材或擠壓吹塑成多層容器,具有降低的霧度且無需任何進一步的活化。這是需要(較)長的儲存壽命(如生鮮或加工肉品、即食性膳食和其他氧敏感性材料)之容器所需求的。
在本發明之範圍內的是具有多層氧阻障組份之多層
膜,包含至少三層,其中該等層中之至少一者為被動氧阻障層(passive oxygen barrier layer)以及該等層中之至少一者為主動氧清除層(active oxygen scavenging layer),該主動氧清除層以比氧滲透過包裝壁還快的速率吸收氧且係夾在被動氧阻障層與包裝內部之間。另外,儲存壽命產品要求使氧清除活性應維持長期的時間。
已驚訝地發現:(a)藉由使用以聚萜烯(polyterpene)為基底之添加劑作為聚烯烴塑料中的主動氧清除劑(active oxygen scavenger)與過渡金屬觸媒組合,如下文所說明,(b)當如(a)中的此系統構成多層塑料膜的一或多層時(其中該等層中至少一者就被動阻障層及包裝內部而言為在內側的),(c)當此多層膜暴於高的相對濕度(65%或更高)及/或高溫(30℃或更高)的條件時,包裝材料之阻障性質係-保持在相當於在較低的r.h.條件(低於65%)下儲存之包裝者,及/或-改進達1.5倍,相較於較低溫(低於30℃)下儲存之包裝物件。
這歸功於主動氧清除層,其能夠補償通過包裝壁增加的氧進入,甚至是在高r.h.或高溫的環境或誘導條件改變被動阻障層之晶體結構(其隨後不再能夠阻擋O2進入)時。
本發明關於多層包裝膜,其包含至少三不同類型的層(A)、(B)及(C):(A)為至少一外層,(B)為至少一被動氧阻障層(passive oxygen barrier layer),(C)為至少一主動氧清除層(active oxygen scavenging layer),其特徵在於-至少一外層(A)為熱塑性聚合物,較佳地選自由下列所組成之群組:聚烯烴(polyolefin)、聚苯乙烯、聚胺甲酸酯(polyurethane)、聚氯乙烯及彼等之共聚物;-至少一被動氧阻障層(B)係選自由下列所組成之群組:乙烯乙烯醇共聚物(ethylene vinyl alcohol copolymer)、聚氯乙烯、聚氯乙烯共聚物、聚乙烯醇(polyvinyl alcohol)、聚偏二氯乙烯(polyvinylidene dichloride)、聚偏二氯乙烯共聚物、聚丙烯腈、聚丙烯腈共聚物、聚對酞酸乙二酯(polyethylene terephthalate)、聚萘二甲酸乙二酯(polyethylene naphthalate)、聚喃二甲酸乙二酯(polyethylenefuranoate)、聚矽氧烷和聚醯胺;-至少一主動氧清除層(C)包含a)塑料,其為聚烯烴、聚烯烴共聚物或聚苯乙烯;以及添加劑(b)和(c):其中b)為聚萜烯樹脂(polyterpenic resin),較佳地藉由環狀或非環狀單萜烯烴類(monoterpene hydrocarbon)之聚合
及/或共聚合而製得;c)為過渡金屬觸媒。
用語外層係定義位於包裝物件外部之層且其通常與周圍環境接觸。
在本發明一較佳的實施態樣中,多層包裝膜進一步包含至少一內層(D),其為熱塑性聚合物,較佳地選自由下列所組成之群組:聚烯烴、聚苯乙烯、聚胺甲酸酯、聚氯乙烯以及彼等之共聚物。
用語內層係定義包裝的最內層之層。內層充當為密封層(sealant layer),其為與容納在包裝內部的產品直接接觸者。
根據本發明,添加劑b)與c)組合在相同的氧清除層中。
在另一實施態樣中,多層包裝膜包含氧阻障組份,其中被動阻障層係夾在兩主動氧清除層之間。
在一些實施態樣中,黏著層(adhesive layer)或功能層(functional layer)可置於不同的層(A)、(B)及/或(C)及/或隨意地(optionally)D之間。
根據本發明之多層包裝膜可用於許多包裝物件中,諸如,但不限於:膜、撓性(flexible)或剛性(rigid)片材、可撓袋(flexible bag)、小袋(pouch)、層合式(laminated)或非層合式(not-laminated)熱成型容器、剛性或半剛性(semi-rigid)容器或彼等之組合。
已如此於本文以通用用語說明本發明,隨後為所附圖
表及圖式之簡要解釋。在應用時,該等不一定按比例繪製。本發明於多層結構的應用性非僅限於下列結構,而是還有類似的層合式或非層合式多層結構。在圖中,〝被動層〞意指被動氧阻障層,〝主動層〞意指主動氧清除層。
圖1:此為依照本發明之一多層膜的橫截面側視圖。可觀察到主動氧清除層係夾在被動氧阻障層與包裝內部或另外的內層/密封層之間。因不同的層之間的相容性問題而需要時,膜可能包括連結層(tie layer)或黏著層。
圖2:此為依照本發明之一多層膜的橫截面側視圖。可觀察到被動氧阻障層係夾在兩主動氧清除層之間。膜可能包括在主動層與被動阻障層之間或在主動層與相鄰的外層及/或隨意的內層之間的連結層。
圖3:此為依照本發明之一多層膜的橫截面側視圖。可觀察到主動氧清除層係夾在兩相繼的被動氧阻障層與包裝內部或另外的內層/密封層之間。因不同的層之間的相容性問題而需要時,膜可能包括連結層或黏著層。
圖4:此為依照本發明之一多層膜的橫截面側視圖。可觀察到主動氧清除層係夾在兩被動氧阻障層之間。膜可能包括在外層與第一被動阻障層之間、在主動氧清除層與兩被動阻障層之間、及在最後的被動阻障層與內層之間的連結層。
圖5:此為依照本發明之一多層膜的橫截面側視圖。
可觀察到被動氧阻障層係夾在兩主動氧清除層之間。膜可能包括在外層與第一主動氧清除層之間、在被動氧阻障層與兩主動氧清除層之間、及在最後的氧清除層與聚乙烯(PE)層之間的連結層。
圖6:此為依照本發明之一多層膜的橫截面側視圖。可觀察到兩主動氧清除層係一者夾在兩被動阻障層之間,及一者夾在一被動阻障層與外層之間。膜可能包括在外層與第一主動氧清除層之間、在第一被動氧阻障層與兩主動氧清除層之間、在第二氧清除層與兩被動阻障層之間、及在最後的被動阻障層與內層之間的連結層。
圖7:此為依照本發明之層合式多層膜之一實例的橫截面側視圖。可觀察到聚偏二氯乙烯(從現在起稱為PVdC)層係夾在作為外層的PET層與第一被動氧阻障層之間。主動氧清除層係夾在兩被動氧阻障層之間。內層可隨意地(optionally)存在。因不同的層之間的相容性問題而需要時,膜可能包括連結層或黏著層。
圖8:此為依照本發明之層合式多層膜之一實例的橫截面側視圖。可觀察到PVdC層係夾在作為外層的PET層與第一主動氧清除層之間。被動氧阻障層係夾在兩主動氧清除層之間。內層可隨意地存在。需要時,膜可能包括連結層或黏著層。
如於本發明中,氧阻障係指藉由提供會與氧反應、吸
收氧及/或消耗氧之物質以減少或消除氧滲透包裝物件內部。此為所知的主動氧阻障(active oxygen barrier)且係不同於試圖密封產物以遠離氧的被動氧阻障(passive oxygen barrier)。被動氧阻障層不總是完全阻隔氧滲透包裝內部,而是某程度地減緩其進入。
就本發明的所有實施態樣而言,較佳的是主動氧清除層中至少一者係夾在被動氧阻障層與內層之間,或沒有該內層時係夾在被動氧阻障層與包裝本身內部之間。
隨後在圖1至圖8中記述之所有例示性實施態樣亦落在此定義範圍內。在該等及其他的實施態樣中,一或更多中間層(例如連結層或黏著層)可配置在多層膜的任何層界面之間,更具體地,配置在任何需要結合兩層(其需使用彼等否則會不相容)處。
圖1至8記述一系列本發明可能的實施態樣,其中各種組份係以各種方式組合以製造多層膜。塑料的改革者通常係基於食品製造商的特定需求及應由包裝容納且防護之貨物的性質來決定多層膜的結構。因此,不可能於本專利中舉出當今所使用的每一可能的多層結構。然,圖1至8描繪實際包裝結構代表性的配置,但非必包含可應用於本發明的所有實施態樣。
一些最常使用的被動阻障之晶體結構係由於暴露在大於65%之濕度(當包裝濕食時或當包裝在運輸或儲存期間暴露於此等環境條件時)或大於30℃之溫度(在包裝滅菌處理期間或儲存及/或運輸的環境條件)而顯著地改變。結晶性
(crystallinity)的修飾不是永久性效應,而如果且一旦避免上述條件時,材料可回復其原來的結晶狀態。發生此可逆過程所需之時間可能花費達一週或更久。在此期間,氧能夠以更快的滲透速率滲透過包裝,因此縮短容納於其中的食品或藥物之儲存壽命。通常為了限制此情況發生,必須將濕氣阻障層(moisture barrier layer)插入被動阻障層與暴露於高濕氣的膜表面之間。
本發明之氧阻障組成物可用於製造能夠補償被動阻障性能損失之多層膜,因此達到與未暴露於高濕度及/或高溫之相同的多層膜近似的透氧率水平。
一般來說,主動氧清除層對來自包裝外部的氧之阻止係於其滲透過聚合物基質時藉由與其化學反應而進行。亦可與可能在密封/包封之時陷入包裝內部而留下的氧發生相同的反應,因而使最終物件內部的氧濃度維持不變或降低達較長時間。主動清除層通常具有至少0.1cc/(g清除劑*天)之吸收能力。
在本發明意義之範圍內,較佳的聚烯烴及聚烯烴共聚物(即,組份(A)及/或(D))為本領域已知的熱塑性聚烯烴且係選自由下列所組成之群組:-聚乙烯(PE),較佳地選自由下列所組成之群組:高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、直鏈低密度聚乙烯(LLDPE)、茂金屬低密度聚
乙烯(mLDPE)以及茂金屬直鏈低密度聚乙烯(metallocene linear low density polyethylene)(mLLDPE),-聚丙烯(PP),較佳地選自由下列所組成之群組:聚丙烯均聚物(PPH)、聚丙烯無規共聚物(PP-R)以及聚丙烯嵌段共聚物(PP-嵌段-COPO),-PE共聚物,較佳地選自由下列所組成之群組:乙烯-乙酸乙烯酯共聚物(ethylene-vinyl acetate copolymers)(EVA)、乙烯與丙烯酸甲酯之共聚物(EMA)、乙烯與丙烯酸丁酯之共聚物(EBA)、乙烯與丙烯酸乙酯之共聚物(EEA)以及環烯烴共聚物(cycloolefin copolymer)(COC),-通用聚苯乙烯(general purpose polystyrene)(GPPS)和高衝擊聚苯乙烯(high impact polystyrene)(HIPS);更佳為-高密度聚乙烯(HDPE)和低密度聚乙烯(LDPE),-聚丙烯均聚物(PPH),-通用聚苯乙烯(GPPS)。
在本發明意義之範圍內,較佳的聚苯乙烯(即,組份(A)及/或(D))可為苯乙烯均聚物,烷基苯乙烯均聚物(alkylstyrene homopolymer),較佳為C1-C4-烷基苯乙烯均聚物,例如α-甲基苯乙烯均聚物;苯乙烯共聚物,尤其為高衝擊聚苯乙烯(HIPS)。
高衝擊聚苯乙烯(HIPS)之製備通常係藉由使苯乙烯與隨意地(optionally)一或更多可共聚合的乙烯基單體
(copolymerizable vinyl monomer)之混合物(較佳為苯乙烯、甲基苯乙烯、乙基苯乙烯、丁基苯乙烯、鹵基苯乙烯(halostyrene)、乙烯基烷基苯(vinylalkylbenzene)(諸如乙烯基甲苯、乙烯基二甲苯)、丙烯腈、甲基丙烯腈、甲基丙烯酸的低碳烷基酯(lower alkyl ester)之混合物),在包含選自聚丁二烯、聚異戊二烯、膠態苯乙烯-二烯共聚物(rubbery styrene-diene copolymer)、丙烯酸系橡膠、腈橡膠(nitrile rubber)和烯烴系橡膠(olefinic rubber)(如丙烯二烯單體橡膠(propylene diene monomer rubber)(PDM)和丙烯橡膠(PR))之共聚物的膠態聚合物主鏈(rubbery polymer trunk)的存在下,藉由接枝(grafting)而聚合(polymerization)。在高衝擊聚苯乙烯中,膠態聚合物主鏈通常構成接枝聚合物之總重量的5至80重量%,較佳為5至50重量%。
組份(A)及/或(D)的較佳密度為1.0至1.1克/立方公分(g/cm3),更佳為1.02至1.06克/立方公分,甚至更佳為1.03至1.05克/立方公分。
較佳的聚苯乙烯為根據ISO 1133在200℃/5公斤下具有MFR為0.1至300克/10分鐘(g/10min),更佳為1至200克/10分鐘,甚至更佳為5至100克/10分鐘,尤其為10至50克/10分鐘,更尤其為15至35克/10分鐘,特別為20至25克/10分鐘的聚苯乙烯。
為聚萜烯樹脂(polyterpene resin)之添加劑(b)含有較佳地選自下列的環狀或非環狀單體:α-蒎烯(alpha-
pinene)、β-蒎烯、γ-萜品烯、薴烯(limonene)、降莰烯(norbornene)、月桂油烯(myrcene)、茴香萜(phellandrene)、香旱芹酮(carvone)、莰烯(camphene)、2-蒈烯(2-carene)、3-蒈烯、紫蘇醇(perillyl alcohol)、紫蘇醛(perillyl aldehyde)、紫蘇酸(perillyl acid)、紫蘇醇之烷基酯、紫蘇醇之芳基酯、紫蘇醇之芳烷基酯(arylalkyl ester)、紫蘇醇之烷芳基酯(alkylaryl ester)、α-紫羅酮(alpha-ionone)、β-紫羅酮、β-香茅醇(beta-citronellol)、β-香茅烯(beta-citronellene)、香茅醛(citronellal)、香茅酸、β-香茅醇之烷基酯、β-香茅醇之芳基酯、β-香茅醇之芳烷基酯、β-香茅醇之烷芳基酯、香葉醇(geraniol)、香葉醛(geranial)、香葉醇之烷基酯、香葉醇之芳基酯、香葉醇之芳烷基酯、香葉醇之烷芳基酯、沈香醇(linalool)、沈香醇之烷基酯、沈香醇之芳基酯、沈香醇之芳烷基酯、沈香醇之烷芳基酯、橙花三級醇(nerolidol)、橙花三級醇之烷基酯、橙花三級醇之芳基酯、橙花三級醇之芳烷基酯、橙花三級醇之烷芳基酯、馬鞭烯醇(verbenol)、馬鞭烯酮(verbenone)、馬鞭烯醇之烷基酯、馬鞭烯醇之芳基酯、馬鞭烯醇之芳烷基酯、馬鞭烯醇之烷芳基酯及彼等之混合物。
在其他特定的實施態樣中,聚萜烯樹脂亦可為不飽和單萜烯(unsaturated monoterpene),諸如α-蒎烯、β-蒎烯、γ-萜品烯、薴烯、降莰烯、月桂油烯、茴香萜、香旱芹酮、莰烯、2-蒈烯、3-蒈烯、紫
蘇醇、紫蘇醛、紫蘇酸、紫蘇醇之烷基酯、紫蘇醇之芳基酯、紫蘇醇之芳烷基酯、紫蘇醇之烷芳基酯、α-紫羅酮、β-紫羅酮、β-香茅醇、β-香茅烯、香茅醛、香茅酸、β-香茅醇之烷基酯、β-香茅醇之芳基酯、β-香茅醇之芳烷基酯、β-香茅醇之烷芳基酯、香葉醇、香葉醛、香葉醇之烷基酯、香葉醇之芳基酯、香葉醇之芳烷基酯、香葉醇之烷芳基酯、沈香醇、沈香醇之烷基酯、沈香醇之芳基酯、沈香醇之芳烷基酯、沈香醇之烷芳基酯、橙花三級醇、橙花三級醇之烷基酯、橙花三級醇之芳基酯、橙花三級醇之芳烷基酯、橙花三級醇之烷芳基酯、馬鞭烯醇、馬鞭烯酮、馬鞭烯醇之烷基酯、馬鞭烯醇之芳基酯、馬鞭烯醇之芳烷基酯、馬鞭烯醇之烷芳基酯,與石油類(petroleum-based)或來自再生來源(renewable source)的乙烯系不飽和單體(ethylenically unsaturated monomer),諸如,苯乙烯、α-甲基苯乙烯(alpha-methylstyrene)、丙烯酸烷基酯、甲基丙烯酸烷基酯、烷酸乙烯酯(vinyl alkonate)(諸如乙酸乙烯酯、丁酸乙烯酯或類似者)、乙烯乙酸乙烯酯、苯乙烯-順丁烯二酸酐(styrene-maleic anhydride)及類似的單體,之共聚物。
添加劑(b)之較佳的實施態樣為不飽和環狀單萜烯(unsaturated cyclic monoterpene)(諸如α-蒎烯、β-蒎烯、d-薴烯(d-limonene)、α/β蒎烯之混合物或類似者)之均聚物或共聚物的聚萜烯樹脂,以及彼等之摻合組合物。
在本發明之一更佳的實施態樣中,添加劑(b)為α-蒎烯、β-蒎烯或α/β蒎烯之混合物的均聚物或共聚物。
一特別佳的添加劑(b)為β-蒎烯樹脂,權宜地具有至少2500克/莫耳(g/mol)之平均Mw。
添加劑(b)的使用量,以各主動氧清除層(C)之總重量為基準計,較佳為0.05至10重量%,更佳為0.1至3.5重量%,最佳為0.1至2重量%。
在本發明意義之範圍內,添加劑(c)為過渡金屬觸媒,其引發及加速氧消耗速率。觸媒可能或可能不與氧消耗,或者若消耗,則可藉由轉變回催化活性態而為僅暫時地消耗。
更佳地,過渡金屬觸媒為鹽類,過渡金屬係選自元素週期表之第一、第二或第三過渡系列。適合的金屬及其氧化態包括,但不限於:錳II或III,鐵II或III,鈷II或III,鎳II或III,銅I或II,銠II、III或IV,以及釕(ruthenium)。當引入時,金屬之氧化態非必定為其活性形式。金屬較佳為鐵、鎳、錳、鈷或銅;更佳為錳或鈷;且甚至更佳為鈷。適合於金屬之相對離子(counterion)包括,但不限於:氯離子(chloride)、乙酸根、乙醯丙酮酸根(acetylacetonate)、丙酸根(propionate)、油酸根(oleate)、硬脂酸根(stearate)、棕櫚酸根(palmitate)、2-乙基己酸根(2-ethylhexanoate)、辛酸根(octanoate)、新癸酸根(neodecanoate)或萘酸根(naphthenoate)。
金屬鹽亦可為離子聚合物(ionomer),在此例子中,使
用聚合物相對離子(polymeric counterion)。此離子聚合物為本領域所熟知。
甚至更佳地,鹽類、過渡金屬及相對離子,就食品接觸材料而言係符合國家法規,或若為包裝物件的一部分,係實質上未顯出從氧阻障組成物遷移至包裝內容物。特別佳的鹽類包括油酸鈷、丙酸鈷、硬脂酸鈷和新癸酸鈷(cobalt neodecanoate)。
過渡金屬觸媒(c)的使用量,以各主動氧清除層(C)之總重量為基準計,較佳為0.001至1重量%,更佳為0.01至0.5重量%。
主動氧清除層的厚度,與多層膜之總厚度相比,可為於1至50%之範圍,較佳為介於5至45%之間,更佳為介於9至43%之間,且甚至更佳為介於7至42%之間。
被動阻障通常包含聚合物材料,其不會與滲透過由其所製成的層之氧起化學反應,而是藉由產生使氧分子從包裝之氧濃度較高的一側滲透至氧濃度較低的另一側之迂迴路徑而減慢氧的進入。
在本發明的範圍內,被動阻障可包括在超過所述及之臨界(threshold)的溫度及r.h.條件下可改變其阻障性能之任何材料。
有許多可用作為被動氧阻障層之氧阻障聚合物。若存在有超過一個被動阻障層,如圖3、4、6和7中,則該等層
可彼此相同或不相同。
氧阻障聚合物可選自包括但不限於下列者之群組:乙烯乙烯醇共聚物(ethylene vinyl alcohol copolymer)、聚氯乙烯和其共聚物、聚乙烯醇(polyvinyl alcohol)、聚偏二氯乙烯(polyvinilydene dichloride)和其共聚物、聚丙烯腈和其共聚物、聚對酞酸乙二酯(polyethylene terephthalate)、聚萘二甲酸乙二酯(polyethylene naphthalate)(PEN)、聚喃二甲酸乙二酯(polyethylene furanoate)(PEF)、聚矽氧(silicone)(SiOx)、聚醯胺(諸如聚己內醯胺(polycaprolactam)(尼龍6)、間-二甲苯己二醯胺(meta-xylene adipamide)(MXD6)、六亞甲己二醯胺(hexamethylene adipamide)(尼龍66)、非晶形聚醯胺(amorphous polyamide)諸如尼龍6I,6T),以及上述者之共聚物和摻合物。
較佳的聚合物為乙烯乙烯醇共聚物和聚醯胺諸如聚己內醯胺(尼龍6)、間-二甲苯己二醯胺(MXD6)、六亞甲己二醯胺(尼龍66)。
歸類為被動氧阻障層之其他材料亦包括金屬箔層、金屬塗層或金屬沈積物、金屬氧化物(如二氧化矽(silica)、氧化鋁(alumina))、奈米黏土(nano clay)和蛭石(vermiculate)。
被動氧阻障層的厚度可根據其他層之數量、功能性及所欲性能而廣泛地變化,且可在1至100微米(μm)之範圍,較佳為介於1.5至50微米之間,更佳為介於2至10微米之
間,且甚至更佳為介於3至5微米之間。
被動氧阻障層的厚度,與多層膜之總厚度相比,可在1至50%之範圍,較佳為介於2至40%之間,更佳為介於3至30%之間,且甚至更佳為介於4至10%之間。
多層膜之內層(inner layer)在本文中定義為直接暴於包裝內容物之層。此層通常作為密封層,因為其係用於在黏附於支撐物件例如盤、另一膜或(如在小袋中)多層膜本身時確保熱密封及後續氣密隔離(airtight isolation)容納於內部的貨物。在本發明之實施態樣範圍內,內層因此可包含單一聚合物材料或其摻合物。
用語〝外層〞係於上文定義。
內層或外層二者可為相同或不同的材料,材料可包括熱塑性聚合物如聚烯烴、聚苯乙烯、聚胺甲酸酯、聚氯乙烯和離子聚合物。在此方面可用的聚合物材料包括乙烯及丙烯之均聚物和共聚物,諸如,但不限於:低密度聚乙烯、乙烯/α-烯烴共聚物、中密度聚乙烯、直鏈低密度聚乙烯、直鏈中密度聚乙烯、極低密度聚乙烯、超低密度聚乙烯、聚丙烯均聚物以及聚丙烯共聚物。所述之聚合物可以許多不同的程序及觸媒製備且可為均質的(homogeneous)或非均質的(heterogeneous)。
內層或外層的厚度,與多層膜之總厚度相比,可在1至50%之範圍,較佳為介於5至45%之間,更佳為介於14
至44%之間,且甚至更佳為介於15至42%之間。
層(A)、(B)、(C)及(D)各亦可包含另外的常用添加劑(d),如相容劑(compatibilizer)、抗氧化劑(antioxidant)(不同於氧清除劑(b))、熱穩定劑、著色劑、填充劑、酸清除劑、加工助劑、偶合劑、潤滑劑、起泡劑(blowing agent)、多元醇、成核劑、抗靜電劑、光穩定劑、加工穩定劑(process stabilizer)、澄清劑(clarifier)、UV吸收劑、滑劑(slip agent)、防霧劑、抗凝結劑(anti-condensation agent)、懸浮穩定劑(suspension stabilizer)、抗結塊劑(anti-blocking agent)、蠟(wax)、及該等物質之混合物。該等輔助劑的濃度,相對於各層之總重量,可在0至20重量%之間變化,較佳為0.001至10重量%,更佳為0.1至5重量%。
該等層可隨意地(optionally)與濕氣阻障層(moisture barrier layer)、強化層(strengthening layer)及黏著層組合。通常用於黏著層之組成物包括熟知的酐官能性聚烯烴,例如Admer®類型(Mitsui)。
當包裝物件暴露在大於65%之r.h.時及/或當包裝物件暴露在大於30℃之溫度時,本發明之多層包裝膜,與不具阻障性質之相同的多層包裝膜相比,係提供透氧率(oxygen transmission rate)(立方公分/平方公尺*天(cm3/m2*day))之改進為至少5%,較佳為超過20%,更佳為超過30%,且甚至更佳為超過50%。
根據本發明之多層包裝膜可為包裝材料,較佳為容
器、膜或片材,尤其用於需要高的氧阻障性之個人護理、化妝品、醫療、醫藥、家用、工業、食品和飲料產品之包裝。
包裝材料可為撓性、剛性、半剛性或彼等之組合。
剛性包裝物件通常具有100至1000微米(micrometer)範圍內的壁厚度。典型的撓性包裝通常具有5至250微米的厚度。
含有本發明之多層包裝膜的具體物件包括用於包裝需要高的氧阻障性之食品、飲料、化妝品、醫藥和個人護理產品的容器、膜及片材。飲料容器的實例為:用於果汁、運動飲料或是氧會不利地影響飲品的氣味、香味、性能(防止維生素降解)或顏色之任何其他飲料的瓶。
本發明之物件亦尤其可作為用於熱成型成剛性包裝之片材及用於撓性結構之膜。剛性包裝包括食品盤和蓋。食品盤應用的實例包括雙烘烤用食品盤(dual ovenable food tray)或冷藏用食品盤(cold storage food tray)(於底部容器及於封蓋(無論是熱成型蓋或膜)二者),其中食品內容物的鮮度會隨氧的進入而腐敗。
本發明之物件亦可用於製造化妝品容器及用於醫藥或醫療裝置之容器。
本發明之較佳物件為剛性包裝物件,諸如瓶及熱成型片材和撓性膜。
本發明之更佳物件為為中空容器,其係藉由本技術中已知的任何種類之吹塑法(blow moulding process)便利地
製造。
本發明之另一目的為製造多層包裝膜之方法,其包含提供根據層(A)、(B)及(C)和隨意地(optionally)(D)之聚合物、提供添加劑(b)和(c)之步驟以及包含混合步驟及成型法。
成型法(shape forming process)係取決於欲製造之包裝物件的所欲形狀而定。
容器較佳地藉由吹塑(blow moulding)、射出模塑(injection moulding)、射出拉伸吹塑(injection and stretch blow moulding)、擠壓吹塑(extrusion blow moulding)、壓縮模塑(compression moulding)、壓縮拉伸吹塑(compression and stretch blow moulding)方法而製造。
膜及片材之製造較佳係依據獲得特定性質所需的厚度及所要求的層數而藉由鑄造(cast)或吹膜擠壓(blown film extrusion)或共擠壓(co-extrusion)方法,最後接著以擠壓後成型法(post-extrusion shaping process)如熱成型、拉伸或層合。在熱成型法(thermoforming process)中,將塑料片材加熱至易曲折的成型溫度(pliable forming temperature)、在模具中形成特定形狀、且經修整(trim)以產生最終物件。若使用真空,則此方法通常被稱為真空成型(vacuum forming)。在擠壓後拉伸法(post-extrusion stretching process)中,經擠壓之膜可例如藉由拉(drawing)而為雙軸定向(biaxially oriented)。所有上文列示之方法為本領域所熟知。
添加劑(b)及(c)以及隨意另外的常用添加劑(d)便利地以母料形式提供,其中聚合物較佳地與待併入各添加劑的層之聚合物相同。
母料可以常用的物理混合法製備。
用於液體母料之混合裝置可為高速分散器(high speed dispersor)(例如CowlesTM型)、介質研磨機(media mill)、三輥研磨機(three-roll mill)、次級研磨機(submill)或轉子-定子型分散器(rotor-stator type dispersor)。
用以製造固體母料MB之混合裝置可為混合機、擠壓機、捏合機、壓製機、研磨機、壓延機、摻合機、射出模塑機、射出拉伸吹塑機(injection and stretch blow moulding machine)(ISBM)、擠壓吹塑機(extrusion blow moulding machine)(EBM)、壓縮模塑機(compression moulding machine)、壓縮拉伸吹塑機(compression and stretch blow moulding machine);更佳為混合機、擠壓機、射出模塑機、射出拉伸吹塑機、壓縮模塑機、壓縮拉伸吹塑機;甚至更佳為混合機、擠壓機、射出拉伸吹塑機和擠壓吹塑機。
擠壓機(extruder)可配備用於將該添加劑及/或母料引入主流聚合物中的計量系統。此計量(metering)可以一或更多純組份或以一或更多母料直接進行。
所使用的計量設備類型係取決於所計量之純組份或母料的形式而定。
在固體組份的例子中,通常使用進給螺桿型(feed
screw type)之計量裝置,且引入點可為擠壓機主要入口,與主要聚合物顆粒進料一起,或者是在沿著擠壓機設置的未加壓射出區(unpressurized injection zone)中。用於固體母料之計量裝置可為包含使母料預熔融、加壓且藉助於計量泵(metering pump)計量之額外擠壓機的系統,計量之母料的量有利地於沿主要擠壓機的點進料(無需壓力)。
用於液體純組份或液體母料之計量裝置可為包含一或更多計量泵之系統,其係在擠壓機主要入口引入液體母料(與主要聚合物顆粒進料一起),無需任何壓力,或者在沿著擠壓機設置的點於壓力下引入液體母料。
除非另有其他指示,產物性質係由下列方法測定:密度之值係依照ASTM D792測定(克/立方公分)。
熔體流動速率(melt flow rate)(MFR)之值係依照ASTM D1238測定(克/10分鐘(g/10min),在指定的溫度及重量下)。
將五(5)克鑄膜(cast film)樣品切成尺寸均勻的細條且置於550毫升兩頸玻璃Schlenk內部。於兩頸之一使用不透氣材料製成的適配蓋子以及於另一入口使用fit-suba-seal®隔片以密封Schlenk。頂隙氧氣(oxygen headspace)測量係
藉由使用CheckMate®儀器的探針刺穿隔片(septum)及取內部的等分空氣(an aliquot of the atmosphere)來進行。以規律的時間間隔收集數據。接著以Schlenk內部的氧濃度相對於時間繪圖。在兩測量之間,在fit-suba-seal®隔片上有額外的黏著隔片以確保沒有氧通過刺穿的孔進入。
所記述之所有OTR測量已根據DIN 53380-3測定且彼等係以得自Fachlaboratorium für Permeationsprüfung,Wiesbaden,Germany之專門設計用於高OTR膜之儀器測量。
置入樣品的OTR槽(OTR cell)有兩端。於一端為氧,其滲透過膜樣品到達具有氮載送氣體(nitrogen carrier gas)的另一端,其載送滲透之氧到達檢測器。可微調膜兩端的相對濕度。
霧度(haze)之值係依照ASTM D1003,程序A而於120微米(μm)膜測定(通過試樣之透射光%,其係由於向前散射(forward scattering)而脫離入射光束)
%霧度=(T漫射/T總) * 100
其中T=透射%。
膜係如下文所述製造且膜之霧度係以霧度計haze-gard dual(BYK Gardner)測定。使用具有CIE 1964 10°標準觀察器之D65發光體(illuminant)。霧度係定義為CIE Y漫透射率(diffuse transmittance)相對於CIE Y總透射(total transmission)之百分比。
所有製造之樣品為107至128微米(μm)五層鑄膜(five-layer cast film),具有LDPE/連結層/EVOH/連結層/LDPE結構及個別厚度為50微米/6微米/5至7微米/6微米/50微米。此多層系統對應於圖1的三層系統,但具有兩個額外的黏著層(連結層)。
在所有的結構中,所使用的低密度聚乙烯為LDPE Lupolene® 2420(LyondellBasell),具有M.F.I.4克/10分鐘190℃ 2.16公斤;密度0.924克/立方公分(ASTM D3236-88)。所使用的乙烯-乙烯醇共聚物(EVOH)為EVAL® H171B,具有38莫耳%之乙烯含量,M.F.I.1.7克/10分鐘190℃ 2.16公斤;密度1.17克/立方公分(ISO 1183)。所使用的連結樹脂為Admer® AT1707(Mitsui),具有M.F.I.4.3克/10分鐘190℃ 2.16公斤;密度0.91克/立方公分(ASTM D1505)。
除非另有其他指示,在下列實施例中所述及之重量%係以混合物、組成物或物件之總重量為基準計;份為重量份;〝ex〞意指實施例;〝cpex〞意指比較例;MB意指
母料;CO意指混合物(compound)。
低密度聚乙烯(LDPE)粉末:LDPE Riblene®,M.F.I.2克/10分鐘190℃ 2.16公斤;密度0.925克/立方公分(ASTM D3236-88)。
Dercolyte® S125
硬脂酸鈷(9.5%鈷濃度)
硬脂酸錳(8.5%錳濃度)。
將組份在Leistritz® ZSE18HP擠壓機上於140℃之溫度一起均質化,以獲得固體母料MB1至MB3;表1列出細節。
將組份A1與母料MB1、MB2和MB3混合且根據表2之比率均質化。
使用所獲得的混合物CO1至CO3於鑄膜機Dr.Collin® Extruder 20P製造上文述及之五層膜(ex1和ex2具有50微米主動氧清除內部層,如圖1之左圖)。一操作模式實例:使組份A1、MB1、MB2或MB3通過進料斗(hopper)(用於Dr.Collin® Extruder 20P(型號20P;30毫米(mm)螺桿直徑1:30比率)之主流)插入,同時內桶溫度(internal barrel temperature)保持在230至240℃之間;將用於擠壓多層膜之其餘層所需的EVOH、連結樹脂及LDPE添加至個別的進
料斗中(各係用於Dr.Collin® Extruder 20P(型號20P;30毫米螺桿直徑1:30比率)之主流);接著從單元捲繞所獲得的共擠壓鑄膜(co-extruded cast film)且將其儲存用於所需測試。
總霧度(total haze)為測量PO物件透明度(clarity)之較佳方法,其可測定該等物件用於要求高透明水平之包裝應用的適合性。霧度係於由混合物CO1至CO3獲得的上文製備之PO膜測量。表3列出細節。
本發明之組成物CO2和CO3清楚地顯示非常類似於如CO1中的純LDPE之透明度(clarity)水平。
對應於上文所製備之膜的氧阻障性能係依照下述方法測量。
表4顯示以一些上文製備之多層膜在氮載送氣體(nitrogen carrier gas)(從現在起稱為載送氣體(carrier gas))
中分別暴露於50%及100% r.h.所測量的OTR(以立方公分/平方公尺*天*大氣壓(cm3/m2*day*atm)計之),其中,主動氧清除層為具有組成物CO1和CO3之50微米厚度的內部LDPE層。
可清楚地觀察到,就各EVOH厚度而言,清除劑能夠補償由於高r.h.而損失的EVOH性能,維持OTR值為相當於無清除劑之膜暴露於低r.h.時。
表5顯示上文製備之多層膜分別暴露於23℃、50℃和90℃及50% r.h.所測量的OTR(以立方公分/平方公尺*天(cm3/m2*day)計之),其中,主動氧清除層為具有組成物CO1和CO3之50微米厚度的內部LDPE層。
在表6中,記述由含有組成物CO2和CO3之多層膜相對於自含有彼等之Schlenk密封(大氣(20.9%氧)留在內部)那刻起經過之時間(以天測量)所耗的氧氣(oxygen atmosphere)。Schlenks內部的氧濃度測量值係以O2%記述。在相同的期間內,每天的氧清除能力(oxygen scavenging capacity)係根據下式以毫升O2/克清除劑(mL O2/g Scavenger)記述
毫升O2/克清除劑=(%O2開始-%O2結束)*0.01*V不含燒瓶/(克主動O2清除劑)
就每一組成物而言,當發生下列狀況之一時,則中止測量:關注之所欲儲存壽命期間(84天)終止、或氧含量為接近於0%(接近測量系統的準確度下限)。
Claims (14)
- 一種多層包裝膜,其包含至少三不同類型的層(A)、(B)及(C):(A)為至少一外層,(B)為至少一被動氧阻障層,(C)為至少一主動氧清除層,其特徵在於-該至少一外層(A)為熱塑性聚合物;-該至少一被動氧阻障層(B)係選自由下列所組成之群組:乙烯乙烯醇共聚物、聚氯乙烯、聚氯乙烯共聚物、聚乙烯醇、聚偏二氯乙烯、聚偏二氯乙烯共聚物、聚丙烯腈、聚丙烯腈共聚物、聚對酞酸乙二酯、聚萘二甲酸乙二酯、聚喃二甲酸乙二酯(polyethylenefuranoate)、聚矽氧烷和聚醯胺;-該至少一主動氧清除層(C)包含a)塑料,其為聚烯烴、聚烯烴共聚物或聚苯乙烯;以及添加劑(b)和(c),其中b)為聚萜烯樹脂;及c)為過渡金屬觸媒,其具有過渡金屬及相對離子(counterion)選自下列所組成之群組:氯離子(chloride)、乙酸根(acetate)、乙醯丙酮酸根(acetylacetonate)、丙酸根(propionate)、油酸根(oleate)、硬脂酸根(stearate)、棕櫚酸根(palmitate)、2-乙基己酸根(2-ethylhexanoate)、辛酸 根(octanoate)、新癸酸根(neodecanoate)及萘酸根(naphthenoate),以及其中,該添加劑(b)的使用量,以該主動氧清除層(C)之總重量為基準計,為0.1至2重量%。
- 根據申請專利範圍第1項之多層包裝膜,其中,添加劑b)與c)係組合在相同的主動氧清除層中。
- 根據申請專利範圍第1或2項之多層包裝膜,其進一步包含至少一內層(D),其為熱塑性聚合物。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該主動氧清除層(C)中至少一者係夾在被動氧阻障層(B)與內層(D)之間,或沒有該內層(D)時係夾在被動氧阻障層(B)與包裝本身內部之間。
- 根據申請專利範圍第3項之多層包裝膜,其中,一或更多選自由濕氣阻障層(moisture barrier layer)、強化層(strengthening layer)及黏著層所組成之群組的其他層係置於該層(A)、(B)、(C)及(D)中至少兩者之間。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該聚萜烯樹脂(b)含有選自下列之單體:α-蒎烯、β-蒎烯、γ-萜品烯、薴烯(limonene)、降莰烯(norbornene)、月桂油烯 (myrcene)、茴香萜(phellandrene)、香旱芹酮、莰烯(camphene)、2-蒈烯(2-carene)、3-蒈烯、紫蘇醇(perillyl alcohol)、紫蘇醛(perillyl aldehyde)、紫蘇酸(perillyl acid)、紫蘇醇之烷基酯、紫蘇醇之芳基酯、紫蘇醇之芳烷基酯(arylalkyl ester)、紫蘇醇之烷芳基酯(alkylaryl ester)、α-紫羅酮(alpha-ionone)、β-紫羅酮、β-香茅醇(beta-citronellol)、β-香茅烯(beta-citronellene)、香茅醛、香茅酸、β-香茅醇之烷基酯、β-香茅醇之芳基酯、β-香茅醇之芳烷基酯、β-香茅醇之烷芳基酯、香葉醇、香葉醛、香葉醇之烷基酯、香葉醇之芳基酯、香葉醇之芳烷基酯、香葉醇之烷芳基酯、沈香醇(linalool)、沈香醇之烷基酯、沈香醇之芳基酯、沈香醇之芳烷基酯、沈香醇之烷芳基酯、橙花三級醇(nerolidol)、橙花三級醇之烷基酯、橙花三級醇之芳基酯、橙花三級醇之芳烷基酯、橙花三級醇之烷芳基酯、馬鞭烯醇(verbenol)、馬鞭烯酮、馬鞭烯醇之烷基酯、馬鞭烯醇之芳基酯、馬鞭烯醇之芳烷基酯、馬鞭烯醇之烷芳基酯及彼等之混合物。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該聚萜烯樹脂(b)為α-蒎烯、β-蒎烯或α/β蒎烯之混合物的均聚物或共聚物。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該過渡金屬觸媒(c)含有鐵、鎳、錳、鈷或銅。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該過渡金屬觸媒(c)的使用量,以各主動氧清除層(C)之總重量為基準計,為0.001至1重量%。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該被動氧阻障層的厚度,與多層包裝膜之總厚度相比,為3至30%之範圍內。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該主動氧清除層的厚度,與多層包裝膜之總厚度相比,為9至43%之範圍內。
- 根據申請專利範圍第1或2項之多層包裝膜,其呈容器形式。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該過渡金屬觸媒係選自下列所組成之群組:油酸鈷、丙酸鈷、硬脂酸鈷和新癸酸鈷(cobalt neodecanoate)。
- 根據申請專利範圍第1或2項之多層包裝膜,其中,該主動氧清除層(C)具有1.9%或更低之霧度(haze)。
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EP16183923.8A EP3281788A1 (en) | 2016-08-12 | 2016-08-12 | Oxygen barrier plastic material |
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EP3871877A1 (en) | 2018-08-08 | 2021-09-01 | Danapak Flexibles A/S | Improved films and laminates for use in packaging reactive compounds |
US20200055279A1 (en) * | 2018-08-20 | 2020-02-20 | Celanese EVA Performance Polymers Corporation | Polymer and Metal Foil Laminates |
US11518149B2 (en) | 2018-11-13 | 2022-12-06 | Campbell Soup Company | Multilayer packaging materials with release of migratory active substances |
WO2021072024A1 (en) * | 2019-10-08 | 2021-04-15 | Kuraray Co., Ltd. | Polyfluoroalkyl substances (pfas) diffusion preventing system |
BR112022007816A2 (pt) * | 2019-11-01 | 2022-07-05 | Dow Global Technologies Llc | Estrutura sobremoldada por injeção transparente, processo de sobremoldagem por injeção, e, estrutura moldada por injeção |
CN110746723A (zh) * | 2019-12-02 | 2020-02-04 | 苏州奥凯高分子材料股份有限公司 | 一种pvc高阻隔片材及其制备方法 |
CN113124309B (zh) * | 2019-12-31 | 2023-03-17 | 中国科学院宁波材料技术与工程研究所 | 一种高压储氢瓶塑料内胆及其制备方法 |
KR20230011943A (ko) * | 2020-04-16 | 2023-01-25 | 뮤셀 익스트루젼, 엘엘씨 | 산소-민감성 제품의 포장을 위한 플라스틱 용기 및 그를 제조하는 방법 |
CN112078210A (zh) * | 2020-08-27 | 2020-12-15 | 上海春宜药品包装材料有限公司 | 聚乙烯复合医用包装膜及生产工艺的制备方法 |
CN114714728A (zh) * | 2022-03-17 | 2022-07-08 | 乐美包装(昆山)有限公司 | 纵封条及其制作方法 |
US20230312217A1 (en) * | 2022-04-05 | 2023-10-05 | F&S Tool, Inc. | Contaminant-resistant packaging |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5776361A (en) * | 1995-02-15 | 1998-07-07 | Chevron Chemical Company | Multi-component oxygen scavenging composition |
US20050104033A1 (en) * | 2003-11-19 | 2005-05-19 | Schmidt Richard P. | Transition metal carboxylates as catalysts for oxygen scavenging |
TW200835746A (en) * | 2006-12-28 | 2008-09-01 | Eastman Chem Co | Oxygen-scavenging polyester compositions useful in packaging |
US20120052225A1 (en) * | 2009-05-28 | 2012-03-01 | The Nippon Synthetic Chemical Industry Co., Ltd. | Evoh resin composition, and molded article and multilayer structure both comprising same |
US20140220281A1 (en) * | 2011-08-24 | 2014-08-07 | M&G Usa Corporation | Oxygen scavengers |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5660761A (en) | 1995-02-15 | 1997-08-26 | Chevron Chemical Company | Multi-component oxygen scavenger system useful in film packaging |
US6333087B1 (en) * | 1998-08-27 | 2001-12-25 | Chevron Chemical Company Llc | Oxygen scavenging packaging |
AU2002213165A1 (en) | 2000-11-02 | 2002-05-15 | Chevron Phillips Chemical Company Lp | Active masterbatch using stearate and an oxidizable resin carrier |
JP2007320576A (ja) | 2006-05-30 | 2007-12-13 | Toyo Seikan Kaisha Ltd | 酸素感受性の内容物を充填した製品 |
US8815360B2 (en) * | 2007-08-28 | 2014-08-26 | Cryovac, Inc. | Multilayer film having passive and active oxygen barrier layers |
EP2112201A1 (en) | 2008-04-25 | 2009-10-28 | INEOS Manufacturing Belgium NV | Oxygen Barrier Composition |
US8609744B2 (en) | 2008-05-06 | 2013-12-17 | Basf Se | Oxygen-scavenging mixtures |
JP2013512978A (ja) | 2009-12-02 | 2013-04-18 | ビーエーエスエフ ソシエタス・ヨーロピア | 包装適用のための酸素吸収/捕捉要素としての金属錯体の使用 |
US9441066B2 (en) * | 2009-12-02 | 2016-09-13 | Basf Se | Use of photosensitive molecules and metal complexes as oxygen scavenger elements |
-
2016
- 2016-08-12 EP EP16183923.8A patent/EP3281788A1/en not_active Withdrawn
-
2017
- 2017-07-25 TW TW106124937A patent/TWI762499B/zh active
- 2017-07-26 KR KR1020197007152A patent/KR102417298B1/ko active IP Right Grant
- 2017-07-26 CN CN201780049421.5A patent/CN109562609A/zh active Pending
- 2017-07-26 CA CA3032576A patent/CA3032576A1/en active Pending
- 2017-07-26 EP EP17752310.7A patent/EP3496946A1/en not_active Ceased
- 2017-07-26 EP EP22155437.1A patent/EP4019248A1/en active Pending
- 2017-07-26 JP JP2019506502A patent/JP7050049B2/ja active Active
- 2017-07-26 WO PCT/EP2017/068927 patent/WO2018028996A1/en active Search and Examination
- 2017-07-26 MX MX2019001566A patent/MX2019001566A/es unknown
- 2017-07-26 SG SG11201900507SA patent/SG11201900507SA/en unknown
- 2017-07-26 US US16/323,985 patent/US20190210337A1/en not_active Abandoned
- 2017-07-26 BR BR112019002751-3A patent/BR112019002751B1/pt active IP Right Grant
- 2017-07-26 RU RU2019106696A patent/RU2768756C2/ru active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5776361A (en) * | 1995-02-15 | 1998-07-07 | Chevron Chemical Company | Multi-component oxygen scavenging composition |
US20050104033A1 (en) * | 2003-11-19 | 2005-05-19 | Schmidt Richard P. | Transition metal carboxylates as catalysts for oxygen scavenging |
TW200835746A (en) * | 2006-12-28 | 2008-09-01 | Eastman Chem Co | Oxygen-scavenging polyester compositions useful in packaging |
US20120052225A1 (en) * | 2009-05-28 | 2012-03-01 | The Nippon Synthetic Chemical Industry Co., Ltd. | Evoh resin composition, and molded article and multilayer structure both comprising same |
US20140220281A1 (en) * | 2011-08-24 | 2014-08-07 | M&G Usa Corporation | Oxygen scavengers |
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EP3281788A1 (en) | 2018-02-14 |
BR112019002751A2 (pt) | 2019-05-14 |
CA3032576A1 (en) | 2018-02-15 |
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CN109562609A (zh) | 2019-04-02 |
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MX2019001566A (es) | 2019-07-01 |
EP4019248A1 (en) | 2022-06-29 |
RU2019106696A (ru) | 2020-09-14 |
TW201817598A (zh) | 2018-05-16 |
RU2768756C2 (ru) | 2022-03-24 |
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