CN109476137A - 氧吸收性包装材料 - Google Patents
氧吸收性包装材料 Download PDFInfo
- Publication number
- CN109476137A CN109476137A CN201780044810.9A CN201780044810A CN109476137A CN 109476137 A CN109476137 A CN 109476137A CN 201780044810 A CN201780044810 A CN 201780044810A CN 109476137 A CN109476137 A CN 109476137A
- Authority
- CN
- China
- Prior art keywords
- layer
- resin
- oxygen absorption
- packaging material
- oxygen
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000001301 oxygen Substances 0.000 title claims abstract description 129
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 129
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 85
- 239000005022 packaging material Substances 0.000 title claims abstract description 53
- 229920005989 resin Polymers 0.000 claims abstract description 92
- 239000011347 resin Substances 0.000 claims abstract description 92
- 239000000853 adhesive Substances 0.000 claims abstract description 45
- 230000001070 adhesive effect Effects 0.000 claims abstract description 45
- 238000007789 sealing Methods 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 29
- 230000004888 barrier function Effects 0.000 claims abstract description 23
- 229920000098 polyolefin Polymers 0.000 claims abstract description 19
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 18
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 18
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 18
- 238000010276 construction Methods 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims description 140
- -1 polyethylene terephthalate Polymers 0.000 claims description 54
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 29
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 29
- 239000002344 surface layer Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000012948 isocyanate Substances 0.000 claims description 12
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 claims description 11
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 229920005906 polyester polyol Polymers 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 claims description 7
- 239000005030 aluminium foil Substances 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 2
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- 229920005372 Plexiglas® Polymers 0.000 claims 1
- 125000003473 lipid group Chemical group 0.000 claims 1
- 239000004615 ingredient Substances 0.000 abstract description 33
- 239000003814 drug Substances 0.000 description 26
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 229940079593 drug Drugs 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- 239000007767 bonding agent Substances 0.000 description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- 229920001225 polyester resin Polymers 0.000 description 12
- 239000004645 polyester resin Substances 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 11
- 150000002632 lipids Chemical group 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 150000008064 anhydrides Chemical class 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 150000001721 carbon Chemical group 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920006267 polyester film Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009820 dry lamination Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 2
- CSHJJWDAZSZQBT-UHFFFAOYSA-N 7a-methyl-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical class C1=CCCC2C(=O)OC(=O)C21C CSHJJWDAZSZQBT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PWLXTFFHCFWCGG-UHFFFAOYSA-N Heneicosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC(O)=O PWLXTFFHCFWCGG-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000857 drug effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000120 polyethyl acrylate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- NJPQAIBZIHNJDO-UHFFFAOYSA-N 1-dodecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCN1CCCC1=O NJPQAIBZIHNJDO-UHFFFAOYSA-N 0.000 description 1
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种在用于含有易氧化性成分和油状成分的贴附剂等的氧吸收性包装材料中既保持了热封强度、又改善了撕裂性的氧吸收性包装材料。本发明涉及一种包含氧阻隔层、氧吸收层和密封膜的层叠结构的易撕裂性氧吸收性包装材料,密封膜是至少包含芯层和具有热封性的内层的层叠树脂膜,相对于芯层总质量,芯层含有20~40质量%的环状聚烯烃系树脂和/或丙烯酸系树脂以及60~80质量%的聚对苯二甲酸乙二醇酯系树脂。
Description
技术领域
本发明涉及氧吸收性包装材料,特别涉及用于含有易氧化性成分和油状成分的贴附剂的氧吸收性包装材料。
背景技术
在贴附剂、特别是粘合剂层中含有药物的经皮吸收用贴附剂中,从保存中的品质保持等观点考虑,一直使用密闭性的包装材料进行密封包装。然而,将在粘合剂中含有易氧化性成分和油状成分的贴附剂用包装材料包装时,由于贴附剂与包装材料的内表面接触,或者易氧化性成分和油状成分气化,因而吸附或转移到包装材料使粘合剂中的易氧化性成分和油状成分的含量变化。另外,在经皮吸收用贴附剂的情况下,指出了所含有的药物的经皮吸收性的降低、因含有药物自身的吸附而药理效果降低等问题。针对这样的问题,提出了一种能够在防止贴附剂的粘合剂中含有的易氧化性成分和油状成分吸附或转移到包装材料的同时防止因氧化所致的变色、药效降低、且能够长时间保存贴附剂的包装材料(日本特开2014-061187号公报)。
由此得到的包装材料除了具有上述特性以外,热封强度也高,机械强度也高。然而,该包装材料的撕裂开封性不足,为了更容易地由使用者、特别是力气小的高龄者或孩子进行开封,仍有改善的余地。
另外,着眼于对作为食品、医药品的包装材料普遍使用的聚酯膜的撕裂性进行改善的课题,提出了在聚对苯二甲酸乙二醇酯中混合改性聚对苯二甲酸丁二醇酯(PBT)而制作的双轴拉伸聚酯膜、在聚对苯二甲酸乙二醇酯中混合聚碳酸酯(PC)而制作的双轴拉伸聚酯膜等(日本特开平11-302405号公报和日本特开2001-329077号公报)。
现有技术文献
专利文献
专利文献1:日本特开2014-061187号公报
专利文献2:日本特开平11-302405号公报
专利文献3:日本特开2001-329077号公报
发明内容
本发明的目的在于提供一种在用于含有易氧化性成分和油状成分的贴附剂等的氧吸收性包装材料中既保持了热封强度、又改善了撕裂性的氧吸收性包装材料。
本发明人等进行了深入研究,结果发现使聚对苯二甲酸乙二醇酯系树脂含有一定量的环状聚烯烃系树脂和/或丙烯酸系树脂而制作的膜能够作为可容易撕裂的膜使用,通过在设置于包装材料的内侧的密封膜中应用该材料从而完成了本发明。
即,本发明涉及氧吸收性包装材料,是包含氧阻隔层、氧吸收层和密封膜的层叠结构的氧吸收性包装材料,密封膜是至少包含芯层和具有热封性的内层的层叠树脂膜,相对于芯层总质量,芯层含有20~40质量%的环状聚烯烃系树脂或丙烯酸系树脂、以及60~80质量%的聚对苯二甲酸乙二醇酯系树脂。
另外,本发明优选芯层含有环状烯烃系树脂,环状烯烃系树脂包含环状烯烃共聚(COC)树脂。
另外,本发明优选芯层含有丙烯酸系树脂,丙烯酸系树脂包含聚甲基丙烯酸甲酯(PMMA)树脂。
另外,本发明优选氧阻隔层为铝箔和双轴拉伸聚对苯二甲酸乙二醇酯膜的层压膜。
另外,本发明优选密封膜的内层含有经间苯二甲酸改性的聚对苯二甲酸乙二醇酯。
另外,本发明优选密封膜的内层和/或芯层为无拉伸膜。
另外,本发明优选氧吸收层为含有具有不饱和脂环结构作为氧吸收部位的氧吸收性聚酯多元醇和异氰酸酯系固化剂的氧吸收性粘接剂层。
另外,本发明优选氧吸收性聚酯多元醇为含有来自于四氢邻苯二甲酸或其衍生物的结构单元的聚酯多元醇。
另外,本发明优选密封膜为依次层叠有表层、芯层和内层的层叠树脂膜,密封膜的表层含有聚对苯二甲酸乙二醇酯系树脂。
另外,本发明还涉及以上述的氧吸收性包装体包装贴附剂而成的包装结构。
根据本发明,可实现在含有易氧化性成分和油状成分的贴附剂等中使用的、既保持了热封强度又改善了撕裂性的氧吸收性包装材料。
附图说明
图1表示本发明的氧吸收性包装材料的一个实施方式的简要截面图。
具体实施方式
<氧吸收性包装材料的构成>
以下,基于作为本发明的氧吸收性包装材料的一个实施方式的简要截面图的图1,对本发明的氧吸收性包装材料的构成进行说明,但本发明不限定于图1的实施方式。
本发明的氧吸收性包装材料100至少由氧阻隔层30、氧吸收层20和密封膜10构成,密封膜10是至少由芯层11和具有热封性的内层12构成的层叠树脂膜。在密封膜10中,更优选以覆盖不与芯层11的内层12接触的面的方式进一步设置表层13,成为由表层13和内层12夹住芯层11的三明治结构。通过密封膜10包含芯层11,从而与以往的热封层相比,撕裂强度降低,其结果,还有助于包装材料100整体的撕裂强度降低。
密封膜10的芯层11、内层12和表层13的各厚度没有特别限定,如果密封膜10整体的厚度中的芯层11的厚度的比例过小,则有可能包装材料100整体的撕裂性无法改善,如果密封膜10整体的厚度中的芯层11的厚度的比例过大,则有可能在制膜时、层压时密封膜会断裂,成型加工性降低。另外,如果内层12的厚度过小,则有可能油状成分的非吸附性降低且热封强度降低,如果内层12和表层13的厚度过大,则撕裂强度变高,有可能撕裂性无法改善。鉴于以上情况,各层的厚度优选内层12:芯层11:表层13设定为10~30:40~80:10~30的比率,优选设定为15~25:50~70:15~25的比率。具体而言,以如下方式设定:芯层11的厚度优选为5~30μm,更优选为7~20μm,内层12的厚度优选为1~10μm,更优选为2~7μm,表层13的厚度优选为1~10μm,更优选为2~7μm。
另外,密封膜10整体的厚度可以考虑氧吸收层20和氧阻隔层30各自的厚度而适当地设定,优选为10~50μm,更优选为10~35μm,进一步优选为10~20μm。
氧阻隔层30和氧吸收层20的厚度没有特别限定,氧阻隔层30的厚度优选为1μm~30μm,特别优选为1μm~25μm,氧吸收层20的厚度优选为1μm~30μm,特别优选为3μm~15μm。
另外,在内层12和芯层11之间、表层13和芯层11之间、表层13和氧吸收层20之间以及芯层11和氧吸收层20之间(不具备表层13的情况)可以适当具备粘接剂层、粘合剂层以及与内层12、芯层11和表层13相同种类的层。即,密封膜10也可以采取例如内层/表层/芯层/表层的构成、内层/芯层/粘合层/表层的构成、内层/芯层/表层/芯层/表层的构成等各种复合三明治结构。另外,包装材料100可以进一步在氧吸收层20和氧阻隔层30之间以及氧阻隔层30之上适当地包含其它功能层(粘接剂层等)。
根据本发明,可实现一种能够在防止贴附剂的粘合剂中含有的易氧化性成分和油状成分吸附或转移到包装材料的同时防止因氧化所致的变色、药效降低,能够进行长时间保存且兼具热封强度和易撕裂性的氧吸收性包装材料。
这里,本发明的包装材料100的撕裂强度是指使用拉伸试验机以小袋形态测定的值。包装材料100的流动方向和垂直方向各自的撕裂强度优选为1.5N以下,特别优选为1.0N以下,但并不限定于此。可以根据包装材料100的用途而适当地设定撕裂强度。另外,膜的撕裂强度例如可以以JIS K7128的裤形试验片的形式进行测定。以下,对各层进行详细说明。
<密封膜>
构成密封膜的各层优选无拉伸或以低倍率拉伸的状态。以高倍率拉伸的聚对苯二甲酸乙二醇酯由于取向结晶化而失去热封性,因而不优选。
《密封膜的芯层》
相对于芯层总质量,芯层含有20~40质量%、优选25~40质量%的环状聚烯烃系树脂和/或丙烯酸系树脂以及60~80质量%、优选60~75质量%的聚对苯二甲酸乙二醇酯系树脂。通过选择上述芯层的组成比,能够成为在聚对苯二甲酸乙二醇酯系树脂中分散有环状聚烯烃系树脂和/或丙烯酸系树脂的颗粒的具有海岛结构的树脂层,且得到撕裂强度低的材料。而且,通过具备该芯层,从而密封膜整体的撕裂强度降低,其结果,有助于包装体整体的撕裂强度的降低。另外,环状聚烯烃系树脂和丙烯酸系树脂可以混合使用,但更优选不混合而仅使用其中任一种。
本发明的芯层中含有的聚对苯二甲酸乙二醇酯系树脂是指以聚对苯二甲酸乙二醇酯为主体的均聚物或共聚聚酯,具体而言,是指二羧酸成分和二醇成分各自的单体的80摩尔%以上由对苯二甲酸和乙二醇构成的聚酯。作为除对苯二甲酸以外的二羧酸成分,可以配合选自间苯二甲酸(IA)、邻苯二甲酸、对-β-氧基乙氧基苯甲酸、2,6-萘二羧酸、二苯氧基乙烷-4,4’-二羧酸、5-磺基间苯二甲酸钠、六氢对苯二甲酸、己二酸、癸二酸、偏苯三酸和均苯四甲酸中的至少一种。作为酸成分,更优选为添加有间苯二甲酸的共聚物,间苯二甲酸的添加量优选为二羧酸成分整体的1摩尔%~15摩尔%,特别优选为1摩尔%~5摩尔%。
另外,二醇成分优选仅由乙二醇构成,但可以在不损害本发明的本质的范围含有除此以外的二醇成分,例如选自丙二醇、1,4-丁二醇、二乙二醇、1,6-己二醇、环己烷二甲醇、双酚A的环氧乙烷加成物等中的一种或二种以上。
作为芯层中可含有的环状聚烯烃系树脂,例如可举出环状烯烃与非环状烯烃的加成共聚物、1种或2种以上的环状聚烯烃的开环复分解聚合物、将上述开环复分解聚合物氢化而得到的聚合物等。作为环状烯烃,可举出降冰片烯系烯烃、四环十二碳烯系烯烃和双环戊二烯系烯烃(这些环状聚烯烃可以被烷基(优选碳原子数1~20)、亚烷基(优选碳原子数1~20)、芳烷基(优选碳原子数6~30)、环烷基(优选碳原子数3~30)、羟基、烷氧基(优选碳原子数1~10)、乙酰基、氰基、酰胺基、酰亚胺基、甲硅烷基、芳香环、醚键、酯键等取代)。本发明中,从经济性和得到性的方面考虑,作为环状聚烯烃系树脂,优选使用环状烯烃共聚(COC)树脂,更优选为碳原子数2~10的链状烯烃与降冰片烯的共聚物,特别优选为乙烯与降冰片烯的共聚物。
芯层中可含有的丙烯酸树脂为丙烯酸酯或甲基丙烯酸酯的聚合物,如上所述,可以使用聚丙烯酸甲酯(PMA)、聚丙烯酸乙酯(PEA)、聚丙烯酸丁酯(PBA)、聚甲基丙烯酸甲酯(PMMA)等,从经济性和得到性的观点考虑,特别优选使用聚甲基丙烯酸甲酯(PMMA)树脂。
芯层通过将聚对苯二甲酸乙二醇酯系树脂以及环状聚烯烃系树脂和/或丙烯酸系树脂混合并利用挤出等公知的方法进行成膜而得到。具体而言,可以使用将聚对苯二甲酸乙二醇酯系树脂的碎片以及环状聚烯烃系树脂和/或丙烯酸系树脂的碎片在投入到挤出机之前进行混合,将该混合碎片投入到挤出机进行熔融混合的方法;将聚对苯二甲酸乙二醇酯系树脂的碎片以及环状聚烯烃系树脂和/或丙烯酸系树脂的碎片在不混合的情况下分别投入到分开的挤出机中进行熔融,将这些用分开的挤出机熔融了的聚对苯二甲酸乙二醇酯系树脂以及环状聚烯烃系树脂和/或丙烯酸系树脂在从T型模头挤出之前混合而导入到模头的方法等中的任一方法。其中,为了将本发明的芯层制成在聚对苯二甲酸乙二醇酯系树脂中微分散有环状聚烯烃系树脂和/或丙烯酸系树脂的颗粒的具有海岛结构的树脂层,聚对苯二甲酸乙二醇酯系树脂与环状聚烯烃系树脂和/或丙烯酸系树脂的混合的混炼温度优选为255℃以上且小于295℃,更优选为255℃以上且小于285℃。另外,在混合树脂的挤出机内的滞留时间优选为5分钟~20分钟。
《密封膜的内层》
具有热封性的内层是指包装材料的最内层,优选由经间苯二甲酸改性的聚对苯二甲酸乙二醇酯构成。进而,内层由间苯二甲酸成分的共聚比率优选为2摩尔%~20摩尔%、更优选为5摩尔%~20摩尔%、特别优选为10摩尔%~20摩尔%的间苯二甲酸改性聚对苯二甲酸乙二醇酯树脂构成。间苯二甲酸成分的共聚比率在上述范围的间苯二甲酸改性聚对苯二甲酸乙二醇酯系树脂由于油状成分的非吸附性优异,并且具有优异的热封性,因而特别优选。间苯二甲酸的共聚比率小于2摩尔%时,有可能因制膜时的结晶化而使热封性降低,另外,共聚比率超过20摩尔%时,有可能非吸附性降低。
也可以在不损害热封特性和非吸附性的范围向内层添加各种添加剂。作为添加剂,可举出抗氧化剂、紫外线吸收剂、水解抑制剂、防霉剂、固化催化剂、增塑剂、颜料、填充剂、二氧化硅等润滑材料等。这些添加剂相对于内层的总质量优选在0质量%~10质量%的范围内。
内层可以利用T型模头成型、充气成型等公知的制膜方法进行制膜。
此时,优选将热熔融状态的膜通过迅速冷却而固化。通过迅速冷却而抑制树脂的结晶化,得到热封特性优异的膜。
另外,内层优选为无拉伸或以低倍率拉伸的状态。以高倍率拉伸的聚对苯二甲酸乙二醇酯由于取向结晶而失去热封性,因而不优选。
《密封膜的表层》
表层是至少覆盖同芯层的与内层接触的面为相反的面的层,优选具有提高油状成分的非吸附性的作用、辅助热封强度的作用。表层可以由树脂等构成,优选为由聚对苯二甲酸乙二醇酯系树脂构成的层,特别优选为由间苯二甲酸成分的共聚比率为0摩尔%~5摩尔%、优选1摩尔%~4摩尔%的间苯二甲酸改性聚对苯二甲酸乙二醇酯构成的层。
优选作为内层材料的间苯二甲酸成分的共聚比率为2摩尔%~20摩尔%的较高改性率的聚对苯二甲酸乙二醇酯由于结晶性低,因而热封特性优异,并且具有优异的非吸附性,与此相对,优选作为表层材料的间苯二甲酸成分的共聚比率为0摩尔%~5摩尔%的低改性率的聚对苯二甲酸乙二醇酯具有更高的非吸附性。另外,低改性率的聚对苯二甲酸乙二醇酯由于通用为PET瓶用材料而大量使用,因此可便宜地获得,经济性优异。即,通过制成用由聚对苯二甲酸乙二醇酯系树脂构成的内层和表层夹住芯层而成的层叠树脂膜构成,能够实现热封特性、非吸附性和经济性优异的密封膜。
<氧吸收层>
氧吸收层是出于为了避免用包装材料包装的物质与氧接触而吸收氧的目的而具备的,且含有具有不饱和脂环结构作为氧吸收部位的氧吸收性树脂。具有不饱和脂环结构作为氧吸收部位的氧吸收性树脂由于伴随着自动氧化反应即氧吸收反应的分解气体的产生少,因此与由分解气体产生量多的不饱和脂肪酸、具有不饱和基团的链状烃聚合物构成的氧吸收剂相比,优选作为贴附剂用的包装材料用途。通过抑制醛、酮、羧酸、醇等分解气体的产生,能够抑制由分解气体与贴附剂成分的化学反应所致的贴附剂的品质降低,能够长期稳定保存。
作为具有不饱和脂环结构作为氧吸收部位的氧吸收性树脂,可以举出具有环己烯环的聚合物,例如乙烯-甲基丙烯酸酯-丙烯酸环己基甲酯共聚物、以四氢邻苯二甲酸酐衍生物为原料的缩聚聚合物。另外,也可以使用共轭二烯系聚合物的环化反应物。
作为优选的具有不饱和脂环结构作为氧吸收部位的氧吸收性树脂,可举出聚丁二烯树脂、聚异戊二烯树脂、聚亚辛烯(ポリオクテニレン)树脂等烯属不饱和烃树脂、将马来酸或富马酸、衣康酸、四氢邻苯二甲酸等不饱和二羧酸或其衍生物作为原料使用的树脂、共轭二烯聚合物环化物、聚(乙烯-丙烯酸甲酯/环己烯-丙烯酸甲酯)树脂等。
这些氧吸收性树脂可以单独使用,另外,也可以混合2种以上的氧吸收性树脂使用。
作为优选的具有不饱和脂环结构作为氧吸收部位的氧吸收性树脂,例如,可举出将含有选自下述单体(i)和单体(ii)中的单体的原料聚合而成的树脂:
(i)与下述结构(a)和(b)这两个基团键合且与1个或2个氢原子键合的碳原子包含于不饱和脂环结构的单体;
(a)不饱和脂环结构内的碳-碳双键基团,
(b)选自含有杂原子的官能团、由该官能团衍生的键合基团、碳-碳双键基团和芳香环中的基团;
(ii)不饱和脂环结构内的与碳-碳双键邻接的碳原子与供电子性取代基和氢原子键合、且与该碳原子邻接的其它碳原子与含有杂原子的官能团或由该官能团衍生的的键合基团键合、该供电子性取代基和含有杂原子的官能团或由该官能团衍生的的键合基团处于顺位的单体。
可以将含有单体(i)和单体(ii)的原料聚合而得到的氧吸收性树脂优选为含有来自于四氢邻苯二甲酸或四氢邻苯二甲酸酐等或其衍生物的结构单元的聚酯。
作为具有(i)的结构的酸成分,可以举出Δ2-四氢邻苯二甲酸或其衍生物、Δ3-四氢邻苯二甲酸或其衍生物、Δ2-四氢邻苯二甲酸酐或其衍生物、Δ3-四氢邻苯二甲酸酐或其衍生物。优选为Δ3-四氢邻苯二甲酸或其衍生物、或者Δ3-四氢邻苯二甲酸酐或其衍生物,特别优选为4-甲基-Δ3-四氢邻苯二甲酸或其衍生物、或者4-甲基-Δ3-四氢邻苯二甲酸酐或其衍生物。4-甲基-Δ3-四氢邻苯二甲酸酐例如可以通过对使以异戊二烯为主成分的石油脑的C5馏分与马来酸酐反应而得的含有4-甲基-Δ4-四氢邻苯二甲酸酐的异构体混合物进行结构异构化而得到,并进行工业制造。
作为具有(ii)的结构的酸成分,特别优选为顺式-3-甲基-Δ4-四氢邻苯二甲酸或其衍生物、或者顺式-3-甲基-Δ4-四氢邻苯二甲酸酐或其衍生物。顺式-3-甲基-Δ4-四氢邻苯二甲酸酐例如可以通过使以反式间戊二烯为主成分的石油脑的C5馏分与马来酸酐反应而得到,并进行工业制造。
将四氢邻苯二甲酸或其衍生物作为原料使用的氧吸收性聚酯树脂由于氧化过程中产生的分解物的量少,因而优选。氧吸收性聚酯树脂可以通过四氢邻苯二甲酸或其衍生物、优选甲基四氢邻苯二甲酸酐异构体混合物与二醇成分的反应而制造。作为二醇成分,例如可举出乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇、二丙二醇、聚丙二醇、三亚甲基二醇、1,3-丁二醇、1,4-丁二醇、3-甲基-1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、新戊二醇、1,4-环己烷二甲醇、2-苯基丙二醇、2-(4-羟基苯基)乙醇、α,α-二羟基-1,3-二异丙基苯、邻二甲苯二醇、间二甲苯二醇、对二甲苯二醇、α,α-二羟基-1,4-二异丙基苯、对苯二酚、4,4-二羟基联苯、萘二醇或它们的衍生物等。优选为脂肪族二醇,例如为二乙二醇、三乙二醇、1,4-丁二醇,进一步优选为1,4-丁二醇。使用1,4-丁二醇时,可得到树脂的氧吸收性能高、进而在氧化过程中产生的分解物的量也少的氧吸收性聚酯树脂。这些二醇成分可以单独或组合2种以上使用。
在氧吸收性聚酯树脂中,除了四氢邻苯二甲酸或其衍生物以外,也可以含有芳香族二羧酸或脂肪族二羧酸、脂肪族羟基羧酸等其它酸成分及其衍生物作为原料。
作为芳香族二羧酸及其衍生物,可举出邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸等苯二羧酸、2,6-萘二羧酸等萘二羧酸、蒽二羧酸、磺基间苯二甲酸、磺基间苯二甲酸钠或它们的衍生物等。其中,优选邻苯二甲酸、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸。
作为脂肪族二羧酸及其衍生物,可举出草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十一烷二酸、十二烷二酸、3,3-二甲基戊二酸或它们的衍生物等。其中,优选己二酸、琥珀酸,特别优选琥珀酸。
另外,也可举出具有脂环结构的六氢邻苯二甲酸、二聚酸及其衍生物。
作为脂肪族羟基羧酸及其衍生物,可举出乙醇酸、乳酸、羟基新戊酸、羟基己酸、羟基己酸或它们的衍生物。
这些酸成分例如可以酯化成对苯二甲酸二甲酯、双(2-羟基二乙基)对苯二甲酸酯。另外,也可以像邻苯二甲酸酐、琥珀酸酐那样为酸酐。
本发明中,作为氧吸收性聚酯,优选为通过将四氢邻苯二甲酸衍生物、1,4-丁二醇和琥珀酸或琥珀酸酐共聚而可以得到的聚酯。
本发明中使用的氧吸收性聚酯树脂可以通过本领域技术人员公知的任意的聚酯的缩聚方法而得到。例如为界面缩聚、溶液缩聚、熔融缩聚和固相缩聚。
在合成本发明中使用的氧吸收性聚酯树脂时,未必需要聚合催化剂,例如可以使用钛系、锗系、锑系、锡系、铝系等通常的聚酯聚合催化剂。另外,也可以使用含氮碱性化合物、硼酸和硼酸酯、有机磺酸系化合物等公知的聚合催化剂。
本发明中使用的氧吸收性聚酯树脂的数均分子量优选为500~100000,更优选为2000~10000。另外,优选的重均分子量为5000~200000,更优选为10000~100000,进一步优选为20000~70000。另外,氧吸收性树脂可以添加过渡金属催化剂来促进氧吸收反应。作为过渡金属催化剂,可举出由锰、铁、钴、镍、铜的过渡金属和有机酸构成的过渡金属盐。
《氧吸收性粘接剂》
氧吸收性粘接剂是指含有上述氧吸收性树脂和固化剂的粘接剂。氧吸收性树脂优选以氧吸收性粘接剂的形态包含于氧吸收层。作为粘接剂,例如可举出对丙烯酸系粘接剂、聚氨酯系粘接剂、环氧系粘接剂、乙烯-乙酸乙烯酯系粘接剂、氯乙烯系粘接剂、有机硅系粘接剂、橡胶系粘接剂等赋予氧吸收功能的粘接剂。特别是作为干式层压用粘接剂使用时,优选聚氨酯系粘接剂,更优选将由氧吸收性聚酯树脂构成的主剂和异氰酸酯系固化剂组合而得的2液固化型聚氨酯系粘接剂。
作为异氰酸酯系固化剂,可以使用芳香族、脂肪族或脂环族的各种公知的异氰酸酯类。作为芳香族二异氰酸酯类,例如可举出4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯等。作为脂肪族异氰酸酯系固化剂,例如,可举出亚二甲苯基二异氰酸酯(XDI)、六亚甲基二异氰酸酯(HDI)、赖氨酸二异氰酸酯、赖氨酸甲酯二异氰酸酯、三甲基六亚甲基二异氰酸酯、正戊烷-1,4-二异氰酸酯等。作为脂环族异氰酸酯系固化剂,例如可举出异佛尔酮二异氰酸酯(IPDI)、环己烷-1,4-二异氰酸酯、甲基环己基二异氰酸酯、二环己基甲烷-4,4’-二异氰酸酯等。其中,作为脂肪族异氰酸酯系固化剂,优选XDI和HDI,作为脂环族异氰酸酯系固化剂,优选IPDI。以上的异氰酸酯类和异氰酸酯类的衍生物可以单独使用,也可以组合2种以上使用。
另外,在氧吸收性粘接剂中,氧吸收性树脂与固化剂的比例以固体成分重量比计优选为100:3~100:20。
在氧吸收性粘接剂层中使用的具有不饱和脂环结构作为氧吸收部位的氧吸收性聚酯多元醇优选为含有上述氧吸收性聚酯作为结构单元的聚酯多元醇。
应予说明,本发明中的氧吸收性粘接剂可以根据需要含有硅烷偶联剂、抗氧化剂、紫外线吸收剂、水解抑制剂、防霉剂、固化催化剂、增稠剂、增塑剂、颜料、填充剂、聚酯树脂、环氧树脂等各种添加剂。
<氧阻隔层>
作为氧阻隔层,由具有防止氧、水蒸气透过的作用的材料构成,出于水蒸气阻隔性和遮光性的理由,特别优选为铝箔和双轴拉伸聚对苯二甲酸乙二醇酯膜的层压膜。在包装材料中,以双轴拉伸聚对苯二甲酸乙二醇酯在外侧且铝箔在内侧的方式进行层叠。
此外,作为氧阻隔层,可以优选使用具有以二氧化硅、氧化铝等金属氧化物或金属的蒸镀薄膜、聚乙烯醇系树脂,乙烯-乙烯醇共聚物,聚丙烯酸系树脂或偏二氯乙烯系树脂等气体阻隔性有机材料为主剂的阻隔涂层的双轴拉伸聚酯膜、双轴拉伸尼龙膜或双轴拉伸聚丙烯膜等。
另外,作为氧阻隔层,也可以优选使用涂覆有由有机材料和无机材料构成的混合阻隔剂的双轴拉伸聚酯膜、双轴拉伸尼龙膜。另外,还可以为乙烯-乙烯醇共聚物膜、聚间二甲苯己二酰胺膜(ポリメタキシリレンアジパミドフィルム)、聚偏二氯乙烯系膜、铝箔等金属箔。另外,作为氧阻隔层,也可以使用相同种类的层或2种以上的不相同种类的层的层叠体。
<氧吸收性包装材料的制造方法>
包装材料的制造可以使用本身公知的挤出成型法。例如通过利用与树脂种类对应的数量的挤出机,使用多层多重模头进行挤出成型,从而能够使层叠体成型。此外,可以使用挤出涂布法、三明治式层压法,另外,也可以对预先形成的膜利用干式层压法来制造层叠体。
层叠体可以通过制袋成三边或四边密封的通常的小袋类、角撑袋类、自立式袋类、枕式袋类等而形成包装袋。制袋可以按照公知的制袋法进行。
<用包装材料包装的贴附剂>
用上述包装材料包装的贴附剂由支撑体层和粘合剂层构成,在粘合剂层中配合药物,使药物经皮吸收而进行各种疾病的治疗或预防。这里所说的药物没有特别限定,可以使用全身性作用药物、局部作用药物中的任一者。作为这样的药物,例如可举出皮质类固醇剂、非甾体类抗炎药、抗风湿剂、安眠药、抗精神病药、抗抑郁药、情绪稳定剂、精神兴奋剂、抗焦虑药、抗癫痫药、偏头痛治疗药物、帕金森病治疗药物、毒蕈碱受体拮抗剂、不安腿综合征治疗剂、脑循环代谢改善剂、抗痴呆药物、植物神经作用药物、肌松药、降压药、利尿药、降血糖药、抗高血脂症药、抗痛风药、全身麻醉剂、局部麻醉剂、抗菌剂、抗真菌剂、抗病毒药物、抗寄生虫药物、维生素药物、抗心绞痛药、血管扩张药、抗心律失常药、抗组胺药、介质释放抑制剂、白三烯拮抗剂性激素药物、甲状腺激素药物、抗甲状腺药物、抗肿瘤药物、止吐药、抗眩晕药物、气管支扩张剂、镇咳药、祛痰药、戒烟辅助药物、抗骨质疏松药等。这些药物可以以游离体的形态使用,也可以以盐的形态使用。另外,这些药物可以单独或混合2种以上使用。
本发明中使用的贴附剂含有不易受到氧的影响的易氧化性成分,具体而言,是分子中含有氨基、苄基、硫醇基和羰基中的至少一种的化合物。例如,其中含有具有胺、酰胺、环式胺、内脂、羧酸结构的化合物。
作为支撑体层,只要在粘贴时没有明显的不协调,就没有特别限定。具体而言,可举出由聚酯、聚乙烯或聚丙烯等聚烯烃、聚氯乙烯、增塑聚氯乙烯、增塑乙酸乙烯酯-氯乙烯共聚物、聚偏二氯乙烯、乙烯-乙酸乙烯酯共聚物、乙酸纤维素、乙基纤维素、乙烯-丙烯酸乙酯共聚物、聚四氟乙烯、聚氨酯、离聚物树脂等合成树脂构成的单独膜或它们的层压膜、或者橡胶制、上述合成树脂制、聚对苯二甲酸乙二醇酯等聚酯制或尼龙等聚酰胺制的多孔性膜或片材、无纺布、织物或它们和上述合成树脂膜的层压物等。
贴附剂优选为经皮吸收制剂,是将含有经皮吸收性药物的粘合剂层形成于支撑体的单面而成的。另外,也可以具有层叠于该粘合剂层的另一面的经剥离处理的脱模膜。
作为贴附剂的形态,为平面状的扁平的形态,平面形状除了大致矩形以外,可举出三角形、五角形等多边形,即大致用直线勾勒轮廓的形状,或椭圆、圆形等用曲线勾勒轮廓的形状,它们的组合等,但不限定于此。
贴附剂的大小可以根据贴附剂的用途、应用位置等而适当地选择。例如,贴附剂的形状为大致矩形时,一般,其一边的长度为15mm~90mm,另一边的长度也为15mm~90mm。
贴附剂的总厚度通常为50μm~2000μm,优选在100μm~1000μm的范围。另外,贴附剂由支承层和粘合剂层构成,支撑体层的厚度通常为1μm~1000μm,粘合剂层通常为10μm~200μm,优选为15μm~150μm。
粘合剂层可以含有油状成分。所含有的油状成分将粘合剂层增塑而赋予柔软感来减少皮肤刺激性,或者对药物的经皮吸收性进行调整。油状成分优选室温(25℃)下为液态的油状成分,或者混合2种以上使用时最终混合物在室温(25℃)下为液态的油状成分。作为这样的油状成分,例如可举出油醇、辛基十二烷醇等高级醇;甘油、乙二醇、聚丙二醇等多元醇;辛酸、油酸等高级脂肪酸;肉豆蔻酸异丙酯、棕榈酸异丙酯、油酸乙酯等脂肪酸酯;癸二酸二乙酯、己二酸二异丙酯等多元酸酯;三异硬脂酸二甘油酯、失水山梨醇单油酸酯、丙二醇二辛酸酯、聚乙二醇单月桂酸酯、山梨醇聚氧乙烯醚四油酸酯等多元醇脂肪酸酯;月桂醇聚氧乙烯醚等聚氧乙烯烷基醚;角鲨烷、液体石蜡等烃;橄榄油、蓖麻油等植物油;有机硅油;N-甲基吡咯烷酮、N-十二烷基吡咯烷酮这样的吡咯烷酮类;癸基甲基亚砜这样的亚砜类等。这些油状成分可以单独或混合2种以上使用。
本发明的贴附剂用的包装体的形状只要是能够包装贴附剂的形状,就没有特别限定,例如除了正方形、长方形等大致矩形以外,可举出三角形、五角形等多边形、圆形、椭圆形、其它图形等。另外,包装成贴附剂用的包装体的形状的贴附剂的形状只要能够实现贴附剂的独立包装(密封),则可以相同也可以不同。
实施例
以下,根据实施例对本发明进行具体说明,本发明不受这些实施例任何限定,可以在不脱离本发明范围的范围进行适当变更。
各值采用以下方法进行测定。
(1)数均分子量(Mn)和重均分子量(Mw)
使用凝胶渗透色谱仪(GPC,东曹公司制;HLC-8120型GPC),以聚苯乙烯换算进行测定。溶剂使用氯仿。
(2)玻璃化转变温度:Tg
使用差示扫描量热测定器(Seiko Instruments公司制DSC6220),在氮气流中,以升温速度10℃/分钟进行测定。
(3)熔体流动速率(MFR)
依据JIS K7210,以温度230℃、负载3.80kg的条件进行测定(单位:g/10min)。
(4)熔体体积率(MVR)
依据JIS K7210,以温度260℃、负载2.16kg的条件进行测定。(单位:cm3/10min)。
(5)撕裂强度
预先,制作100mm×100mm(密封宽度10mm)的扁袋,在各边的中央部切开狭缝长度10mm的切口,利用拉伸试验机在23℃-50%RH环境下,测定试验速度200mm/min下的撕裂强度。此时,将行程范围40~140mm内的平均试验力作为撕裂强度,在实施例和比较例中,将MD(流动方向)和TD(垂直方向)的撕裂强度为1.5N/mm以下的情况评价为合格。
向具备搅拌装置、氮导入管、Dean-Stark型水分离器的3L的可分离式烧瓶中装入摩尔比为0.9的作为酸成分的甲基四氢邻苯二甲酸酐异构体混合物(日立化成;HN-2200)、摩尔比为0.1的作为其它酸成分的琥珀酸酐、摩尔比为1.3的作为二醇成分的1,4-丁二醇、作为聚合催化剂的钛酸异丙酯300ppm,一边除去在氮气氛中以150℃~200℃生成的水一边使其反应约6小时。接着,在0.1kPa的减压下,以200~220℃进行约3小时聚合,得到氧吸收性聚酯树脂(A)。氧吸收性聚酯树脂(A)的Mn为5200,Mw为54600。
在得到的氧吸收性聚酯树脂(A)中以固体成分换算计为10phr(每百分比树脂含量,parts per hundred resin)的方式混合作为异氰酸酯系固化剂的HDI/IPDI系固化剂(KL-75DIC Graphics公司制),溶解于乙酸乙酯,制备成固体成分浓度32wt%的氧吸收性粘接剂树脂组合物的乙酸乙酯溶液。
作为氧阻隔层,准备由厚度7μm的铝箔、聚氨酯系粘接剂层和12μm的双轴拉伸PET膜构成的干式层压膜,使用氧吸收性粘接剂树脂组合物的乙酸乙酯溶液,以粘接剂涂布量为4.5g/m2的方式利用干式层压机对作为总厚度17μm的层叠树脂膜的密封膜进行层压和层叠,进一步在35℃氮气氛下保存5天。然后,得到由氧阻隔层/氧吸收层/密封膜构成的氧吸收性层叠膜。
上述的密封膜使用将与氧吸收层接触的表层、作为无拉伸树脂层的芯层和作为热封面的内层依次层叠而成的3层结构的层叠膜。层叠膜的表层为PET/IA2单质,作为热封面的内层为添加有作为润滑材料的平均粒径为2.5μm的球状二氧化硅的PET/IA15。夹持于表层和内层的芯层的材料为将表2中记载的混合比的树脂以270℃混合而得到的混合物。将它们3层的材料同时使用挤出机以成型温度270℃混炼,进行共挤出,由此得到总厚度17μm的由层叠树脂膜构成的密封膜。此时,层叠树脂膜的各层的厚度为表层:芯层:内层=3.6:9.8:3.6μm。
以下示出将在膜中使用的材料。
[表1]
使用所得到的氧吸收性层叠膜来制作扁袋,实施撕裂试验。在表1中示出MD(流动方向)和TD(垂直方向)的撕裂强度的测定结果。
[表2]
如表2所示,在包装体中,在芯层为含有环状聚烯烃系树脂或丙烯酸系树脂和聚对苯二甲酸乙二醇酯系树脂的无拉伸树脂层时,能够在包装材料的流动方向和垂直方向分别实现低的撕裂强度。
应该认为这次公开的实施方式和实施例在所有方面都是例示,并非限制性的。本发明的范围并非通过上述说明示出而是由专利请求的保护范围示出,旨在包含与专利请求的保护范围均等的含义和范围内的全部变更。
符号说明
10 密封膜
11 芯层
12 内层
13 表层
20 氧吸收性层
30 氧阻隔层
100 氧吸收性包装材料
Claims (10)
1.一种氧吸收性包装材料,是包含氧阻隔层、氧吸收层和密封膜的层叠结构的氧吸收性包装材料,
密封膜是至少包含芯层和具有热封性的内层的层叠树脂膜,
相对于芯层总质量,芯层含有20~40质量%的环状聚烯烃系树脂和/或丙烯酸系树脂以及60~80质量%的聚对苯二甲酸乙二醇酯系树脂。
2.根据权利要求1所述的氧吸收性包装材料,其中,
芯层含有环状烯烃系树脂,
环状烯烃系树脂包含环状烯烃共聚树脂、即COC树脂。
3.根据权利要求1所述的氧吸收性包装材料,其中,
芯层含有丙烯酸系树脂,
丙烯酸系树脂包含聚甲基丙烯酸甲酯树脂、即PMMA树脂。
4.根据权利要求1~3中任一项所述的氧吸收性包装材料,其中,氧阻隔层为铝箔和双轴拉伸聚对苯二甲酸乙二醇酯膜的层压膜。
5.根据权利要求1~4中任一项所述的氧吸收性包装材料,其中,密封膜的内层含有经间苯二甲酸改性的聚对苯二甲酸乙二醇酯。
6.根据权利要求1~5中任一项所述的氧吸收性包装材料,其中,密封膜的内层和/或芯层为无拉伸膜。
7.根据权利要求1~6中任一项所述的氧吸收性包装材料,其中,氧吸收层为含有具有不饱和脂环结构作为氧吸收部位的氧吸收性聚酯多元醇和异氰酸酯系固化剂的氧吸收性粘接剂层。
8.根据权利要求7所述的氧吸收性包装材料,其中,氧吸收性聚酯多元醇为含有来自于四氢邻苯二甲酸或其衍生物的结构单元的聚酯多元醇。
9.根据权利要求1~8中任一项所述的氧吸收性包装材料,其中,密封膜为依次层叠有表层、芯层和内层的层叠树脂膜,密封膜的表层含有聚对苯二甲酸乙二醇酯系树脂。
10.一种包装结构,是以权利要求1~9中任一项所述的氧吸收性包装体包装贴附剂而成的。
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