CN102947383B - Poly-olefin resin compound, film, packaging material, multi-chamber container and cover material - Google Patents
Poly-olefin resin compound, film, packaging material, multi-chamber container and cover material Download PDFInfo
- Publication number
- CN102947383B CN102947383B CN201180029100.1A CN201180029100A CN102947383B CN 102947383 B CN102947383 B CN 102947383B CN 201180029100 A CN201180029100 A CN 201180029100A CN 102947383 B CN102947383 B CN 102947383B
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- China
- Prior art keywords
- film
- weight
- composition
- based resin
- polyethylene
- 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.)
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- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims description 30
- 150000001875 compounds Chemical class 0.000 title abstract description 9
- 239000005022 packaging material Substances 0.000 title 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 94
- 229920005678 polyethylene based resin Polymers 0.000 claims description 84
- 238000007789 sealing Methods 0.000 claims description 64
- 229920005673 polypropylene based resin Polymers 0.000 claims description 50
- 239000000805 composite resin Substances 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 239000004711 α-olefin Substances 0.000 claims description 31
- 238000002844 melting Methods 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 18
- 229920005604 random copolymer Polymers 0.000 claims description 17
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 abstract description 27
- 229920005989 resin Polymers 0.000 abstract description 26
- -1 Polypropylene Polymers 0.000 abstract description 22
- 239000005977 Ethylene Substances 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 5
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 description 114
- 238000000034 method Methods 0.000 description 45
- 238000012545 processing Methods 0.000 description 42
- 239000002245 particle Substances 0.000 description 40
- 238000012360 testing method Methods 0.000 description 40
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 19
- 229920000098 polyolefin Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 229920005629 polypropylene homopolymer Polymers 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 229920001684 low density polyethylene Polymers 0.000 description 12
- 239000004702 low-density polyethylene Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000004677 Nylon Substances 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 229920001778 nylon Polymers 0.000 description 10
- 229920000573 polyethylene Polymers 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 101710113246 Pectinesterase 3 Proteins 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 8
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 8
- 238000002955 isolation Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000002093 peripheral effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 230000000873 masking effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 241000863032 Trieres Species 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002632 lipids Chemical class 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- PEMDHCGOAOHYTL-UHFFFAOYSA-N C=CCCCC.CC1=C(C=C(C(=O)O)C=C1)C(=O)O Chemical compound C=CCCCC.CC1=C(C=C(C(=O)O)C=C1)C(=O)O PEMDHCGOAOHYTL-UHFFFAOYSA-N 0.000 description 2
- 206010009866 Cold sweat Diseases 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002193 fatty amides Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000005908 glyceryl ester group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-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
- VSKRSEHLMRRKOS-QJWNTBNXSA-N (z,12r)-12-hydroxyoctadec-9-enamide Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(N)=O VSKRSEHLMRRKOS-QJWNTBNXSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- XNQLVVSDYOHIND-UHFFFAOYSA-N 3,4,5-tris(fluoromethyl)phenol Chemical compound FCC=1C=C(C=C(C1CF)CF)O XNQLVVSDYOHIND-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical class CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229950007687 macrogol ester Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000414 obstructive effect Effects 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
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-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
- 229940113162 oleylamide Drugs 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 235000015108 pies Nutrition 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
- B65D81/3261—Flexible containers having several compartments
- B65D81/3266—Flexible containers having several compartments separated by a common rupturable seal, a clip or other removable fastening device
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/52—Details
- B65D75/58—Opening or contents-removing devices added or incorporated during package manufacture
- B65D75/5861—Spouts
- B65D75/5872—Non-integral spouts
- B65D75/5883—Non-integral spouts connected to the package at the sealed junction of two package walls
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Health & Medical Sciences (AREA)
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- Laminated Bodies (AREA)
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Abstract
The disclosed poly-olefin resin compound contains components (A) and (B) as described below. Components (A) and (B) have a total of 100 mass%: component (A) is 20-95 mass% and component (B) is 5-80 mass%. (A): Poly-olefin resin compound that satisfies requirements (a1), (a2) and (a3). (a1): The amount of monomer unit based on ethylene is 95 mol% or more (however, the total of monomer unit that constitutes poly-olefin resin is 100 mol%). (a2): The 5-carbon branching factor (Nc5) measured by 13C-NMR is less than 1000 carbon atoms per 0.1. (a3): Flow activation energy (Ea) is 40 kJ/mol or more. (B): Polypropylene resin.
Description
Technical field
The present invention relates to a kind of polyolefin resin composite, use this resin combination and the film, wrapping material, multichamber vessel and the lid material that obtain.
Background technology
In packing bag and packaging vessel, from the view point of protection content, there is not the stripping of hermetic unit in conveying and in operation, the material of stopping property excellence that the mode spilt of content requires stripping strength high.On the other hand, when stripping strength is too high, existence hand not easily break a seal hermetic unit problem, sometimes break a seal time content fly out, easy separability (Kaifeng property) reduce.Like this, in the wrapping material for packing bag, packaging vessel, require the performance of stopping property and the such antinomy of easy separability (Kaifeng property), up to now, various wrapping material film is studied, motion.Such as, as using the wrapping material film having polyolefin polymkeric substance, in patent documentation 1, record a kind of wrapping body, as sealing ply, comprise polypropylene-based resin and be the composition of ethylene ' alpha '-olefin random copolymers of 75 ~ 95 % by mole based on the content of the monomeric unit of ethene.In addition, in patent documentation 2, record and be the ethylene ' alpha '-olefin random copolymers of 70 ~ 90 % by mole by the content of the monomeric unit based on ethene, be the stacked film that the propylene alpha olefin random copolymers of 80 ~ 99 % by mole and poly composition are formed based on the content of the monomeric unit of propylene.
Patent documentation 1: Japanese Laid-Open Patent Publication 61-246061 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-264332 publication
Usually, be the film that the straight-chain ethene-alpha-olefin random copolymers of 95 ~ 99 % by mole and the composition of polypropylene-based resin are formed by the content of the monomeric unit based on ethene, its stripping strength is high, so, use difficulty as easy separability film.Therefore, in patent documentation 1 and patent documentation 2, use based on the few ethene-alpha-olefin random copolymers of the monomer unit content of ethene and manifest easy separability.But the easy separability film recorded in patent documentation 1 and patent documentation 2 uses the poor ethene-alpha-olefin random copolymers based on the monomeric unit of ethene, and therefore, fusing point is low, in thermotolerance, require improvement further.
Summary of the invention
Based on described situation, the problem that the present invention will solve is, provides a kind of and is suitable for manufacturing the balancing good of easy separability and stopping property and the polyolefin resin composite of the film of excellent heat resistance, the film with the sealing ply comprising this resin combination, wrapping material and lid material.
Namely, first aspect present invention is a kind of polyolefin resin composite, it contains following composition (A) and composition (B), wherein, when the total amount of composition (A) and composition (B) is set as 100 % by weight, the content of composition (A) is for being greater than 20 % by weight and less than 95 % by weight, and the content of composition (B) is more than 5 % by weight and lower than 80 % by weight
(A): the polyethylene-based resin meeting following important document (a1), (a2) and (a3);
(a1): the content based on the monomeric unit of ethene is more than 95 % by mole (wherein, the total of the whole monomeric unit forming polyethylene-based resin being set as 100 % by mole);
(a2): utilize
13branches (the N of the carbon number 5 that C-NMR measures
c5) for every 1000 carbon atoms are lower than 0.1;
(a3): the activation evergy (Ea) of flowing is more than 40kJ/mol;
(B): polypropylene-based resin.
Second aspect present invention is said polyolefins based resin composition, wherein, described composition (A) is for having the monomeric unit based on ethene and the monomeric unit based on the alpha-olefin of carbonatoms 3 ~ 20 and meeting the ethene-alpha-olefin copolymer of following important document (a4)
(a4): molecular weight distribution (Mw/Mn) is 5 ~ 25.
Third aspect present invention is a kind of polyolefin resin composite, and wherein, described composition (B) is for alfon or containing the propylene system random copolymers based on the monomeric unit more than 90 % by weight of propylene.
Fourth aspect present invention is a kind of polyolefin resin composite, it contains polyethylene-based resin (X) and polypropylene-based resin (Y), wherein, the content of polyethylene-based resin (X) is for being greater than 20 % by weight and less than 95 % by weight, the content of polypropylene-based resin (Y) is more than 5 % by weight and lower than 80 % by weight (wherein, the total amount of polyethylene-based resin (X) and polypropylene-based resin (Y) is set as 100 % by weight), and meet following important document (x1) and (x2)
(x1): utilize
13branches (the N of the carbon number more than 6 that C-NMR measures
lCB) for every 1000 carbon atoms be more than 0.01, and the branches (N of carbon number 5
c5) for every 1000 carbon atoms are lower than 0.1;
(x2): melting tension force (MT when 230 DEG C; Unit is cN.) for more than 1.5cN.
Fifth aspect present invention is a kind of film, and it is made up of polyolefin resin composite described above.
Sixth aspect present invention is a kind of multilayer film, and it has the sealing ply be made up of polyolefin resin composite described above.
Seventh aspect present invention is above-mentioned film, and it is wrapping material.
Eighth aspect present invention is a kind of multichamber vessel, and it is made up of film described above.
Ninth aspect present invention is above-mentioned film, and it is lid material.
Tenth aspect present invention is a kind of container, and above-mentioned lid material and polyolefin-based resins container body seal form by it.
The present invention the 11 aspect is a kind of container, and wherein, the polyolefin-based resins container main body of above-mentioned record is made up of polyethylene-based resin or polypropylene-based resin.
The present invention the 12 aspect is a kind of film, it has the different region of 2 of being made up of lower than the scope of the stripping strength of 1.5N/15mm fabric width the heat seal temperature scope of more than 15 DEG C and the maximum value of stripping strength and the difference of minimum value, and the difference of the mean peel strength in each region is more than 2.0N/15mm fabric width.
Accompanying drawing explanation
Fig. 1 is the sketch chart of the embodiment representing multichamber vessel of the present invention.
Nomenclature
1 reception room
2 peripheral parts
3 isolation parts (part between isolation reception room)
4: extract mouth
Embodiment
A mode of the present invention is a kind of polyolefin resin composite, it contains following composition (A) and composition (B), wherein, when total metering of composition (A) and composition (B) is set as 100 % by weight, the content of composition (A) is for being greater than 20 % by weight and less than 95 % by weight, the content of composition (B) is more than 5 % by weight and lower than 80 % by weight
(A): the polyethylene-based resin meeting following important document (a1), (a2) and (a3);
(a1): the content based on the monomeric unit of ethene is more than 95 % by mole (wherein, the total of the whole monomeric unit forming polyethylene-based resin being set as 100 % by mole);
(a2): utilize
13branches (the N of the carbon number 5 that C-NMR measures
c5) for every 1000 carbon atoms are lower than 0.1;
(a3): the activation evergy (Ea) of flowing is more than 40kJ/mol;
(B): polypropylene-based resin.
The polyethylene-based resin of composition (A) is have monomeric unit based on ethene as the polymkeric substance of formant, can enumerate manufacture by high-pressure free radical polymerization high-pressure process low-density polyethylene, with the polycomplexation ethene-alpha-olefin copolymer etc. manufactured such as legal.Composition (A) is preferably ethene-alpha-olefin copolymer.Ethene-alpha-olefin copolymer is the alpha-olefin of ethene and carbonatoms 3 ~ 20 is carried out the ethene-alpha-olefin copolymer that copolymerization obtains, for having the multipolymer based on the monomeric unit of ethene and the monomeric unit based on the alpha-olefin of carbonatoms 3 ~ 20.As the alpha-olefin of carbonatoms 3 ~ 20, can enumerate such as: propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene etc., be preferably 1-hexene, 1-octene.In addition, the alpha-olefin of above-mentioned carbonatoms 3 ~ 20 can be used alone, and also two or more kinds may be used.
As ethene-alpha-olefin copolymer, can enumerate such as: ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethylene-l-octane copolymer, ethene-1-butylene-1-hexene copolymer, ethene-1-butylene-1-octene copolymer etc., be preferably ethene-butene-1 copolymer, ethene-1-hexene copolymer, ethene-1-butylene-1-hexene copolymer, ethene-1-butylene-1-octene copolymer.
From the view point of be clamminess suppression, the thermotolerance of film, when the total of the whole monomeric unit forming polyethylene-based resin is set as 100 % by mole, the content of the monomeric unit based on ethene in the polyethylene-based resin of composition (A) is more than 95 % by mole, is preferably more than 96 % by mole.Therefore, the content based on the monomeric unit of the alpha-olefin of carbonatoms 3 ~ 20 is less than 5 % by mole, is preferably less than 4 % by mole, is more preferably less than 3 % by mole.From the view point of the flexibility of film, when the total of the whole monomeric unit forming polyethylene-based resin is set as 100 % by mole, be preferably less than 99 % by mole.Therefore, the content based on the monomeric unit of the alpha-olefin of carbonatoms 3 ~ 20 is preferably more than 1 % by mole.
With regard to the polyethylene-based resin of composition (A), utilize
13the branches of the carbon number 5 that C-NMR measures (below, is recited as " N sometimes
c5".) for every 1000 carbon atoms are lower than 0.1.N
c5preferably every 1000 carbon atoms are lower than 0.05, more preferably less than 0.01, most preferably are zero.
With regard to the polyethylene-based resin of composition (A), utilize
13the branches of the carbon number more than 6 that C-NMR measures (below, is recited as " N sometimes
lCB".) be preferably more than 0.01 for every 1000 carbon atoms.N
lCBwhen being more than 0.01, separability is good, therefore preferably.N
lCBpreferably every 1000 carbon atoms are more than 0.1.From the view point of raising stopping property, N
lCBpreferably every 1000 carbon atoms are less than 1, are more preferably less than 0.7.
The N of composition (A)
lCB, N
c5can adjust according to polymerizing conditions such as the kind of the selection of the selection of the manufacture method such as vapour phase polymerization, slurry polymerization, polymerizing catalyst, polymerization temperature, polymerization pressure, comonomer and additions.Such as, when reducing hydrogen concentration or ethylene pressure, the N of ethene-alpha-olefin copolymer
lCBbecome large.In addition, by carrying out prepolymerization, N can be made
lCBincrease.
N
lCBcan obtain by following method.By the 600MHz that is suitable for index in window function, use cold probe
13c-NMR spectrum, is set as 1000 by the summation at all peaks observed on 5 ~ 50ppm, the peak area at the peak near 38.09 ~ 38.27ppm with summit is set as A.This A is the value of the quantity of the branch's methine carbon being equivalent to carbon number more than 4.In order to the peak of branch's methine carbon of carbon number less than 5 with branch's methine carbon of carbon number more than 6 is separated, in window function, is suitable for Gauss, is being suitable for Gauss's
13in C-NMR spectrum, the peak that 38.21 ~ 38.27ppm observes is set as B, the peak that 38.21 ~ 38.09ppm observes is set as C.And, obtain N by following formula
lCB.
N
LCB＝A×B/(B+C)
N
c5obtain by following method.Index is suitable in window function
13in C-NMR spectrum, the summation at all peaks that 5 ~ 50ppm observes is set as 1000, obtains the peak area at the peak near 32.5 ~ 32.7ppm with summit.This peak area is the quantity (C in following constitutional formula of the branch's mesomethylene carbon being equivalent to carbon number 5
*) value.
····CH
2-CH-CH
2-····
Be explained, the position at peak of methine carbon from the branch being bonded with above-mentioned carbon number more than 5 is departed from the difference of determinator and condition determination sometimes, therefore, usually corresponds to each determinator and condition determination carries out the mensuration of mark product and determines.In addition, in spectroscopic analysis, as window function, preferably use negative exponential function.
From the view point of easy separability, the activation evergy (Ea) of the flowing of the polyethylene-based resin of composition (A) is more than 40kJ/mol, be preferably more than 50kJ/mol, be more preferably more than 55kJ/mol, more preferably more than 60kJ/mol.In addition, from the view point of stopping property, Ea is preferably below 100kJ/mol, is more preferably below 90kJ/mol.Above-mentioned Ea can change according to hydrogen concentration when being such as polymerized or ethylene pressure, and when reducing hydrogen concentration or ethylene pressure, the Ea of ethene-alpha-olefin copolymer becomes large.
The activation evergy (Ea) of flowing be based on Temperature-time superposition theorem, by shifted divisor (shift factor) (a during radian frequency (unit: rad/sec) the dependent principal curve of melting complex viscosity (unit: Pasec) at making display 190 DEG C
t) numerical value that utilizes Arrhenius (Arrhenius) type equation to calculate, be the value obtained by method shown below.Namely, by the melting complex viscosity-radian frequency curve of the ethene-alpha-olefin copolymer in 130 DEG C, 150 DEG C, 170 DEG C and 190 DEG C of respective temperature (T, unit: DEG C), (unit of melting complex viscosity is Pasec, and the unit of radian frequency is rad/sec.) based on Temperature-time superposition theorem, according to the every bar melting complex viscosity-radian frequency curve at each temperature (T), obtain the shifted divisor (a at each temperature (T) obtained when the melting complex viscosity-radian frequency curves overlapped with the vinyl copolymer at 190 DEG C
t), by the shifted divisor (aT) at respective temperature (T) and each temperature (T), utilize least square method to calculate [ln (a
t)] and the first-order approximation formula (following (I) formula) of [1/ (T+273.16)].Then, Ea is obtained by the inclination m of this expression of first degree and following formula (II).
ln(a
T)＝m(1/(T+273.16))+n (I)
Ea＝|0.008314×m| (II)
A
t: shifted divisor
Ea: the activation evergy (unit: kJ/mol) of flowing
T: temperature (unit: DEG C)
V.4.4.4 etc. above-mentioned calculating can use commercially available software for calculation, as this software for calculation, can enumerate Rheometrics Inc. Rhios.
Be explained, shifted divisor (a
t) for making two logarithmic curves of the melting complex viscosity-radian frequency in respective temperature (T) move (wherein along log (Y)=-log (X) direction of principal axis, Y-axis is set as melting complex viscosity, X-axis is set as radian frequency.), overlapping on melting complex viscosity-radian frequency curve at 190 DEG C time amount of movement, in this overlap, two logarithmic curves of the melting complex viscosity-radian frequency in respective temperature (T), corresponding to each curve, make radian frequency move as a
tdoubly, melting complex viscosity is moved as 1/a
tdoubly.In addition, relation conefficient when obtaining (I) formula by the value least square method of 4 of 130 DEG C, 150 DEG C, 170 DEG C and 190 DEG C is generally more than 0.99.
The mensuration of melting complex viscosity-radian frequency curve uses determination of viscoelasticity device (such as Rheometrics Inc. Rheometrics Mechanical Spectrometer RMS-800 etc.), usually solid be parallel plate, board diameter is 25mm, plate is spaced apart 1.5 ~ 2mm, strain is 5%, radian frequency carries out under being the condition of 0.1 ~ 100rad/ second.Be explained, measure under nitrogen atmosphere, in addition, preferably in mensuration sample, coordinate appropriate (such as 1000ppm in advance.) antioxidant.
The density of the polyethylene-based resin of composition (A) is generally 900 ~ 950kg/m
3.From the view point of the stability of thermotolerance, obstructive, stripping strength, this density is preferably 910kg/m
3~ 940kg/m
3, be more preferably 920kg/m3 ~ 930kg/m
3.Be explained, density use carried out the annealing recorded in JISK6760-1995 sample, measure according to substitution method in the water specified in JIS K7112-1995.
The melt flow rate (MFR) (MFR) of the polyethylene-based resin of composition (A) is generally 0.01 ~ 50g/10 minute, from the view point of raising stopping property, is preferably less than 5g/10 minute, is more preferably less than 3g/10 minute.MFR utilize specify in JIS K7210-1995 method, measure under the condition of temperature 190 DEG C, load 21.18N.
From the view point of film processibility, the molecular weight distribution (Mw/Mn) of the polyethylene-based resin of composition (A) is preferably more than 5, is more preferably more than 6, and more preferably more than 7, be particularly preferably more than 8.In addition, from the view point of the physical strength of film, the molecular weight distribution of the polyethylene-based resin of composition (A) is preferably less than 25, is more preferably less than 20.Be explained, this molecular weight distribution (Mw/Mn) is obtained the weight-average molecular weight (Mw) of polystyrene conversion and number-average molecular weight (Mn) by gel permeation chromatography, by the value (Mw/Mn) of Mw divided by Mn gained.Above-mentioned Mw/Mn can change according to hydrogen concentration when being such as polymerized or polymerization temperature, and when improving hydrogen concentration or polymerization temperature, the Mw/Mn of ethene-alpha-olefin copolymer becomes large.
With regard to the polyethylene-based resin of composition (A), be preferably 0.70 ~ 0.95 with the g* that following formula (II) defines.
g＊＝[η]/([η]
GPC×g
SCB＊) (II)
[in formula, [η] represents the limiting viscosity (unit: dl/g) of polyethylene-based resin, utilizes following formula (II-I) to define.Be set as utilizing following formula (II-II) to define.G
sCB* following formula (II-III) is utilized to define.
[η]＝23.3×log(ηrel)(II-I)
(in formula, η rel represents the relative viscosity of polyethylene-based resin.)
[η]
GPC＝0.00046×Mv
0.725(II-II)
(in formula, Mv represents the viscosity-average molecular weight of polyethylene-based resin.)
g
SCB＊＝(1-A)
1.725(II-III)
(in formula, A is the content of the short chain branch measured in polyethylene-based resin, utilizes following formula (II-V) to define.
A＝((12×n+2n+1)×y)/((1000-2y-2)×14+(y+2)×15+y×13)(II-V)
In formula, n represents that branch's carbonatoms of short chain branch is (such as, as alpha-olefin, use the situation having butylene, n=2, use the situation having hexene, n=4), y represents the short chain branches of every 1000 carbon atoms utilizing NMR or infrared spectroscopy to obtain.)]
Be explained, about g*, document with reference to following: Developments in PolymerCharacterisation-4 .J.V..Dawkins .Ed., .Applied Science, London .1983, Chapter.I,. " Characterization.of.Long Chain Branching in Polymers, " Th.G.Scholte work
[η]
gPCrepresent that molecular weight distribution is the molecular weight distribution identical with polyethylene-based resin and putative molecule chain is the limiting viscosity (unit: dl/g) of the polymkeric substance of straight-chain.
G
sCB* the contribution to g* produced by importing short chain branch in polyethylene-based resin is represented.
Formula (II-II) uses L.H.Tung work Journal of Polymer Science, the formula recorded in 36,130 (1959) 287-294 pages.
The relative viscosity (η rel) of polyethylene-based resin can measure by following method.Containing in the tetraline 100ml as the butylhydroxy toluene (BHT) 0.5 % by weight of heat deterioration inhibitor, polyethylene-based resin 100mg is dissolved at 135 DEG C, prepare sample solution, use Ubbelodhe type viscometer, by above-mentioned sample solution with only by calculating the fall time of the blank solution formed containing the tetraline as the BHT 0.5 % by weight of heat deterioration inhibitor.
Viscosity-average molecular weight (Mv) following formula (II-IV) definition of polyethylene-based resin, if a=0.725.
G* be represent result from long chain branches, the index of the shrink grading of molecule in solution; The amount of the long chain branches that per minute subchain contains is more, and the contraction of molecular chain is larger, and g* is less.From the view point of easy separability, the g* of polyethylene-based resin is preferably 0.70 ~ 0.95, is more preferably 0.75 ~ 0.90, and more preferably 0.75 ~ 0.85.When g* is less than 0.95, owing to containing long chain branches fully, therefore, stripping strength can not be too high, and easy separability is excellent, thus preferably.In addition, when g* is more than 0.70, the expansion of molecular chain during formation crystallization is abundant, so the generating probability of tie molecule (tie molecule) is high, and in addition, the time of relaxation of molecular chain is short, stopping property is excellent, thus preferably.
As the polyethylene-based resin preferably used as composition (A), the polyethylene-based resin recorded in No. 2008-106264, Japanese Unexamined Patent Publication can be enumerated.
The polypropylene-based resin of composition (B) can utilize propylene is carried out homopolymerization method, the method etc. that propylene and other copolymerizable comonomer carry out copolymerization is manufactured.As catalyst for polymerization, can enumerate such as: (a) comprises with magnesium, titanium and halogen the Ti-Mg series catalysts of the solid catalyst component being required composition; (b) with magnesium, titanium and halogen be must be combined with in the solid catalyst component of composition organo-aluminium compound and as required to ternary catalyzer systems such as electro compounds; (c) metallocene series catalysts etc.
The polypropylene-based resin of composition (B) can be the homopolymer (homo-polypropylene) of propylene, also can for based on propylene, make can with the comonomer of its copolymerization with on a small quantity, the ratio of such as less than 20 % by weight, preferably less than 10 % by weight carries out copolymerization and the multipolymer formed.Polypropylene-based resin is the situation of multipolymer, and the amount of comonomer is preferably more than 2 % by weight, is more preferably more than 3 % by weight.
In addition, when the film and sym-propene polymer resin sheet with the sealing ply comprising polyolefin resin composite of the present invention are carried out heat seal and use, composition (B) is preferably homo-polypropylene.
And when the film and polyethylene-based resin sheet with the sealing ply comprising polyolefin resin composite of the present invention are carried out heat seal and use, composition (B) is preferably the propylene copolymer containing a small amount of comonomer.
The polypropylene-based resin of composition (B) is the situation of multipolymer, as comonomer, can enumerate the alpha-olefin of ethene and carbonatoms 4 ~ 20.As the alpha-olefin of carbonatoms 4 ~ 20, can enumerate such as: 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene etc.From the view point of copolymerizable, comonomer optimal ethylene, 1-butylene, 1-amylene, 1-hexene and 1-octene, more preferably ethene, 1-butylene and 1-hexene.In addition, the alpha-olefin of above-mentioned ethene and carbonatoms 4 ~ 20 can be used alone, and also two or more kinds may be used.
When the polypropylene-based resin of composition (B) is multipolymer, multipolymer both can be random copolymers, also can be segmented copolymer.As preferred multipolymer, can be random copolymers, specifically, propylene-ethylene random copolymer, propylene/1-butene random copolymer can be enumerated.In propylene-ethylene random copolymer, propylene/1-butene random copolymer, the content of the content based on the monomeric unit of ethene, the monomeric unit based on 1-butylene can utilize such as the method recorded in the 616th page of " polymer analysis handbook " (nineteen ninety-five, the distribution of Kinokuniya bookstore) carry out infrared rays (IR) spectrometry and obtain.
With regard to the polypropylene-based resin of composition (B), according to JIS K 7210, at temperature 230 DEG C with load 21.18N measure melt flow rate (MFR) (MFR) preferably in the scope of 0.1 ~ 200g/10 minute, from the viewpoint of plasticity, more preferably in the scope of 0.5 ~ 50g/10 minute.
The stereoregularity of the polypropylene-based resin of composition (B) can be isotactic, a rule, random any one.In the present invention, from the viewpoint of thermotolerance, the polypropylene-based resin of rule or isotactic between preferably using.
The polypropylene-based resin of composition (B) can utilize such as to use and manufacture with the solution polymerization process of the hydrocarbon compounds such as hexane, heptane, octane, decane, hexanaphthene, methylcyclohexane, the benzene,toluene,xylene inert solvent that is representative, the mass polymerization that liquid monomer is used as solvent, the gaseous polymerization etc. that makes the monomer of gas directly carry out being polymerized.Utilize the polymerization of these methods both can carry out with intermittent type, also can carry out with continous way.
Polyolefin resin composite of the present invention contains the polyethylene-based resin of mentioned component (A) and the polypropylene-based resin of composition (B).With regard to the content of the composition (A) in this resin combination, composition (B), when total metering of composition (A) and composition (B) is set as 100 % by weight, the content of composition (A) is for being greater than 20 % by weight and less than 95 % by weight, and the content of composition (B) is more than 5 % by weight and lower than 80 % by weight.
In order to obtain more excellent easy separability and the balance of stopping property, the content of preferred component (A) is less than more than 25 % by weight 80 % by weight, and the content of composition (B) is less than more than 20 % by weight 75 % by weight.When the content of composition (A) is many, be favourable in the viewpoint of flexibility or shaping processability, when the content of composition (B) is many, be favourable in the viewpoint of thermotolerance.
In polyolefin resin composite of the present invention, the content of composition (A) is less than more than 40 % by weight 80 % by weight, when the content of composition (B) is below more than 20 % by weight 60 % by weight, the film with the sealing ply be made up of above-mentioned resin combination becomes following film, thus preferably: carried out each other in thermosealed purposes by sealing ply, there is the region that 2 of being made up of lower than the scope of the stripping strength of 1.5N/15mm fabric width the heat seal temperature scope of more than 15 DEG C and the maximum value of stripping strength and the difference of minimum value are different, and the difference of the mean peel strength in each region is the film of more than 2.0N/15mm fabric width.More preferably the content of composition (A) is less than more than 50 % by weight 75 % by weight, and the content of composition (B) is less than more than 25 % by weight 50 % by weight.
There is the different region of 2 of being made up of lower than the scope of the stripping strength of 1.5N/15mm fabric width the heat seal temperature scope of more than 15 DEG C and the maximum value of stripping strength and the difference of minimum value and the difference of the mean peel strength in each region is the film of more than 2.0N/15mm fabric width, by changing heat seal temperature in 1 film, different stripping strengths can be obtained, therefore preferably.
As the method determining region, such as, every 5 DEG C of transformation temperatures and carry out heat seal, measure stripping strength under respective heat seal temperature, determine that the maximum value of stripping strength and the difference of minimum value are lower than the maximum value of the heat seal temperature of 1.5N/15mm fabric width and minimum value.The situation being more than 15 DEG C by the difference of the maximum value of above-mentioned heat seal temperature and minimum value is set as 1 region.
When the sealing ply of above-mentioned film is sealed each other, preferably there are above-mentioned 2 different regions, the difference of mean peel strength in each region is more than 2.0N/15mm fabric width.
In addition, when sealing ply being carried out each other heat seal, the mean peel strength in preferred each region is 3N/15mm fabric width ~ 15N/15mm fabric width.
The film with the sealing ply be made up of polyolefin resin composite of the present invention is being carried out in thermosealed purposes each other with sealing ply, have the different region of 2 of being made up of lower than the scope of the stripping strength of 1.5N/15mm fabric width the heat seal temperature scope of more than 15 DEG C and the maximum value of stripping strength and the difference of minimum value and the difference of the mean peel strength in each region is the film of more than 2.0N/15mm fabric width to make, the difference of the fusing point of the polyethylene-based resin of preferred component (A) and the polypropylene-based resin of composition (B) is lower than 30 DEG C.
From the same viewpoint, the density of the polyethylene-based resin of preferred component (A) is 915kg/m
3above.
From the same viewpoint, the polypropylene-based resin of preferred component (B) is propylene system random copolymers.
In addition, the film having the sealing ply be made up of polyolefin resin composite of the present invention may be used for multichamber vessel.Multichamber vessel is the container in the space (reception room) in 1 container with mutually isolated more than 2.Isolate by having carried out thermosealed part (sealing) between reception room.
As shown in Figure 1, multichamber vessel carries out thermosealed mode each other with the sealing ply of film and stacks, the part 3 formed between the peripheral part 2 of container and isolation reception room is carried out heat seal and manufactured.
If multichamber vessel such as will carry out mix; interactional many kinds of substance (medicament etc.) occurs and is partitioned to different reception rooms respectively and accommodates, in preservation, many kinds of substance does not mix, and can be kept in 1 container.Further, in use, by making the sealing between isolation reception room be communicated with, mixing is contained in the material of different reception rooms.Therefore, sealing between the reception room of isolation multichamber vessel requires to have following character: in preservation, above-mentioned sealing is not communicated with, there is the stopping property can isolated between each reception room, in use, by applying strong extruding to any one reception room, above-mentioned peeling off at least partially of sealing and the easy separability (Kaifeng property) be communicated with between reception room; Require the balancing good of stopping property and easy separability.
In addition, even if apply strong extruding to any one reception room in use, also require that the sealing of the peripheral part forming container maintains sealed state.
Popularizing in field of medicaments mainly expected by this multichamber vessel.
When the film with the sealing ply be made up of polyolefin resin composite of the present invention is used for multichamber vessel, the content of the composition (A) in this resin combination is preferably greater than 20 % by weight and is less than 40 % by weight, the content of composition (B) is preferably more than 60 % by weight and lower than 80 % by weight, more preferably the content of composition (A) is greater than 20 % by weight and is less than 30 % by weight, and the content of composition (B) is more than 70 % by weight and lower than 80 % by weight.When using the film with the sealing ply be made up of above-mentioned resin combination to manufacture multichamber vessel, by the peripheral part forming container is at high temperature carried out heat seal, even if apply strong extruding when the use of multichamber vessel to reception room, the sealing of peripheral part is not also peeled off and maintains sealed state, by the sealing between isolation reception room is carried out heat seal at low temperatures, the material of the balancing good of stopping property and easy separability can be made, therefore preferably.
When the film with the sealing ply be made up of polyolefin resin composite of the present invention is used for multichamber vessel, from the same viewpoint, the difference of the fusing point of the polyethylene-based resin of preferred component (A) and the polypropylene-based resin of composition (B) is lower than 30 DEG C.
When the film with the sealing ply be made up of polyolefin resin composite of the present invention is used for multichamber vessel, from the same viewpoint, the density of the polyethylene-based resin of preferred component (A) is 915kg/m
3above.
From the same viewpoint, the polypropylene-based resin of preferred component (B) is propylene system random copolymers.
The film being suitable for multichamber vessel of the present invention is following film: when sealing ply being carried out each other heat seal, there is the 1st region be made up of lower than the scope of the stripping strength of 4N/15mm fabric width the heat seal temperature scope of more than 15 DEG C and the maximum value of stripping strength and the difference of minimum value, the mean peel strength in the 1st region is below the above 15N/15mm fabric width of 3N/15mm fabric width, when carrying out heat seal at the temperature higher than the 1st region, stripping strength becomes more than 30N/15mm fabric width.Now, for higher than the temperature in the 1st region and stripping strength when carrying out heat seal at least 1 temperature is more than 30N/15mm fabric width.
As the film of this character of display, the film such as above with the sealing ply be made up of polyolefin resin composite can be enumerated.
When using such film to manufacture multichamber vessel, by by formed container peripheral part for higher than above-mentioned 1st region temperature and carry out heat seal become the temperature of more than 30N/15mm fabric width in stripping strength under, even if apply strong extruding when the use of multichamber vessel to reception room, the sealing of peripheral part is not also peeled off and maintains sealed state, by the sealing between isolation reception room is carried out heat seal in the temperature range in the 1st region, the material of the balancing good of stopping property and easy separability can be made, therefore preferably.
In the unclear situation of amount when coordinating, polyethylene-based resin contained in resin combination and the amount of polypropylene-based resin can bases
13c-NMR obtains.
Index has been suitable in window function
13in C-NMR spectrum, with regard to regard to polyacrylic peak, 19.6-22.2ppm observes the peak of methyl, 28.4-29.2ppm observes the peak of methyne, 45.8-47.3ppm observes the peak of methylene radical.When the integrated value of 5 ~ 50ppm is set as 1000, the content based on the monomeric unit of propylene contained in composition can be obtained with following formula,
Propylene content (% by weight)=P × 3/1000 × 100
The integrated intensity of P:19.6-22.2ppm.
Alternate manner of the present invention is a kind of polyolefin resin composite, it contains polyethylene-based resin (X) and polypropylene-based resin (Y), wherein, the content of polyethylene-based resin (X) is for being greater than 20 % by weight and less than 95 % by weight, the content of polypropylene-based resin (Y) is more than 5 % by weight and lower than 80 % by weight (wherein, the total amount of polyethylene-based resin (X) and polypropylene-based resin (Y) is set as 100 % by weight), meet following important document (x1) and (x2).
(x1): utilize
13branches (the N of the carbon number more than 6 that C-NMR measures
lCB) for every 1000 carbon atoms be more than 0.01, and the branches (N of carbon number 5
c5) for every 1000 carbon atoms are lower than 0.1;
(x2): melting tension force (MT when 230 DEG C; Unit is cN.) for more than 1.5cN.
The N of said polyolefins based resin composition of the present invention
lCBwhen every 1000 carbon atoms are more than 0.1, become and be suitable for, as inflation processing, needing the composition of the film formed machining of melting tension force, thus preferably.In addition, the N of said polyolefins based resin composition
lCBand N
c5for with total metering of polyethylene-based resin (X) and polypropylene-based resin (Y) being the value of the composition measuring gained of 100 % by weight.
With regard to melting tension force (MT) during temperature 190 DEG C with regard to polyolefin resin composite of the present invention, from the view point of the composition becoming the film formed machining being more suitable for needing melting tension force, be preferably 1.7cN ~ 10cN, be more preferably 2.0cN ~ 10cN.In addition, the MT of said polyolefins based resin composition is be the value of the composition measuring gained of 100 % by weight with total metering of polyethylene-based resin (X) and polypropylene-based resin (Y).
Melting tension force (MT; Unit is cN.) by use by Toyo Seiki make institute wait the melt tension trier of sale, in temperature be the condition of 230 DEG C under, by the molten resin being filled in the bucket of 9.5mm φ with piston rotation perdurability 5.5mm/ minute, carry out melt extruding from the hole of diameter 2.09mm φ, length 8mm and make molten resin tow, by the roller of this tow use diameter 150mm, make speed of rotation per minute rising 40rpm/ minute while when reeling, the tension value before above-mentioned tow disconnects.
[polyethylene-based resin (X)]
As polyethylene-based resin (X), the ethene-alpha-olefin copolymer had based on the monomeric unit of ethene and the monomeric unit based on the alpha-olefin of carbonatoms 3 ~ 20 can be enumerated, from the view point of be clamminess suppression, the thermotolerance of film, when the total of the whole monomeric unit forming polyethylene-based resin (X) is set as 100 % by mole, the content of the monomeric unit based on ethene in polyethylene-based resin (X) is preferably more than 95 % by mole, and the content based on the monomeric unit of the alpha-olefin of carbonatoms 3 ~ 20 is preferably less than 5 % by mole.
The utilization of polyethylene-based resin (X)
13branches (the N of the carbon number 5 that C-NMR measures
c5) preferably every 1000 carbon atoms are lower than 0.1.N
c5more preferably every 1000 carbon atoms are lower than 0.05, preferred lower than 0.01 further, are particularly preferably zero.
Branches (the N of the carbon number more than 6 of polyethylene-based resin (X)
lCB) preferably every 1000 carbon atoms be less than more than 01.Such as, as N
lCBbe the polyethylene-based resin of more than 0.01, above-mentioned polyethylene-based resin (A) can be enumerated, as N
lCBbe more than 0 and lower than 0.01 polyethylene-based resin, straight-chain Low Density Polyethylene can be enumerated.
With the branches (N of the carbon number more than 6 of polyolefin resin composite
lCB) adjust the N of polyethylene-based resin (X) contained in resin combination for every 1000 carbon atoms mode that is more than 0.01
lCB, polypropylene-based resin (Y) N
lCB, polyethylene-based resin (X) and polypropylene-based resin (Y) content.As polyethylene-based resin (X), at use N
lCBbe more than 0 and polyethylene-based resin lower than 0.01 when, as polypropylene-based resin (Y), use N
lCBit is the polypropylene-based resin of more than 0.01.
The activation evergy (Ea) of polyethylene-based resin (X) is preferably more than 10kJ/mol below 100kJ/mol.Such as, be more than 10kJ/mol as Ea and lower than the polyethylene-based resin of 40kJ/mol, straight-chain Low Density Polyethylene can be enumerated, be more than 40kJ/mol as Ea and lower than the polyethylene-based resin of 100kJ/mol, above-mentioned polyethylene-based resin (A) can be enumerated.
The melt flow rate (MFR) (MFR) of polyethylene-based resin (X) is 0.01 ~ 50g/10 minute, from the view point of raising stopping property, is preferably less than 5g/10 minute.MFR utilize specify in JIS K7210-1995 method, measure under the condition of temperature 190 DEG C, load 21.18N.
As polyethylene-based resin (X), the polyethylene-based resin of preferred component (A).
[polypropylene-based resin (Y)]
As polypropylene-based resin (Y), can enumerate propylene homopolymer (homo-polypropylene) and based on propylene, make can with the comonomer of its copolymerization with on a small quantity, the ratio of such as less than 20 % by weight, preferably less than 10 % by weight carries out copolymerization and the multipolymer formed.
Branches (the N of the carbon number more than 6 of polypropylene-based resin (Y)
lCB) preferably every 1000 carbon atoms be less than more than 01.
The melt flow rate (MFR) (MFR) of polypropylene-based resin (Y) is generally 0.01 ~ 200g/10 minute, in order to the melting tension force (MT) when 230 DEG C of the polyolefin resin composite containing polyethylene-based resin (X) and polypropylene-based resin (Y) is set as more than 1.5cN, the MFR of polypropylene-based resin (Y) is preferably less than 10g/10 minute.The MFR of polypropylene-based resin utilize specify in JIS K7210-1995 method, measure under the condition of temperature 230 DEG C, load 21.18N.
As polypropylene-based resin (Y), the polypropylene-based resin of preferred component (B).
Use polyolefin resin composite containing composition (A) and composition (B) of the present invention and the polyolefin resin composite containing polyethylene-based resin (X) and polypropylene-based resin (Y) and the film that obtains, the balancing good of its easy separability and stopping property, and thermotolerance is also excellent.Use polyolefin resin composite and the film that obtains both can be individual layer, also can for being laminated with the stacked film of other layer of more than the layer and one deck that are made up of above-mentioned resin combination.When for stacked film, the layer be preferably made up of above-mentioned resin combination is the top layer of at least one party, and this layer is used as sealing ply.As other layer in stacked film, other synthetic resin layer, ply of paper, ink layer, evaporation layer, aluminium foil layer etc. can be enumerated.As other synthetic resin layer, the layer as resinous principle such as such as, polyvinyl alcohol resin saponified using polyethylene-based resin, polypropylene-based resin, polystyrene resin, vibrin, polyvinyl chloride (PVC) RESINS, polyamide resin, methacrylic resin, polyvinylidene chloride, ethylene/vinyl acetate copolymer can be enumerated.As above-mentioned polyethylene-based resin, can enumerate: Low Density Polyethylene, straight-chain Low Density Polyethylene, high-pressure process low-density polyethylene, ethylene-vinyl acetate copolymer etc.As polystyrene resin, styrene-butadiene-styrene etc. can be enumerated.
The thickness of the film be made up of polyolefin resin composite of the present invention is generally 5 ~ 500 μm.
The thickness (when for unitary film, film thickness) with the sealing layer in the film of the sealing ply be made up of polyolefin resin composite of the present invention is generally 5 ~ 150 μm, is preferably 10 ~ 100 μm.When making stacked film, film thickness is set as 100%, the thickness of sealing ply is preferably 3 ~ 70%, is more preferably 5 ~ 50%.
Use polyolefin resin composite of the present invention and the film obtained can contain more than a kind additive and other resin such as other composition, such as antioxidant, lubricant, antiblocking agent, static inhibitor, pigment, tinting material, processibility modifying agent as required.
As above-mentioned antioxidant, hindered phenol based compound and phosphorus system ester cpds can be enumerated.As hindered phenol based compound, such as 2,6-dialkyl benzene amphyls and 2-alkylphenol derivative etc. can be enumerated.As phosphorus system ester cpds, the phosphorus system ester cpds of the phosphorus atom containing 3 valencys can be enumerated, such as phosphorous acid ester based compound, diphosphite based compound etc. can be enumerated.These antioxidants can be used alone, and also two or more kinds may be used.Particularly from the view point of tone stabilization, preferably also with hindered phenol based compound and phosphorus system ester cpds.In addition, when the weight set of the film obtained using said polyolefins based resin composition is 100 % by weight, preferably containing antioxidant 0.01 ~ 1 % by weight, more preferably containing 0.03 ~ 0.5 % by weight.
As above-mentioned lubricant, can enumerate: the glyceryl ester etc. of lipid acid, fatty amide, fatty acid ester, higher fatty acid.As lipid acid, can enumerate: stearic acid, oleic acid, lauric acid etc.As fatty amide, can enumerate: oleylamide, erucicamide, ricinoleamide, two lauramides etc.As fatty acid ester, can enumerate: sorbitan ester, normal-butyl stearate etc.
As above-mentioned antiblocking agent, can enumerate: synthetic silica, native silicon dioxide, silicone resin, polymethylmethacrylate etc.As synthetic silica, can enumerate: dry type silicon-dioxide, wet silicon dioxide etc.As native silicon dioxide, diatomite etc. can be enumerated.
As above-mentioned static inhibitor, can enumerate such as: the alkyl di alkanolamide, macrogol ester, alkyldiethanolamine etc. of the lipid acid of the glyceryl ester of the lipid acid of carbonatoms 8 ~ 22, sorbitan acid esters, carbonatoms 8 ~ 22.
As above-mentioned pigment, can enumerate such as: white pigment, carbon black etc.
As other above-mentioned resin, can polyolefin-based resins etc. be enumerated, can enumerate such as: high density polyethylene(HDPE), high-pressure process low-density polyethylene, polypropylene, polybutene, elastomerics etc.
When using polyolefin resin composite of the present invention to manufacture film, after composition (A) and composition (B) or polyethylene-based resin (X) and polypropylene-based resin (Y) and the composition (above-mentioned additive and other resin etc.) that coordinates as required further being mixed with tumbler mixer, Henschel mixer etc., can be shaped as film.Can by with after the above-mentioned each composition of the mixing such as tumbler mixer, Henschel mixer, carry out melting mixing with single screw extrusion machine, multiple screw extruder etc. further or the mixing thing that carries out melting mixing by kneading machine, banbury mixers etc. and obtain is configured as film.
As the method using polyolefin resin composite of the present invention to manufacture unitary film, inflation moulding method and T-shaped mould casting forming method etc. can be enumerated.As the manufacture method of stacked film, coextrusion inflation moulding method, coextrusion T-shaped mould casting forming method, coextrusion method cascading into shape etc. can be utilized to manufacture.In addition, can enumerate: coextrusion method cascading into shape; Dry type layered manner is utilized to fit the method for preshaped film; The method etc. of heat pressurization is carried out after stacked preshaped film.
Film of the present invention is due to the balancing good of easy separability and stopping property, and thermotolerance is also excellent, therefore, is suitable for, as easy separability film, being suitable for as wrapping material.In addition, film of the present invention can be made lid material, carry out sealing with polyolefin-based resins container main body and obtain container.Be particularly suitable for the lid material as the polyolefin-based resins container main body be made up of polyethylene-based resin or polypropylene-based resin.
In addition, film of the present invention also can manifest stopping property and easy separability when being sealed each other by this film, therefore, may be used for the various uses needing easy separability with 3 limit sealing bags, pillow type packaging film etc. that bread packaging, poultry pork pies dress, cake bag etc. are representative.In addition, the sealing material as multichamber vessel also can preferably use.
Below, the present invention will be described to utilize embodiment and comparative example.
The physical property of embodiment and comparative example measures according to following method.
(1) melt flow rate (MFR) (MFR, unit: g/10 minute) of polyethylene-based resin and polypropylene-based resin
According to the method specified in JIS K 7210-1995, with load 21.18N, polyethylene-based resin under the condition of temperature 190 DEG C, polypropylene-based resin measures under the condition of temperature 230 DEG C.
(2) density (unit: kg/m of polyethylene-based resin
3)
Measure according to the method specified in the A method in JIS K 7112-1995.Be explained, measure coupons carry out annealing according to the method for the Low Density Polyethylene recorded in JIS K6760-1995 and for measure.
(3) molecular weight distribution (Mw/Mn, unit:-) of polyethylene-based resin
Use gel permeation chromatography (GPC) method, utilize following condition (1) ~ (9) to measure weight-average molecular weight (Mw) and number-average molecular weight (Mn), obtain molecular weight distribution (Mw/Mn).
Condition determination
(1) device: Waters Inc. 150CVALC/GPC
(2) separator column: Showa electrician Inc. Shodex GPC AT-806MS
(3) temperature: 140 DEG C
(4) solvent: orthodichlorobenzene
(5) stripping solvent flow rate: 1.0ml/ minute
(6) sample solution concentration: 1mg/ml
(7) injection rate is measured: 400 μ l
(8) molecular weight standard material: polystyrene standard (Dong Cao Inc.; Molecular weight=6000000 ~ 500)
(9) detector: differential refraction
(4) activation evergy (Ea, unit: kJ/mol) of the flowing of polyethylene-based resin
Use determination of viscoelasticity device (Rheometrics Inc. Rheometrics MechanicalSpectrometer RMS-800), melting complex viscosity-radian frequency curve measure 130 DEG C, 150 DEG C, 170 DEG C and 190 DEG C under following condition determination at, then, activation evergy (Ea) is V.4.4.4 obtained by the melting complex viscosity-radian frequency curve obtained, use Rheometrics Inc. software for calculation Rhios.
< condition determination >
Solid: parallel plate
Board diameter: 25mm
Plate interval: 1.5 ~ 2mm
Strain: 5%
Radian frequency: 0.1 ~ 100rad/ second
Measure atmosphere: under nitrogen
(5) fusing point (Tm, unit: DEG C)
(5-1) fusing point of polyethylene-based resin
The sheet material being about 0.5mm from the thickness made by heat pressurization is cut the test film of about 10mg and the sheet material that formed is set as test sample, use differential scanning calorimeter (Perkinelmer Inc. DSC-7) to measure.In mensuration, after being kept 5 minutes at 150 DEG C by test sample, be cooled to 40 DEG C with 1 DEG C/min, then, keep 5 minutes at 40 DEG C, thereafter, be warming up to 150 DEG C with the speed of 10 DEG C/min.By obtaining fusing point with the speed of 10 DEG C/min from the melting peak of 40 DEG C of melting curves obtained when being warming up to 150 DEG C.
(5-2) fusing point of polypropylene-based resin
The sheet material being about 0.5mm from the thickness made by heat pressurization is cut the test film of about 10mg and the sheet material that formed is set as test sample, use differential scanning calorimeter (Perkinelmer Inc. Diamond DSC) to measure.In mensuration, after being kept 5 minutes at 220 DEG C by test sample, be cooled to 150 DEG C rapidly, keep 1 minute at 150 DEG C, thereafter, be cooled to 50 DEG C with the cooling rate of 5 DEG C/min.Thereafter, after keeping 1 minute at 50 DEG C, be warming up to 180 DEG C with 5 DEG C/min, the temperature of the maximum peak of the melting endothermic curve obtained is set as fusing point (Tm).
(6) g* of polyethylene-based resin
g＊＝[η]/([η]GPC×gSCB＊) (II)
G* is obtained according to above-mentioned formula (II).
[η] obtains by following method.First, sample solution is being prepared containing being dissolved at 135 DEG C by polyethylene-based resin 100mg in tetraline 100ml as the butylhydroxy toluene (BHT) 0.5 % by weight of heat deterioration inhibitor, use Ubbelodhe (Ubbelohde) type viscometer, by above-mentioned sample solution and the relative viscosity (η rel) calculating polyethylene-based resin fall time by the blank solution only formed containing the tetraline as the BHT 0.5 % by weight of heat deterioration inhibitor.The relative viscosity calculated (η rel) is substituted in formula (II-I), obtains [η].
[η]
gPCobtain by following method.Viscosity-average molecular weight (Mv) is calculated by the measurement result of above-mentioned (3) molecular weight distribution.The Mv calculated is substituted in formula (II-II), obtains [η]
gPC.
The A that will obtain according to formula (II-V) substitutes in formula (II-III), obtains g
sCB*.
Be explained, the mensuration of the branch short chain number n of the short chain branch of polyethylene-based resin and the short chain branches y of every 1000 carbon atoms and calculating are according to document (Die MakromoleculareChemie, 177,449 (1976) McRae, M.A., Madams, W.F.) record method, utilize the characteristic absorption from alpha-olefin and implement.Infrared absorption spectrum uses infrared spectrophotometer (Japanese light splitting industrial FT-IR7300) to measure.
(7) calculation method of the various branches of polyethylene-based resin and resin combination
Utilize nuclear magnetic resonance of carbon method, according to following condition determination measure nuclear magnetic resonance of carbon spectrum (
13c-NMR), the following method that calculates is utilized to obtain.
< condition determination >
Device: Bruker Inc. AVANCE600 (600MHz)
Measure probe: 10mm cold probe
Measure solvent: 1,2-dichlorobenzene/1, the mixed solution of 2-dichlorobenzene-d4=75/25 (volumetric ratio)
Measure temperature: 130 DEG C
Measuring method: proton decoupling method
Pulse fabric width: 45 degree
Pulse repetition time: 4 seconds
Assay standard: tetramethylsilane
Window function: index or Gauss
Cumulative number: 2500 times
The calculation method > of < degree of branching
Calculation method (the N of carbon number 5
c5, unit: 1/1000C)
Index has been suitable in window function
13in C-NMR spectrum, the summation at all peaks that 5 ~ 50ppm observes is set as 1000, obtains the peak area at the peak near 32.5 ~ 32.7ppm with summit.
Branches (the N of carbon number more than 6
lCB, unit: 1/1000C)
Index has been suitable in window function
13in C-NMR spectrum, the summation at all peaks that 5 ~ 50ppm observes is set as 1000, the peak area at the peak near 38.09 ~ 38.27ppm with summit is set as A.This A is the value of the branch's methine carbon being equivalent to carbon number more than 4.In order to the peak of branch's methine carbon of carbon number less than 5 with branch's methine carbon of carbon number more than 6 is separated, in window function, is suitable for Gauss, is being suitable for Gauss's
13in C-NMR spectrum, the peak that 38.21 ~ 38.27ppm observes is set as B, the peak that 38.21 ~ 38.09ppm observes is set as C.And, obtain N by following formula
lCB.
N
LCB＝A×B/(B+C)
(8) the melting tension force (MT, unit: cN) of resin combination
Toyo Seiki is used to make made melt tension trier, be under the condition of 230 DEG C in temperature, the molten resin being filled in the bucket of 9.5mm φ was extruded from the hole of diameter for 2.09mm φ, length 8mm with piston rotation perdurability 5.5mm/ minute, the molten resin this extruded uses the wind up roll that diameter is 150mm φ to reel with the winding lift velocity of 40rpm/ minute, measures the tension value before molten resin fracture.This value is larger, represents that melting tension force is larger.
[physical property of film]
(9) the easy separability of sealing ply thermal seal each other
< heat seal >
The sealing ply of the overlapping stacked film obtained by embodiment each other after, according to following sealing conditions, use heat sealing machine (trier industrial system) to carry out heat seal.
Heat seal temperature: 110 DEG C ~ 180 DEG C (every 10 DEG C.Every 5 DEG C an of part)
The heat seal time: 1 second
Heat seal pressure: 0.3MPa
Heat seal fabric width: 20mm
< stripping strength >
The mensuration of stripping strength is carried out according to JIS K6854-2.Peeling rate is set as 300mm/ minute.As long as stripping strength is 3N/15mm fabric width ~ 15N/15mm fabric width, the stripping strength of the appropriateness for having stopping property and easy separability simultaneously just can be said.
When the maximum value of stripping strength and the difference of minimum value are more than 15 DEG C lower than the heat seal temperature of 5N/15mm fabric width, relative to the stripping strength excellent in stability of heat seal temperature, thus preferably.
(10) with the easy separability of the thermal seal of homo-polypropylene plate
< heat seal >
After the sealing ply of the overlapping stacked film obtained by embodiment and homo-polypropylene plate (thickness 0.4mm), according to following sealing conditions, heat sealing machine (trier industrial system) is used to carry out heat seal.
Heat seal temperature: 120 DEG C ~ 200 DEG C (every 10 DEG C.Every 5 DEG C an of part)
The heat seal time: 1 second
Heat seal pressure: 3.1MPa
Heat seal fabric width: 20mm
< stripping strength >
The mensuration of stripping strength is carried out according to JIS K6854-2.Peeling rate is set as 300mm/ minute.As long as stripping strength is 3N/15mm fabric width ~ 15N/15mm fabric width, the stripping strength of the appropriateness for having stopping property and easy separability simultaneously just can be said.
When the maximum value of stripping strength and the difference of minimum value are more than 15 DEG C lower than the heat seal temperature of 5N/15mm fabric width, relative to the stripping strength excellent in stability of heat seal temperature, thus preferably.
(11) with the easy separability of the thermal seal of polyethylene board
< heat seal >
After the sealing ply of the overlapping stacked film obtained by embodiment and the polyethylene board (thickness 0.25mm) that is made up of high-pressure process low-density polyethylene, according to following sealing conditions, heat sealing machine (trier industrial system) is used to carry out heat seal.
Heat seal temperature: 110 DEG C ~ 180 DEG C (every 10 DEG C.Every 5 DEG C an of part)
The heat seal time: 1 second
Heat seal pressure: 3.1MPa
Heat seal fabric width: 20mm
< stripping strength >
The mensuration of stripping strength is carried out according to JIS K6854-2.Peeling rate is set as 300mm/ minute.As long as stripping strength is 3N/15mm fabric width ~ 15N/15mm fabric width, the stripping strength of the appropriateness for having stopping property and easy separability simultaneously just can be said.
When the maximum value of stripping strength and the difference of minimum value are more than 15 DEG C lower than the heat seal temperature of 5N/15mm fabric width, relative to the stripping strength excellent in stability of heat seal temperature, thus preferably.
Embodiment 1
(1) preparation of promotor carrier
Carried out nitrogen replace have in the reactor of stirrer nitrogen circulation under, be placed in silicon-dioxide (the Debison Inc. Sylopol948 having carried out heat treated at 300 DEG C; 50% volume average particle size=55 μm; Pore capacity=1.67ml/g; Specific surface area=325m
2/ g) 2.8kg and toluene 24kg stirring.Thereafter, be cooled to after 5 DEG C, the temperature of reactor is remained on 5 DEG C, while dripped the mixing solutions of 1,1,1,3,3,3-hexamethyldisilazane 0.9kg and toluene 1.4kg with 30 minutes.After dropping terminates, at 5 DEG C, 1 stirring hour, then, is warming up to 95 DEG C, stirs and also filter for 3 hours at 95 DEG C.The solid product toluene 20.8kg obtained is cleaned 6 times.Thereafter, add toluene 7.1kg and make slurries, leaving standstill a whole night.
Drop into hexane solution (the zinc ethyl concentration: 50 % by weight) 3.46kg and hexane 2.05kg stirring of zinc ethyl in by slurries obtained above.Thereafter, be cooled to after 5 DEG C, the temperature of reactor is remained on 5 DEG C, while dripped the mixing solutions of 3,4,5-trifluoromethyl phenol 1.55kg and toluene 2.88kg with 60 minutes.After dropping terminates, stir 1 hour at 5 DEG C, then, be warming up to 40 DEG C, stir 1 hour at 40 DEG C.Thereafter, be cooled to 5 DEG C, the temperature of reactor is remained on 5 DEG C, while dripped H with 1.5 hours
2o 0.221kg.After dropping terminates, stir 1.5 hours at 5 DEG C, then, be warming up to 40 DEG C, stir 2 hours at 40 DEG C, be warming up to 80 DEG C further, stir 2 hours at 80 DEG C.After stirring, at room temperature extract supernatant liquor out to residual 16L, drop into toluene 11.6kg, then, be warming up to 95 DEG C and stir 4 hours.After stirring, at room temperature extract supernatant liquor out, obtain solid product.The solid product toluene 20.8kg obtained is cleaned 4 times, with hexane 24 liters cleaning 3 times.Thereafter, by carrying out drying, solids component is obtained (hereinafter referred to as promotor carrier (a).)。
(2) preparation of pre-polymerized catalyst composition (1)
Drop into butane 80 liters in the band stirrer autoclave having carried out the internal volume 210 liters that nitrogen replaces in advance after, drop into two (1-indenyl) the zirconium diphenyl oxide compound 91.8mmol of racemize-ethene, autoclave be warming up to 50 DEG C and stir 2 hours.Then, drop into above-mentioned promotor carrier (a) 0.7kg, autoclave is cooled to 31 DEG C, after stable in system, add ethene 0.1kg, hydrogen 0.1 liter (normal temperature and pressure volume), continue to drop into triisobutyl aluminium 267mmol and start polymerization.On one side respectively with 0.6kg/Hr and 0.5 liter (normal temperature and pressure volume) supply ethene and hydrogen continuously, while after 30 minutes, be warming up to 50 DEG C, meanwhile, by implementing the total prepolymerization of 6 hours with the supply ethene of 3.6kg/ hour and 10.9 liters (normal temperature and pressure volume)/hour continuously and hydrogen respectively.After polymerization terminates, remove ethene, butane, hydrogen etc. and residual solid at room temperature carried out vacuum-drying, obtaining every promotor carrier (a) 1g and contain the poly pre-polymerized catalyst composition (1) of 37g.
(3) manufacture of ethene-1-hexene copolymer
Use above-mentioned pre-polymerized catalyst composition (1), implement the copolymerization of ethene and 1-hexene with continous way thermopnore gas phase polymerization apparatus.Polymerizing condition is: temperature 85 DEG C, total pressure 2MPa, be 1.22% relative to the mol ratio of the hydrogen of ethene, be 1.31% relative to the mol ratio of the 1-hexene of ethene, in polymerization, in order to gas composition be maintained necessarily, supply ethene, 1-hexene, hydrogen continuously.And total powder weight of thermopnore is maintained 80kg, and the mode being 4hr with the average polymerization time supplies above-mentioned pre-polymerized catalyst composition and triisobutyl aluminium in certain proportion continuously.By polymerization, obtain ethene-1-hexene copolymer (hereinafter referred to as PE-1 with the polymerization efficiency of 20.5kg/hr.) powder.
(4) granulation of ethene-1-hexene copolymer powder
By the powder by PE-1 obtained above being utilized forcing machine (refreshing Kobe Zhi Gangsuo Inc. LCM50), carrying out granulation under input speed 50kg/hr, screw speed 450rpm, gatage 4.2mm, suction pressure 0.2MPa, resin temperature 200 ~ 230 DEG C of conditions, obtain the particle of PE-1.Table 1 represents the evaluation result of the particle of PE-1.
(5) film processing
By be 75 % by weight by the particle of PE-1 obtained above, based on the content of the monomeric unit of ethene be the Propylene-ethylene random copolymer of 5 % by weight (following, be set as PP-1.Table 1 represents the basic physical properties of PP-1.) particle be 25 % by weight matter utilization PLACO (strain) the 50mm φ processed expansion processing machine that is mixed into of mode at 210 DEG C, carry out film processing, obtain the polyolefin unitary film of thickness 30 μm.
(6) manufacture of stacked film
By said polyolefins system unitary film and biaxial stretch-formed nylon membrane (thickness 15 μm) use-testing coating machine (Kang Jing essence machine (strain) system), utilize two-solution curing type polyurethane series tackiness agent (military field pharmaceutical industries (strain) タ processed ケ ラ Star Network A310/ タ ケ ネ mono-ト A-3) to carry out the stacked processing of dry type, obtain the stacked film of the formation becoming polyolefin unitary film/adhesive layer/biaxial stretch-formed nylon membrane.In addition, in the stacked processing of dry type, after laminating at 40 DEG C aging 48 hours.Table 2 and table 7 represent the evaluation of physical property result of the stacked film obtained.
The stacked film obtained is in sealing ply stripping test each other, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 130 DEG C ~ 180 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 50 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 4.3N/15mm fabric width.
This stacked film is following film: when sealing ply is sealed against one another, has the different region of 2 of being made up of lower than the scope of the stripping strength of 1.5N/15mm fabric width the heat seal temperature scope of more than 15 DEG C and the maximum value of stripping strength and the difference of minimum value, the difference of mean peel strength in each region is more than 2.0N/15mm fabric width.Namely, the first area S1 that the scope that it is the stripping strength of 0.6N/15mm fabric width that the stacked film obtained has by the difference as the heat seal temperature scope of 120 DEG C ~ 140 DEG C and the maximum value of stripping strength and minimum value is formed, and the second area S2 that the scope that to have by the difference as the heat seal temperature scope of 160 DEG C ~ 180 DEG C and the maximum value of stripping strength and minimum value be the stripping strength of 1.1N/15mm fabric width is formed, the mean peel strength P of first area S1
(S1)for 3.0N/15mm fabric width, the mean peel strength P of second area S2
(S2)for 6.6N/15mm fabric width, the mean peel strength P of S1
(S1)with the mean peel strength P of S2
(S2)difference be 3.6N/15mm fabric width.The maximum value of the heat seal temperature in S1 and the difference of minimum value are 20 DEG C, and the maximum value of the heat seal temperature in S2 and the difference of minimum value are 20 DEG C.
In addition, with the stripping test of homo-polypropylene plate, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 135 DEG C ~ 200 DEG C, and the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 40 DEG C.In the heat seal temperature scope of the stripping strength of display appropriateness, the maximum value of stripping strength and the difference of minimum value are 160 DEG C ~ 200 DEG C lower than the heat seal temperature scope of 5N/15mm fabric width, and stripping strength keeps stable across 40 DEG C continuously.
Embodiment 2
In blown film processing, the particle except PE-1 is 50 % by weight, the particle of PP-1 is except 50 % by weight, carries out similarly to Example 1.Table 2 and table 9 represent the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 120 DEG C ~ 180 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 60 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 5.4N/15mm fabric width.
This stacked film is following stacked film: when sealing ply is sealed against one another, has the different region of 2 of being made up of lower than the scope of the stripping strength of 1.5N/15mm fabric width the heat seal temperature scope of more than 15 DEG C and the maximum value of stripping strength and the difference of minimum value, the difference of mean peel strength in each region is more than 2.0N/15mm fabric width.Namely, the first area S1 that the scope that it is the stripping strength of 0.7N/15mm fabric width that the stacked film obtained has by the difference as the heat seal temperature scope of 120 DEG C ~ 135 DEG C and the maximum value of stripping strength and minimum value is formed, the second area S2 that the scope that to have by the difference as the heat seal temperature scope of 160 DEG C ~ 180 DEG C and the maximum value of stripping strength and minimum value be the stripping strength of 0.2N/15mm fabric width is formed, and the mean peel strength P of first area S1
(S1)for 3.3N/15mm fabric width, the mean peel strength P of second area S2
(S2)for 8.3N/15mm fabric width, the mean peel strength P of S1
(S1)with the mean peel strength P of S2
(S2)difference be 5.0N/15mm fabric width.The maximum value of the heat seal temperature in S1 and the difference of minimum value are 15 DEG C, and the maximum value of the heat seal temperature in S2 and the difference of minimum value are 20 DEG C.
In addition, with the stripping test of polyethylene board, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 130 DEG C ~ 180 DEG C, and the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 50 DEG C.In the heat seal temperature scope of the stripping strength of display appropriateness, the maximum value of stripping strength and the difference of minimum value are 135 DEG C ~ 180 DEG C lower than the heat seal temperature scope of 5N/15mm fabric width, and stripping strength keeps stable across 45 DEG C continuously.
Embodiment 3
In blown film processing, the particle except PE-1 is 25 % by weight, the particle of PP-1 is except 75 % by weight, carries out similarly to Example 1.Table 2 and table 9 represent the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 125 DEG C ~ 140 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 15 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 3.7N/15mm fabric width.
The 1st region that the scope that it is the stripping strength of 3.7N/15mm fabric width that this stacked film has by the difference as the heat seal temperature scope of 125 DEG C ~ 140 DEG C and the maximum value of stripping strength and minimum value is formed, the mean peel strength in the 1st region is 5.2N/15mm fabric width, stripping strength when carrying out heat seal at as 160 DEG C of the temperature higher than the 1st region is 32N/15mm fabric width, therefore, this stacked film preferably uses as the film for making multichamber vessel.
In addition, with the stripping test of polyethylene board, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 160 DEG C ~ 180 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 20 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 0.3N/15mm fabric width.
Comparative example 1
(1) film processing
By with commercially available metallocene anchor line (string) shape Low Density Polyethylene, (Sumitomo Chemical Zhu Shihui Inc. ス ミ カ セ Application E FV205: following, is set as LL-1.The basic physical properties of LL-1 shown in table 1.) particle be 75 % by weight, PP-1 be 25 % by weight matter utilization PLACO (strain) the 50mm φ processed expansion processing machine that is mixed into of mode at 210 DEG C, carry out film processing, obtain the polyethylene-based unitary film of thickness 30 μm.
(2) manufacture of stacked film
By said polyolefins system unitary film and biaxial stretch-formed nylon membrane (thickness 15 μm) use-testing coating machine (test coater) (Kang Jing essence machine (strain) system), utilize two-solution curing type polyurethane series tackiness agent (military field pharmaceutical industries (strain) タ processed ケ ラ Star Network A310/ タ ケ ネ mono-ト A-3) to carry out the stacked processing of dry type, obtain the stacked film of the formation becoming polyolefin unitary film/adhesive layer/biaxial stretch-formed nylon membrane.In addition, in the stacked processing of dry type, after laminating, at 40 DEG C aging 48 hours.Table 3, table 8 and table 9 represent the evaluation of physical property result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, there is not the heat seal temperature that display stripping strength is the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width.In addition, with the stripping test of homo-polypropylene plate, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 135 DEG C ~ 150 DEG C, and the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 15 DEG C.In the heat seal temperature scope of the stripping strength of display appropriateness, the maximum value of stripping strength and the difference of minimum value are 140 DEG C ~ 150 DEG C lower than the heat seal temperature scope of 5N/15mm fabric width, relative to the stripping strength poor stability of heat seal temperature.And, with the stripping test of polyethylene board, display stripping strength is that the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is only 125 DEG C, and the heat seal temperature narrow scope of the stripping strength of display appropriateness, is not suitable as easy separability film.
Comparative example 2
In blown film processing, the particle except LL-1 is 50 % by weight, the particle of PP-1 is except 50 % by weight, carries out in the same manner as comparative example 1.Table 3, table 8 and table 9 represent the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is that the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is only 125 DEG C.In addition, with the stripping test of homo-polypropylene plate, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 135 DEG C ~ 150 DEG C, and the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 15 DEG C.In the heat seal temperature scope of the stripping strength of display appropriateness, the maximum value of stripping strength and the difference of minimum value are 140 DEG C ~ 150 DEG C lower than the heat seal temperature scope of 5N/15mm fabric width, relative to the stripping strength poor stability of heat seal temperature.And, with the stripping test of polyethylene board, display stripping strength is that the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is only 125 DEG C, and the heat seal temperature narrow scope of the stripping strength of display appropriateness, is not suitable as easy separability film.
Comparative example 3
In blown film processing, the particle except LL-1 is 25 % by weight, the particle of PP-1 is except 75 % by weight, carries out in the same manner as comparative example 1.Its result, the melting tension force of polyolefin resin composite is low, therefore, film occurs in film masking and disconnects, can not masking.
Comparative example 4
In blown film processing, except not using the particle of PE-1, only using except the particle of PP-1, carry out similarly to Example 1.Table 3 represents the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is that the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is only 140 DEG C.
Comparative example 5
(1) film processing
By with commercially available high-pressure process low-density polyethylene, (Sumitomo Chemical Zhu Shihui Inc. ス ミ カ セ Application F200-0: following, is set as LD-1.The basic physical properties of LD-1 shown in table 1.) particle be 75 % by weight, PP-1 be 25 % by weight matter utilization PLACO (strain) the 50mm φ processed expansion processing machine that is mixed into of mode at 210 DEG C, carry out film processing, obtain the polyethylene-based unitary film of thickness 30 μm.
(2) manufacture of stacked film
By said polyolefins system unitary film and biaxial stretch-formed nylon membrane (thickness 15 μm) use-testing coating machine (test coater) (Kang Jing essence machine (strain) system), utilize two-solution curing type polyurethane series tackiness agent (military field pharmaceutical industries (strain) タ processed ケ ラ Star Network A310/ タ ケ ネ mono-ト A-3) to carry out the stacked processing of dry type, obtain the stacked film of the formation becoming polyolefin unitary film/adhesive layer/biaxial stretch-formed nylon membrane.In addition, in the stacked processing of dry type, after laminating at 40 DEG C aging 48 hours.Table 4 represents the evaluation of physical property result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, there is not the heat seal temperature that display stripping strength is the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width.
Comparative example 6
In blown film processing, the particle except LD-1 is 50 % by weight, the particle of PP-1 is except 50 % by weight, carries out in the same manner as comparative example 5.Table 4 and table 9 represent the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, there is not the heat seal temperature that display stripping strength is the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width.
In addition, with the stripping test of polyethylene board, display stripping strength is that the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is only 120 DEG C, and the heat seal temperature narrow scope of the stripping strength of display appropriateness, is not suitable as easy separability film.
Comparative example 7
In blown film processing, except not using the particle of PP-1, only using except the particle of PE-1, carry out similarly to Example 1.Table 4 represents the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is that the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is only 120 DEG C.
Embodiment 4
(1) manufacture of ethene-1-hexene copolymer
Use above-mentioned pre-polymerized catalyst composition (1), implement the copolymerization of ethene and 1-hexene with continous way thermopnore gas phase polymerization apparatus.Polymerizing condition is: temperature 80 DEG C, total pressure 2MPa, be 1.48% relative to the mol ratio of the hydrogen of ethene, be 1.70% relative to the mol ratio of the 1-hexene of ethene, in polymerization, in order to gas composition be maintained necessarily, supply ethene, 1-hexene, hydrogen continuously.And, total powder weight of thermopnore is maintained 80kg, the mode being 4hr with the average polymerization time, supply above-mentioned pre-polymerized catalyst composition and triisobutyl aluminium in certain proportion continuously.By polymerization, obtain ethene-1-hexene copolymer (hereinafter referred to as PE-2 with the polymerization efficiency of 20.3kg/ hour.) powder.
(2) granulation of ethene-1-hexene copolymer powder
By the powder by PE-2 obtained above is utilized forcing machine (refreshing Kobe Zhi Gangsuo Inc. LCM50), input speed 50kg/ hour, screw speed 450rpm, gatage 4.2mm, suction pressure 0.2MPa, carry out granulation under resin temperature 200 ~ 230 DEG C of conditions, obtain the particle of PE-2.Table 1 represents the evaluation result of the particle of PE-2.
(3) film processing
By be 50 % by weight by the particle of PE-2 obtained above, the particle of PP-1 be 50 % by weight matter utilization PLACO (strain) the 50mm φ processed expansion processing machine that is mixed into of mode at 210 DEG C, carry out film processing, obtain the polyolefin unitary film of thickness 30 μm.
(4) manufacture of stacked film
By said polyolefins system unitary film and biaxial stretch-formed nylon membrane (thickness 15 μm) use-testing coating machine (test coater) (Kang Jing essence machine (strain) system), utilize two-solution curing type polyurethane series tackiness agent (military field pharmaceutical industries (strain) タ processed ケ ラ Star Network A310/ タ ケ ネ mono-ト A-3) to carry out the stacked processing of dry type, obtain the stacked film of the formation becoming polyolefin unitary film/adhesive layer/biaxial stretch-formed nylon membrane.In addition, in the stacked processing of dry type, after laminating at 40 DEG C aging 48 hours.Table 4 represents the evaluation of physical property result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 125 DEG C ~ 140 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 15 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 4.3N/15mm fabric width.
Embodiment 5
(1) manufacture of ethene-1-hexene copolymer
Use above-mentioned pre-polymerized catalyst composition (1), implement the copolymerization of ethene and 1-hexene with continous way thermopnore gas phase polymerization apparatus.Polymerizing condition is: temperature 85 DEG C, total pressure 2MPa, be 1.59% relative to the mol ratio of the hydrogen of ethene, be 1.25% relative to the mol ratio of the 1-hexene of ethene, in polymerization, in order to gas composition be maintained necessarily, supply ethene, 1-hexene, hydrogen continuously.And, total powder weight of thermopnore is maintained 80kg, the mode being 4hr with the average polymerization time, supply above-mentioned pre-polymerized catalyst composition and triisobutyl aluminium in certain proportion continuously.By polymerization, obtain ethene-1-hexene copolymer (hereinafter referred to as PE-3.) powder.
(2) granulation of ethene-1-hexene copolymer powder
By the powder by PE-3 obtained above is utilized forcing machine (refreshing Kobe Zhi Gangsuo Inc. LCM50), input speed 50kg/ hour, screw speed 450rpm, gatage 4.2mm, suction pressure 0.2MPa, carry out granulation under resin temperature 200 ~ 230 DEG C of conditions, obtain the particle of PE-3.Table 5 represents the evaluation result of the particle of PE-3.
(3) film processing
By be 50 % by weight by the particle of PE-3 obtained above, homo-polypropylene (following, be set as PP-2.Table 5 represents the basic physical properties of PP-2.) particle be 50 % by weight the T-shaped mould processing machine of matter utilization Sumitomo hoisting machinery modern (strain) 50mm processed φ that is mixed into of mode at processing temperature 250 DEG C, chill-roll temperature 70 DEG C, carry out film processing, obtain the polyolefin unitary film of thickness 30 μm.
(4) manufacture of stacked film
By said polyolefins system unitary film and biaxial stretch-formed nylon membrane (thickness 15 μm) use-testing coating machine (Kang Jing essence machine (strain) system), utilize two-solution curing type polyurethane series tackiness agent (military field pharmaceutical industries (strain) タ processed ケ ラ Star Network A310/ タ ケ ネ mono-ト A-3) to carry out the stacked processing of dry type, obtain the stacked film of the formation becoming polyolefin unitary film/adhesive layer/biaxial stretch-formed nylon membrane.In addition, in the stacked processing of dry type, after laminating at 40 DEG C aging 48 hours.Table 6 and table 7 represent the evaluation of physical property result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 180 DEG C ~ 200 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 20 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 1.0N/15mm fabric width.In addition, with the stripping test of homo-polypropylene plate, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 160 DEG C ~ 200 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 40 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 2.8N/15mm fabric width.
Embodiment 6
In T-shaped mould film processing, the particle except PE-3 is 25 % by weight, the particle of PP-2 is except 75 % by weight, carries out similarly to Example 5.Table 6 and table 7 represent the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 160 DEG C ~ 200 DEG C, and the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 40 DEG C.In the heat seal temperature scope of the stripping strength of display appropriateness, the maximum value of stripping strength and the difference of minimum value are 170 DEG C ~ 200 DEG C lower than the heat seal temperature scope of 5N/15mm fabric width, and stripping strength keeps stable across 30 DEG C continuously.In addition, with the stripping test of homo-polypropylene plate, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 170 DEG C ~ 200 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 30 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 1.6N/15mm fabric width.
Comparative example 8
Will with MFR=3.7g/10 minute, density is for 918kg/m
3commercially available metallocene anchor line (string) shape Low Density Polyethylene (following, be set as LL-2.Table 5 represents the basic physical properties of LL-2.) particle be 50 % by weight, PP-2 be 50 % by weight the T-shaped mould processing machine of matter utilization Sumitomo hoisting machinery modern (strain) 50mm processed φ that is mixed into of mode at processing temperature 250 DEG C, chill-roll temperature 70 DEG C, carry out film processing., there is film and disconnect in its result, can not masking in film masking.
Comparative example 9
In T-shaped mould film processing, the particle except LL-2 is 25 % by weight, the particle of PP-2 is except 75 % by weight, carries out in the same manner as comparative example 8., there is film and disconnect in its result, can not masking in film masking.
Comparative example 10
In T-shaped mould film processing, except not using the particle of PE-3, only using except the particle of PP-2, carry out similarly to Example 5.Table 6 and table 8 represent the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, in sealing ply stripping test each other, display stripping strength is that the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is only 160 DEG C.In addition, with the stripping test of homo-polypropylene plate, there is not the heat seal temperature that display stripping strength is the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width.
Embodiment 7
In T-shaped mould film processing, the particle except PE-3 is 75 % by weight, the particle of PP-2 is except 25 % by weight, carries out similarly to Example 5.Table 7 represents the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, with the stripping test of homo-polypropylene plate, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 180 DEG C ~ 200 DEG C, the heat seal temperature scope of the stripping strength of display appropriateness is continuously across 20 DEG C, and the maximum value of the stripping strength in this heat seal temperature scope and the difference of minimum value are 0.2N/15mm fabric width.
Comparative example 11
In blown film processing, the particle except LD-1 is 25 % by weight, the particle of PP-1 is except 75 % by weight, carries out in the same manner as comparative example 5.Table 10 represents the evaluation result of the stacked film obtained.
With regard to the stacked film obtained, with the stripping test of polyethylene board, display stripping strength is the heat seal temperature of the stripping strength of the appropriateness of 3N/15mm fabric width ~ 15N/15mm fabric width is 140 DEG C ~ 150 DEG C, the heat seal temperature narrow scope of the stripping strength of display appropriateness, is not suitable as easy separability film.
(table 1)
(table 2)
(table 3)
(table 4)
NG: mother metal disconnects (in stripping, sealing ply disconnects, and can not peel off)
(table 5)
(table 6)
(table 7)
(table 8)
(table 9)
NG: mother metal disconnects (in stripping, sealing ply disconnects, and can not peel off)
(table 10)
The possibility of industrial application
According to the present invention, can provide a kind of and be suitable for manufacturing the balancing good of easy separability and stopping property and the polyolefin resin composite of the film of excellent heat resistance, the film with the sealing ply comprising this resin combination, wrapping material and lid material.
Claims (10)
1. a polyolefin resin composite, it contains following composition (A) and composition (B), wherein, when the total amount of composition A and composition B is set as 100 % by weight, the content of composition A is for being greater than 20 % by weight and less than 95 % by weight, the content of composition B is more than 5 % by weight and lower than 80 % by weight, and described polyolefin resin composite meets following important document x1 and x2
A: the polyethylene-based resin meeting following important document a1, a2 and a3;
A1: the content based on the monomeric unit of ethene is more than 95 % by mole, wherein, is set as 100 % by mole by the total of the whole monomeric unit forming polyethylene-based resin;
A2: utilize
13the branches N of the carbon number 5 that C-NMR measures
c5for every 1000 carbon atoms are lower than 0.1;
A3: the activation evergy Ea of flowing is more than 40kJ/mol;
B: polypropylene-based resin,
X1: utilize
13the branches N of the carbon number more than 6 that C-NMR measures
lCBfor every 1000 carbon atoms are more than 0.01, and the branches N of carbon number 5
c5for every 1000 carbon atoms are lower than 0.1;
Melting tension force MT during x2:230 DEG C, unit is cN, is more than 1.5cN.
2. polyolefin resin composite as claimed in claim 1, wherein,
Described composition A is the ethene-alpha-olefin copolymer having the monomeric unit based on ethene and the monomeric unit based on the alpha-olefin of carbonatoms 3 ~ 20 and meet following important document a4,
A4: molecular weight distribution mw/mn is 5 ~ 25.
3. polyolefin resin composite as claimed in claim 1 or 2, wherein,
The propylene system random copolymers that described composition B is alfon or contains based on the monomeric unit more than 90 % by weight of propylene.
4. a film, it comprises the polyolefin resin composite according to any one of claims 1 to 3.
5. a multilayer film, it has the sealing ply of the polyolefin resin composite comprised according to any one of claims 1 to 3.
6. the film as described in claim 4 or 5, it is wrapping material.
7. a multichamber vessel, it comprises the film described in claim 4 or 5.
8., as claim 4 or film according to claim 5, it is lid material.
9. a container, lid material according to claim 8 and polyolefin-based resins container body seal form by it.
10. container as claimed in claim 9, wherein,
Described polyolefin-based resins container main body is the container be made up of polyethylene-based resin or polypropylene-based resin.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010142398 | 2010-06-23 | ||
| JP2010-142398 | 2010-06-23 | ||
| JP2011-028261 | 2011-02-14 | ||
| JP2011028261 | 2011-02-14 | ||
| PCT/JP2011/064603 WO2011162396A1 (en) | 2010-06-23 | 2011-06-20 | Poly-olefin resin compound, film, packaging material, multi-chamber container and cover material |
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| CN102947383A CN102947383A (en) | 2013-02-27 |
| CN102947383B true CN102947383B (en) | 2015-02-25 |
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| JP (1) | JP5842397B2 (en) |
| CN (1) | CN102947383B (en) |
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| EP2862712A1 (en) | 2013-10-16 | 2015-04-22 | Dow Global Technologies LLC | Flexible film composition for heat seals and container thereof |
| WO2018164169A1 (en) * | 2017-03-10 | 2018-09-13 | 住友化学株式会社 | Film |
| JP7277148B2 (en) * | 2019-01-18 | 2023-05-18 | 株式会社プライムポリマー | sealant film |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1128005A (en) * | 1994-03-15 | 1996-07-31 | 株式会社大塚制药工场 | Contamination-proof sealant film and product fabricated therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS59210961A (en) * | 1983-05-16 | 1984-11-29 | Nippon Petrochem Co Ltd | Resin composition for forming film having blocking resistance |
| US5212246A (en) * | 1990-09-28 | 1993-05-18 | Himont Incorporated | Olefin polymer films |
| JPH09216319A (en) * | 1996-02-09 | 1997-08-19 | Kureha Chem Ind Co Ltd | Multilayer film for packaging skin pack |
| US6743523B1 (en) * | 2000-03-16 | 2004-06-01 | Baxter International Inc. | Multiple layer film of a new non-PVC material |
| JP2002003663A (en) * | 2000-06-16 | 2002-01-09 | Tosoh Corp | Polyethylene resin composition and container using it |
| JP2005097358A (en) * | 2003-09-22 | 2005-04-14 | Showa Denko Plastic Products Co Ltd | Polypropylenic molding and container |
| JP2005330347A (en) * | 2004-05-19 | 2005-12-02 | Shin Etsu Chem Co Ltd | Cerium-containing oxide |
| JP2006056914A (en) * | 2004-08-17 | 2006-03-02 | Sumitomo Chemical Co Ltd | Resin composition for extrusion lamination and laminate |
| JP2006257332A (en) * | 2005-03-18 | 2006-09-28 | Sumitomo Chemical Co Ltd | Thermoplastic elastomer composition for vacuum molding and layered product |
| JP4788510B2 (en) * | 2005-07-21 | 2011-10-05 | 住友化学株式会社 | Resin composition, waterproof sheet and method for producing waterproof sheet |
| JP2012107222A (en) * | 2010-10-29 | 2012-06-07 | Sumitomo Chemical Co Ltd | Ethylene resin composition, crosslinked foam, member for footwear, and footwear |
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| CN1128005A (en) * | 1994-03-15 | 1996-07-31 | 株式会社大塚制药工场 | Contamination-proof sealant film and product fabricated therefrom |
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| WO2011162396A1 (en) | 2011-12-29 |
| CN102947383A (en) | 2013-02-27 |
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| JP5842397B2 (en) | 2016-01-13 |
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