NZ599088B - High density polyethylene blend films - Google Patents
High density polyethylene blend films Download PDFInfo
- Publication number
- NZ599088B NZ599088B NZ599088A NZ59908812A NZ599088B NZ 599088 B NZ599088 B NZ 599088B NZ 599088 A NZ599088 A NZ 599088A NZ 59908812 A NZ59908812 A NZ 59908812A NZ 599088 B NZ599088 B NZ 599088B
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- NZ
- New Zealand
- Prior art keywords
- film
- weight
- blend
- layer
- mil
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- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 140
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 138
- 239000000203 mixture Substances 0.000 title claims abstract description 137
- 230000004888 barrier function Effects 0.000 claims abstract description 132
- 238000004806 packaging method and process Methods 0.000 claims abstract description 99
- 239000002667 nucleating agent Substances 0.000 claims abstract description 71
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 70
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 70
- 230000005540 biological transmission Effects 0.000 claims abstract description 65
- -1 glycerol alkoxide salts Chemical class 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 31
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000554 ionomer Polymers 0.000 claims abstract description 10
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical class OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920002959 polymer blend Polymers 0.000 claims abstract description 7
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 235000007586 terpenes Nutrition 0.000 claims abstract description 6
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 5
- 150000003505 terpenes Chemical class 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims description 88
- 239000000463 material Substances 0.000 claims description 67
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 13
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 13
- LRGQZEKJTHEMOJ-UHFFFAOYSA-N propane-1,2,3-triol;zinc Chemical class [Zn].OCC(O)CO LRGQZEKJTHEMOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract description 18
- 238000005520 cutting process Methods 0.000 abstract description 12
- 238000007789 sealing Methods 0.000 abstract description 12
- 238000011049 filling Methods 0.000 abstract description 10
- 235000013305 food Nutrition 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 314
- 230000000052 comparative effect Effects 0.000 description 80
- 239000005977 Ethylene Substances 0.000 description 53
- 229920000642 polymer Polymers 0.000 description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 51
- 239000000126 substance Substances 0.000 description 39
- 229920005669 high impact polystyrene Polymers 0.000 description 33
- 239000004797 high-impact polystyrene Substances 0.000 description 33
- 229920001684 low density polyethylene Polymers 0.000 description 33
- 239000004702 low-density polyethylene Substances 0.000 description 33
- 239000005038 ethylene vinyl acetate Substances 0.000 description 31
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 31
- 238000000034 method Methods 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 26
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 21
- 229920000092 linear low density polyethylene Polymers 0.000 description 21
- 239000004707 linear low-density polyethylene Substances 0.000 description 21
- 239000004711 α-olefin Substances 0.000 description 21
- 229920001778 nylon Polymers 0.000 description 19
- 239000004677 Nylon Substances 0.000 description 18
- 239000004793 Polystyrene Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 150000002148 esters Chemical class 0.000 description 16
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- 229920005992 thermoplastic resin Polymers 0.000 description 16
- 239000006057 Non-nutritive feed additive Substances 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 13
- 235000008504 concentrate Nutrition 0.000 description 13
- 239000012141 concentrate Substances 0.000 description 13
- 229920002647 polyamide Polymers 0.000 description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 229920002302 Nylon 6,6 Polymers 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000003856 thermoforming Methods 0.000 description 12
- 229920003182 Surlyn® Polymers 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 10
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 239000012263 liquid product Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000009740 moulding (composite fabrication) Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 9
- 239000003348 petrochemical agent Substances 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229920003313 Bynel® Polymers 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 229920005629 polypropylene homopolymer Polymers 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 238000007655 standard test method Methods 0.000 description 6
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 5
- XXHCQZDUJDEPSX-UHFFFAOYSA-L calcium;cyclohexane-1,2-dicarboxylate Chemical compound [Ca+2].[O-]C(=O)C1CCCCC1C([O-])=O XXHCQZDUJDEPSX-UHFFFAOYSA-L 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 229920005606 polypropylene copolymer Polymers 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 229920006249 styrenic copolymer Polymers 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 101100389815 Caenorhabditis elegans eva-1 gene Proteins 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 229920000954 Polyglycolide Polymers 0.000 description 4
- 229920006097 Ultramide® Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229920003232 aliphatic polyester Polymers 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000012536 packaging technology Methods 0.000 description 4
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229920006132 styrene block copolymer Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
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- 229920006262 high density polyethylene film Polymers 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
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- 239000002184 metal Chemical class 0.000 description 3
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- 239000004626 polylactic acid Substances 0.000 description 3
- 235000020357 syrup Nutrition 0.000 description 3
- 239000006188 syrup Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
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- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
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- 239000004187 Spiramycin Substances 0.000 description 2
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- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000002129 Malva sylvestris Species 0.000 description 1
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- 229920001007 Nylon 4 Polymers 0.000 description 1
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- 239000004687 Nylon copolymer Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
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- 241000490025 Schefflera digitata Species 0.000 description 1
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- 239000005035 Surlyn® Substances 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 229920003810 Ultramid® B36 Polymers 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
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- 235000015218 chewing gum Nutrition 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 235000013409 condiments Nutrition 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- FTZSDHHWPWGCDI-UHFFFAOYSA-N dodecanediamide Chemical compound NC(=O)CCCCCCCCCCC(N)=O FTZSDHHWPWGCDI-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical compound C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- QMYWABFEOZMOIL-UHFFFAOYSA-N heptanediamide Chemical compound NC(=O)CCCCCC(N)=O QMYWABFEOZMOIL-UHFFFAOYSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
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- 239000000543 intermediate Substances 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
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- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
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- 229920005684 linear copolymer Polymers 0.000 description 1
- 235000015250 liver sausages Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000001035 marshmallow Nutrition 0.000 description 1
- 238000002483 medication Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- NFVUAUVSFDFOJT-UHFFFAOYSA-N octanediamide Chemical compound NC(=O)CCCCCCC(N)=O NFVUAUVSFDFOJT-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 235000014594 pastries Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
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- 229920013716 polyethylene resin Polymers 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 229920006296 quaterpolymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
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- 239000002453 shampoo Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009822 solventless lamination Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 235000015149 toffees Nutrition 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B32B1/02—
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08L57/02—Copolymers of mineral oil hydrocarbons
Abstract
ABSTRACT - 599088 The disclosure relates to film comprising (A) at least one moisture barrier layer comprising a polymer blend comprising (a) high density polyethylene in an amount from about 69 % about 90 % by weight of the blend, wherein the high density polyethylene has a melt index of at least 1.0 g/10 min and a density greater than 0.958 g/cc; (b) hydrocarbon resin in an amount from about 5 % about 30 % by weight of the blend, wherein the hydrocarbon resin comprises petroleum resins, terpene resins, styrene resins, cyclopentadiene resins, saturated alicyclic resins or blends thereof; and (c) nucleating agent in an amount from about 0.01 % to about 1 % by weight of the blend, wherein the nucleating agent comprises glycerol alkoxide salts, hexahydrophthalic acid salts, similar salts or blends thereof; and (B) at least one additional layer comprising an ionomer, a high density polyethylene, a polyester, a styrene butadiene copolymer or blends thereof; wherein the film has normalized moisture vapour transmission rate of no greater than 0.30 g-mil/100 in2/day measured at about 100 °F and 90 % external relative humidity. These films are tear-resistance and chlorine-free that have no significant sticking, forming, cutting, filling or sealing issues, which makes them suitable as packaging sheets that can be thermoformed into articles, such as trays, cups, etc., which may then be used to package food, non-food, medical and industrial products. t 1.0 g/10 min and a density greater than 0.958 g/cc; (b) hydrocarbon resin in an amount from about 5 % about 30 % by weight of the blend, wherein the hydrocarbon resin comprises petroleum resins, terpene resins, styrene resins, cyclopentadiene resins, saturated alicyclic resins or blends thereof; and (c) nucleating agent in an amount from about 0.01 % to about 1 % by weight of the blend, wherein the nucleating agent comprises glycerol alkoxide salts, hexahydrophthalic acid salts, similar salts or blends thereof; and (B) at least one additional layer comprising an ionomer, a high density polyethylene, a polyester, a styrene butadiene copolymer or blends thereof; wherein the film has normalized moisture vapour transmission rate of no greater than 0.30 g-mil/100 in2/day measured at about 100 °F and 90 % external relative humidity. These films are tear-resistance and chlorine-free that have no significant sticking, forming, cutting, filling or sealing issues, which makes them suitable as packaging sheets that can be thermoformed into articles, such as trays, cups, etc., which may then be used to package food, non-food, medical and industrial products.
Description
Patents Form 5
NZ. No.
NEW ZEALAND
Patents Act 1953
COMPLETE SPECIFICATION
HIGH DENSITY HYLENE BLEND FILMS
We, CURWOOD, INC, a company of the United States of America of 2200 Badger ,
Oshkosh, Wisconsin 54903, United States of America, do hereby declare the invention, for which we
pray that a patent may be granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:-
(Foilowed by 1A)
HIGH DENSITY POLYETHYLENE BLEND FILMS
BACKGROUND OF THE INVENTION
This present application relates to a packaging film, specifically a high density
polyethylene (HDPE) blended with a nucleating agent and arbon resin.
Moisture protection is an important function of many packages. For example, in
the cereal market, HDPE is ly used for its moisture barrier property. Film
thickness is increased to match the desired level of moisture barrier, but this adds
weight and cost to the package.
US 6,969,556 (which is incorporated in its entirety in this application by this
reference) relates to a sheet or film which comprises at least one layer comprising a first
al which is very highly crystalline polymer (preferably polypropylene of 99% or
greater isotacity) er with at least one second material in an amount sufficient to
improve one or more of the r properties, mechanical properties and/or optical
properties 'of the sheet. The second material comprises (a) a nucleating agent; (b) a
polymeric material having a ring and ball softening point from about 110° C. to about
170° C. and/or (c) a hydrogenated resin such as dicyclo-pentadiene hydrogenated
resin, a hydrogenated mixed monomer resin; and/or a resin obtainable from a mixture of
a-methyl styrene, indene and/or vinyl toluene monomers.
-1A-
US 2008/0118749 (which is incorporated in its entirety in this application by this
reference) relates to r films prepared from a blend of two high density
polyethylene blend ents and a high. mance organic nucleating agent. The
two high density polyethylene blend components have substantially different meit
indices. Large reductions. in the moisture vapor transmission rate of the film are
observed in the ce of the nucleating agent when the melt s of the two blend
components have a ratio of greater than 10/1.
US 6,432,496, 6,969,740, and 7,176,259 (each of which is incorporated in its
entirety in this application by this reference) relate to oriented HDPE films containing
arbon resins having improved moisture barrier. The effects of hydrocarbon
resins in oriented films are not predictive of the effect on non-oriented films. The
mechanical properties of non-oriented films are more likely to be adversely affected by
additives than are oriented films.
(which is incorporated in its entirety in this application by this
reference) relates to polyoiefin composition blends comprising an additive composition
comprising a hydrocarbon resin and a high performance nucleating agent. The
nucleating agent is used to se the crystallization temperature and, therefore,
decrease the amount of hydrocarbon resin needed. According to ,
reducing the amount of hydrocarbon resin reduces the compromising effects of the
hydrocarbon resin on the film’s ical properties, WC 2010/1 04628 provides
examples of polypropylene polyolefin itions.
What is needed are HDPE films with improved barrier properties without
increased film thickness.
In other aspects, the application s to a sheet, ically, a chlorine-free
packaging sheet with tear-resistance properties. Packaging sheets are used for many
purposes. One of these many purposes includes thermoforming the sheet into articles,
such as trays, cups, etc., which may then be used to package food, non-food, medical
and industrial products.
One packaging sheet that is currently used for thermoforming into packaging
es comprises a fully coextruded sheet with nylidene chloride (PVdC)
ched between high impact polystyrene (HIPS), with ethylene vinyl acetate
copolymer (EVA) used to laminate the central PVdC layer to the outer HIPS layers.
This PVdC sheet generally has no significant sticking, forming, cutting, filling or sealing
issues when used for thermoforming into articles. However, it is well known that PVdC
has many environmental health concerns. with chlorine as the source of many of these
concerns. Both the cture and the al of PVdC produce dioxin, a highly
carcinogenic chemical; and many localities do not permit a converter or packager to
reprocess or landfill-dispose of packaging materials ning PVdC. As a result,
chlorine-free materials may be preferred.
A chlorine-free ing sheet that is currently used comprises a fully
coextruded sheet with ethylene vinyl alcohol copolymer (EVOH) sandwiched between
HIPS, with high density polyethylene (HDPE) between the central EVOH tayer and the
outer HIPS iayers. (See, for example, US Patent 5,972,447, pubtished February 15,
2007, which is incorporated in its entirety in this application by this reference.) Such a
sheet may have a layer structure of HIPS / HDPE / EVOH / HDPE / HIPS or
HIPS / tie / HDPE / tie / EVOH /tie / HDPE / tie / HIPS (where “/” is used to
indicate the layer boundary). Both ures are ne-free. However,
both structures are known to have significant forming and cutting issues when
used for thermoforming into articles. What is needed is a chlorine-free
packaging sheet that has no icant sticking, forming, cutting, filling or
sealing issues when used for thermoforming into articles.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to a film comprising (A) at least one
moisture barrier layer comprising a polymer blend comprising (a) high density
polyethylene in an amount from about 69 % about 90 % by weight of the
blend, wherein the high density polyethylene has a melt index of at least 1.0
g/10 min and a density r than 0.958 g/cc; (b) hydrocarbon resin in an
amount from about 5 % about 30 % by weight of the blend, wherein the
hydrocarbon resin comprises petroleum resins, terpene resins, styrene resins,
cyclopentadiene , saturated alicyclic resins or blends thereof; and (c)
nucleating agent in an amount from about 0.01 % to about 1 % by weight of
the blend, wherein the nucleating agent comprises glycerol alkoxide salts,
hexahydrophthalic acid salts, similar salts or blends f; and (B) at least
one additional layer comprising an ionomer, a high density polyethylene, a
polyester, a styrene ene copolymer or blends thereof; wherein the film
has normalized moisture vapor transmission rate of no greater than 0.30 gmil
/100 in2/day ed at about 100 °F and 90 % external ve
humidity.
The need for HDPE films with improved barrier properties without
increased film thickness is met by a non-oriented film having a moisture
(followed by page 4A)
barrier layer. The moisture barrier layer ses a blend of high density
polyethylene, hydrocarbon resin and nucleating agent. The blend comprises
from about 69 % by weight to about 90 % by weight high density polyethylene
or from about 75 % by weight to about 85 % by weight high density
polyethylene. The high density polyethylene has a melt index of at least 1.0
g/10 min and a density greater than 0.958 g/cc. The blend further comprises
from about 5 % by weight to about 30 % by weight hydrocarbon resin or from
about 5 % by weight to about 20 % by weight arbon resin or from about
% by weight to about 15 % by weight hydrocarbon resin. The blend also
comprises from about 0.01 % by weight to about 1 % by weight ting
agent or from about 0.04% by weight to about 0.10% by weight nucleating
agent. The film has normalized moisture vapor transmission rate of no
greater than 0.30 100 in2/day measured at about 100 °F and 90 %
external relative humidity. The nucleating agent may be a glycerol alkoxide
salt, hexahydrophthalic acid salt, glycerolate salt or calcium
hexahydrophthalate.
In some s, the film further comprises an oxygen barrier material, and
the film has a normalized oxygen transmission rate of less than about 150 ccmil
/100
- 4A -
(Followed by page 5)
in2/day or less than about 100 cc-mil/100 in2/day. In other aspects, the film may further
comprise at least one layer comprising an ionomer, at least one layer comprising a high
density hylene, at least one layer comprising a copolymer of ethylene and an
ester, at least one layer comprising an ethylene vinyl acetate copolymer (EVA), at least
one layer sing a styrene butadiene copolymer, or combinations of the above.
The film may have a thickness of less than 3.00 mil or less than 1.70 mil.
In yet other aspects, the film may comprise a second moisture barrier layer
sing a blend. The blend comprises high density polyethylene, hydrocarbon resin
and nucleating agent. The blend comprises from about 69 % by weight to about 90 %
by weight high density hylene, wherein the high density polyethylene has a melt
index of at least 1.0 g/10 min and a y‘greater than 0.958 g/cc. The blend r
comprises from about 5 0/o by weight to about 30 % by weight hydrocarbon resin and
from about 0.01 % by weight to about 1 % by weight nucleating agent.
in one embodiment, a polymer blend of at least three polymers is provided. The
blend comprises high density polyethylene, hydrocarbon resin and ting agent.
The blend comprises from about 69% by weight to about 90% by weight high density
polyethylene or from about 75 % by weight to about 85 % by weight high density
polyethylene. The high density polyethylene has a melt index of at least 1.0 g/10 min
and a density greater than 0.958 9/00. The blend further comprises from about 5% by
weight to about 30% by weightlhydrocarbon resin or from about 10 % by weight to
about 15 % by weight hydrocarbon resin. The blend also comprises from about 0.01%
by weight to about 1% by weight nucleating agent or from about 0.04% by weight to
about 0.10% by weight nucleating agent.
In another embodiment, a film layer comprising a blend of high y
poiyethylene, hydrocarbon resin and nucleating agent is provided. The blend comprises
from about 69% by weight to about 90% by weight high density polyethylene or from
about 75 % by weight to about 85 % by weight high density polyethylene, wherein the
high density polyethylene has a melt index of at least 1.0 g/10 min and a density greater
than 0.958 g/cc. The blend further comprises from about 5% by weight to about 30% by
weight hydrocarbon resin or from about 10 % by weight to about 15 % by weight
hydrocarbon resin. The blend also comprises from about 0.01% by weight to about 1%
by weight nucleating agent or from about 0.04% by weight to about 0.10% by weight
nucleating agent. The film layer is non-oriented and has a normalized moisture vapor
transmission rate of no greater than 0.30 g-mil/1OO in2/day or no greater than 0.20 g-
mil/1OO y or no r than 0.15 100 in2/day, as measured at about 100 °F
and 90 % external relative ty.
in still another embodiment, a packaging e comprises the non-oriented film
having the moisture barrier layer as described above. in some aspects, the packaging
article is a rigid article or a semi-rigid article.
The need for a ne-free packaging sheet that has no significant sticking,
forming, cutting, filling or sealing issues when used for thermoforming into articles is met
by a chlorine—free packaging sheet comprising a first rigid component, a second rigid
component and a multilayer film. The multilayer film is positioned between the first rigid
component and the second rigid component. The packaging sheet has a normalized
combined tear initiation and propagation resistance in both the machine direction and
the transverse ion of less than about 0.115 in*lbf/ mil energy to break and less
than about 0.800 % / mil elongation as measured in accordance with ASTM D1004, and
has a normalized tear propagation resistance in both the machine direction and the
transverse direction of less than about 0.300 in*lbf/ mil energy to break and less than
about 0.145 [bf / mil peak load as measured in accordance with ASTM D1938. Lower
tear ance values are tive of an ease of cutting the packaging sheet. The first
rigid component and the second rigid component may comprise various materials. The
multilayer film may be of any number of multiple layers (i.e., two or more layers) and
may comprise various materials.
In one embodiment, the multilayer film comprises a blown, coextruded film. In
another embodiment, the multilayer film comprises an n-layer blown, coextruded tubular
extrudate that is collapsed and ed upon itself to form two inner r extrudate
layers and that is thermally laminated to itself at the two inner tubular extrudate layers
such that the two inner tubular extrudate layers form one inner layer and a romic,
2n-1 layer film results.
In further ments, the multilayer film ses various barrier
components, including but not limited to a barrier component comprising a single barrier
layer, a barrier ent comprising a first barrier layer and a second barrier layer and
a barrier component comprising a first r component layer, a first intermediate
layer, an oxygen barrier layer, a second intermediate layer and a re barrier layer.
In another embodiment, the multilayer film comprises an oxygen barrier material
and the barrier layer or layers have a normalized oxygen transmission rate of less than
about 0.1 cc—mil/1 00 inz/day as measured in accordance with ASTM D3985. In a further
embodiment, the multilayer film comprises a moisture barrier material and the barrier
layer or layers have a normalized water vapor transmission rate of less than about 0.15
g-mil/100 inzlday as measured in accordance with ASTM F1249.
In still another embodiment, a package comprises the packaging sheet. In
further embodiments, the packaging sheet may be thermoformed into various packages
and n various products.
In still yet another embodiment, s s of manufacturing the packaging
sheet are described. in general, the methods comprise the sequential steps of (a)
adding thermoplastic resins to extruders to extrude an outer layer of an n-layer
multilayer barrier film, to extrude a barrier component of the multilayer barrier film and to
extrude an inner layer of the ayer barrier film, such that the barrier component is
oned between the outer layer and the inner layer of the multilayer barrier film and
such that the multilayer r film has a first surface and an opposing second surface;
(b) heating the thermoplastic resins to form streams of melt-plastified polymers; (0)
forcing the streams of melt-plastified polymers through a die having a central orifice to
form a tubular extrudate having a diameter and a hollow interior; (d) expanding the
diameter of the tubular extrudate by a volume of fluid entering the hollow interior via the
central orifice; (e) collapsing the tubular extrudate; (f) flattening the r extrudate to
form two inner r extrudate iayers; (g) attaching a first rigid ent to the first
surface of the multilayer barrier film; and (h) attaching a second rigid component to the
opposing second surface of the multilayer barrier film.
BRIEF DESCRIPTION OF THE DRAWINGS
is a diagrammatic cross-sectional view of the general ment of the
chlorine~free packaging sheet described in the present‘application.
is a diagrammatic cross-sectionai view of a first embodiment of the
chlorine-free packaging sheet described in the present application.
is a diagrammatic cross-sectional view of a second embodiment of the
chlorine-free packaging sheet described in the present application.
is a mmatic cross-sectional view of a third embodiment of the
ne-free packaging sheet described in the present appiication.
HS. 5 is a schematic representation of a blown film process for producing a
multilayer film included in the ne-free packaging sheet described in the present
ation.
is a cross-sectional view of a tubular extrudate made according to the
process of
is a diagrammatic cross-sectional view of a non-oriented three layer film
having at least one moisture barrier layer.
is a diagrammatic sectional view of a non-oriented five layer film
having at ieast one moisture barrier layer.
is a diagrammatic cross-sectional view of a non-oriented nine layer film
having at least one moisture barrier layer.
is a diagrammatic cross-sectional view of a non-oriented thirteen layer
film having at ieast one moisture barrier layer.
DETAILED DESCRIPTION OF THE INVENTION
As used throughout this application, the term "chiorine-free" refers to rs
without chlorine within the repeating backbone (i.e., chain) of the r. Such
polymers may contain trace amounts of al chlorine present from a chlorine-
containing catalyst (e.g., TiCI3) used to produce the polymers. Examples of chlorine-
free polymers include but are not limited to ne vinyl alcohol copolymer, polyamide,
polyglycolic acid and acrylonitrile-methyl acrylate copolymer. Examples of lorine-
free polymers include but are not limited to polyvinyl chloride and nyiidene
chloride.
As used throughout this application, the term "sheet" refers to a plastic web of
any ess and is not limited to a plastic web having a thickness of greater than
about 10 mil. The term “film" means a plastic web of any thickness and is not limited to
a plastic web having a ess of less than about 10 mil. For convenience, this
application may refer to a sheet having a thickness greater than or including a film; but
the terms are not limited to such interpretation.
As used throughout this application, the term "about” refers to approximately,
rounded up or down to, reasonably close to, in the vicinity of, or the like. The term
“approximate” is synonymous with the term “about.”
As used throughout this application, the term "component” refers to a monolayer
or multilayer film sing thermoplastic resin.
As used throughout this application, the term “rigid component” refers to a
component selected from the group consisting of styrenic polymer, aromatic polyester,
aliphatic polyester, polypropylene homopolymer and blends of such. Examples include,
but are not limited to, high impact polystyrene (HIPS), l purpose polystyrene
, styrene block copolymer (880) (including but not limited to styrene butadiene
copolymer (88)), polyethylene terephthalate (PET), ed polyethylene terephthalate
(OPET), amorphous polyethylene terephthalate (APET), glycol-modified polyethylene
thalate (PETG), polylactic acid (PLA) and blends of such.
As used throughout this application, the term "multilayer” refers to a plurality of
layers in a single film ure lly in the form of a sheet or web which can be
made from a polymeric material or a non-polymeric material bonded together by any
conventional means known in the art (i.e., coextrusion, lamination, coating or a
combination of such). The ne—free packaging sheet described in the present
application comprises a multilayer film including as many layers as desired and,
preferably, at least three .
As used throughout this application, the term ”tear—resistance properties”
includes but is not limited to the ed tear initiation and propagation resistance in
both the machine direction and the transverse (i.e., cross) direction of a sheet (as
measured in accordance with ASTM D1004 and further explained below) and the tear
propagation ance in both the machine direction and the transverse ion of a
sheet (as measured in accordance with ASTM D1938 and further explained below).
As used throughout this application, the term "polystyrene” or “PS” refers to a
homopolymer or copolymer having at least one styrene monomer linkage (such as
benzene (i.e., CsH5) having an ethylene substituent) within the repeating backbone of
the polymer. The styrene linkage can be represented by the general formula: [CH2 ~CH2
(C6H5)]n. Polystyrene may be formed by any method known to those skilled in the art.
As used throughout this application, the term “coextruded” refers to the process
of extruding two or more polymer materials through a single die with two or more
orifices arranged so that the extrudates merge and weld er into a laminar
structure before ng (i.e., quenching.) 'Coextrusion methods known to a person of
ordinary skill in the art include but are not limited to blown film coextrusion, slot cast
coextrusion and extrusion coating. The flat die or slot cast process includes extruding
polymer streams through a flat or slot die onto a chilled roll and subsequently winding
the film onto a core to form a roll of film for further processing.
As used throughout this application, the term “blown film” refers to a film
produced by the blown coextrusion s. In the blown coextrusion process, streams
of melt-plastified polymers are forced through an annular die having a central mandrel
to form a tubular extrudate. The r extrudate may be expanded to a desired wall
thickness by a volume of fluid (e.g., air or other gas) entering the hollow interior of the
extrudate via the mandrel, and then rapidly cooled or quenched by any of various
methods known to those of skill in the art.
As used throughout this application, the term “layer” refers to a discrete film or
sheet component which is nsive with the film or sheet and has a substantially
uniform composition. In a monolayer film, "film, )1 il sheet” and "layer” would be
synonymous.
As used throughout this application, the term "barrier" refers to any al
which controls a permeable element of the film or sheet and includes but is not limited
to oxygen barrier, moisture barrier, al barrier, heat barrier and odor r.
As used throughout this application, the term "tie material” refers to a polymeric
material serving a primary purpose or on of adhering two surfaces to one another,
presumably the planar surfaces of two film layers. A tie material adheres one film layer
e to another film layer surface or one area of a film layer e to another area
of the same film layer surface. The tie material may comprise any polymer, copolymer
or blend of polymers having a polar group or any other polymer, lymer,
copolymer or blend of polymers, including modified and unmodified polymers (such as
grafted mers), which provide sufficient interlayer adhesion to adjacent layers
comprising otherwise nonad hering polymers.
As used throughout this application, the term “polyester” refers to a homopoiymer
or copolymer having an ester linkage between monomer units which may be formed, for
example, by condensation polymerization ons n a dicarboxylic acid and a
diol. The ester linkage can be represented by the general formula: C(O)-R'~
'10 C(O)]n where R and R' are the same or different alkyl (or aryl) group and may be
lly formed from the polymerization of dicarboxylic acid and diol monomers
containing both carboxylic acid and hydroxyl moieties. The dicarboxylic acid (including
the carboxylic acid moieties) may be linear or aliphatic (e.g., lactic acid, oxalic acid,
maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azeiaic
acid, sebacic acid, and the like) or may be aromatic or alkyl substituted aromatic (e.g.,
various isomers of ic acid, such as paraphthalic acid (or terephthalic acid),
isophthalic acid and naphthalic acid). Specific es of a useful diol include but are
not limited to ethylene glycol, propylene glycol, trimethylene , 1,4-butane diol,
neopentyl giycol, cyclohexane diol and the like. Polyesters may include a homopolymer
or copolymer of alkyl-aromatic esters ing but not limited to polyethylene
terephthalate (PET), amorphous polyethylene terephthalate (APET), crystalline
poiyethylene terephthalate (CPET), glycol-modified polyethylene terephthalate (PETG)
and poiybutylene terephthalate; a copolymer of terephthalate and halate including
but not limited to polyethylene thalate/isophthalate copolymer; a homopolymer or
copolymer of aliphatic esters including but not limited to polylactic acid (PLA);
polyhydroxyalkonates including but not limited to polyhydroxypropionate, poly(3-
hydroxybutyrate) , poly(3-hydroxyvalerate) , poly(4-hydroxybutyrate)
(PH4B), poly(4—hydroxyvalerate) (PH4V), poly(5-hydroxyvalerate) (PHSV), poly(6—
hydroxydodecanoate) (PH6D); and blends of any of these materials.
As used throughout this application, the term “anchor coat material" refers to a
material that is placed n one layer and an adjacent layer to anchor one layer to
another layer. It may also be referred to as an “undercoat material.”
As used throughout this application, the term "polyethylene" or “PE” refers
(unless indicated otherwise) to ethylene homopolymers as well as mers of
ethylene with at least one alpha-olefin. The term will be used without regard to the
presence or absence of substituent branch groups.
As used throughout this application, the term “high density hylene” or
“HDPE" es but is not limited to both (a) homopolymers of ethylene which have
densities from about 0.960 g/cm3 to about 0.970 g/cm3 and (b) copolymers of ethylene
and an alpha-olefin (usually 1-butene or 1-hexene) which have densities from about
0.940 g/cm3 to about 0.958 g/cm3. HDPE includes polymers made with Ziegler or
Phillips type sts and polymers made with single-site metallocene catalysts. HDPE
also includes high molecular weight "polyethylenes." In contrast to HDPE, whose
polymer chain has some branching, are "ultra high molecular weight poiyethylenes,"
which are essentially unbranched specialty polymers having a much higher molecular
weight than the high molecular weight HDPE.
As used throughout this application, the term "low density polyethylene” or
“LDPE” refers to branched homopolymers having densities between 0.915 g/cm3 and
0.930 g/cms, as well as mers containing polar groups resulting from
copolymerization (such as with vinyl acetate or ethyl acrylate). LDPE typically contains
long branches off the main chain (often termed “backbone") with alkyt substituents of
two to eight carbon atoms.
As used throughout this application, the term “copolymer” refers to a polymer
product obtained by the polymerization on or copolymerization of at teast two
monomer species. Copoiymers may also be referred to as bipolymers. The term
“copolymer” is also inclusive of the rization on of three, four or more
monomer s having reaction products referred to terpolymers, quaterpolymers,
etc.
As used throughout this application, the term “copolymer of ethylene and at least
one alpha-olefin” refers to a modified or unmodified copolymer ed by the co-
polymerization of ne and any one or more alpha-oiefins. Suitable alpha-olefins
include, for e, 03 to Czo alpha-olefins such as propene, 1-butene, 1-pentene, 1-
hexene, 1-octene, 1—decene and combinations of such. The co-potymerization of
ethylene and an olefin may be produced by heterogeneous catalysis, such as oo—
polymerization reactions with Ziegter-Natta catalysis systems, including, for example,
metal halides activated by an organometallic catalyst (e.g., titanium chloride) and
optionally containing magnesium chloride complexed to trialkyl aluminum.
Heterogeneous catalyzed copolymers of ethylene and an alpha-otefin may include
linear low density polyethylene (LLDPE), very low density hytene (VLDPE) and
ultra low density poiyethylene (ULDPE) (commercially available as, for example,
DowlexTM from The Dow Chemical Company (Midland, Michigan)). Additionally, the co-
polymerization of ethylene and an olefin may also be produced by homogeneous
catalysis, such as co-polymerization reactions with metallocene catalysis s which
include constrained ry catalysts, (e.g., monocyclopentadienyl transition-metal
complexes). Homogeneous catalyzed copolymers of ne and aipha-olefin may
include modified or unmodified ethylene alpha-olefin copolymers having a long-chain
branched (i.e., 8-20 pendant carbons atoms) alpha-olefin co-monomer rcially
available as, for example, AffinityTM and AttaneTM from The Dow Chemical Company
(Midland, Michigan», linear copolymers (commercially available as, for example,
TafmerTM from the Mitsui Petrochemical Corporation (Tokyo, Japan», and modified or
fied ethylene olefin copolymers having a short-chain branched (i.e., 3-6
pendant carbons atoms) alpha-olefin co-monomer (commercially available as, for
example, ExactTM from ExxonMobii al Company (Houston, Texas». in general,
neous zed ethylene alpha-olefin copolymers may be characterized by one
or more methods known to those of skill in the art, including but not limited to molecular
weight distribution (MW/Mn), composition distribution breadth index (CDBI), narrow
melting point range and single g point behavior.
As used throughout this application, the term "modified" refers to a al
derivative, such as one having any form of anhydride functionality (e.g., anhydride of
maleic acid, crotonic acid, citraconic acid, itaconic acid, fumaric acid, etc.), whether
grafted onto a polymer, copolymerized with a polymer or blended with one or more
polymers. The term is also inclusive of derivatives of such functionalities, such as
acids, esters and metal salts derived from such.
As used throughout this application, the term ating agent” refers to an
additive which forms nuclei in a polymer melt to promote the growth of crystals.
As used throughout this application, the term “hydrocarbon resin" refers to a
product produced by polymerization from coal tar, petroleum and turpentine feedstocks,
as defined by ISO Standard 472, ics — Vocabulary,” which is incorporated in its
entirety in this ation by this reference.
As used throughout this ation, the term "intermediate layer” refers to a layer
that is positioned between two other layers.
As used throughout this application, the term “ethylene vinyl alcohol copolymer”
or “EVOH” refers to copolymers sed of repeating units of ne and vinyl
alcohol. Ethylene vinyl alcohol copolymers can be represented by the l formula:
[(CHg-CH2)m-(CH2 -CH(OH))]n. Ethylene vinyl alcohol copolymers may include
saponified or hydrolyzed ethylene vinyl acrylate copolymers. EVOH refers to a vinyl
alcohol copolymer having an ethylene co-monomer and prepared by, for example,
hydrolysis of vinyl acrylate copolymers or by chemical reactions with vinyl alcohol. The
degree of hydrolysis is preferably at least 50% and, more preferably, at least 85%.
Preferably, ethylene vinyl alcohol copolymers comprise from about 28 mole percent to
about 48 mole percent ethylene, more ably, from about 32 mole percent to about
44 mole percent ethylene, and, even more preferably, from about 38 mole percent to
about 44 mole t ethylene.
As used throughout this application, the term "poiyamide" or “PA” or “nylon”
refers to a homopolymer or mer having an amide linkage between monomer units
which may be formed by any method known to those skilled in the art. The amide
linkage can be represented by the general formula: [C(O)-R-C(O)-N H-R’~NH]n where R
and R' are the same or different alkyl (or aryl) group. Examples of nylon potymers
include but are not limited to nylon 6 aprolactam), nylon 11 (polyundecanoiactam),
nylon 12 (polyauryllactam), nylon 4,2 (polytetramethylene ethylenediamide), nylon 4,6
(polytetramethylene adipamide), nylon 6,6 (polyhexamethylene adipamide), nylon 6,9
(polyhexamethylene azelamide), nylon 6,10 (polyhexamethylene mide), nylon
6,12 (polyhexamethylene dodecanediamide), nylon 7,7 (polyheptamethylene
pimelamide), nylon 8,8 (polyoctamethylene suberamide), nylon 9,9 (polynonamethylene
azelaiamide), nylon 10,9 (polydecamethyiene azelamide), and nylon 12,12
odecamethylene dodecanediamide). Examples of nylon copolymers include but
are not limited to nylon 6,6/6 copolymer (polyhexamethylene adipamide/caprolactam
copolymer), nylon 6,6/9 copolymer (polyhexamethylene adipamide/azelaiamide
copolymer), nylon (3/66 mer aprolactam/hexarnethylene adipamide
copolymer), nylon 6,2/6,2 copolymer examethylene
ethylenediamide/hexamethylene ethylenediamide copolymer), and nylon 6,6/6,9/6
copolymer (polyhexamethylene adipamide/hexamethylene azelaiamide/caprolactam
copolymer). Examples of ic nylon polymers include but are not limited to nylon
4,|, nylon 6,|, nylon 6,6/6l copolymer, nylon 6,6/6T copolymer, nlen MXD6 (poly-m—
xylylene adipamide), poly-p-xylylene adipamide, nylon 61/6T copolymer, nylon 6T/6l
copolymer, nylon MXDI, nylon 6/MXDT/l copolymer, nylon 6T (polyhexamethylene
terephthalamide), nylon 12T (polydodecamethylene terephthaiamide), nylon 66T, and
nylon 6-3—T (poiy(trimethyl hexamethylene terephthalamide).
As used throughout this application, the term “ionomer” refers to a partialty
neutralized acid copolymer.
As used throughout this application, the term "polypropylene” or “PP” refers to a
homopolymer or copolymer having at least one propylene monomer e within the
repeating backbone of the polymer. The propylene linkage can be represented by the
general formula: H(CH3)]n.
As used throughout this application, the term "palindromic film” refers to a multi-
layer film, the layers of which are ntially symmetrical. Examples of palindromic
films are film or sheet having the layer configurations A/B/A or A or A/B/C/B/A or
A/B/C/D/E/D/C/F/C/D/E/D/C/B/A, etc. An example of a layer configuration of a non-
palindromic film would be A/B/C/A.
As used throughout this application, the term “thermoformed” refers to polymer
film or sheet permanently formed into a desired shape by the application of a differential
of heat, by the
pressure between the film or sheet and a mold, by the ation
combination of heat and the ation of a differential pressure between the film or
sheet and a mold, or by any thermoforming technique known to those skilled in the art
As used hout this application, the term oplastic” refers to a polymer
or polymer mixture that softens when exposed to heat and then returns to its original
condition when cooled to room temperature. In general, thermoptastic materiats may
include natural or synthetic polymers. Thermoplastic materials may further include any
polymer that is cross-linked by either radiation or chemical reaction during
manufacturing or post-manufacturing processes.
As used throughout this application, the term “polymer” refers to a material which
is the product of a polymerization or copolymerization reaction of natural, synthetic or
combined l and synthetic monomers and/or co-monomers and is inclusive of
homopolymers, copolymers, terpolymers, etc. In general, the layers of the chlorine-free
packaging sheet bed in the present application may comprise a single polymer, a
mixture of a single polymer and non-polymeric material, a combination of two or more
polymers blended er, or a mixture of a blend of two or more polymers and non-
polymeric al. It will be noted that many polymers may be synthesized by the
mutual on of complementary monomers. it will also be noted that some polymers
are obtained by the chemical modification of other polymers such that the structure of
the macromolecules that constitute the ing polymer can be thought of as having
been formed by the homopolymerization of a etical monomer.
As used throughout this application, the term "polyvinylidene chloride” or “PVDC”
refers to a polymer derived from vinylidene chloride. PVdC may be formed from the
polymerization of vinylide chloride with various rs including but not limited to
acrylic esters and unsaturated yl groups.
Referring now to the drawings, is a diagrammatic cross-sectional view of
the general embodiment of the chlorine-free packaging sheet described in the present
application. Generic packaging sheet 60 comprises three layers: first rigid component
61, c multilayer film 62 and second rigid component 63. (In each of the figures of
the present application, the dimensions are not to scale and may be exaggerated for
clarity.)
First rigid component 61 and second rigid component 63 may comprise the same
material or may se different materials (relative to each . First rigid
component 61 and second rigid component 63 comprise styrenic r, aromatic
polyester, aliphatic polyester, polypropylene homopolymer, or blends of such.
Examples of styrenic polymers include but are not limited to high impact
polystyrene (HIPS), general purpose polystyrene (GPPS) and styrene block copolymer
(SBC). HIPS is sometimes called rubber-modified yrene and is normally
produced by copolymerization of styrene and a synthetic rubber. (See Wagner, et al.,
“Polystyrene,” The Wiley Encyclopedia of Packaging Technology, Second Edition, 1997,
pp. 768-771 (John Wiley & Sons, lnc., New York, New York), which is incorporated in its
entirety in this application by this reference.) Examples of HIPS include but are not
limited to Impact Polystyrene 825E and Impact Polystyrene 945E, both of which are
available from Total Petrochemicals USA, Inc; E86025 Rubber Modified High Impact
Polystyrene, which is ble from Chevron ps Company (The Woodlands,
Texas); and 6210 High Impact Polystyrene, which is available from Ineos Nova LLC
(Channahon, is). GPPS is often called crystal polystyrene, as a nce to the
clarity of the resin. Examples of GPPS include but are not limited to Crystal Polystyrene
5248 and Crystal Polystyrene 5258, both of which are ble from Total
Petrochemicals USA, inc. Styrene block copolymers (880) include styrene butadiene
copolymers (SB). The styrene-butadiene copolymers that are suitable for packaging
applications are those resinous block copolymers that typically contain a greater
proportion of e than butadiene and that are predominantly polymodal with respect
to molecular weight distribution. (See Hartsock, ne-Butadiene Copolymers,” The
Wiley Encyclopedia of Packaging Technology, Second Edition, 1997, pp. 863-864 (John
Wiley & Sons, Inc., New York, New York), which is incorporated in its entirety in this
application by this reference.) A non-limiting example of SB is DK13 K-Resin® Styrene-
Butadiene Copolymer, which is available from Chevron ps Chemical Company
(The Woodlands, Texas).
Examples of aromatic ters include but are not limited to polyethylene
terephthalate (PET), oriented polyethylene thalate (OPET), amorphous
polyethylene terephthalate (APET) and glycol-modified polyethylene terephthalate
. A non-limiting example of APET is EastmanTM PET 9921, which is available
from Eastman Chemical Company (Kingsport, Tennessee). A non-limiting e of
PETG is EastarTM Copolyester 6762, which is also available from Eastman Chemical
Company (Kingsport, Tennessee). An example of an aliphatic polyester includes but is
not d to polylactic acid (PLA).
Examples of polypropylene homopolymer include but are not limited to those
polypropylene homopolymers traditionally used to cast . Non-limiting examples
of such polypropylenes include Polypropylene 3287WZ, which is available from Total
Petrochemicals USA, Inc. on, Texas); and HOZC—OO Polypropylene
Homopolymer, which is available from lneos Olefins & Polymers USA (League City,
Texas).
More specifically, first rigid component 61 and second rigid component 63 may
each comprise HIPS, APET, PETG, a blend of GPPS and SB, a blend of HIPS and
GPPS, a blend of HIPS, GPPS and SB, a blend or APET and SB, or blends of such.
First rigid component 61 and second rigid component 63 may each also
comprise processing aids and/or color concentrates. Examples of processing aids
e but are not limited to slip/antiblock concentrates, such as SKR 17 available from
Chevron Phillips Corporation (The Woodlands, Texas); release agents, such as SF18-
350 Polydimethylsiloxane Fluid available from DC Products Pty Ltd (Mt. Waverley,
Victoria, Australia); and slip agents, such as axTM PS available from Croda
Polymer ves (Cowick, United Kingdom). Examples of color concentrates include
but are not limited to Accel A14477SGCP1 White Color Concentrate and Accel
A19111S4CP1 Blue Color trate, both of which are available from Accel
Corporation (Naperville, Illinois).
Returning to as described above, generic packaging sheet 60 also
comprises generic multilayer film 62. shows the general embodiment of the
packaging sheet 60 described in the present application. As such, generic multilayer
film 62 may be a three-layer, four-layer, five-layer, layer, nine—layer, thirteen-layer
or any other mUltilayer film (i.e., film having two or more layers), provided that the
resulting generic packaging sheet 60 has a normalized ed tear initiation and
propagation resistance in both the e direction and the erse direction of less
than about 0.115 in*lbf / mil energy to break and less than about 0.800 % / mil
elongation and has a normalized tear propagation resistance in both the machine
ion and the transverse direction of less than about 0.300 in*lbf/ mil energy to
break and less than about 0.145 lbf/ mil peak load (as further defined and described in
the ES below). Embodiments of a chlorine-free packaging sheet comprising a
five-layer film, a nine-layer film and a thirteen—layer film are shown in FIGS 2, 3 and 4,
respectively. Generic multilayer film 62 may be a blown, coextruded film.
Referring to is a diagrammatic cross-sectional view of a first
embodiment of the chlorine-free packaging sheet described in the present application.
First packaging sheet 70 comprises first rigid component 61, first ayer film 72 and
second rigid component 63. First rigid component 61 and second rigid component 63
are as described above.
First multilayer film 72 comprises outer layer 74, first barrier component 78 and
inner layer 76. In first ayer film 72 is shown as a yer romic film,
resulting from a blown, coextruded three-layer tubular extrudate that is collapsed and
flattened upon itself to form two inner tubular extrudate layers 50 (see and that
is thermally laminated to itself at the two inner tubular extrudate layers 50 to form one
inner layer 76.
Outer layer 74 may comprise ic copolymer, tie material, polyester anchor
coat material, copolymer of ethylene and an ester, copolymer of ethylene and at least
one alpha olefin, or polypropylene copolymer.
Outer layer 74 may comprise styrenic copolymer when first rigid component 61
and/or second rigid component 63 comprise styrenic copolymer. Styrenic copoiymers
are as described above. As described above, a miting example of a styrenic
copolymer is to DK13 K-Resin® Styrene-Butadiene Copolymers, which is ble from
Chevron Phillips Chemical Company (The Woodlands, Texas).
.- Outer layer 74 may comprise tie material when first rigid component 61 and/or
second rigid component 63 comprise tic polyester. Tie material includes but is not
limited to glycidyl methacrylate—modified copolymers of ethylene (e.g., epoxy-functional
tie materials), anhydride-modified (such as maleic anhydride modified) copolymers of
ethylene, copolymers of ethylene and a carboxylic acid (such as an acrylic acid),
copolymers of ethylene and an ester (such as an te), and blends of such. Further
es of tie material are provided below.
Outer layer 74 may se polyester anchor coat material when first rigid
ent 61 and/or second rigid component 63 comprise aromatic polyester.
Polyester anchor coat materials may be polyethylene-based and are known in the art.
Outer layer 74 may comprise copolymer of ethylene and an ester when first rigid
component 61 and/or second rigid component 63 comprise polypropylene
lymer. Examples of copolymers of ethylene and an ester include but are not
limited to ethylene vinyl acetate copolymer (EVA). Non-limiting examples of EVA are
described below.
Outer layer 74 may comprise copolymer of ethylene and at least one alpha olefin
when first rigid component and/or second rigid component 63 comprise polypropylene
homopolymer. Examples of copolymers of ethylene and at least one alpha olefin
include but are not limited to linear low density polyethylene and piastomers. c
non-limiting examples of such ethylene copolymers are DowlexTM 2045 Polyethylene
Resin available from The Dow Chemical Company nd, Michigan) and ExactlM
Plastomers (various grades) available from ExxonMobil al Company (Houston,
Texas). Copolymers of ethylene and at least one alpha olefin are further described
below.
Outer layer 74 may comprise polypropylene copolymer when first rigid
ent 61 and/or second rigid ent 63 comprise polypropylene
homopolymer. Polypropylene copolymers include but are not limited to impact
copolymers, such as Propylene 4170 ble from Total Petrochemicals USA, Inc.
(Houston, Texas).
Outer layer 74 may also comprise processing aids. es of processing aids
include but are not limited to slip/antiblock concentrates, such as SKR 17 available from
Chevron ps ation (The Woodlands, Texas); and thermal stabilizers, such as
SKR 20 available from Chevron Phillips Corporation (The nds, Texas).
For a palindromic film, inner layer 76 may comprise any material that is e
of thermally laminating or heat sealing to itself. Examples of materials for inner layer 76
include but are not limited to high density polyethylene, low density polyethylene,
copolymers of ethylene and at least one alpha-olefin, copolymers of ethylene and an
ester, anhydride-modified copolymers of ethylene, copolymers of ethylene and a
carboxylic acid, ionomers, styrenic copolymers, pressure sensitive adhesives,
polypropylene copolymers or blends of such.
Examples of high density polyethylene (HDPE) include but are not limited to
HDPE as described below.
Examples of copolymers of ethylene and at least one alpha-olefin include but are
not d to butene LLDPE, such as ExxonMobilTM LLDPE LL1001.32 available from
ExxonMobil Chemical Company (Houston, Texas); Dow LLDPE DFDA—7047 NT 7
available from the Dow Chemical Company (Midland, Michigan); Novapol® PF—O118—F
available from Nova Chemicals Corporation (Calgary, Alberta, Canada); Sabic® LLDPE
118N available from Sabic Europe (Sittard, The Netherlands); and ExactTM Plastomers
ble from ExxonMobil al Corporation (Houston, Texas).
Examples of copolymers of ethylene and an ester include but are not limited to
ethylene vinyl acetate copolymer (EVA), ethylene methyl methacrylate copolymer,
ethylene ethyl methacrylate copolymer and ethylene alkyi acrylates such as ethylene
methyl acrylate, ethylene ethyl te and ethylene butyl acrylate. Non-limiting
examples of EVA include EscoreneTM Ultra LD 705.MJ available from ExxonMobil
Chemical Company (Houston, , EscoreneT'V' Ultra LD 768.MJ available from
ExxonMobil Chemical Company (Houston, Texas) and Ateva® 2861AU available from
se Corporation (Edmonton, a, Canada).
es of anhydride-modified copolymers of ethylene include are but not
limited to tie materials as described above and below.
Examples of mers of ethylene and a carboxylic acid include but are not
limited to ethylene-methacrylic acid (EMAA) and ethylene acrylic acid (EAA).
A non-limiting example of ionomers (i.e., partially neutralized acid copolymers) is
Surlyn® ble from E. l. du Pont de Nemours and Company (Wilmington,
Delaware).
Examples of styrenic copolymers are as described above.
Examples of pressure sensitive adhesives (PSA) include but are not limited to
those compositions that comprise a base meric resin and a tackifier to enhance
the ability of the ve to instantly bond and to enhance the bond strength.
es of eiastomers used as the base resin in tackified multicomponent PSA
include but are not limited to natural rubber, polybutadiene, polyorganosiioxanes,
styrene-butadiene rubber, carboyxlated e-butadiene , poiyisobutylene, butyl
rubber, halogenated butyl rubber, block polymers based on styrene with isoprene,
butadiene, ethylene-propylene or ethylene-butylene, or combinations of such
elastomers. (See Yorkgitis, “Adhesive Compounds," Encyclopedia of Polymer Science
and logy, Third Edition, 2003, Volume 1, pp. 256-290 (John Wiley & Sons, inc,
Hoboken, New Jersey), which is incorporated in its entirety in this application by this
reference.) A non-limiting specific example of a PSA is an ve comprising a block
'10 copolymer of styrene and elastomer having a density of 0.96 g/cm3 and available as
M3156 from Bostik Findley, Inc. (Wauwatosa, Wisconsin).
Examples of polypropylene copolymers include but are not limited to propylene,
ethyiene and/or butene copolymers. A miting specific e of such
copolymers is VersifyT'V' Plastomers and Elastomers us grades) available from The
'15 Dow Chemical Company nd, Michigan).
Inner layer 76 may comprise a blend of any of the above materials. As a non-
iimiting example, this blend may be a blend of copolymers of ethylene and an ester and
copolymers of ethylene and at least one alpha olefin. As a further non-limiting example,
this blend may be a blend of EVA and LLDPE. As an even further non—limiting example,
this blend may be a biend of EscoreneTM Ultra LD 768.MJ and ExxonMobilTM LLDPE
LL1001.32.
inner layer 76 may also comprise processing aids. es of processing aids
include but are not limited to antiblock additives, such as t® 10853 ble
from Ampacet Corporation (Tarrytown, New York).
Returning to as described above, first multilayer film 72 of first packaging
sheet 70 also comprises first barrier component 78. In this embodiment, first barrier
component 78 comprises a single layer, which may be a barrier layer comprising high
y hylene (HDPE), low density polyethylene (LDPE), copolymer of ethylene
and at least one alpha olefin, or blends of such.
LDPE and copblymer of ethylene and at least one alpha olefin is each described
above; HDPE-is also described above. HDPE may be further described as a
semicrystalline polymer. It may be a lymer when the density is 3 0.960 g/cm3
and a copolymer when the density is below this value. HDPE is available in a wide
range of molecular weights as determined by either melt index (Ml) or HLMl load
melt . (See Carter, “Polyethylene, High-Density," The Wiley opedia of
Packaging Technology, Second Edition, 1997, pp. 745-748 (John Wiley & Sons, inc,
New York, New York), which is incorporated in its entirety in this application by this
reference.) Specific non—limiting examples of HDPE include Alathon® M6020 available
from Equistar als LP (Houston, Texas); Alathon® L5885 available from Equistar
Chemicals LP (Houston, Texas); ExxonMobilTM HDPE HD 7925.30 available from
ExxonMobil Chemical Company (Houston, Texas); Exxonil/lobilTM HDPE HD 7845.30
available from ExxonMobil Chemical Company (Houston, Texas); and Surpass®
HPs167—AB available from Nova Chemicals Corporation (Calgary, Alberta, Canada
First barrier component 78 may also comprise tie material. As described above,
tie material includes but is not limited to glycidyl methacrylate—modified copolymers of
ethylene (e.g., epoxy-functional tie materials), anhydride-modified (such as maleic
anhydride modified) copolymers of ethylene, copolymers of ethylene and a carboxylic
acid (such as an acrylic acid), copolymers of ethylene and an ester (such as an
acrylate), and blends of such. Specific non-limiting examples of tie material inciude
Lotader® AX 8900 available from Arkema Inc. (Philadelphia, Pennsylvania); GT4157
availabte from Westlake Chemical Corporation (Houston, Texas); DuPontTM Bynel®
41 E710 available from El du Pont de s and Company, Inc. (Wilmington,
re); T'V' Bynel® 41 E687 available from El du Pont de Nemours and
Company, Inc. (Wilmington, Delaware); Plexar® PX 3084 available from Equistar
Chemicals LP (Houston, Texas); M A available from Mitsui als
America, Inc. (Rye Brook, New York); DuPontTM Bynel® 40E529 available from El. du
Pont de Nemours and Company, lnc. (Wilmington, Delaware); DuPontTM Bynel® 4164
available from El du Pont de Nemours and Company, Inc. (Wilmington, Delaware);
Plexar® PX 3080 available from ar Chemicals LP on, Texas); and
r® 2210 available from Arkema Inc. (Philadelphia, Pennsylvania).
First barrier component 78 may also comprise a nucleating agent, a hydrocarbon
resin or blends of such.
In embodiments of the present ation in which the barrier component
comprises HDPE blended with nucleating agent, the HDPE may have a medium
molecular weight, a melt index within the range of about 0.5 to about 50 dg/min, a
density greater than or equal to about 0.941 g/cm3, a iong chain branching index or less
_30-
than or equal to about 0.5 and a melt flow ratio less than or equal to about 65. (See US
Patent Apptication 2007/0036960, published February 15, 2007, which is incorporated
in its entirety in this application by this nce.)
A nucleating agent may comprise any of those nucleating agents disclosed in US
Patent 556, issued November 29, 2005, which is incorporated in its ty in this
application by this reference. More specifically, as a non-limiting example, the
nucleating agent may comprise glycerol alkoxide Salts, hexahydrophthalic acid salts,
similar salts or mixtures of such salts, as disclosed in US Patent Application
2008/0227900, hed September 18, 2008, and in US Patent Application
2007/0036960, published February 15, 2007, both are which are incorporated in their
entireties in this application by this reference. Such salts include ammonium and metal
salts, including but not limited to zinc, magnesium, calcium and mixtures of such metals.
An example of a zinc olate nucleating agent is lrgastab® 287 available from Ciba
Specialty Chemicals Holding. inc. (Basel, Switzerland). An example of a calcium
hexahydrophthalate is Hyperform® HPN-ZOE available from Millikan & Company
(Spartanburg, South na). Calcium hexahydrophthalate is also available d
with LDPE as Polybatch® CLR122 available from A. Schulman Inc. , Ohio). The
nucleating agent may be included in barrier component layer (or layers) in an amount
from about 0.001% to about 1% by weight (of the layer), from about 0.002% to about
0.2% by weight, from about 0.02% to about 0.12% by weight, or from about 0.04% to
about 0.10%.
A arbon resin may comprise any of those hydrocarbon resins disclosed in
US Patent 6,432,496, issued August 13, 2002, or in US Patent Application
2008/0286547, published November 20, 2008, both of which are incorporated in their
entireties in this ation by this nce. More specifically, as a non-limiting
e, the hydrocarbon resin may include petroleum resins, terpene resins, styrene
resins, cyclopentadiene , saturated alicyclic resins or mixtures of such resins.
Additionaily, as a non-limiting e, the hydrocarbon resin may comprise
hydrocarbon resin derived from the polymerization of olefin feeds rich in
dicyclopentadiene (DCPD), from the polymerization of olefin feeds produced in the
petroleum cracking process (such as crude Cg feed streams), from the polymerization of
pure monomers (such as styrene, d-methylstyrene, 4-methylstyrene, vinyltoluene or
combination of these or similar pure monomer feedstocks), from the polymerization
terpene olefins (such as d-pinene, B—pinene or d-limonene) or from a combination of
such. The hydrocarbon resin may be fully or partially hydrogenated. Specific examples
of hydrocarbon resins include but are not limited to Plastolyn® R1140 arbon
Resin available from n Chemical Company (Kingsport, Tennessee),
Regalite®
T1140 available from Eastman Chemical y (Kingsport, Tennessee),
Arkon® P-
140 available from Arakawa Chemical industries, Limited (Osaka, Japan) and
Piccoiyte® S135 Polyterpene Resins available from Hercules Incorporated (Wilmington,
Delaware). The hydrocarbon resin may be included in barrier component layer (or
layers) in an amount from about 5% to about 30% by weight (of the layer), from about 5
to about 20 % by weight, from about 10% to about 20% by weight,
or from about 10% to
about 15% by weight.
is a diagrammatic sectiona| view of a second embodiment of the
chlorine-free packaging sheet bed in the present ation. Second
packaging
sheet 80 comprises first rigid component 61, second multilayer fiim 82 and second rigid
component 63. First rigid component 61 and second rigid component 63 are as
described above.
Second multilayer film 82 ses outer layer 74, second barrier component 88
and inner layer 76. in second multilayer film 82 is shown as a seven-layer
palindromic film, resulting from a blown, coextruded four-layer r extrudate that is
collapsed and flattened upon itself to form two inner tubular extrudate layers 50 (see
and that is thermally laminated to itself at the two inner tubular extrudate layers
50 to form one inner layer 76. Outer layer 74 and inner layer 76 are as described
above.
Second barrier component 88 comprises two layers: first barrier layer 83 and
second r layer 84. First barrier layer 83 and second barrier layer 84 may each
comprise HDPE, LDPE, copolymer of ethylene and at least one alpha olefin, or blends
of such; each of these materials is as described above. First barrier layer 83 may also
comprise tie material; this tie material is as described above. Furthermore, first barrier
iayer 83 may also comprise nucleating agent, arbon resin or blends of such; each
of these materials is as described above.
is a diagrammatic cross-sectional view of a third embodiment of the
chlorine-free packaging sheet described in the present application. Third packaging
sheet 90 ses first rigid component 61, third multilayer film 92 and second rigid
component 63. First rigid component 61 and second rigid ent 63 are as
described above.
Third ayer film 92 comprises outer layer 74, third barrier component 98 and
inner layer 76. in FlG. 4, third multilayer film 92 is shown as a thirteen-layer palindromic
film, resulting from a blown, coextruded seven-layer tubular extrudate that is sed
and flattened upon itself to form two inner tubular extrudate layers 50 (see FtG. 6) and
that is thermally laminated to itself at the two inner tubular extrudate layers 50 to form
one inner layer 76. Outer layer 74 and inner layer 76 are as described above.
Third barrier component 98 comprises five layers: first barrier ent layer
93, first intermediate iayer 94, oxygen barrier layer 95, second intermediate iayer 96
and moisture barrier layer 97.
In one ment of third packaging sheet 90, first r component layer 93
and at least one alpha olefin, or
may comprise HDPE, LDPE, copolymer of ethylene
blends of such; each of these als is as described above. First barrier component
layer 93 may also comprise tie material; this tie material is as described above.
rmore, first barrier component layer 93 may also comprise nucleating agent,
hydrocarbon resin or blends of such; each of these materials is as described above. As
such, in one embodiment of third packaging sheet 90, first r component layer 93
and nucleating agent.
may comprise a blend of HDPE, tie material
In another embodiment of third packaging sheet 90, first barrier component layer
93 may comprise a copolymer of ethylene and an ester. Copolymers of ethylene and
of a
an ester are as described above. As described above, a non-limiting example
copolymer of ethylene and an ester is EVA. As described above, one non-limiting
example of EVA is EscoreneT'V' Ultra LD 705.MJ available from Exxoanlobii Chemical
Company (Houston, Texas).
First ediate layer 94 may se tie material or polyamide, Tie material
is as described above. Polyamide (which is further described above) may be ed
.for clarity, thermoformability, high strength and toughness over a broad ature
range, chemical ance and/or barrier properties. (See “Nylon,” The Wiley
Encyclopedia of ing Technology, Second Edition, 1997, pp. 681-686 (John Wiley
& Sons, Inc., New York, New York), which is incorporated in its ty in this
application by this reference.) Specific, miting examples of polyamide include
UBE Nylon 5033 8 available from UBE Engineering Plastics, S.A. (Castellén, Spain);
Ultramid® C40 L 01 available from BASF Corporation (Florham Park, New Jersey);
Ultramid® C33 01 available from BASF Corporation (Florham Park, New Jersey); and a
blend of 85% by weight (of the blend) of Ultramid® BB6 available from BASF
Corporation (Florham Park, New Jersey) and 15% by weight ofDuPontTM Selar®
PA3426 ble from El. du Pont de Nemours and Company, Inc. (Wilmington,
Delaware).
Oxygen barrier layer 95 may comprise any chlorine-free oxygen barrier al.
ln the embodiment of third packaging sheet 90 comprising third multilayer film 98, the
barrier material is split (i.e., in non-adjacent layers) as a result of the seven-layer tubular
extrudate being collapsed and flattened upon itself to form two inner tubular extrudate
layers and thermally laminated to itself at the two inner tubular extrudate layers.
Examples of chlorine—free barrier materials include but are not limited to EVOH,
polyamide, polyglycolic acid and acrylonitrile-methyl acrylate copolymer.
EVOH is as described above. Specific non—limiting examples of EVOH include
EVALTM H171 available from EVAL Company of America (Houston, Texas); Evasin EV-
3801V available from Chang Chun Petrochemical Co., Ltd. (Taipei, Taiwan); and
Soarnol® ET3803 available from Soarus L.L.C. (Arlington Heights, Illinois).
Polyamide is as described above. Specific non-limiting examples of polyamide
include Nylon MX06® (various grades) available from Mitsubishi Gas Chemical
Company, inc. (Tokyo, Japan); and a blend of 85% by weight (of the blend) of
Ultramid® B36 available from BASF ation (Florham Park, New Jersey) and 15%
by weight of DuPontTM Selar® PA3426 available from El. du Pont de Nemours and
Company, Inc. (Wilmington, Delaware).
ycolic acid (PGA) (or polyglycolide) is a biodegradable, thermoplastic
polymer and the simplest linear, aliphatic polyester. It offers high gas barrier to carbon
dioxide and , llable hydrolysis and excellent ical strength.
AcrylonitriIe—methyl acrylate copolymer imparts high barrier to gases (such as
oxygen), aromas and fragrances as well as chemical resistance and inertness. A
specific non-limiting example of acrylonitrile~methyl acrylate mer is Barex®
(various grades) available from Ineos Olefins & Polymers USA e City, Texas).
Second intermediate layer 96 may comprise tie material or polyamide. Tie
material and polyamide are each as described above.
Moisture r layer 97 may comprise HDPE, LDPE, copolymer of ethylene and
at least one alpha olefin, or blends of such; each of these materials is as described
above. Moisture barrier layer 97 may also comprise tie material; this tie material is as
described above. Furthermore, moisture barrier layer 97 may also comprise ting
agent, hydrocarbon resin or biends of such; each of these materials is as described
above. As such, in one embodiment of third packaging sheet 90, moisture barrier layer
97 may se a blend of HDPE and nucleating agent. In another embodiment of
third packaging sheet 90, moisture barrier layer 97 may se a blend of HDPE, tie
material and nucleating agent.
in an alternate ment, a non-oriented film comprises at least one moisture
barrier layer comprising a blend. The blend comprises high y polyethylene,
hydrocarbon resin and nucleating agent.
The blend comprises from about 69 °/o by weight to about 90 % by weight high
density polyethylene or from about 72 % by weight to about 88 % by weight high density
polyethylene or from about 75 % by weight to about 85 % by weight high density
polyethylene. it is important that the high density polyethylene has a melt index of at
least 1.0 g/10 min and a density greater than 0.958 g/cc. High density polyethylenes
which do not y these requirements afford poor results. An example of a high
density polyethylene which has a melt index of at least 1.0 g/10 min and a density
greater than 0.958 g/cc is Alathon® M6020 (Equistar Chemicals, LP, Houston, Texas).
Other high density polyethylenes such as Alathon® L5485 (Lyondell Chemical
Company, Houston, Texas), ExxonMobilTM HDPE HD 7845.30 (ExxonMobil Chemical
Company, Houston, Texas) and n® L5885 (Lyondell Chemical Company,
Houston, Texas) do not have the required density and/or melt index and are not
preferred for the blend of the moisture barrier layer of the non-oriented film of the
t application.
The blend further comprises a hydrocarbon resin as described above. The blend
comprises from about 5 % by weight to about 30 % by weight hydrocarbon resin or from
about 5 % by weight to about 20 % by weight hydrocarbon resin or from about 10 % by
weight to about 20 % by weight hydrocarbon resin or from about 10 % by weight to
about 15 % by weight hydrocarbon resin.
The blend of the non-oriented film further comprises a nucleating agent as
described above. The blend comprises from about 0.01 % by weight to about 1 % by
weight nucleating agent or from about 0.04 % by weight to about 0.10 % by weight
nucleating agent. The nucleating agent may be a glycerol alkoxide salt, a
hexahydrophthalic acid salt, zinc glycerolate salts or calcium hexahydrophthalate.
The non-oriented film may, in some aspects, se an oxygen barrier material
as described above. When the non-oriented fiim comprises an oxygen barrier material,
the film has a normalized oxygen transmission rate of less than about 150 /100
y or less than about 100 cc—mil/100 in2/day.
The non-oriented film may have a thickness of less than 3.00 mil, preferably less
than 1.70 mil.
Referring to non~oriented film 100 may be a three-layer film comprising a
re barrier layer but not necessarily the first rigid component nor the second rigid
component as described above. The moisture barrier layer comprises a blend
comprising a high density polyethylene, n the high y polyethylene has a
melt index of at least 1.0 g/10 min and a density greater than 0.958 g/cm3, a
hydrocarbon resin and a nucleating agent.
With reference to a generic non-oriented film may comprise the moisture
barrier layer in any of the three layers 101, 102 or 103 of the multilayer film. For
example, the moisture barrier layer may be middle layer 102 or, alternatively, outer layer
101 or inner layer 103. The non-oriented film may be a three-layer, four-layer, five-
layer, layer, nine~layer, thirteen-layer or any other ayer film (i.e., film having
two or more layers), provided that the non-oriented film has a normalized moisture
vapor transmission rate of no greater than 0.30 g-mil/100 in2/day measured at about
100 °F and 90 % external relative humidity (as further defined and described in the
EXAMPLES below). Embodiments of a non-oriented film comprising afive—layer film, a
nine-layer film and a thirteen-layer film are shown in FIGS. 8, 9 and 10, respectively.
The non-oriented film may be a blown, coextruded film.
The non-oriented film may comprise layers other than the re barrier layer.
For example, the film may se at least one layer comprising an ionomer, at least
one layer comprising a high density polyethylene, at least one layer comprising a
copolymer of ethylene and an ester, at least one layer comprising an ethylene vinyl
acetate copolymer (EVA), at least one layer comprising a styrene butadiene copolymer,
or combinations of the above. In some aspects, the film comprises a layer comprising
high density polyethylene in addition to the moisture barrier layer. In other aspects, the
film comprises the moisture barrier layer and a t layer coated with PET.
is a diagrammatic cross-sectional View of a second alternate embodiment
of non-oriented film 110, as described in the present application. Any of the five layers
111, 112, 113, 114, and 115 may comprise the moisture barrier layer comprising a
HDPE, a hydrocarbon resin and nucleating agent. in some aspects, more than one
layer may comprise the moisture barrier layer. For example, layers 115 and 113 may
comprise the barrier layer. One e of a five-layer film is layer 115 as a 0.8 mil
thick layer with a blend of HPDE, nucleating agent and arbon resin, layer 114 as
a 0.8 mil thick layer with a blend of LLDPE, LDPE and nucleating agent, layer 113 as a
0.2 mil thick layer with a blend of HDPE, nucleating agent and arbon resin, layer
112 as a 0.1 mil thick layer with a blend of EVA and polybutylene and layer 111 as a 0.1
mil thick layer with EVA.
is a diagrammatic cross-sectional view of a third alternate embodiment of
the non-oriented film described in the present application. The multilayer film 120 is
shown as a nine-layer palindromic film, resulting from a blown, coextruded five—layer
tubular extrudate that is collapsed and flattened upon itself to form two inner tubular
extrudate layers 50 (see and that is thermally laminated to itself at the two inner
tubular extrudate layers 50 to form one inner layer 125.
FIG 10 is a mmatic cross~sectional view of a fourth alternate embodiment
of the iented film bed in the present application. The multilayer film 130 is
shown as a thirteen—layer palindromic film, resulting from a blown, coextruded seven-
layer tubular extrudate that is collapsed and flattened upon itself to form two inner
tubular extrudate layers 50 (see and that is thermally laminated to itself at the
two inner tubular extrudate layers 50 to form one inner layer 137. The multilayer film
comprises at least one moisture barrier layer and may ally comprise more than
one moisture barrier layer. As described above, the moisture barrier layer comprises
HDPE, hydrocarbon resin and nucleating agent. In some aspects, moisture barrier
layers comprising a HDPE, a hydrocarbon resin and a nucleating agent may be used for
layers 132, 134, and 136. In other aspects, a moisture barrier layer comprising a
HDPE, a hydrocarbon resin and a nucleating agent may be used for layer 136.
Generic ing sheet 60, as embodied in first ing sheet 70, second
packaging sheet 80, third packaging sheet 90 or ise, and the non-oriented film,
as embodied in film 100, 110, 120, 130 or otherwise, may be included in a package for
a product. In one embodiment, the package comprising the chlorine-free ing
sheet or non-oriented film described in this application may be a thermoformed package
ing from the packaging sheet or iented film having been thermoformed.
A description of “thermoformed” is provided above. rmore, thermoforming
and other similar techniques are well known in the art for packaging. (See Throne,
“Thermoforming,” Encyclopedia of Polymer e and Technology, Third Edition,
2003, Volume 8, pp. 222-251 (John Wiley & Sons, Inc., Hoboken, New Jersey), which is
incorporated in its entirety in this ation by this reference; see also InNin,
“Thermoforming,” Modern Plastics Encyclopedia, 19844985, pp. 329-336 (McGraw—Hill,
inc., New York, New York), which is incorporated in its entirety in this application by this
reference; see also “Thermoforming,” The Wiley Encyclopedia of Packaging
Technology, Second Edition, 1997, pp. 1 (John Wiley & Sons, Inc., New York,
New York), which is incorporated in its entirety in this application by this reference.)
Suitable thermoforming methods include standard, deep-draw or plug-assist vacuum
forming. During rd vacuum forming, a thermoplastic web, such as a film or sheet,
is heated and a vacuum is applied beneath the web allowing atmospheric pressure to
force the web into a preformed mold. When relatively deep molds are employed, the
process is referred to as a "deep-draw" ation. In a plug—assist vacuum forming
method, after the thermoplastic web has been heated and sealed across a mold cavity,
a plug shape similar to the mold shape impinges on the thermoplastic web and, upon
the appiication of vacuum, the thermoplastic web conforms to the mold surface.
The thermoformed package comprising the chlorine-free packaging sheet or non-
oriented film described in the present ation may be a cup, a tub, a bucket, a tray
or a myriad of other items. Furthermore, the product contained in the thermoformed
e may be a food, od, medical and/or industrial product. Examples of such
products include but are not limited to syrups ding but not limited to breakfast
syrup, cough syrup, etc), creams, cheeses, condiments (including but not limited to
salad dressings, jellies, jams, ketchup, etc.), personal care items (including but not
limited to shampoos, hand creams, ashes, toothpastes, antacids, etc),
medications, liquid detergents, oils, pates, pet foods, glues, ges (including
alcoholic and non-alcoholic) and confections (including but not d to hard ,
fudge, toffee, licorice, chocolate, jelly candies, marshmallow, marzipan, divinity, pastry,
chewing gum, ice cream, etc).
Generic ing sheet 60, as embodied in first packaging sheet 70, second
packaging sheet 80, third packaging sheet 90 or othen/vise, and iented film, as
embodied in films 100, 110, 120, 130 or otherwise, may manufactured by various
methods. In general, the methods comprise the sequential steps of (a) adding
thermoplastic resins to extruders to extrude the various layers of the sheet or film, such
as, for example, an outer layer of an n—layer multilayer barrier film, an intermediate layer
(which may be but not necessarily is a barrier component of the multilayer barrier film)
and an inner layer of the multilayer barrier film, such that the intermediate layer is
positioned between the outer layer and the inner layer of the multilayer barrier film and
such that the multilayer barrier film has a first surface and an opposing second surface;
(b) heating the thermoplastic resins to form streams of melt-plastifiecl polymers; (0)
forcing the streams of melt-plastified polymers h a die having a central orifice to
form a tubular ate having a diameter and a hollow interior; (d) expanding the
diameter of the tubular extrudate by a volume of fluid (such as a volume of gas) entering
the hollow interior via the central orifice; (e) collapsing the tubular ate; (f)
flattening the tubular extrudate to form two inner tubular extrudate layers. In
embodiments of the generic packaging sheet 60, the method further comprises the
steps of (g) attaching a first rigid component to the first surface of the multilayer barrier
film; and (h) attaching a second rigid component to the opposing second surface of the
multilayer barrier film. It is to be understood that steps (g) and (h) are not ed for
the non—oriented film.
Referring again to the drawings, is a schematic representation of a blown
film process for producing a multilayer film included in the chlorine-free ing sheet
or non-oriented film described in the present application. ageousiy, this
multilayer blown film may be extruded, blown, cooled, collapsed, etc, using well known
and available equipment.
depicts a schematic view of a typical s 10 for steps (a) — (f) above.
' In the depicted process 10, first thermoplastic resin 11 for an outer layer of a multilayer
barrier film is placed in first hopper 12 of first extruder 13. The er 13 is heated to
an appropriate temperature above the melting point of the first thermoplastic resin 11
such that first thermoplastic resin 11 is heated to form streams of melt-plastified
polymers. Extruder 13 may also be provided with a jacketed chamber through which a
cooiing medium is circulating. The rotation of a screw within first extruder 13 forces
melt—plastified polymer h first connecting pipe 14 through coextrusion die 15.
Simultaneous with the introduction of the melt-plastified first thermoplastic resin
11 to coextrusion die 15, second thermoplastic resin 16 (which has been placed in
second hopper 17 of second extruder 18) is similarly heated to form streams of melt-
plastified rs and forced by second extruder 18 through second connecting pipe
19 through coextrusion die 15. Third thermoplastic resin 20 is similarly heated to form
streams of melt-plastified polymers and forced by third extruder 22 through third
connecting pipe 23 through usion die 15. In the embodiment of first packaging
sheet 70, three extruders are typically used to produce first multilayer film 72. In other
ments, additional extruders may be used. For example, four extruders are
typically used to produce second multilayer film 82; five extruders are typically used to
produce multilayer film 120 and seven extruders are typically used to produce third
multilayer film 92 or multilayer film 130. However, in the coextrusion art it is also known
that when the same thermoplastic resin is used in more than one layer of a multilayer
film, the melt-plastified resin from one extruder may be divided at the die and used for
multiple . In this way, a five-layer film may be made using three or four extruders.
The usion die 15 has an annular, preferably circular, opening and is
designed to bring together the first, second and third melt—plastified thermoplastic resins
such that the first, second and third melt-plastified thermoplastic resins are coextruded
out of the coextrusion die 15 as tubular extrudate 24. In the art, the term “tubular
ate" is synonymous with the terms “bubble” and “blown .” Coextrusion die
is equipped, as is known in the art, with a central orifice h which a fluid, such
as a volume of gas, is typically introduced to radially expand the er of tubular
extrudate 24 forming an expanded tubular extrudate 24 having an exterior surface 25
and interior surface 26. in a multilayer film, such as first multilayer film 72, outer layer
74 of first multilayer film 72 ponds to the outermost layer of tubular extrudate 24
and inner layer 76 of first ayer film 72 corresponds to the innermost layer of tubular
extrudate 24.
Tubular extrudate 24 may be externally cooled by cooling means such as air ring
27 which blows cooling air along lower outer surface 28 of tubular extrudate 24.
Simultaneously, internal surface 26 may be , such as by contact with refrigerated
air (at a temperature of, for example 5 °C — 15 °C) delivered through an internal bubble
cooling unit having perforated pipe 29. Perforated pipe 29 is concentrically disposed
around longer pipe 30 of narrower diameter. Longer pipe 30 is open at distal end 31 to
e and remove warmer air which has risen to upper end 32 of tubular extrudate 24.
The s of external and internal cooling fluids, such as air and/or water, constitute a
cooling zone serving to chill or set r ate 24 at the desired diameter.
Tubular extrudate 24 may be stabilized by external concentric cage 33 to help
maintain tubular extrudate 24 along a straight path to a collapsing frame or ladder
comprising a series of converging rolls 34. Concentric cage 33 may be particularly
useful to stabilize films made using an internal bubble cooling unit.
Tubular extrudate 24 is collapsed in converging rolls 34 and flattened by driven
nip rolls 35, which may also assist in collapsing tubular extrude 24. Driven nip rolls 35
function to pull and/or transport tubular extrudate 24 and also to collapse tubuiar
extrudate 24 to form flattened extrudate 26. However, other ort means and
collapsing means may be employed and are known in the art; these means e but
are not limited to such apparatus as collapsing ladders and drive belts.
Referring now to a cross-sectional view of tubular extrudate 24, made
according to the process of is shown having or surface 25 and interior
surface 26. r extrudate 24 has three layers: inner tubular extrudate layer 50,
intermediate tubular extrudate layer 51 (which may be but not necessarily is a barrier
component extrudate layer) and outer tubular extrudate layer 52. Each extrudate layer
may comprise any number of layers. For example, as a barrier component extrudate
of layers,
layer, intermediate tubular extrudate layer 51 may se any number
including but not limited to one layer as in first barrier component 78 (see FlG. 2), two
third barrier
layers as in second barrier component 88 (see and five layers as in
component 98 (see .
As tubular extrudate 24 is collapsed and flattened by converging rolls 34
driven nip rolls 35 to form flattened extrudate 36, two inner tubular extrudate layers
laminate to
are formed. The two inner tubular extrudate layers 50 may thermally
themselves to form one inner layer, resulting in a palindromic multilayer film having a
first surface and a second surface. This is ed if the blown film equipment is
operated at a high enough output rate (as ined by a person of ordinary skill in
art without undue experimentation) so that the flattened extrudate 36 is of sufficient
ature for such thermal lamination. If flattened extrudate 36 is laminated to itself,
the resulting palindromic, ayer film is conveyed by rollers (not shown in to a
wind-up reel (not shown in FlG. 5) for r sing.
Alternatively, flattened extrudate 36 may be slit open into one or more sheets
which may be wound on paperboard or plastic cores for subsequent dispensing or use.
slitter
in the embodiment depicted in FlG. 5, flattened extrudate 36 is ed through
37 where the flattened extrudate is slit by knives to form a first multilayer film 38 and a
second multilayer film 39. First ayer film 38 is conveyed by first rollers 40 to first
wind-up reel 41 for further processing, and second multilayer film 39 is conveyed by
second rollers 42 to second wind—up reel 43 for further processing.
In producing a multilayer film included in the chlorine-free packaging sheet or
non—oriented film described in the present application, it will be appreciated by those
skilled in the art that such parameters as the usion die diameter, nip roll speed,
amount and temperature of fluid (e.g., air) uced and captured between the
coextrusion die and nip rolls, flow rate of the tubular extrudate from the coextrusion die,
melt temperatures, type of cooling medium (e.g. water or air), and internal and external
tubular ate cooling temperatures may all be adjusted to optimize process
conditions. For example, the circumference or lay-flat width of the r ate
die diameter by
may be increased to varying degrees above that of the usion
modification of one or more of the above parameters. Similarly, the tubular extrudate
and
may be conditioned or d, such as by internal and/or external application
ion of the types, amounts and characteristics of als (including gaseous or
liquid fluids contacting the tubular extrudate) as well as by setting and changing such
parameters as pressures and atures. It will be understood in the art that such
parameters may vary and will depend upon practical considerations, such as the
particular thermoplastic resins comprising the tubular extrudate, the presence or
absence of modifying agents, the equipment used, desired rates of production, desired
tubular extrudate size (including diameter and thickness), and the quality and desired
performance characteristics of the tubular extrudate. These and other process
parameters are expected to be set by one skilled in the art without undue
experimentation. Also, n non-uniformities in processing, including but not d
to variation in film thickness, unequal heating or cooling of the tubular extrudate and
iform air flows, may be obviated by rotation with or without oscillation, either
alone or in combination, of the usion die, the air ring or other apparatus with
respect to the vertical axis of the tubular extrudate. It should also be understood that
while manufacture of the tubular extrudate has been described above with respect to a
coextrusion process which used vertical upward transport of the tubular extrudate and
expanded tubular extrudate, those skilled in the art may extrude and expand the tubular
extrudate in other directions ing vertically downward.
After the multilayer film included in the chlorine-free packaging sheet is
produced, a first rigid ent is attached to a first surface of the film. A second rigid
component is then attached to the opposing second e. The first rigid component
and the second rigid component may be attached by various methods as known in the
art. These methods include but are not limited to thermal tion, adhesive
lamination (including solvent or solvent-less lamination), extrusion iamination and
extrusion coating. As described above, the parameters for such lamination or coating
are expected to be set by one skiiled in the art without undue experimentation.
Examples 1—8 are chiorine-free packaging sheets exemplifying the present
invention. Each of these packaging sheets is produced, generally, as foliows: A
multilayer, blown, coextruded film is produced and thermally ted to itself at the
inner layers, then a first rigid ent is extrusion coated on a first surface of‘the
blown film and then a second rigid component is extrusion coated on the ng
second surface of the blown film.
Comparative Examples are also produced and/or were ed. ative
Examples 1, 5 and 6 are ed, generally, as follows: A multilayer, blown,
coextruded film is produced and then a first rigid component is extrusion coated on a
first surface of the blown film. Comparative Examples 2, 3 and 4 were obtained and are
further described below.
More specifically, in producing the blown films of Examples 1-8 and Comparative
Examples 1, 5 and 6, various materials are first added to the extruders of a blown film
line to produce a seven—layer blown, coextruded film. The seven-layer blown,
coextruded films of Examples 1-8 have the compositions (by approximate weight
percent) shown in TABLE 1 and TABLE 2; and the seven—layer blown, coextruded films
on Comparative Examples 1, 5 and 6 have the compositions (by approximate weight
percent) shown in TABLE 3.
TABLE 1
; Exam les 2-5
Weight % Component Weight % Weight % Component Weight %
of Film of Layer of Film of Layer
First 1390— 98.50 9‘50
(or ") processing aid 1.50
corocessin aid
12.60 EVA 1 100.00 24.00 HDPE 78.0
(or "First Barrier Tie Resin 2 20.0
Component") LDPE/Nucleating No000
Agent Blend
Third 7.60 Tie Resin 1 100.00 7.60 Tie Resin 2 —L o .0oo
(or "First
lntermedate"
100.00
(or "Oxygen
Barrier"
Fifth 7.60 Tie Resin 1 100.00 7.60 Tie Resin 2 100.00
(or "Second
Intermediate"
Sixth 31.50 HDPE 98.00 29.00 HDPE 98.0
(or "Moisture LDPE/Nucleating 2.00 LDPE/Nucleating Nooo
Barrier") Agent Blend Agent Blend
Seventh 14.00 EVA 2 45.70 9.50 EVA 2 45.70
(or "inner") LLDPE 54.30 LLDPE 54.30
-50_
TABLE 2
Exam oles 7—8
Weight A) Component Weight A: Weight% Component Weight%
of Film of Layer of Film of Layer
First 12.90 SB 100.00 14.90 88 98.50
(or "Outer") processing aid
Second 21.10—— 13.70 EVA 1 100.00
(or "First Barrier
Component") ucleating 2.00
Agent Blend
Third 6.80 Polyamide 100.00 7.60 Tie Resin 1 100.00
(or "First Copolym er
Intermedate"
(or "Oxygen
Barrier"
Fifth 6.80 Polyamide 100.00 7.60 Tie Resin 1 100.00
(or "Second m er
Intermediate"
Sixth 17.00 28.50 HDPE
(or "Moisture LDPE/Nucleating 2.00
Barrier") LDPE/Nucleating 2.00 Agent Blend
Agent Blend
Seventh 15.00 EVA 1 100.00
(or "lnner")
TABLE 3
Weight A: Component Werght% Weight% ent Weight % Weight% Component Weight%
of Film of Layer of Film of Layer of Film of Layer
First 11.50—_11.40_—11.50——
(or "Outer'l
Hrocessin aid
100.00
Second 14 20 DPE 79.0 23.20__13.2oTie Resin 4
(or "First ie Resin 3 20.0 LDPEINucleating 2.00
Barrier LDPE/Nucleating 1 00. Agent Blend
Component") Agent Blend
Third
100.00
' 7.00 Polyamide 100.00 Tie Resin 1 100.00 7.00 Polyamide
(or "First Copoiym er Copoiymer
lntermedate"
Fourth 22.00 EVOH 100.00 21.80 EVOH 100.00 25.10 EVOH 100.00
(or "Oxygen
Barrier"
100.00
Fifth 7.00 ide 100.00 Tie Resin 1 100.00 7.00 Poiyamide
(or "Second Copoiymer mer
Intermediate"
Sixth 13.5O 79.0 24.00 11.50 Tie Resin 4 100.00
(or "Moisture Tie Resin 3 20.0 LDPE/Nucleating 2.00
Barrier“) 'LDPE/Nucleating _\ ODOO. Agent Blend
Agent Blend
Seventh 24.80 HDPE 97.00 5.80 Polypropylene 100.00 24.70 HDPE
(or "lnner") processing aid OC) Copolymer Hydrocarbon
Resin
LDPE/Nucleating 1.00 LDPE/Nucleating 1 .00
Agent Blend Agent Blend
As noted in TABLE 1, the blown films included in the chlorine-free ing
sheets of Examples 2-5 are identical; and, as noted in TABLE 2, the blown films
included in the chlorine-free packaging sheets of Example 7—8 are cal.
The materials included in the various blown films are as follows:
EVA 1 has a reported vinyl acetate content of about 12.8% by weight (of total
EVA composition), a reported melt index of about 0.4 g/10 min, a ed density of
about 0.934 g/cm3 and a reported peak melting temperature of about 94°C and is
commercially available as EscoreneTM Ultra LD 705.MJ from ExxonMobil Chemical
Company (Houston, Texas).
EVA 2 has a reported vinyl acetate content of about 26.2% by weight (of total
EVA composition), a ed melt index of about 2.3 g/10 min, a reported y of
about 0.951 g/cm3 and a reported peak melting temperature of about 74°C and is
commercially available as neTM Ultra LD 768.MJ from ExxonMobil Chemical
Company (Houston, Texas).
EVOH has a reported ethylene content of about 38 mole percent, a reported
density of about 1.17 g/cm3 and a reported melting point of about 173°C and is
commerciaity available as l® ET3803 from Soarus L.L.C. (Arlington s,
Illinois).
HDPE has a reported melt index of about 2.0 g/10 min and a reported density of
about 0.960 g/cm3 and is commercially available as Alathon® M6020 from Equistar
Chemicals LP (Houston, Texas).
_15 Hydrocarbon Resin is an amorphous, lecular-weight hydrocarbon resin
derived from aromatic petrochemical feedstocks, has a reported ring and ball softening
point of about 140°C and a reported density of about 0.98 g/cm3 and is commercially
available as Plastoiyn® R1140 Hydrocarbon Resin from Eastman al Company
(Kingsport, Tennessee).
LDPE/Nucleating Agent Blend is a ying agent masterbatch having a
reported specific gravity of about 0.93 and is commercially available as Polybatch®
CLR122 from A. Schulman Inc. (Akron, Ohio).
0.918
LLDPE comprises butene LLDPE resin, has a reported density of about
g/cm3, a reported melt index of about 1.0 g/10 min, a reported peak g ature
and is commercially
of about 121°C and a reported crystallization point of about 106°C
available as ExxonMobil LLDPE LL1001.32 from ExxonMobil Chemical Company
(Houston, Texas).
of about
Polyamlde Copolymer comprises nylon 6/6,6, has a reported density
1.129/cm3 and a reported melting point of about 193°C and is commercially available as
Ultramid® C40 L 01 from BASF ation (Florham Park, New Jersey).
flow of
opylene Copolymer is an impact copolymer, has a reported melt
and a reported melting
about 0.75 9/10 min, a reported density of about 0.905 g/cm3
point range of about 160°C-165°C and is commercially available as Propylene 4170
from Total Petrochemicals USA, inc. (Houston, Texas).
and e
Processing aids used vary depending on the equipment used
Such aids are
antibiock , slip agents, stabilizing agents and release agents.
t undue
known to a person of ordinary skill in the art and may be ined
experimentation.
melt flow rate
SB has a reported specific gravity of about 1.02 g/cm3, a reported
of about 61°C
(200°C/5.0 kg) of about 10.0 g/10 min and a reported vicat softening point
from
and is commercially available as DK13 K-Resin® Styrene Butadiene Copolymers
Chevron Phillips Chemical Company LP (The Woodlands, Texas).
Tie Resin 1 comprises ide-modified LLDPE resin, has a reported density
of about 1.7 g/10 min, a
of about 0.91 g/cm3, a reported melt flow rate (190°C/2.16 kg)
of about 84°C
reported melting point of about 119°C and a reported vicat softening point
and is commercially available as DuPontTM Bynel® 41 E687 from El. du Pont de
Nemours and Company, lnc. (Wilmington, Delaware).
Tie Resin 2 comprises ide-modified LLDPE resin, has a reported density
of about 0.93 g/cm3, a reported melt flow rate (190°C/2.16 kg) of about 1.2 g/10 min, a
reported melting point of about 127°C and a reported vicat softening point of about
110°C and is commercially available as DuPontTM Bynel® 4164 from El. du Pont de
Nemours and Company, lnc. (Wilmington, Delaware).
Tie Resin 3 comprises anhydride-modified LLDPE resin, has a reported density
of about 0.91 g/cm3, a reported melt flow rate (190°C/2.16 kg) of about 2.7 g/10 min, a
IO reported melting point of about 115°C and a reported vicat softening point of about
103°C and is commercially available as DuPontTM Bynel® 41 E710 from El. du Pont de
Nemours and Company, Inc. (Wilmington, Delaware).
Tie Resin 4 comprises maleic anhydride-modified LLDPE resin, has a reported
melt index of about 1.0 g/10 min and a reported density of about 0.9200 g/cm3 and is
commercially available as GT4157 from ke Chemical Corporation (Houston,
Texas).
In making the blown films of Examples 1-8 and Comparative Examples 1, 5 and
6, one extruder is used for each layer. If a layer comprises more than one thermoplastic
resin (as in, for example, the first, sixth and seventh layers of Example 1), the resins for
that tayer are pre-blended prior to being added to the er. The layer ents
are then heated to form streams of melt-plastified rs and extruded h a die.
The coextruded plastified, extruded components then form a tubular ate (or
bubble). The outer layer of the blown film is the outermost layer of the tubular
extrudate; the inner layer of the blown film is the innermost layer of the tubular
extrudate. The diameter of the tubular extrudate is expanded by air entering the
extrudate at the die. The approximate die diameter, lay-flat width of the expanded
tubular ate and blow-up ratio (i.e., the ratio of the diameter of the expanded
tubular extrudate to the er of the die) used to produce the blown films of
Examples 1-8 and Comparative Examples 1, 5 and 6 are shown in TABLE 4.
TABLE4
—l-lll—inches inches
-—--__—
The expanded tubular extrudate is then collapsed by a collapsing frame and flattened
through nip rolls. in the collapsing and flattening, two inner tubular ate layers are
formed.
For Examples 1-8. the blown film ent is ed at a high enough output
rate (as determined by a person of ordinary skill in the art without undue
experimentation) so that the collapsed, flattened r extrudate is of a sufficient
temperature to laminate to itself at the two inner tubular extrudate layers. In laminating
to themseives, the two inner r extrudate layers form one inner layer and a
palindromic thirteen-layer film results.
For Comparative Examples 1, 5 and 6, the collapsed, flattened tubular extrudate
is not laminated to itself at the two inner tubular extrudate layers. For these
comparative examptes, the tubular extrudate is slit into two seven-layer films.
For the thirteen-layer films of Examples 1-8, the first surface of each en-
layer film is then extrusion coated with a rigid component. After the first surface is
ion coated with a rigid component, the second surface is extrusion coated with a
rigid component. For the seven-layer films of Comparative Examples 1, 5 and 6 only
the first surface (i.e., the surface comprising EVA) is extrusion coated with a rigid
component. The rigid ents have the compositions (by approximate weight
percent) shown in TABLE 5.
_ Q U '
Second Rigid Component
HIPSi HlPSZ PPSi G 2 Color Processing HIP81 HIPSZ GPPS 1 GPPSZ Color Processing
Concentrate Aid Concentrate Aid
_-_—_--__----
_--_—---20.15%-_—
___--__----—
—--_—-----__
_------_--_—
_--__-_----—_
_--__—-75.45%---—_
—--—_--75.40%-21.50%-__
Comparative 76.00% 20.00% 2.80% 1.20% not applicable
Example 1
Comparative 76.00% 20.00% 2.80% 1.20% not applicable
Example 5
Comparative 97.20% 2.80% not applicable
Example 6
The cempositions shown in TABLE 5 may be achieved by a blend of s
layers comprising HIPS, GPPS, coior concentrate and processing aid. For example, for
e 2, each of the first rigid component and the second rigid component ses
three layers. The first iayer comprises 73.50% by weight (of the first layer) HtPS 1,
20.50% by weight GPPS 1, 4.00% by weight color concentrate and 2.00% by weight
processing aid; the second layer comprises 76.00% by weight (of the second layer)
HIPS 1, 20% by weight GPPS 1 and 4.00% by weight color concentrate; and the third
layer comprises 73.50% by weight (of the third layer) HIPS 1, 20.50% by weight GPPS
1, 4.00% by weight color concentrate and 2.00% by weight sing aid. Taken
together, these three layers result in a first rigid component and a second rigid
component each with the ition shown in TABLE 5.
As noted in TABLE 5, for Examples 1-8 the same rigid component is used for
each surface of the thirteen-layer film (i.e., for both the first rigid component and the
second rigid component). Also, the rigid component used for Example 2 is identical to
the rigid component used for Example 3, the rigid component used for Example 4 is
identical to the rigid component used for Example 5, and the rigid components used for
Exampies 2 and 3 are substantially similar to that used for Examples 4 and 5. As noted
by the “not applicabie," Comparative Examples 1, 5 and 6 have only a first rigid
component (i.e., are extrusion coated only on the surface comprising EVA).
The materials ed in the various rigid components are as follows:
Color concentrates are chosen based on the desired color of the chlorine-free
packaging sheet. Such concentrates are known to a person of ordinary skill in the art
and may be determined without undue mentation.
GPPS 1 is a crystal (i.e., genera! purpose) polystyrene, has a reported melt flow
/5 kg) of about 9.0 g/10 min, a ed vicat softening of about 101°C and a
reported density of about 1.04 g/cm3 and is commercialiy available as Crystal
Polystyrene 5258 from Total Petrochemicals USA, inc. (Houston, Texas).
GPPS 2 is a crystal (l.e., general purpose) polystyrene, has a reported melt flow
(200°C/5 kg) of about 9.09/10 min, a reported vicat softening of about 101°C and a
reported density of about 1.04 g/cm3 and is commercially available as Crystal
Polystyrene 5248 from Total Petrochemicals USA, Inc. (Houston, Texas).
HIPS 1 is a high impact polystyrene, has a reported melt flow (200°C/5 kg) of
about 3.0 g/10 min, a reported vicat softening of about 102°C and a reported density of
about 1.04 g/cm3 and is commercially available as Impact Polystyrene 8255 from Total
Petrochemicals USA, Inc. (Houston, Texas).
HIPS 2 is a super high impact polystyrene, has a reported melt flow (200°C/5 kg)
of about 3.5 g/10 min, a reported vicat softening of about 98°C and a ed density of
about 1.04 g/cm3 and is commercially available as Impact Polystyrene 945E from Total
Petrochemicals USA, Inc. on, Texas).
Processing aids vary depending on the equipment used and include antiblock
agents, slip , stabilizing agents and release agents. Such aids are known to a
person of ry skill in the art and may be determined without undue
experimentation.
As ned above, Comparative es 2, 3 and 4 were obtained.
Comparative Example 2 is a fully coextruded nine-layer sheet having the following
structure: HIPS / tie / HDPE ltie / EVOH ltie / HDPE / tie / HIPS. Comparative
Example 3 is a fully coextruded five-layer sheet having the following structure: HIPS /
HDPE / EVOH / HDPE / HIPS. And comparative Example 4 is a fully uded five-
layer sheet having the following structure: PPS / EVA/ PVdC / EVA/
HIPS+GPPS. (For these sheets, “l” is used to indicate the iayer boundary.) As futly
coextruded sheets, the rigid components (i.e., HIPS or HiPS+GPPS) are extruded with
the other layers and not coated on or laminated to a previously produced film (as in
Examples 1-8 and Comparative Examples 1, 5 and 6).
es 1-8 and ative Examples 1-6 were tested for various properties.
in measuring the various ties, the thicknesses of the overall sheet, of the blown
film, of the blown film’s barrier components and of the sheet’s rigid components may be
considered. These thicknesses, listed in mil, for each of the es and comparative
examples are shown in TABLE 6.
TABLE 6
Overall Biown Moisture Barrier First Rigid Second Rigid
(I) 3' CDet Film Com «onents Corn oonents Com orient Com . onent
Exam ale 1 3 5 not relevant 9.75 9.75
Exam ole 2 NNM (no:—l 3 5 1.65 9.75 9.75
Exam ole 3 3 5 not relevant 8.75 8.75
Exam ole 4 18.5 3.5 not relevant 7.5 ‘1 ()1
Exam ole 5 3 5 6.75 not relevant 6.75
Exam ole 6 |\)|’\?I\JI\J—‘k OVQUWUINI 4 not relevant 10.5 10.5
Examle 7 3 5 1.00 10.75 10.75
Exam ole 8 3 5 1.00 9.75 9.75
Comparative 4 not relevant not relevant 21 not applicable
Exam ole 1
Comparative 25 not applicable not relevant
Exam u le 2
Comparative 25 8.00 m 01
ExamoleS
Comparative 25 1.30 A. N 10.5
Exam . Ie 4
Comparative 25 4 -0.70 not relevant not applicable
Exam le 5
Comparative 25 4 .83 0.85 not appiicable
Exam nle 6
A thickness is listed as “not applicable" if the sheet does not contain a blown film (as in
Comparative Examples 2, 3 and 4) or a second rigid component (as in Comparative
es 1, 5 and 6). A thickness is listed as “not relevant” if the r property was
not determined for that example (as the oxygen transmission rate was not measured for
Examples 1, 3, 4 and 5 and Comparative Examples 1 and 2 and as the water vapor
transmission rate was not measured for Examples 1, 3, 4, 5 and 6 and Comparative
Examples 1, 2, and 5).
Properties measured include the properties described beiow, with a reference to
an ASTM Standard Test Method. Each standard test method referenced below is
incorporated in its entirety in this application by this reference.
Combined Tear initiation and Propagation Resistance is a measure of the force
required to both initiate and ate (or continue) a tear in a plastic fiim or sheet. To
determine this force, both energy to break and eiongation are ined in both the
machine direction and the transverse (or cross) direction of the sheet. Energy to break
is expressed in in*lbf (or “inch pounds” or “pounds inch") and elongation is expressed as
a percentage, and both are measured in accordance with ASTM D1004, “Standard Test
Method for Tear ance (Graves Tear) of Plastic Film and Sheeting.” For this
application, both ements are normalized as per one mil of the packaging sheet
thickness.
Tear Propagation ance is a measure of the force required to propagate (or
continue) a tear in a plastic film or sheet. To determine this force, both energy to break
and peak load are determined in both the machine direction and the transverse (or
cross) direction of the sheet. Energy to break is sed in in*lbf (or “inch pounds” or
“pounds inch") and peak load is expressed in lbf (or “pound force”), and both are
measured in ance with ASTM D1938, “Standard Test Method for Tear-
Propagation Resistance (Trouser Test) of Plastic Film and Thin Sheeting by a Single—
Tear Method." For this appiication, both measurements are normalized as per one mil
of the packaging sheet thickness.
Oxygen Transmission Rate (OTR) is a measure of the rate of the transmission of
oxygen gas through plastics in the form of film, ng, laminates, coextrusions, etc. It
is expressed in ems/100 in2/day and is measured in accordance with ASTM D3985,
“Standard Test Method for Oxygen Gas Transmission Rate h Plastic Film and
Sheeting Using a Coutometric Sensor.” For Examples 2, 6, 7 and 8 and ative
Examples 3- 6, the ed value is normalized as per one mil of thickness of the
oxygen barrier material (i.e., PVdC or EVOH) in the packaging sheet tested, such that
an oxygen transmission rate for a sheet expressed as 0.1 cc-mil/1OO in2/day refers to
0.1 cc of oxygen transmitted h one mil of oxygen barrier in a 100 inZ-size sheet
per day. For Examples 4a — 7a and Comparative Examples 8a — 9a, the measured
value is normalized as per one mil of thickness of the film, such that an
oxygen
transmission rate for a sheet expressed as 76.8 cc—mil/100in2/day refers to 76.8 cc of
oxygen transmitted through one mil of film in a 100in2-size sheet per day. For
Examples 4a — 7a and Comparative Examples, 8a — 9a, OTR was measured at 73°F
and 0 % relative humidity.
Water Vapor Transmission Rate (WVTR) or Moisture Vapor Transmission Rate
(MVTR) is a measure of the rate of the transmission of water vapor or moisture through
flexible r materials. It is expressed in g/100in2/day and is measured in accordance
with ASTM F1249, “Standard Test Method for Water Vapor Transmission Rate Through
Plastic Film and Sheeting Using a Moduiated ed Sensor." For Examples 2, 7 and
8 and ative Examples 3, 4, and 6, the ed value is normaiized as
per one
mil of thickness of the moisture barrier material (i.e., PVdC or HDPE) in the packaging
sheet tested, such that a water vapor transmission rate for a sheet expressed as 0.15
mil/100 inzlday refers to 0.15 g of water transmitted through one mil of moisture barrier
in a 100in2-size sheet per day. For Examples 1a — 10a and Comparative Examples 1a
— 10a, the measured value is normalized as per one mil of thickness of the film, such
that a re vapor transmission rate for a film expressed as 0.254 g—mil/1OO in2/day
refers to 0.254 g of moisture transmitted through one mil of film in a 100in2-size sheet
per day.
The measured values of the various properties of Examples 1-8 and
Comparative es 1-6 are reported in TABLE 7 and in TABLE 8. Each value is an
average of at least two measurements.
(The “**” in TABLE 7 and TABLE 8 are explained as s: For Examples 2-5,
the Combined Tear Initiation and Propagation Resistance and the Tear Propagation
Resistance were determined by measuring the values for at least three samples of each
ing sheet and then averaging the at least twelve data points. This approach was
selected as Examples 2-5 only vary by the thicknesses of the first rigid component and
the thicknesses of the second rigid component; the compositions of the first rigid
components, the compositions of the second rigid component and the itions and
the thicknesses of the thirteen~|ayer films are either substantially similar or cai.
For Example 2, the Normaiized Oxygen Transmission Rate is assumed to be at least
equal to (if not less than) the Normalized Oxygen Transmission Rate for Example 7, as
the itions and thicknesses of the oxygen barrier layers are identical.)
TABLE 7
Tear Propa-ation Resistance
.,_.-..,,,. Wa'fi . .
Mach eD on Transverse ion Machine Direction Transverse Direction
Normalized Normalized Normalized Normalized Normalized Normalized Normalized Normalized
Energy to Break Elongation Energyto Break Elongation Energy to Break Peak Load Energy to Break Peak Load
(in‘lbf/ mil) (°o / mil) f / mil) (% / mil) (in*lbf/ mil) (lbf I mii) f/ mil) (lbf Imil)
Example1 0123
Examples 2-5“ 0.133
Exam'IeG 0.138
Example 1 0 101 0.432 0.116 0 827 0 176 0.114 0.304 0.149
Example 2 0 260 1.184 0.432 1.812 0.497 0.269 0.493 0.345
Example3 0.127 0.440 not determined not determ. 0.264 0.141 0.366 0.237
Example 4 0.071 0.296 0.072 0.330 0.112 0.062 0.090 0.076
TABLE 7 reports the normalized combined tear initiation and propagation
ance and the normalized tear propagation resistance for the ing sheets of
Examples 1-6 and Comparative Examples 1-4. As reported in TABLE 7, each of the
sheets exemplifying the present invention has a normalized combined tear initiation and
propagation resistance in both the machine direction and the erse direction of less
than about 0.115 in*lbf/ mil energy to break and less than about 0.800 % / mil
elongation, and has a normalized tear propagation ance in both the machine
direction and the transverse direction of less than about 0.300 in*lbf/ mil energy to
break and less than about 0.145 lbf/ mil peak load. The packaging sheets of
Comparative Examples 1-3 exceed the normalized combined tear initiation and
propagation resistance and the normalized tear ation resistance achieved by the
ne-free packaging sheets Examples 1-6 and, therefore, do not exemplify the
present invention. The packaging sheet of Comparative Example 4 achieves similar
tear resistance vaiues as the chlorine-free packaging sheets of Examples 1-6.
However, this sheet is not chlorine-free (as it inciudes PVdC) and, therefore, does not
exemplify the present invention.
.As Shown by the following observations, lower tear resistance numbers correlate
to an ease of processing the packaging sheet. (And lower oxygen or water vapor
transmission rates have no correlation to ease of processing.)
The chlorine-free ing sheet of e 1 was thermoformed into a cup
and filled with a liquid product. Sticking of the sheet to the contact heater plate was
observed, resuiting in sealing issues. However, the sticking was attributed to the
processing aid in the rigid component and not due to the overall structural components
(e.g., rigid component(s) and multilayer film) of the chlorine-free packaging sheet.
The chlorine-free packaging sheet of Example 2 was thermoformed into a cup
and filled with a liquid product. No ng, forming, cutting, filling or sealing issues
were ed.
The ne-free packaging sheet of e 3 was thermoformed into a cup
and filled with a liquid product. No sticking, forming, cutting, filling or sealing issues
were observed.
The chlorine-free packaging sheet of Example 5 was thermoformed into a cup
and filled with a liquid product. No sticking, forming, cutting, filling or sealing issues
were observed.
The chlorine-free ing sheet of Example 7 was thermoformed into a cup
and filled with a liquid product. No significant sticking, forming, g, filiing or sealing
issues were observed.
-65..
The chlorine-free ing sheet of Example 8 was thermoformed into a cup
and filied with a liquid product. No sticking, forming, cutting, filling or sealing issues were
observed.
The packaging sheet of Comparative Example 1 was formed into a cup
and filled with a liquid product. Moderate sticking of the sheet to the contact heater
plate was observed. In filling the cup with the liquid product, the moderate sticking
caused the sheet to ripple and the product to splash out of the cup. The sticking was
attributed to the seven-layer blown film used in the packaging sheet and to the absence
of a second rigid component.
The packaging sheet of Comparative Example 5 was thermoformed into a cup
and filled with a liquid product. Some splashing of the product was observed. The
splashing was uted to the sticking of the sheet to the contact heater piate, which
and to the
was attributed to the seven-layer blown film used in the packaging sheet
e of a second rigid component.
The packaging sheet of Comparative Example 6 was thermoformed into a cup
and filled with a liquid product. Some ng of the sheet to the contact heater plate
and small ers left after trimming (i.e., cutting) were both observed. These were
attributable to the seven-layer blown film used in the packaging sheet and to the
absence of a second rigid component.
—66-
TABLE 8
Normalized Normalized
Oxygen Transmission Rate Water Vapor Transmission Rate
(cc-mil/100in2/day) (g-mil/1 00in2/day)
Example 2 “'0 0608 0.1172
Exam sle 6 0 0625 not ined
Examole 7 0 0608 0.0966
Example 7 -
Thermoformed Cup 0 0299 0.0036
Example 8 0.078
Com arative Exam . le 3 0.3056
Com-arative e 4 0.0456
Comparative e 4 --
Thermoformed Cup 0.0970 0.0129
Comparative Exam ale 5 nOt determined
Com oarative Exam ale 6 0.0827
Comparative Example 6 -
Thermoformed Cup 0.0634 0.0025
TABLE 8 reports the normalized oxygen ission rate for the packaging
sheets of Examples2, 6, 7 and 8 and Comparative Examples 3—6. TABLE 8 further
reports the normalized water vapor ission rate for the packaging sheets of
Examples 2, 7 and 8 and Comparative Examples 3, 4 and 6. Additionally, the
packaging sheets of Example 7, Comparative Example 4 and Comparative Example 6
were thermoformed into cups and also measured for oxygen transmission rate and
water vapor transmission rate. The oxygen transmission rates for the packaging sheets
of Example 2, 6, 7 and 8 and Comparative Examples 3-6 were measured at about 23°C,
80% internal relative humidity and 80% external relative humidity. The water vapor
transmission rates for the packaging sheets of Example 2, 7 and 8 and Comparative
Examples 3, 4 and 6 were measured at about 38°C, 0% internal relative humidity and
90% al relative humidity. The oxygen ission rates for the thermoformed
cups of the packaging sheets of Example 7, Comparative Example 4 and Comparative
Example 6 were measured at about 23°C, 80% internal relative humidity and 50%
al relative ty. The water vapor transmission rates for the thermoformed
cups of the packaging sheets of Example 7, Comparative Example 4 and Comparative
Example 6 were measured at about 38°C, 0% al relative humidity and 50%
external relative humidity.
As reported in TABLE 8, each of the sheets (and thermoformed cup)
exemplifying the present invention has a normalized oxygen transmission rate of less
than about 0.1 /100 in2/day and a ized water vapor transmission rate of
less than about 0.15 g-mil/100 inzlday. The packaging sheet of Comparative Example 3
exceeds the normalized oxygen transmission rate and the normalized water vapor
transmission rate achieved by the chlorine-free packaging sheets (and thermoformed
cup) of Examples 2, 6, 7 and 8 and also exceeds the ized ed tear
initiation and propagation resistance and the normalized tear propagation resistance
achieved by the chlorine—free packaging sheets of Examples 1-6; therefore,
Comparative Example 3 does not exemplify the t invention. The packaging sheet
(and thermoformed cup) of Comparative Example 4 es similar transmission rates
as the chlorine—free packaging sheets (and thermoformed cup) of Examples 2, 6, 7 and
8. However, this sheet is not chlorine-free (as it es PVdC) and, therefore, does
not exemplify the present invention. The ing sheet of Comparative Example 5
achieves similar oxygen transmission rates as the chlorine-free ing sheets (and
thermoformed cup) of Examples 2, 6, 7 and 8. However, as noted above, this sheet
had processing issues attributable to structural components (i.e., the multilayer film and
the absence of a second rigid component) of the packaging sheet. The packaging
sheet (and thermoformed cup) of Comparative Example 6 achieves similar transmission
rates as the packaging sheets (and thermoformed cup) of Examples 2, 6, 7 and 8 (albeit
the oxygen transmission rate for the packaging sheet of Comparative Example 6 is
somewhat higher). However, as noted above, this sheet had processing issues
utable to structural components (i.e.. the multilayer film and the absence of a
second rigid component) of the packaging sheet.
Examples 1a — 10a are non-oriented films also exemplifying the present
invention. ative Examples 1a — 10a were also ed. Example 1a and
Comparative Examples 2a — 5a were extruded as monolayer films on a Labtech
Engineering cast extrusion line. Examples 23 — 10a and Comparative es 63 —
10a were produced, generally, as follows: A multilayer, blown, coextruded film was
produced and thermally laminated to itself at the inner layers. atively, the
coextruded film was slit open-into one or more films.
TABLE 9 reports the normalized water vapor transmission rate for the monolayer
films of e 1a and Comparative Examples 1 a-4a. The moisture vapor
transmission rates for the films of Example 1a and Comparative Examples ta — 5a were
measured at about 100°C and 90 % external relative humidity. Example ta comprises
83 % by weight M6020 HDPE, 15 % by weight hydrocarbon resin and 0.08 % by weight
nucieating agent; the normalized moisture vapor transmission rate for this film is 0.254
g-mil/100in2/day. By comparison, Comparative Example 1a comprises 100 % by weight
M6020 HDPE and has a greater normalized moisture vapor transmission rate of 0.396
100in2/day. The addition of 0.08 % by weight nucleating agent to M6020 HDPE
decreases the normalized moisture vapor transmission rate to 0.351 g-mil/1 00in2/day as
shown in Comparative Example 2a. The addition of 15 % by weight hydrocarbon resin
to M6020 HDPE increases the ized moisture vapor transmission rate to 0.434 g-
mil/100in2/day as shown in Comparative Example 3a. Thus, the nucleating agent and
hydrocarbon resin have opposing effects on the normalized moisture vapor
transmission rate. When the nucleating agent and hydrocarbon agent are combined as
in Example 1a, a synergistic effect is observed. Example 13 has a lower normalized
re vapor transmission rate than any of Comparative Examples 1a-3a, including
Comparative Example 2a which comprises the nucleating agent. Thus, the effect of
adding a nucleating agent and hydrocarbon resin in combination is not predicted based
on the results of the nucleating agent and hydrocarbon resin alone and, therefore, is a
surprising result.
Comparing Comparative Examples 4a and 5a illustrate that, although a ion
in normalized re vapor transmission rate is observed with polypropylene instead
of M6020 HDPE, the magnitude of the effect is smaller and therefore does not predict
the results rated in Example 1a.
TABLE 9
- Plastolyn R1140
Alathon M6020 Polypropylene hydrocarbon HPN-ZOE
HDPE resin ting agent Thickness MVTR Normalized MVTR
(% by weight) ( 'g ) (% by ) (% by weight) ( y (mils) (gliOOinZ/day) (g—mil/1 00in2/da )
_—_ . 6 0061—.
---Exampleia 100 “m
-m-Example2a
---Example3a 85 m—
--Example4a 3.
ative-
Example 53 1.92
The moisture vapor transmission rates for the films of TABLES 10-14, were
measured at about 100 °F and 90 % external relative humidity.
TABLE 10 illustrates 1.75 mil collapsed blown films with a total ess of
approximately 3.5 mil and en layers. In Example 2a and Comparative Example 6a,
layers six and eight se M6020 HDPE and nucleating agent. Example 2a differs
from Comparative Example 6a in that layers six and eight of Example 2a further
se Piccolyte® 8135 hydrocarbon resin. Example 2a has an improved normalized
moisture vapor transmission rate of 0.22 g-mil/100in2/day as compared to Comparative
Example 6a which has a normalized moisture vapor transmission rate of 0.23 g-
mil/100in2/day.
TABLE 11 reports different collapsed blown films of about 10 mil total ess
and thirteen layers. Example 3a differs from Comparative e 7a in that layers
two, four, six, eight, ten, and twelve of Example 3a comprise M6020 HDPE in
combination with hydrocarbon resin and nucleating agent while layers two, four, six,
eight, ten, and twelve of Comparative Example 7a do not comprise Piccolyte® S135
hydrocarbon resin. As shown in TABLE 11, Example 3a affords a reduced normalized
moisture vapor ission rate of 0.22 g-mil/100in2/day as compared to Comparative
Example 7a, which affords a normalized re vapor transmission rate of 0.35 g~
mil/1005n2/day. in further embodiments, a polyethylene terephthalate, such as PETG, or
another rigid component (as described above) may be coated on either or both sides of
the film of Example 3a.
TABLE 10
Com arative Exam -!e 6a
Weight % Weight % of Weight % of Component Weight %
of Film La er Film of La er
First 4,75 e 95.50 4.75 Styrene 95.00
butadiene butadiene
co-ol mer cool mer
O Pol st rene l01'O
thermal stabilizer- thermal 0.50
stabilizer
Second 1200— 79 00 12.00 Alathon M6020 84.00
HDPE IU'0 [TI
O LLDPE 15.0o
—_m l—DPE
.h HPN-ZOE
100.00
100.00
100.00
Sixth 1 —4.50 Alathon M6020 14.50 Alathon M6020 99.00
HDPE HDPE
O l—U '0 lTl
_.I=E
A HPN-2OE 0.04
Seventh 9.50——D 9.50 I—LDPE 40.0
a).0 ooo
Eighth 14 50 Alathon M6020 14.50 Aiathon M6020 co$90o
HDPE
O l‘I00‘U'ul'l'lrn
—_EE
0. & E
Twelfth 12.00 12.00 Alathon M6020 ooooo5‘9??? 000A
HDPE IU'Um
_-m —-E§
Thirteenth 4.75 Styrene 95.50 4.75 Styrene 95.00
butadiene butadiene
cool mer co.ol mer
stabilizer
(mils)
(9/1 00in2/day)
(g-mil/100in2/day) .
, ”Bi-1511 .
Com oarative Exam ule 7a
Weight % -Weight% of Weight %0- Weight %
of Film La er Film of La er
First —-ma _-§Eil
\J 01O
HDPE HDPE
-—m -m
HDPE HDPE
—-m -W
Fifth a00-. 100.00 8.00-100.00
Sixth 5.50 Alathon M6020 009NO 5.50 Alathon M6020 99.00
HDPE HDPE
"""""Piccol e S135 14.8O
DPE -LDPE
—HPN-20E .o O-b —HPN-ZOE 0.04
h 12% EVA 12% EVA 50.0o
28% EVA 28% EVA 50.00
Eighth 5.50 Alathon M6020 84.20 5 50 Aiathon M6020 <05°oo
HDPE HDPE
Piccol e S135 14.80 LDPE
LDPE
HPN-20E HPN-ZOE
_l Ooo OOCh 8.00 LLDPE d 09.0 oo0&-
Tenth 9.50- 00A NO. 9 50 Alathon M6020 co$9oo
HDPE HDPE
LDPE
- _.E§
HPN—ZOE
A o.09 oo04:-
Twelth 7.50 7.50 Alathon M6020 (D.‘0 oo
HDPE HDPE
Piccol e 8135 14.80 LDPE
LDPE m -
HPN-20E E O O. 4:
Thirteenth 28% EVA
LLDPE 35.00 LLDPE 35.0
antiblock 4.00 antibiock 5‘0oo
9.89 9 4
(mils)
(gl100in2/day)
(g-mil/100in2/day)
TABLE 12 s three layer films with approximately 1.5 mil thickness.
Example 4a is a fiim with a third layer blend containing nominally 85 % by weight M6020
HDPE, 15 % by weight Regalite® T1140 hydrocarbon resin and 800 ppm (0.08 % by
weight) nucleating agent. The hydrocarbon resin was compounded into the M6020
HDPE at 15 % by weight prior to extrusion. This compound was blended with a
nucleating agent masterbatch (e.g., Polybatch® CLR 122 comprising LDPE and calcium
hexahydrophthalate) at the film line and extruded in the third layer of the film. The same
film ure was run with both unmodified M6020 HDPE (Comparative Example 9a)
thinned to 1.5 mil and M6020 HDPE combined with nucleating agent (Comparative
Example 8a). A ized moisture vapor transmission rate measured after one week
shows a barrier improvement of 20% for the HDPE M6020 with nucleating agent
(Comparative Example Be) as compared to unmodified M6020 HDPE (Comparative
Example 9a), and a barrier improvement of 50% for the blend of M 6020 HDPE,
arbon resin and nucleating agent le 4a) as compared to unmodified
M6020 HDPE (Comparative Example 9a) (all values normalized for gauge). Without
wishing to be bound by , it is believed that the nucleation acts on the crysta!
phase, and the hydrocarbon resin reduces the free volume in the amorphous phase,
leading to the additive effect of the two technologies.
TABLE 12
-Weight% Weight % Weight % Weight % eight %
of Film of La er of Film of La er of Film of La er
17.70 Surlyn 96.00 17.70 Surlyn 96.00 14.80 Surlyn
(with slip and (with slip and (with slip and
antiblock antiblock antiblock
% antiblock in 4.00 10% antiblock in 4.00 10% antiblock in 5.00
acid copolymer acid copolymer acid mer
Second 62.20 Alathon L5885 100.00 6220 Alathon L5885 100.00
HDPE HDPE 70.20--HDPE
Third 20.10-- 20.10-- 15.10 Alathon M6020
HDPE HDPE
Reallte T1140
Thickness for MVTR
(mils)
MVTR
(g/100in2/day)
Normalized MVTR
(g-mil/100in2/day)
Thickness for MVTR
after 1 week
mils)
MVTR after 1 week
(gl100in2/day)
Normalized MVTR
after 1 week
(g-miI/100in2lday
—mils)
(cc/100in2/day)
ized OTR
(cc-milllOOinZ/day) .
TABLE 13 reports additional three layer films with approximately 1.5 mil
thickness. The films of TABLE 13 have an ionomer/HDPE/HDPE blend structure. The
first and second layers of each of the films in TABLE 13 are the cal. The third
layers (the outer skin ) are different. Comparative Example 10a includes an outer
skin layer with 85 % by weight M6020 HDPE and 15 % by weight hydrocarbon resin.
This film has a normalized water vapor ission rate of 0.19 g-mil/100in2/day. The
addition of nucleating agent decreases the normalized moisture vapor transmission
rate, as shown by Examples 5a, 6a and 7a. Examples 5a, 6a and 7a further illustrate
the optimization of the amount of hydrocarbon resin for 0.08 % by weight nucleating
agent. Example 5a presents the lowest moisture vapor ission rate reported in
TABLE 13. in this example, hydrocarbon resin is present at 10.2 % by weight.
Examples 6a and 7a illustrate that increasing the % by weight of hydrocarbon resin has
an undesired effect of increasing the moisture vapor transmission rate. Thus, without
wishing to be bound by theory, it is postulated that when the % by weight hydrocarbon
resin content is too high, the activity of the ting agent is ed. and the
synergistic effect of the hydrocarbon resin and the nucleating agent is minimized.
TABLE 13
Exam-Ia 63 am
Wt % Component Wt % Component Wt % o Compone o Wt % Component Wt %
of Film of of Film of of Film of of Film of
La er La er La er La er
First 17.70 Surlyn 95.00 1?.70 Surlyn 95.0 17.70 Surlyn 95.00 17.70 Surlyn 95.00
(with slip and .
, (with slip and (with slip and (with slip and
antiblock antiblock - antiblock antiblock
% antiblock 5.00 10% antiblock 5.00 10% antiblock 5.00 10% antiblock 5.00
in acid in acid in acid in acid
cool mer co-ol mer co-ol mer cool mer
NNo Alathon L5885
HDPE HDPE . HDPE HDPE
Third 7.80 20.10Alathon M6020 78.20 2010-- 20.10--
HDPE HDPE HDPE HDPE
.20 RegaliteT1140 19.80 RegaliteT1140 15.00
LDPE 1.92 DPE _x .92 LDPE
E 08 HPN-ZOE 08 HPN-20E
Thickness for 1.49
MVTR
(mils)
MVTR
(g/1 day)
Normalized MVTR
(g-mil/100in2/day)
Thickness for OTR
(mils)
(cc/100in2/day)
Nomalized OTR
(cc-mill100in2/day)
~76-
TABLE 14 reports additional three-layer films using different hydrocarbon resins.
Examples 8a and 9a illustrate the use of Piccolyte® S135 and Arkon® P-140
hydrocarbon resins in combination with M6020 HDPE and nucleating agent in the third
layer of the film. The normalized moisture vapor transmission rate for each of these
films is 0.19 and 0.20 g-mil/100in2/day, respectively. Example 10a illustrates the use of
Plastolyn® R1140 arbon resin in combination with M6020 HDPE and nucleating
agent in the middle layer of the film; this structure affords a ized re vapor
transmission rate of 0.15 g-miI/100/in2/day.
TABLE 14
Wt "/0 Component Wt % Wt % Component Wt % 0 Component 0
of Film of of Film of of Film of
La er La er La er
First 17.70 Surlyn 95.00 17.70 Surlyn 95.00 9.8 Surlyn 95.00
. (with slip and (with slip‘and (With slip and
antiblock antiblock antiblock
% antiblock 5.00 10% antiblock 5.00 10% antiblock
in acid in acid in acid
cool mer cool mer co-ol mer
Second 62.20 Alathon L5885 100.00 62.20 Alathon L5885 100.00 70.20
Plastoiyn 15.00
R1140
. —m
Third 20.10 Alathon M6020 19.90 Alathon L5885 100.00
HDPE 20.10- 84.00 HDPE
yte 3135 20.00
—-m —-m
H 39.5 .—
Thickness for
MVTR
mils)
-(g/100in2/day) f
. g-rnil/100in2/day)
The above description, the examples and the embodiments disclosed in the
examples and othenlvise are illustrative only and should not be interpreted as limiting.
The t ion includes the description, the examples and the embodiments
disclosed; but it is not limited to such description, examples or embodiments.
Modifications and other embodiments will be apparent to those skilled in the art, and all
such modifications and other embodiments are intended and deemed to be within the
scope of the present invention as defined by the claims.
Claims (20)
1. A film comprising (A) at least one moisture barrier layer comprising a polymer blend comprising (a) high density polyethylene in an amount from about 69 % about 90 % by weight of the blend, wherein the high density polyethylene has a melt index of at least 1.0 g/10 min and a density greater than 0.958 g/cc; (b) hydrocarbon resin in an amount from about 5 % about 30 % by weight of the blend, wherein the hydrocarbon resin comprises petroleum resins, terpene resins, styrene resins, cyclopentadiene resins, saturated alicyclic resins or blends thereof; and (c) nucleating agent in an amount from about 0.01 % to about 1 % by weight of the blend, wherein the nucleating agent comprises glycerol alkoxide salts, hexahydrophthalic acid salts, similar salts or blends thereof; and (B) at least one additional layer comprising an ionomer, a high density polyethylene, a ter, a styrene ene copolymer or blends thereof; wherein the film has normalized moisture vapor ission rate of no greater than 0.30 g-mil/100 y measured at about 100 °F and 90 % external relative humidity.
2. The film of claim 1, wherein the high y hylene comprises from about 75 % to about 85 % by weight of the blend.
3. The film of claim 1, wherein the hydrocarbon resin comprises from about 5 % to about 20 % by weight of the blend.
4. The film of claim 1, wherein the hydrocarbon resin comprises from about 10 % to about 15 % by weight of the blend.
5. The film of claim 1, n the nucleating agent comprises from about 0.04% to about 0.10% by weight of the blend. ‐ 79 ‐
6. The film of claim 1, wherein the nucleating agent is selected from the group consisting of zinc glycerolate salts and m hexahydrophthalate.
7. The film of claim 1, wherein the moisture barrier layer comprises a polymer blend comprising the high density hylene in an amount from about 72% to about 88% by weight of the blend; the arbon resin in an amount from about 10% to about 20% by weight of the blend; and nucleating agent in an amount from about 0.04% to about 0.10 % by weight of the blend.
8. The film of claim 1 wherein the film has a normalized water vapor transmission rate of less than about 0.30 100 in2/day as measured at about 100 °F and 90 % external relative humidity.
9. The film of claim 1, wherein the film comprises an oxygen barrier material and the film has a normalized oxygen transmission rate of less than about 150 cc-mil/100 in2/day.
10.The film of claim 10, wherein the film has a normalized oxygen transmission rate of less than about 100 /100 in2/day.
11.The film of claim 1, wherein the polyester is a polyethylene terephthalate.
12.The film of claim 1, r comprising a second moisture barrier layer comprising the polymer blend of claim 1.
13.The film of claim 1, wherein the film has a thickness of less than 3.00 mil.
14.The film of claim 1, wherein the film has a thickness of less than 1.70 mil.
15.The film of claim 8, wherein the film has a normalized moisture vapor transmission rate of no greater than 0.20 g-mil/100 in2/day as measured at about 100 °F and 90 % external relative humidity. ‐ 80 ‐
16.The film layer of claim 15, wherein the film has a normalized moisture vapor transmission rate of no greater than 0.15 g-mil/100 in2/day as ed at about 100 °F and 90 % al relative ty.
17.A packaging article comprising the film of claim 1.
18. The packaging article of claim 17, wherein the packaging article is a rigid article or a semi-rigid article.
19.A film according to claim 1 substantially as herein described or exemplified.
20.A packaging article according to claim 17 substantially as herein described or exemplified.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/100,250 | 2011-05-03 | ||
US13/100,250 US20120107542A1 (en) | 2009-11-03 | 2011-05-03 | High Density Polyethylene Blend Films |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ599088A NZ599088A (en) | 2013-10-25 |
NZ599088B true NZ599088B (en) | 2014-01-28 |
Family
ID=
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