JP6716473B2 - 通気性フィルム及びそれを組み込んだ物品 - Google Patents
通気性フィルム及びそれを組み込んだ物品 Download PDFInfo
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- JP6716473B2 JP6716473B2 JP2016574257A JP2016574257A JP6716473B2 JP 6716473 B2 JP6716473 B2 JP 6716473B2 JP 2016574257 A JP2016574257 A JP 2016574257A JP 2016574257 A JP2016574257 A JP 2016574257A JP 6716473 B2 JP6716473 B2 JP 6716473B2
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- Prior art keywords
- ethylene
- breathable film
- composition
- film
- polymer
- Prior art date
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- 239000000203 mixture Substances 0.000 claims description 153
- 229920000642 polymer Polymers 0.000 claims description 98
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 76
- 239000005977 Ethylene Substances 0.000 claims description 63
- 239000000155 melt Substances 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 229920001684 low density polyethylene Polymers 0.000 claims description 14
- 239000004702 low-density polyethylene Substances 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 229920001903 high density polyethylene Polymers 0.000 claims description 11
- 239000004700 high-density polyethylene Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 229920000098 polyolefin Polymers 0.000 claims description 9
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 claims description 8
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 claims description 8
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 claims description 8
- 229920000034 Plastomer Polymers 0.000 claims description 8
- 239000004708 Very-low-density polyethylene Substances 0.000 claims description 8
- 229920001400 block copolymer Polymers 0.000 claims description 8
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 8
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 8
- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical compound C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 claims description 8
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 8
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 8
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 8
- 239000005042 ethylene-ethyl acrylate Substances 0.000 claims description 8
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 8
- 239000005043 ethylene-methyl acrylate Substances 0.000 claims description 8
- 229920000554 ionomer Polymers 0.000 claims description 8
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 8
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 8
- 229920001179 medium density polyethylene Polymers 0.000 claims description 8
- 239000004701 medium-density polyethylene Substances 0.000 claims description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 8
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 8
- 229920001866 very low density polyethylene Polymers 0.000 claims description 8
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 7
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 7
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 claims description 7
- 229920002367 Polyisobutene Polymers 0.000 claims description 6
- 239000012764 mineral filler Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 229920006178 high molecular weight high density polyethylene Polymers 0.000 claims 2
- 150000007513 acids Chemical class 0.000 claims 1
- 229920001112 grafted polyolefin Polymers 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- 239000000523 sample Substances 0.000 description 50
- 238000000034 method Methods 0.000 description 47
- 239000003054 catalyst Substances 0.000 description 46
- -1 polyethylene Polymers 0.000 description 40
- 238000012360 testing method Methods 0.000 description 35
- 239000010410 layer Substances 0.000 description 33
- 239000004711 α-olefin Substances 0.000 description 29
- 238000009826 distribution Methods 0.000 description 24
- 238000005227 gel permeation chromatography Methods 0.000 description 23
- 239000002904 solvent Substances 0.000 description 23
- 239000004698 Polyethylene Substances 0.000 description 19
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 17
- 229920000573 polyethylene Polymers 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 16
- 238000005259 measurement Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 230000006870 function Effects 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 150000005309 metal halides Chemical class 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 229910007926 ZrCl Inorganic materials 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 6
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 6
- 150000007517 lewis acids Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 5
- QVLAWKAXOMEXPM-DICFDUPASA-N 1,1,1,2-tetrachloro-2,2-dideuterioethane Chemical compound [2H]C([2H])(Cl)C(Cl)(Cl)Cl QVLAWKAXOMEXPM-DICFDUPASA-N 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 238000012417 linear regression Methods 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 150000003623 transition metal compounds Chemical class 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 4
- 206010008531 Chills Diseases 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 206010021639 Incontinence Diseases 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000012644 addition polymerization Methods 0.000 description 4
- 230000002730 additional effect Effects 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000013480 data collection Methods 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 229910021482 group 13 metal Inorganic materials 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 150000002901 organomagnesium compounds Chemical class 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000012549 training Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000079 presaturation Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 3
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 3
- QXALIERKYGCHHA-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)borane Chemical compound BC1=C(F)C(F)=C(F)C(F)=C1F QXALIERKYGCHHA-UHFFFAOYSA-N 0.000 description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 241000282376 Panthera tigris Species 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
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- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
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- 150000001639 boron compounds Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
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- 229910052735 hafnium Chemical group 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- CRRUGYDDEMGVDY-UHFFFAOYSA-N 1-bromoethylbenzene Chemical compound CC(Br)C1=CC=CC=C1 CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 description 1
- 125000004134 1-norbornyl group Chemical group [H]C1([H])C([H])([H])C2(*)C([H])([H])C([H])([H])C1([H])C2([H])[H] 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- NMXLXQGHBSPIDR-UHFFFAOYSA-N 2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCCO1 NMXLXQGHBSPIDR-UHFFFAOYSA-N 0.000 description 1
- JOUWCKCVTDSMHF-UHFFFAOYSA-N 2-bromo-2-methylbutane Chemical compound CCC(C)(C)Br JOUWCKCVTDSMHF-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- HYLHFOVZFADXNK-UHFFFAOYSA-N CCCCCC[Mg]CC Chemical compound CCCCCC[Mg]CC HYLHFOVZFADXNK-UHFFFAOYSA-N 0.000 description 1
- ZKSADANYBSWZAB-UHFFFAOYSA-N CCCCCC[Mg]CCCCCC Chemical compound CCCCCC[Mg]CCCCCC ZKSADANYBSWZAB-UHFFFAOYSA-N 0.000 description 1
- MDCNUULPPQFEAB-UHFFFAOYSA-N CCCC[Mg]C(C)C Chemical compound CCCC[Mg]C(C)C MDCNUULPPQFEAB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Description
通気性フィルムは、おむつバックシート等の衛生用途で広く使用されている。当業者は、通気性フィルムが、水蒸気の通過を可能にするいくらかの能力をもつ微小孔性形態を有することを一般的に理解している。例えば、Wu et al.,“Novel Microporous Films and Their Composites,”Journal of Engineered Fibers and Fabrics,Vol.2,Issue 1の49−59(2007)を参照されたい。
重合プロセスとしては、限定されるものではないが、1つ以上の従来型の反応器、例えば、ループ反応器、等温反応器、断熱反応器、撹拌槽反応器、オートクレーブ反応器を、並列で、直列で、ならびに/またはそれらの任意の組み合わせで用いる、溶液重合プロセスが挙げられる。エチレン系ポリマー組成物は、例えば、1つ以上のループ反応器、断熱反応器、及びそれらの組み合わせを用いる、溶液相重合プロセスを介して生成することができる。
ChemicalからISOPAR Eの名で市販されている。結果として生じる、エチレン系ポリマー組成物と溶媒との混合物はその後、反応器(複数可)から取り出され、エチレン系ポリマー組成物が単離される。溶媒は典型的には溶媒回収装置、すなわち熱交換器及び分離容器(separator vessel)を介して回収され、その後溶媒は重合システム中にリサイクルされる。
構造Iの金属−配位子錯体を含む触媒系の存在下で、エチレン、及び任意選択で少なくとも1つのコモノマーを溶液中で重合させて、第1のエチレン系ポリマーを形成することと、
チーグラー/ナッタ触媒を含む触媒系の存在下で、エチレン、及び任意選択で少なくとも1つのコモノマーを重合させて、第2のエチレン系ポリマーを形成することと、を含み、構造Iは以下の通りであり:
Mはチタン、ジルコニウム、またはハフニウムであり、各々は独立して+2、+3、または+4の形式酸化状態であり、
nは0〜3の整数であり、nが0の場合、Xは存在せず、
各Xは、独立して、中性、モノアニオン性、もしくはジアニオン性である単座配位子であるか、または2つのXが一緒になって、中性、モノアニオン性、もしくはジアニオン性である二座配位子を形成し、
X及びnは、式(I)の金属−配位子錯体が全体的に中性であるような方法で選択され、
各Zは、独立して、O、S、N(C1−C40)ヒドロカルビル、またはP(C1−C40)ヒドロカルビルであり、
Z−L−Zフラグメントは式(1)で構成され、
任意選択で、2つ以上のR基(R1〜R16)は、1つ以上の環構造へと一緒に組み合わさってもよく、そのような環構造が各々、独立して、環中にいかなる水素原子も除いて3〜50個の原子を有する。
上記の触媒系は、活性化共触媒とこの触媒系を接触させるか、もしくはそれとこの触媒系を組み合わせることによって、または金属ベースのオレフィン重合反応を伴う使用のために、当該技術分野において公知の技法等の活性化技法を使用することによって、触媒的に活性化することができる。本発明における使用にとって好適な活性化共触媒としては、アルキルアルミニウム;ポリマー性またはオリゴマー性アルモキサン(アルミノキサンとしても知られる);中性ルイス酸;及び非ポリマー性、非配位性、イオン形成化合物(酸化条件下におけるそのような化合物の使用を含む)が挙げられる。好適な活性化技法は、バルク電解である。前述の活性化共触媒及び技法のうちの1つ以上の組み合わせもまた企図される。用語「アルキルアルミニウム」は、モノアルキルアルミニウムジハイドライドもしくはモノアルキルアルミニウムジハライド、ジアルキルアルミニウムハイドライドもしくはジアルキルアルミニウムハライド、またはトリアルキルアルミニウムを意味する。アルミノキサン及びそれらの調製法については、例えば米国特許第6,103,657号において公知である。好ましいポリマー性またはオリゴマー性アルモキサンの例は、メチルアルモキサン、トリイソブチルアルミニウム修飾メチルアルモキサン、及びイソブチルアルモキサンである。
発明的組成物は、1つ以上の添加剤を含んでもよい。添加剤としては、限定されるものではないが、帯電防止剤、増色剤、染料、潤滑剤、充填剤(TiO2またはCaCO3)、乳白剤、核剤、加工助剤、顔料、一次酸化防止剤、二次酸化防止剤、UV安定剤、粘着防止剤、スリップ剤、粘着付与剤、難燃剤、抗微生物剤、臭気低減剤、抗真菌剤、及びそれらの組み合わせが挙げられる。一部の実施形態においては、発明的組成物は、そのような添加剤を含む本組成物の重量に基づいて、合計重量が約0.001〜約10重量パーセントである、そのような添加剤を含んでもよい。
否定されない限り、文脈から暗示されない限り、または当該技術分野において通例でない限り、全ての部及びパーセントは重量に基づくものであり、全ての試験方法は、本開示の出願日時点で最新のものである。
メルトインデックス
メルトインデックスI2(またはI2)及びI10(またはI10)は、ASTM D−1238(方法B)に従って、190℃で、それぞれ2.16kg及び10kgの荷重で測定した。これらの値は、g/10分で報告される。
密度測定のための試料は、ASTM D4703に従って調製した。測定は、試料を押圧して1時間以内に、ASTM D792、方法Bに従って行った。
各試料は、空気中、10MPaの圧力下において、177℃で5分間、「厚さ3mm×直径25mm」の円板状プラークへと圧縮成型した。次いで、試料を圧搾機から取り出し、冷却するために台上に置いた。
PolymerChar(Valencia,Spain)からのGPC−IR高温クロマトグラフィーシステムには、Precision Detectors(Amherst,MA)の2角レーザー光散乱検出器モデル2040、PolymerCharからのIR5赤外線検出器及び4キャピラリー粘度計を装備した。データ収集は、PolymerChar Instrument Controlソフトウェア及びデータ収集インターフェイスを用いて行った。システムには、Agilent Technologies(Santa Clara,CA)からのオンライン溶媒脱気デバイス及びポンプシステムを装備した。
Mポリエチレン=A×(Mポリスチレン)B (等式1)、
式中、Mは分子量であり、Aは0.4316に等しく、Bは1.0に等しい。
Oneソフトウェア(バージョン2.013H)」を用いて行った。
190℃において「25mm径」平行板を用いてAR−G2応力制御レオメーター(TA Instruments;New Castle,Del)で行われたクリープ試験を介して、ゼロせん断粘度を得た。備品を零点規正する前に、レオメーターオーブンを少なくとも30分間試験温度に設定した。試験温度において、圧縮成型試料ディスクを板の間に挿入し、5分間平衡化させた。次いで、上板を、所望の試験ギャップ(1.5mm)の50μm(機器設定)上まで下げた。任意の余分な材料を切り取り、上板を所望のギャップまで下げた。測定は、5L/分の流量において、窒素パージ下で行った。初期設定のクリープ時間は、2時間に設定した。各試料は、空気中、10MPaの圧力下において、177℃で5分間、「厚さ2mm×直径25mm」の円板状プラークへと圧縮成型した。次いで、試料を圧搾機から取り出し、冷却するために台上に置いた。
保存溶液(3.26g)を、10mmのNMRチューブ中の「0.133gのポリマー試料」に添加した。保存溶液は、0.001MのCr3+を有する、テトラクロロエタン−d2(TCE)とペルクロロエチレンとの混合物(50:50、w:w)であった。チューブ中の溶液をN2で5分間パージして、酸素量を減少させた。蓋をした試料チューブを室温で一晩放置して、ポリマー試料を膨潤させた。試料を110℃で定期的に渦流混合しながら溶解させた。試料は、不飽和に寄与し得る添加剤、例えばエルカミド等のスリップ剤を含まなかった。各1H NMR分析を、Bruker AVANCE 400MHz分光計で、120℃において10mmクライオプローブを用いて行った。
NCH2=I合計/2 (等式1A)
Nビニレン=Iビニレン/2 (等式2A)、
N三置換=I三置換 (等式3A)、
Nビニル=Iビニル/2 (等式4A)、
Nビニリデン=Iビニリデン/2 (等式5A)。
Nビニレン/1,000C=(Nビニレン/NCH2)*1,000 (等式6A)、
N三置換/1,000C=(N三置換/NCH2)*1,000 (等式7A)、
Nビニル/1,000C=(Nビニル/NCH2)*1,000 (等式8A)、
Nビニリデン/1,000C=(Nビニリデン/NCH2)*1,000 (等式9A)、
化学シフト基準は、TCE−d2からの残留プロトンからの1H信号に対しては6.0ppmに設定した。対照は、ZGパルス、NS=4、DS=12、SWH=10,000Hz、AQ=1.64秒、D1=14秒で実行した。ダブル予備飽和実験は、修正パルス配列、O1P=1.354ppm、O2P=0.960ppm、PL9=57db、PL21=70db、NS=100、DS=4、SWH=10,000Hz、AQ=1.64秒、D1=1秒(D1は予備飽和時間である)、D13=13秒で実行した。ビニルレベルのみを下の表2で報告した。
0.025MのCr(AcAc)3を含有する、テトラ−クロロエタン−d2/オルトジクロロベンゼンのおよそ3gの50/50混合物を、10mmのNMRチューブ中の「0.25gの試料」に添加することで、試料を調製する。窒素でチューブのヘッドスペースをパージすることにより、試料から酸素を取り除く。次いで、加熱ブロック及びヒートガンを用いてチューブ及びその内容物を150℃に加熱することで、試料を溶解させ、均質化する。均質化を確保するため、各溶解試料を目視検査する。
PolymerChar(Valencia,Spain)からのGPC−IR高温クロマトグラフィーシステムには、Precision Detectors(Amherst,MA)の2角レーザー光散乱検出器モデル2040、ならびにPolymerCharからのIR5赤外線検出器(GPC−IR)及び4キャピラリー粘度計を装備した。光散乱検出器の「角15度」は、計算目的のために使用した。データ収集は、PolymerChar Instrument Controlソフトウェア及びデータ収集インターフェイスを用いて行った。システムには、Agilent Technologies(Santa Clara,CA)からのオンライン溶媒脱気デバイス及びポンプシステムを装備した。
Mポリエチレン=A×(Mポリスチレン)B (等式1B)、
式中、Mは分子量であり、Aはおよそ0.40の値を有し、Bは1.0に等しい。Aの値は、下の等式3Bで計算される通り、NBS 1475A(NIST)直鎖ポリエチレンの重量平均分子量が52,000g/モルに対応するように、0.385〜0.425に調節した(特定のカラムセットの効率性に応じて)。
SCB/総C1000個=A0+[A1×(IR5メチルチャネル領域/IR5測定 チャネル領域)](等式4B)、
式中、A0は「IR5領域比」ゼロにおける「SCB/総C1000個」の切片であり、A1は、「SCB/総C1000個」対「IR5領域比」の勾配であり、「IR5領域比」の関数としての「SCB/総C1000個」における増加を表す。
コモノマーモルパーセント={SCBf/[SCBf+((1000−SCBf*コモノマーの長さ)/2)]}*100(等式5B)、
式中、「SCBf」は、「総C1000個当たりのSCB」であり、「コモノマーの長さ」は、オクテンの場合8であり、ヘキサンの場合6であり、以下同様である。
測定した「総C1000個当たりのSCB(=SCBf)」対SCB標準の観察した「IR5領域比」のプロットを生成し(図1を参照)、切片(A0)及び勾配(A1)を決定した。ここでは、A0=−90.246SCB/総C1000個であり、A1=499.32SCB/総C1000個である。
生成したフィルムについて、以下の物理的特性を測定した(実験的セクションを参照)。
● 光沢度(45°):ASTM D−2457。
● 透明度:ASTM:D−1746。
内部ヘイズ及び全体的(トータル)ヘイズについて測定する試料は、ASTM D1003に従ってサンプリング及び調製した。内部ヘイズは、フィルムの両面において鉱物油を用いて屈折率整合することで得た。Hazeguard Plus(BYK−Gardner USA;Columbia,MD)を試験のために使用した。表面ヘイズは、トータルヘイズと内部ヘイズとの間の差異として決定した。トータルヘイズは、5つの測定値の平均として報告した。
エルメンドルフ引裂試験は、エルメンドルフ型引裂き試験機を用いて、引裂きが開始された後、プラスチックフィルムまたは非剛性シートの特定の長さを開裂して伝播する平均力を決定する。
フィルムのMD(機械方向)及びCD(交差方向)のセカント係数、及び引張破断強度(または引張強度)を、ASTM D882−10に従って、Instron万能試験機を用いて測定した。報告されるセカント係数の値は、5つの測定値の平均であった。引張破断強度は、5つのフィルム試料を各方向で使用して決定し、各試料は「1インチ×6インチ」の大きさであった。破断強度は、所与の材料を破裂または破断させるのに必要な引張荷重または力である。これは、毎平方インチに対する重量ポンド(psi)として測定される。破断ひずみは、材料が破断する時点のひずみであり、破断時の長さを初期長さで除し、100を乗じたもの(%)として測定される。
突刺試験は、標準低速、単一試験速度における、プローブの貫通に対するフィルムの耐性を判定する。突刺試験方法は、ASTM D5748に基づく。フィルムを生成した後、このフィルムを、少なくとも40時間、23℃(+/−2℃)、及びASTM標準により50%R.H(+/−5)の条件に馴化させた。標準試験条件は、23℃(+/−2℃)及びASTM標準により50%R.H(+/−5)であった。突刺は、引張試験機で測定した。シートから、「6インチ×6インチ」のサイズに四角い標本を切り出した。この標本を、「直径4インチ」の円形の標本ホルダーに固定し、突刺プローブをこの固定されたフィルムの中心に、10インチ/分のクロスヘッド速度で押し当てた。内部試験方法はASTM D5748に従うが、1つの修正を伴う。この方法は、ASTM D5748の方法とは、使用されたプローブが(D5748において規定されている直径0.75インチの洋ナシ型プローブではなく)、「0.25インチ」の支持具上の「直径0.5インチ」の磨製鋼球であったという点において異なった。
フィルムダート落下試験は、自由落下するダートによる衝撃の規定条件下において、プラスチックフィルムの破損を引き起こすエネルギーを決定する。試験結果は、試験される標本の50%の破損をもたらし得る、規定の高さから落ちる飛翔体の重量として表されるエネルギーである。
水蒸気透過速度(すなわちWVTR)は、絶対透過速度である。WVTRはASTM D−6701に従って決定し、g/m2 /日の単位で報告する。
発明的第1の組成物1、2、及び3
発明的第1の組成物1、2、及び3は、各々、2つのエチレン−オクテンコポリマーを含有する。各組成物は、米国特許第5,977,251号に記載の二連ループ反応器システム(dual series loop reactor system)(この特許の図2を参照)において、第1の反応器内における下に記載の第1の触媒系、ならびに第2の反応器内における下に記載の第2の触媒系の存在下で、溶液重合を介して調製した。
比較組成物A及びBは、2つのエチレン−オクテンコポリマーを各々含有し、二重ループ反応器システムにおいて、第1の反応器内における下に記載の第1の触媒系、ならびに第2の反応器内における下に記載の第2の触媒系の存在下で、溶液重合を介して各々調製した。第1の触媒系は、チタン,[N−(1,1−ジメチルエチル)−1,1−ジメチル−1−[(1,2,3,3a,8a−η)−1,5,6,7−テトラヒドロ−2−メチル−s−インダセン−1−イル]シランアミナト(2−)−κN][(1,2,3,4−η)−1,3−ペンタジエン]−(CAT3、幾何拘束触媒)を含んだ。第2の触媒系は、上に考察したチーグラー・ナッタ予混合物(CAT2)を含んだ。
比較Cはエチレン−ヘキセンコポリマー組成物であり、これはEXXONMOBIL Chemical CompanyからEXCEED 1018CAという取引上の表示の下に市販されており、およそ0.918g/cm3の密度、190℃及び2.16kgにおいて測定された、およそ1.0g/10分のメルトインデックス(I2またはI2)を有する。比較例Cの追加的な特性を測定し、表2において報告する。GPC MWDプロファイル及び対応するコモノマー分布の重ね合わせを、図5において示す。
比較Dはエチレン−オクテンコポリマー組成物であり、これはThe Dow Chemical CompanyからELITE 5230Gという取引上の表示の下に提供されており、およそ0.916g/cm3の密度、190℃及び2.16kgにおいて測定された、およそ4.0g/10分のメルトインデックス(I2またはI2)を有する。比較例Dの追加的な特性を測定し、表2において報告する。GPC MWDプロファイル及び対応するコモノマー分布の重ね合わせを、図7において示す。
発明的組成物4及び5
発明的組成物4及び5は、各々、エチレン−オクテンコポリマーを含有する。発明的組成物4及び5は、表3において報告される重合条件を除いて、発明的組成物1〜3と同じ様式で、また同じ触媒系を使用して調製した。
発明的組成物4及びDOWLEX(商標)2047Gポリエチレン樹脂(The Dow Chemical Companyから市販されている)の伸展域を、表7に示されるようにロール温度が修正された上記のMDO条件を使用して決定した。
発明的組成物6及び7
発明的組成物6及び7は、各々、エチレン−オクテンコポリマーを含有する。発明的組成物6及び7は、表9において報告される重合条件を除いて、発明的組成物1〜3と同じ様式で、また同じ触媒系を使用して調製した。
Claims (15)
- 第1の組成物を含む通気性フィルムであって、前記第1の組成物が、少なくとも1つのエチレン系ポリマーを含み、前記第1の組成物が、0.9を上回るMWCDI値と、以下の等式:I10/I2≧7.0−1.2×log(I2)を満たすメルトインデックス比(I10/I2)とを含む、通気性フィルム。
- 前記通気性フィルムが、40〜65重量パーセントの鉱物充填剤を更に含む、請求項1に記載の通気性フィルム。
- 前記第1の組成物が、10.0以下のMWCDI値を有する、請求項1または請求項2に記載の通気性フィルム。
- 前記第1の組成物が、0.910〜0.940g/cm3の密度及び0.5〜30g/10分のメルトインデックス(I2)を有する、請求項1〜3のいずれか1項に記載の通気性フィルム。
- 前記フィルムが、10〜20g/m2の基本重量を有する、請求項1〜4のいずれか1項に記載の通気性フィルム。
- 第2のポリマーを更に含み、前記第2のポリマーが、以下:LLDPE、VLDPE、LDPE、MDPE、HDPE、HMWHDPE、プロピレン系ポリマー、ポリオレフィンプラストマー、ポリオレフィンエラストマー、オレフィンブロックコポリマー、エチレン酢酸ビニル、エチレンアクリル酸、エチレンメタクリル酸、エチレンメチルアクリレート、エチレンエチルアクリレート、エチレンブチルアクリレート、ポリイソブチレン、無水マレイン酸グラフトポリオレフィン、前述のいずれかのアイオノマー、またはそれらの組み合わせから選択される、請求項1〜5のいずれか1項に記載の通気性フィルム。
- 前記通気性フィルムが、前記第1の組成物を含む第1の層、及び第2の層を備え、前記第2の層が、以下:前記第1の組成物、LLDPE、VLDPE、LDPE、MDPE、HDPE、HMWHDPE、プロピレン系ポリマー、ポリオレフィンプラストマー、ポリオレフィンエラストマー、オレフィンブロックコポリマー、エチレン酢酸ビニル、エチレンアクリル酸、エチレンメタクリル酸、エチレンメチルアクリレート、エチレンエチルアクリレート、エチレンブチルアクリレート、ポリイソブチレン、無水マレイン酸グラフトポリオレフィン、前述のいずれかのアイオノマー、またはそれらの組み合わせから選択されるポリマーを含む、請求項1〜6のいずれか1項に記載の通気性フィルム。
- 前記通気性フィルムが、少なくとも30重量パーセントの前記第1の組成物を含む、請求項1〜7のいずれか1項に記載の通気性フィルム。
- 前記通気性フィルムが、少なくとも500g/m2−day−atmかつ最大10,000g/m2−day−atmの水蒸気透過速度を示す、請求項1〜8のいずれか1項に記載の通気性フィルム。
- 前記通気性フィルムが、機械方向及び交差方向のうちの少なくとも1つに延伸される、請求項1〜9のいずれか1項に記載の通気性フィルム。
- 前記通気性フィルムが、機械方向及び交差方向に延伸される、請求項1〜10のいずれか1項に記載の通気性フィルム。
- 請求項1〜11のいずれか1項に記載の通気性フィルムを含む積層品。
- 不織材料を更に含む、請求項12に記載の積層品。
- 請求項12または請求項13に記載の積層品を備える物品。
- 請求項1〜11のいずれか1項に記載の通気性フィルムを備える物品。
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