JP2020143215A - Modified polyolefin material and method for producing the same, and resin film and packaging material - Google Patents
Modified polyolefin material and method for producing the same, and resin film and packaging material Download PDFInfo
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- JP2020143215A JP2020143215A JP2019040572A JP2019040572A JP2020143215A JP 2020143215 A JP2020143215 A JP 2020143215A JP 2019040572 A JP2019040572 A JP 2019040572A JP 2019040572 A JP2019040572 A JP 2019040572A JP 2020143215 A JP2020143215 A JP 2020143215A
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- modified polyolefin
- sulfonate
- based copolymer
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 40
- 229920005989 resin Polymers 0.000 title claims abstract description 27
- 239000011347 resin Substances 0.000 title claims abstract description 27
- 239000005022 packaging material Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 55
- 229920001577 copolymer Polymers 0.000 claims abstract description 54
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001336 alkenes Chemical group 0.000 claims abstract description 17
- 150000003839 salts Chemical group 0.000 claims abstract description 13
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 12
- -1 sulfonate compound Chemical class 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 18
- 125000000962 organic group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical class [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical group CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 12
- 230000035699 permeability Effects 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 2
- 235000012055 fruits and vegetables Nutrition 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- 125000004809 1-methylpropylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- RNVJDIGFTGLKCE-UHFFFAOYSA-N 2,3,3-trifluoro-2-(trifluoromethyl)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C(F)(F)F)(F)C2(F)F RNVJDIGFTGLKCE-UHFFFAOYSA-N 0.000 description 1
- JPUKSAVXNUITKN-UHFFFAOYSA-N 2,3,3-trimethylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(C)C2(C)C JPUKSAVXNUITKN-UHFFFAOYSA-N 0.000 description 1
- LAZHUUGOLCHESB-UHFFFAOYSA-N 2,3-dimethylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(C)C(C)C1C=C2 LAZHUUGOLCHESB-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 125000004810 2-methylpropylene group Chemical group [H]C([H])([H])C([H])(C([H])([H])[*:2])C([H])([H])[*:1] 0.000 description 1
- KKDZMSWHDHBHEU-UHFFFAOYSA-N 3,4-dimethylcyclohexene Chemical compound CC1CCC=CC1C KKDZMSWHDHBHEU-UHFFFAOYSA-N 0.000 description 1
- JOVGLRSLWFSVNB-UHFFFAOYSA-N 3,4-dimethylcyclopentene Chemical compound CC1CC=CC1C JOVGLRSLWFSVNB-UHFFFAOYSA-N 0.000 description 1
- PUPAPFTXLYVYPX-UHFFFAOYSA-N 3,5-dimethylcyclopentene Chemical compound CC1CC(C)C=C1 PUPAPFTXLYVYPX-UHFFFAOYSA-N 0.000 description 1
- CXOZQHPXKPDQGT-UHFFFAOYSA-N 3-Methylcyclopentene Chemical compound CC1CCC=C1 CXOZQHPXKPDQGT-UHFFFAOYSA-N 0.000 description 1
- LNGQLHZIYFQUIR-UHFFFAOYSA-N 3-chlorocyclohexene Chemical compound ClC1CCCC=C1 LNGQLHZIYFQUIR-UHFFFAOYSA-N 0.000 description 1
- LPSWJRSLXCPGBK-UHFFFAOYSA-N 3-chlorocyclopentene Chemical compound ClC1CCC=C1 LPSWJRSLXCPGBK-UHFFFAOYSA-N 0.000 description 1
- UZPWKTCMUADILM-UHFFFAOYSA-N 3-methylcyclohexene Chemical compound CC1CCCC=C1 UZPWKTCMUADILM-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- FWMRUAODTCVEQK-UHFFFAOYSA-N 4-methylcyclopentene Chemical compound CC1CC=CC1 FWMRUAODTCVEQK-UHFFFAOYSA-N 0.000 description 1
- LZAIJFHJQZYVLF-UHFFFAOYSA-N 5,5-dichlorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Cl)(Cl)CC1C=C2 LZAIJFHJQZYVLF-UHFFFAOYSA-N 0.000 description 1
- UVFFMASFIIKUOD-UHFFFAOYSA-N 5-(chloromethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCl)CC1C=C2 UVFFMASFIIKUOD-UHFFFAOYSA-N 0.000 description 1
- UDOJACSDSIHAAT-UHFFFAOYSA-N 5-benzylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CC2C1CC1=CC=CC=C1 UDOJACSDSIHAAT-UHFFFAOYSA-N 0.000 description 1
- PSCJIEZOAFAQRM-UHFFFAOYSA-N 5-chlorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Cl)CC1C=C2 PSCJIEZOAFAQRM-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- LFBHYIUTPVORTR-UHFFFAOYSA-N 5-fluorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(F)CC1C=C2 LFBHYIUTPVORTR-UHFFFAOYSA-N 0.000 description 1
- RCDOWRWNYHNLLA-UHFFFAOYSA-N 5-methoxybicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(OC)CC1C=C2 RCDOWRWNYHNLLA-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 1
- AKHDGSRSWWFVIZ-UHFFFAOYSA-N 5-propylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCC)CC1C=C2 AKHDGSRSWWFVIZ-UHFFFAOYSA-N 0.000 description 1
- AVFRNNALLLVPGJ-UHFFFAOYSA-N 7-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1C2C AVFRNNALLLVPGJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000005163 aryl sulfanyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical compound C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 1
- 125000006363 carbonyl oxy alkylene group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940126086 compound 21 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LLXZODPVPXJXPD-UHFFFAOYSA-N n,n-dimethylbicyclo[2.2.1]hept-2-en-5-amine Chemical compound C1C2C(N(C)C)CC1C=C2 LLXZODPVPXJXPD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical group C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Wrappers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、変性ポリオレフィン材料及びその製造方法、並びに、樹脂フィルム及び包装材料に関する。 The present invention relates to a modified polyolefin material and a method for producing the same, and a resin film and a packaging material.
水蒸気を透過する機能を有し、かつ液体に対する透過性は示さない通気性液体不透過フィルムが、使い捨てオムツに代表される使い捨てのパーソナルケアおよびヘルスケアの物品や、野菜や果実等の青果物の包装材として用いられることが多い。このようなフィルムとしては、エチレンと、アクリル酸またはメタクリル酸と、アクリル酸アルキルまたはメタクリル酸アルキルとの３元共重合体組成物を含む水蒸気透過膜が知られている。（例えば、特許文献１）。 A breathable liquid opaque film that has the function of permeable to water vapor and does not show permeability to liquids is used for packaging disposable personal and healthcare products such as disposable diapers, and fruits and vegetables such as vegetables and fruits. Often used as a material. As such a film, a water vapor permeable membrane containing ethylene, a ternary copolymer composition of acrylic acid or methacrylic acid, and alkyl acrylate or alkyl methacrylate is known. (For example, Patent Document 1).
本発明の一側面の目的は、水蒸気に対する高い透過性を有する、ポリオレフィン系共重合体を含む樹脂フィルムを提供することにある。樹脂フィルム自体が水蒸気に対する高い透過性を有していれば、より簡易に包装材料を製造できることが期待される。 An object of one aspect of the present invention is to provide a resin film containing a polyolefin-based copolymer, which has high permeability to water vapor. If the resin film itself has high water vapor permeability, it is expected that the packaging material can be manufactured more easily.
本発明の一側面は、オレフィン単位と、スルホン酸基と含窒素基とによって形成された塩であるスルホネート基を有するスルホネート単位と、を有する変性ポリオレフィン系共重合体を含む、変性ポリオレフィン材料に関する。 One aspect of the present invention relates to a modified polyolefin material comprising a modified polyolefin-based copolymer having an olefin unit and a sulfonate unit having a sulfonate group which is a salt formed by a sulfonic acid group and a nitrogen-containing group.
本発明の別の一側面は、上記変性ポリオレフィン材料を含む樹脂フィルムに関する。この樹脂フィルムは、それ自体、水蒸気に対する高い透過性を有することができる。そのため、樹脂フィルムを、単独で又は必要により他の層と組み合わせることで、例えば包装材料を容易に形成することができる。 Another aspect of the present invention relates to a resin film containing the modified polyolefin material. The resin film itself can have high permeability to water vapor. Therefore, for example, a packaging material can be easily formed by using the resin film alone or in combination with other layers if necessary.
本発明によれば、ポリオレフィンフィルムの水蒸気に対する透過性を高めることができる。 According to the present invention, the permeability of the polyolefin film to water vapor can be increased.
以下、本発明のいくつかの実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
一実施形態に係る変性ポリオレフィン材料は、オレフィン単位と、スルホネート基を有するスルホネート単位とを有する変性ポリオレフィン系共重合体を含む。一実施形態に係る変性ポリオレフィン系共重合体は、主としてオレフィン単位から構成される。オレフィン単位は、オレフィンに由来するモノマー単位である。オレフィン単位の割合は、例えば、変性ポリオレフィン系共重合体中の全モノマー単位の量に対して、８０モル％以上、又は９０モル％以上である。 The modified polyolefin material according to one embodiment contains a modified polyolefin-based copolymer having an olefin unit and a sulfonate unit having a sulfonate group. The modified polyolefin-based copolymer according to the embodiment is mainly composed of olefin units. The olefin unit is a monomer unit derived from an olefin. The ratio of the olefin units is, for example, 80 mol% or more, or 90 mol% or more, based on the amount of all monomer units in the modified polyolefin-based copolymer.
オレフィン単位を誘導するオレフィンの例としては、エチレン、炭素数３〜２０の直鎖状のα−オレフィン、及び環状オレフィンが挙げられる。変性ポリオレフィン系共重合体に含まれるオレフィン単位のうち、エチレン単位の割合が５０〜１００モル％、７０〜１００モル％、又は９０〜１００モル％であってもよい。 Examples of olefins that induce olefin units include ethylene, linear α-olefins having 3 to 20 carbon atoms, and cyclic olefins. The proportion of ethylene units in the olefin units contained in the modified polyolefin-based copolymer may be 50 to 100 mol%, 70 to 100 mol%, or 90 to 100 mol%.
炭素数３〜２０の直鎖状のα−オレフィンの例としては、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−へプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−ノナデセン、及び１−エイコセンが挙げられる。 Examples of linear α-olefins having 3 to 20 carbon atoms are propylene, 1-butene, 1-pentene, 1-hexene, 1-hepten, 1-octene, 1-nonene, 1-decene, 1 -Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene.
環状オレフィンの例としては、ノルボルネン、５−メチルノルボルネン、５−エチルノルボルネン、５−プロピルノルボルネン、５，６−ジメチルノルボルネン、１−メチルノルボルネン、７−メチルノルボルネン、５，５，６−トリメチルノルボルネン、５−フェニルノルボルネン、５−ベンジルノルボルネン、５−エチリデンノルボルネン、５−ビニルノルボルネン、１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２−メチル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２−エチル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２，３−ジメチル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２−ヘキシル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２−エチリデン−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２−フルオロ−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、１，５−ジメチル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２−シクロへキシル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２，３−ジクロロ−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、２−イソブチル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン、１，２−ジヒドロジシクロペンタジエン、５−クロロノルボルネン、５，５−ジクロロノルボルネン、５−フルオロノルボルネン、５，５，６−トリフルオロ−６−トリフルオロメチルノルボルネン、５−クロロメチルノルボルネン、５−メトキシノルボルネン、５，６−ジカルボキシルノルボルネンアンハイドレート、５−ジメチルアミノノルボルネン、５−シアノノルボルネン、シクロペンテン、３−メチルシクロペンテン、４−メチルシクロペンテン、３，４−ジメチルシクロペンテン、３，５−ジメチルシクロペンテン、３−クロロシクロペンテン、シクロへキセン、３−メチルシクロへキセン、４−メチルシクロヘキセン、３，４−ジメチルシクロヘキセン、３−クロロシクロヘキセン、シクロへプテン、及びビニルシクロヘキサンが挙げられる。 Examples of cyclic olefins include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidene norbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-Methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1, 2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8- Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4a, 5,8, 8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1, 4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-Octahydronaphthalene, 2,3-dichloro-1,4,5,8-Dimethano-1,2,3 4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4a,5,8,8a-octahydronaphthalene, 1, 2-Dihydrodicyclopentadiene, 5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene , 5,6-Dicarboxynorbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3 -Chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohe Examples include xene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, cycloheptene, and vinylcyclohexane.
変性ポリオレフィン系共重合体を構成するスルホネート単位が有するスルホネート基は、スルホン酸基（−ＳＯ３Ｈ）と含窒素基とにより形成された塩である。スルホネート基は、変性ポリオレフィン系共重合体の主鎖に結合した含窒素基と、スルホン酸化合物との塩であってもよいし、変性ポリオレフィン系共重合体の主鎖に結合したスルホン酸基と、アンモニア又は含窒素有機化合物との塩であってもよい。 Sulfonate group of the sulfonate units constituting the modified polyolefin copolymer is a sulfonic acid group (-SO 3 H) and salts formed with a nitrogen-containing group. The sulfonate group may be a salt of a nitrogen-containing group bonded to the main chain of the modified polyolefin-based copolymer and a sulfonic acid compound, or a sulfonic acid group bonded to the main chain of the modified polyolefin-based copolymer. , Ammonia or a salt with a nitrogen-containing organic compound.
スルホネート基を構成する含窒素基は、スルホン酸基と塩を形成し得るカチオン性の基であればよく、その例としては、脂肪族アミノ基、芳香族アミノ基又は含窒素複素芳香環にプロトンが付加して形成された含窒素カチオン基、４級アンモニウム基、及びアンモニウムイオン（ＮＨ４ ＋）が挙げられる。 The nitrogen-containing group constituting the sulfonate group may be a cationic group capable of forming a salt with the sulfonic acid group, and examples thereof include a proton on an aliphatic amino group, an aromatic amino group or a nitrogen-containing heteroaromatic ring. There is formed by adding a nitrogen-containing cationic groups, quaternary ammonium groups, and ammonium ion (NH 4 +) and the like.
スルホネート単位の一例は、下記式（１）で表される単位である。
Ｒ１、Ｒ２及びＲ３は、それぞれ独立に、水素原子、又は、非イオン性の有機基を示し、互いに結合して環状基を形成していてもよい。Ｚは非イオン性の有機基を示す。Ｘは、直接結合、又は、非イオン性の有機基を示す。
An example of the sulfonate unit is a unit represented by the following formula (1).
R 1 , R 2 and R 3 each independently represent a hydrogen atom or a nonionic organic group, and may be bonded to each other to form a cyclic group. Z represents a nonionic organic group. X indicates a directly bonded or nonionic organic group.
Ｒ１、Ｒ２及びＲ３は、それぞれ独立に、水素原子、又は、炭素数１〜１０のアルキル基（例えば、メチル基、エチル基、プロピル基）であってもよく、互いに結合して脂環基を形成していてもよい。Ｒ１及びＲ２がそれぞれ独立に炭素数１〜１０のアルキル基で、Ｒ３が水素原子であってもよい。 R 1 , R 2 and R 3 may be independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group), and are bonded to each other to form a fat. It may form a ring group. R 1 and R 2 may be independently alkyl groups having 1 to 10 carbon atoms, and R 3 may be a hydrogen atom.
Ｘは、非イオン性の２価の有機基であればよく、その例としては、カルボニルオキシアルキレン基が挙げられる。 X may be a nonionic divalent organic group, and examples thereof include a carbonyloxyalkylene group.
Ｚは、下記式（１０）で表されるアルキルポリオキシアルキレン基であってもよい。Ｚが式（１０）のアルキルポリオキシアルキレン基であると、親水性の表面を有しながら、水蒸気に対するより一層高い透過性を有する樹脂フィルムが得られ易い。
式中、Ｒ４は直鎖状又は分岐状のアルキレン基を示し、ｎは２〜５０の整数を示し、ｎ個のＲ４は同一でも異なってもよく、Ｒ５は置換されていてもよい直鎖状又は分岐状のアルキル基を示す。式（１０）のアルキルポリオキシアルキレン基が、Ｒ４が異なる２種以上のオキシアルキレン単位（−Ｒ４Ｏ−）を含む場合、それらはランダムに結合していても、ブロックを形成していてもよい。 Wherein, R 4 represents a linear or branched alkylene group, n is an integer of 2 to 50, n pieces of R 4 may be the same or different, R 5 may be substituted Indicates a linear or branched alkyl group. Alkyl polyoxyalkylene group of the formula (10), if R 4 contains two or more different oxyalkylene units (-R 4 O-), they be bonded randomly to form a block May be good.
Ｒ４は、炭素数２〜４の直鎖状又は分岐状のアルキレン基であってもよく、その例としては、エチレン基、トリメチレン基、プロピレン基（−ＣＨ２−ＣＨ（ＣＨ３）−）、ｎ−ブチレン基、１−メチルプロピレン基（−ＣＨ２−ＣＨ２−ＣＨ（ＣＨ３）−）、２−メチルプロピレン基（−ＣＨ２−ＣＨ（ＣＨ３）−ＣＨ２−）、ジメチルエチレン基（−ＣＨ２−Ｃ（ＣＨ３）２−）、及びエチルエチレン基（−ＣＨ２−ＣＨ（ＣＨ２ＣＨ３）−）が挙げられる。Ｒ４が、エチレン基、プロピレン基及びエチルエチレン基からなる群より選択される少なくとも１種であってもよく、これらから選ばれる２種であってもよい。 R 4 may be linear or branched alkylene group having 2 to 4 carbon atoms, and examples thereof include ethylene group, trimethylene group, propylene group (-CH 2 -CH (CH 3) -) , N-butylene group, 1-methylpropylene group (-CH 2- CH 2- CH (CH 3 )-), 2-methylpropylene group (-CH 2- CH (CH 3 ) -CH 2- ), dimethylethylene Examples include a group (-CH 2- C (CH 3 ) 2- ) and an ethylethylene group (-CH 2- CH (CH 2 CH 3 )-). R 4 may be at least one selected from the group consisting of an ethylene group, a propylene group and an ethyl ethylene group, or may be two selected from these.
ｎは、２〜３０、又は２〜２０の整数であってもよい。変性ポリオレフィン材料中に含まれる式（１０）のアルキルポリオキシアルキレン基におけるｎの平均値が、これら数値範囲内にあってもよい。 n may be an integer of 2 to 30 or 2 to 20. The average value of n in the alkylpolyoxyalkylene group of the formula (10) contained in the modified polyolefin material may be within these numerical ranges.
Ｒ５は、置換されていてもよい炭素数１〜２０の直鎖状又は分岐状のアルキル基であってもよい。このアルキル基の炭素数は、８以上又は１２以上であってもよく、１６以下又は１４以下であってもよく、１３であってもよい。アルキル基の炭素数がこれら数値範囲内にあると、親水性の表面を有しながら、水蒸気に対するより一層高い透過性を有する樹脂フィルムが得られ易い。 R 5 may be a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted. The number of carbon atoms of this alkyl group may be 8 or more or 12 or more, 16 or less or 14 or less, or 13 carbon atoms. When the number of carbon atoms of the alkyl group is within these numerical ranges, it is easy to obtain a resin film having a hydrophilic surface and having higher permeability to water vapor.
Ｒ５のアルキル基の例としては、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、及びｎ−テトラデシル基が挙げられる。Ｒ５のアルキル基は、例えば、ハロゲン原子、アリール基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アシルオキシ基、アシル基、アルキルスルファニル基、及びアリールスルファニル基からなる群より選ばれる少なくとも１種の置換基で置換されていてもよい。 Examples of the alkyl group R 5 is, n- octyl, n- nonyl, n- decyl, n- undecyl, n- dodecyl group, n- tridecyl group, and n- tetradecyl group. The alkyl group of R 5 is at least one selected from the group consisting of, for example, a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acyl group, an alkylsulfanyl group, and an arylsulfanyl group. It may be substituted with a substituent.
変性ポリオレフィン系共重合体は、オレフィン単位及びスルホネート単位に加えて、その他のモノマー単位を更に有してもよい。 The modified polyolefin-based copolymer may further have other monomer units in addition to the olefin unit and the sulfonate unit.
変性ポリオレフィン材料は、スルホン酸基と含窒素基とによって形成された塩であるスルホネート基を有するスルホネート化合物を更に含んでもよい。このスルホネート化合物は、ポリオレフィン系共重合体ではない、比較的低分子量の化合物である。このスルホネート化合物は、例えば下記式（２）で表される。
Ｚは、非イオン性の有機基を示し、式（１）中のＺと同様の基であることができる。Ｑ＋は含窒素カチオンを示す。式（１）中のＺと式（２）中のＺは同一でも異なってもよい。Ｑ＋は、スルホン酸基と塩を形成し得る含窒素カチオンであればよく、その例としては、脂肪族アミン、芳香族アミン又は含窒素複素芳香化合物にプロトンが付加して形成された含窒素カチオン、４級アンモニウム化合物、及びアンモニウムイオン（ＮＨ４ ＋）が挙げられる。 Z represents a nonionic organic group and can be a group similar to Z in the formula (1). Q + indicates a nitrogen-containing cation. Z in the formula (1) and Z in the formula (2) may be the same or different. Q + may be a nitrogen-containing cation capable of forming a salt with a sulfonic acid group, and examples thereof include nitrogen-containing amines, aromatic amines, or nitrogen-containing heteroaromatic compounds formed by adding protons. cationic, quaternary ammonium compounds, and ammonium ion (NH 4 +) and the like.
変性ポリオレフィン材料における上記スルホネート化合物の含有量は、変性ポリオレフィン材料の質量を基準として、０〜５質量％、０〜４質量％、０〜３質量％、０〜２質量％又は０〜１質量％であってもよい。 The content of the sulfonate compound in the modified polyolefin material is 0 to 5% by mass, 0 to 4% by mass, 0 to 3% by mass, 0 to 2% by mass, or 0 to 1% by mass based on the mass of the modified polyolefin material. It may be.
変性ポリオレフィン材料が上記スルホネート化合物を含む場合、変性ポリオレフィン材料中には、変性ポリオレフィン系共重合体のスルホネート単位が有するスルホネート基、及び、スルホネート化合物が有するスルホネート基が存在する。変性ポリオレフィン材料において、スルホネート単位が有するスルホネート基、及びスルホネート化合物が有するスルホネート基の合計の割合が、変性ポリオレフィン系共重合体中の全モノマー単位の量に対して、０．１〜２．０モル％であってもよい。これにより、より一層優れた水蒸気に対する透過性を有する樹脂フィルムが得られ易い。 When the modified polyolefin material contains the above-mentioned sulfonate compound, the modified polyolefin material contains a sulfonate group contained in the sulfonate unit of the modified polyolefin-based copolymer and a sulfonate group contained in the sulfonate compound. In the modified polyolefin material, the total ratio of the sulfonate group contained in the sulfonate unit and the sulfonate group contained in the sulfonate compound is 0.1 to 2.0 mol with respect to the amount of all monomer units in the modified polyolefin-based copolymer. May be%. As a result, it is easy to obtain a resin film having even better water vapor permeability.
変性ポリオレフィン材料は、変性ポリオレフィン系共重合体及びスルホネート化合物の他に、必要によりその他の成分を更に含んでもよい。その他の成分の例としては、架橋剤、酸化防止剤、紫外線吸収剤、光安定剤、充填剤、補強剤、帯電防止剤、顔料、及び改質用樹脂が挙げられる。その他の成分の合計の含有量は、変性ポリオレフィン材料の質量を基準として、０〜２０質量％、又は０〜１０質量％であってもよい。 The modified polyolefin material may further contain other components, if necessary, in addition to the modified polyolefin-based copolymer and the sulfonate compound. Examples of other components include cross-linking agents, antioxidants, UV absorbers, light stabilizers, fillers, reinforcing agents, antistatic agents, pigments, and modifying resins. The total content of the other components may be 0 to 20% by mass or 0 to 10% by mass based on the mass of the modified polyolefin material.
変性ポリオレフィン材料は、例えば、オレフィンと、スルホネート基及び重合性不飽和基を有するスルホネートモノマーとを含むモノマー混合物を重合する方法、又は、官能基を有する変性ポリオレフィン系共重合体にスルホネート基を導入する方法により、製造することができる。 The modified polyolefin material is, for example, a method of polymerizing a monomer mixture containing an olefin and a sulfonate monomer having a sulfonate group and a polymerizable unsaturated group, or introducing a sulfonate group into a modified polyolefin-based copolymer having a functional group. It can be manufactured by the method.
オレフィンと、スルホネート基及び重合性不飽和基を有するスルホネートモノマーとを含むモノマー混合物を重合する方法の場合、高圧重合法等の任意の重合法を採用することができる。この場合、スルホネートモノマー及び／又はこれから誘導されたスルホネート化合物が、変性ポリオレフィン材料中に残存し得る。 In the case of a method of polymerizing a monomer mixture containing an olefin and a sulfonate monomer having a sulfonate group and a polymerizable unsaturated group, any polymerization method such as a high-pressure polymerization method can be adopted. In this case, the sulfonate monomer and / or the sulfonate compound derived from the sulfonate compound may remain in the modified polyolefin material.
官能基を有する変性ポリオレフィン系共重合体にスルホネート基を導入する方法は、例えば、オレフィンと官能基を有する共重合モノマーとを含むモノマー混合物を重合させて、官能基を有する変性ポリオレフィン系共重合体を形成する工程と、官能基が関与する反応を含む方法によってスルホネート基を導入する工程とを含む。 The method of introducing a sulfonate group into a modified polyolefin-based copolymer having a functional group is, for example, a method of polymerizing a monomer mixture containing an olefin and a copolymerized monomer having a functional group to polymerize a modified polyolefin-based copolymer having a functional group. Includes a step of forming the sulfonate group and a step of introducing a sulfonate group by a method involving a reaction involving a functional group.
共重合体モノマーの官能基が含窒素基である、すなわち、変性ポリオレフィン系共重合体が含窒素モノマー単位を含む場合、含窒素基とスルホネート化合物との反応により、スルホネート化合物のスルホン酸基と含窒素基とによって形成された塩であるスルホネート基を導入することができる。共重合体モノマーの官能基と含窒素化合物との反応により含窒素基を導入し、導入された含窒素基とスルホネート化合物との反応によりスルホネート基を導入してもよい。スルホネート化合物は、上述の式（２）で表される化合物であってもよい。少量のスルホネート化合物が、変性ポリオレフィン材料中に残存し得る。 When the functional group of the copolymer monomer is a nitrogen-containing group, that is, when the modified polyolefin-based copolymer contains a nitrogen-containing monomer unit, the reaction between the nitrogen-containing group and the sulfonate compound contains the sulfonic acid group of the sulfonate compound. A sulfonate group, which is a salt formed by a nitrogen group, can be introduced. A nitrogen-containing group may be introduced by a reaction between a functional group of a copolymer monomer and a nitrogen-containing compound, and a sulfonate group may be introduced by a reaction between the introduced nitrogen-containing group and a sulfonate compound. The sulfonate compound may be a compound represented by the above formula (2). A small amount of sulfonate compound may remain in the modified polyolefin material.
下記反応式は、共重合モノマーが官能基としてアルキルエステル基を有するメチルアクリレートである場合に、アルキルエステル基が関与する反応を含む、スルホネート基を導入する方法の一例を示す。この反応式は、アルキルエステル基を有する変性ポリオレフィン系共重合体２０とアミノ基及び水酸基を有する含窒素化合物２１との反応により、アミノ基を有するアミン変性ポリオレフィン系共重合体２２を得ることと、アミン変性ポリオレフィン系共重合体２２と式（２）で表されるスルホネート化合物との反応により、スルホネート基を有する変性ポリオレフィン系共重合体２３を得ることとを含む。 The following reaction formula shows an example of a method for introducing a sulfonate group, which comprises a reaction involving an alkyl ester group when the copolymerization monomer is a methyl acrylate having an alkyl ester group as a functional group. This reaction formula is to obtain an amine-modified polyolefin-based copolymer 22 having an amino group by reacting a modified polyolefin-based copolymer 20 having an alkyl ester group with a nitrogen-containing compound 21 having an amino group and a hydroxyl group. The reaction of the amine-modified polyolefin-based copolymer 22 with the sulfonate compound represented by the formula (2) includes obtaining a modified polyolefin-based copolymer 23 having a sulfonate group.
上記反応式中、ｐ及びｑは、それぞれ、オレフィン及びメチルアクリレートの重合度を示す整数であり、Ｒ１及びＲ２は式（１）中のＲ１及びＲ２と同義であり、Ｒ４はアルキレン基（例えばエチレン基）を示す。各反応は、必要により触媒を用いて行われる。 In the above reaction formula, p and q are integers indicating the degree of polymerization of olefin and methyl acrylate, respectively, R 1 and R 2 are synonymous with R 1 and R 2 in the formula (1), and R 4 is Indicates an alkylene group (for example, an ethylene group). Each reaction is carried out with a catalyst, if necessary.
スルホネート基を有する変性ポリオレフィン系共重合体のメルトフローレート（ＭＦＲ）の上限値は、樹脂フィルム製造の容易性の観点から、５０ｇ／１０分、又は４０ｇ／１０分以下であってもよい。ＭＦＲの下限値は、樹脂フィルム製造時の負荷低減の観点から、０．１ｇ／１０分、又は１ｇ／１０分であってもよい。ＭＦＲは、ＪＩＳ Ｋ７２１０−１９９５に規定された方法により、温度１９０℃、荷重２１．１８Ｎで測定される。 The upper limit of the melt flow rate (MFR) of the modified polyolefin-based copolymer having a sulfonate group may be 50 g / 10 minutes or 40 g / 10 minutes or less from the viewpoint of ease of producing a resin film. The lower limit of MFR may be 0.1 g / 10 minutes or 1 g / 10 minutes from the viewpoint of reducing the load during resin film production. MFR is measured at a temperature of 190 ° C. and a load of 21.18 N by the method specified in JIS K7210-1995.
スルホネート基を有する変性ポリオレフィン系共重合体の分子量分布（Ｍｗ／Ｍｎ）の下限値は、樹脂フィルム製造時の押出負荷の低減の観点から、２、２．５、又は３であってもよい。分子量分布（Ｍｗ／Ｍｎ）の上限値は、樹脂フィルムの高い機械的強度の観点から、８、５、４．５、又は４であってもよい。ここでの分子量分布（Ｍｗ／Ｍｎ）は、ゲル・パーミエイション・クロマトグラフを用いて求められる、標準ポリスチレン換算の重量平均分子量Ｍｗ、及び標準ポリスチレン換算の数平均分子量Ｍｎから計算される値である。 The lower limit of the molecular weight distribution (Mw / Mn) of the modified polyolefin-based copolymer having a sulfonate group may be 2, 2.5, or 3 from the viewpoint of reducing the extrusion load during the production of the resin film. The upper limit of the molecular weight distribution (Mw / Mn) may be 8, 5, 4.5, or 4 from the viewpoint of the high mechanical strength of the resin film. The molecular weight distribution (Mw / Mn) here is a value calculated from the weight average molecular weight Mw converted to standard polystyrene and the number average molecular weight Mn converted to standard polystyrene, which are obtained using a gel permeation chromatograph. is there.
スルホネート基を有する変性ポリオレフィン系共重合体のポリエチレン換算の重量平均分子量は、樹脂フィルムのロールからのより良好な剥離性の観点から、４００００以上８００００以下、又は５００００以上７００００以下であってもよい。ポリエチレン換算の重量平均分子量は、ゲル・パーミエイション・クロマトグラフ測定によって求められた標準ポリスチレン換算の重量平均分子量と、ポリエチレンとポリスチレンのＱファクターの比（１７．７／４１．３）との積である。 The polyethylene-equivalent weight average molecular weight of the modified polyolefin-based copolymer having a sulfonate group may be 40,000 or more and 80,000 or less, or 50,000 or more and 70,000 or less, from the viewpoint of better peelability from the roll of the resin film. The polyethylene-equivalent weight average molecular weight is the product of the standard polystyrene-equivalent weight average molecular weight determined by gel permeation chromatograph measurement and the ratio of the Q factor of polyethylene to polystyrene (17.7 / 41.3). Is.
一実施形態に係る樹脂フィルムは、以上説明した変性ポリオレフィン材料からなる成形体である。樹脂フィルムの厚さは、例えば１０〜１００μｍであってもよい。樹脂フィルムは、Ｔ−ダイ法、インフレーション法またはプレス成形等の通常の方法で製造することができる。 The resin film according to one embodiment is a molded product made of the modified polyolefin material described above. The thickness of the resin film may be, for example, 10 to 100 μm. The resin film can be produced by a usual method such as a T-die method, an inflation method or press molding.
樹脂フィルムは、水蒸気に対する高い透過性を有することから、例えば包装材料として有用である。包装材料は、青果物等の食品用包装材料であってもよい。包装材料は、変性ポリオレフィン材料を含む単層の樹脂フィルムであってもよいし、微多孔膜、接着層等の他の層を更に有する積層フィルムであってもよい。包装材料の厚さは、１０μｍより薄いと、均一な厚みに製膜することが困難であり、２００μｍより厚いと水蒸気の透過度が小さくなる。樹脂フィルム（包装材料）の厚さが１５〜１５０μｍであってもよい。 Since the resin film has high permeability to water vapor, it is useful as a packaging material, for example. The packaging material may be a food packaging material such as fruits and vegetables. The packaging material may be a single-layer resin film containing a modified polyolefin material, or may be a laminated film further having another layer such as a microporous film or an adhesive layer. If the thickness of the packaging material is thinner than 10 μm, it is difficult to form a film with a uniform thickness, and if it is thicker than 200 μm, the water vapor permeability becomes small. The thickness of the resin film (packaging material) may be 15 to 150 μm.
以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
１．含窒素基を有する変性ポリオレフィン系共重合体の合成
合成例１
５００ｍＬのセパラブルフラスコに、１００ｇのエチレン−メチルアクリレート共重合体と、２００ｍＬのジエチルアミノエタノールとを入れた。フラスコ内の反応液を、１６０℃に加熱しながらメカニカルスターラーにて攪拌した。反応液が均一な粘性溶液になった時点で、０．４ｍＬのテトライソプロポキシチタンを注入し、反応液を１６０℃で更に８時間攪拌した。その後、反応液を多量のエタノールに注ぎ込み、生成したアミン変性ポリオレフィン系共重合体をエタノール中で固化させた。回収した固形のアミン変性ポリオレフィン系共重合体Ａを８０℃で８時間、真空乾燥した。
エチレン−メチルアクリレート共重合体として、エチレン単位の含有量が８０質量％、メチルアクリレート単位の含有量が２０質量％、メルトフローレート（ＭＦＲ）が７ｇ／１０分のものを用いた。
1. 1. Synthesis of modified polyolefin-based copolymer having a nitrogen-containing group Synthesis Example 1
100 g of ethylene-methylacrylate copolymer and 200 mL of diethylaminoethanol were placed in a 500 mL separable flask. The reaction solution in the flask was stirred with a mechanical stirrer while heating at 160 ° C. When the reaction solution became a uniform viscous solution, 0.4 mL of tetraisopropoxytitanium was injected, and the reaction solution was stirred at 160 ° C. for another 8 hours. Then, the reaction solution was poured into a large amount of ethanol, and the produced amine-modified polyolefin-based copolymer was solidified in ethanol. The recovered solid amine-modified polyolefin-based copolymer A was vacuum-dried at 80 ° C. for 8 hours.
As the ethylene-methyl acrylate copolymer, one having an ethylene unit content of 80% by mass, a methyl acrylate unit content of 20% by mass, and a melt flow rate (MFR) of 7 g / 10 minutes was used.
合成例２
エチレン−メチルメタクリレート共重合体として、エチレン単位の含有量が７５質量％、メチルアクリレート単位の含有量が２５質量％、ＭＦＲが７ｇ／１０分のものを用いたこと以外は合成例１と同様にして、固形のアミン変性ポリオレフィン系共重合体Ｂを得た。
Synthesis example 2
The same as in Synthesis Example 1 except that an ethylene-methylmethacrylate copolymer having an ethylene unit content of 75% by mass, a methylacrylate unit content of 25% by mass, and an MFR of 7 g / 10 minutes was used. A solid amine-modified polyolefin-based copolymer B was obtained.
２．スルホネート基を有する変性ポリオレフィン系共重合体の合成
以下のスルホン酸アンモニウム化合物１〜６を準備した。
実施例１
３００ｍＬのフラスコバイアルに、アミン変性ポリオレフィン系共重合体Ａを２０ｇと、トルエン１００ｍｌと、スルホン酸アンモニウム化合物１を１．２８ｇとを入れ、フラスコバイアル内の反応液を１００℃で加熱しながら８時間攪拌した。スルホン酸アンモニウム化合物１の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．３４モル％であった。加熱攪拌の後、反応液を大量のアルコールに注ぎ込み、生成したスルホネート基を有する変性ポリオレフィン系共重合体をアルコール中で固化させた。固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を８０℃で８時間、真空乾燥した。
Example 1
20 g of amine-modified polyolefin-based copolymer A, 100 ml of toluene, and 1.28 g of ammonium sulfonate compound 1 were placed in a 300 mL flask vial, and the reaction solution in the flask vial was heated at 100 ° C. for 8 hours. Stirred. The ratio of the charged amount of the ammonium sulfonate compound 1 was 0.34 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit. After heating and stirring, the reaction solution was poured into a large amount of alcohol, and the generated modified polyolefin-based copolymer having a sulfonate group was solidified in the alcohol. The modified polyolefin material containing the solid modified polyolefin-based copolymer was vacuum dried at 80 ° C. for 8 hours.
実施例２
３００ｍＬのフラスコバイアルに、アミン変性ポリオレフィン系共重合体Ｂを２０ｇと、トルエン１００ｍｌと、スルホン酸アンモニウム化合物１を１．４０ｇとを入れ、フラスコバイアル内の反応液を１００℃で加熱しながら８時間攪拌した。スルホン酸アンモニウム化合物１の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．４０モル％であった。加熱攪拌の後、反応液を大量のアルコールに注ぎ込み、生成したスルホネート基を有する変性ポリオレフィン系共重合体をアルコール中で固化させた。固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を８０℃で８時間、真空乾燥した。
Example 2
20 g of amine-modified polyolefin-based copolymer B, 100 ml of toluene, and 1.40 g of ammonium sulfonate compound 1 were placed in a 300 mL flask vial, and the reaction solution in the flask vial was heated at 100 ° C. for 8 hours. Stirred. The ratio of the charged amount of the ammonium sulfonate compound 1 was 0.40 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit. After heating and stirring, the reaction solution was poured into a large amount of alcohol, and the generated modified polyolefin-based copolymer having a sulfonate group was solidified in the alcohol. The modified polyolefin material containing the solid modified polyolefin-based copolymer was vacuum dried at 80 ° C. for 8 hours.
実施例３
スルホン酸アンモニウム化合物１に代えて、スルホン酸アンモニウム化合物２の１．２８ｇを用いたこと以外は実施例１と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物２の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．３６モル％であった。
Example 3
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was prepared in the same manner as in Example 1 except that 1.28 g of ammonium sulfonate compound 2 was used instead of ammonium sulfonate compound 1. Obtained. The ratio of the charged amount of the ammonium sulfonate compound 2 was 0.36 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例４
スルホン酸アンモニウム化合物１に代えて、スルホン酸アンモニウム化合物３の１．２８ｇを用いたこと以外は実施例１と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物３の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．３２モル％であった。
Example 4
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was prepared in the same manner as in Example 1 except that 1.28 g of ammonium sulfonate compound 3 was used instead of ammonium sulfonate compound 1. Obtained. The ratio of the charged amount of the ammonium sulfonate compound 3 was 0.32 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例５
スルホン酸アンモニウム化合物１に代えて、スルホン酸アンモニウム化合物４の１．００ｇを用いたこと以外は実施例２と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物３の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．４０モル％であった。
Example 5
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was prepared in the same manner as in Example 2 except that 1.00 g of ammonium sulfonate compound 4 was used instead of the ammonium sulfonate compound 1. Obtained. The ratio of the charged amount of the ammonium sulfonate compound 3 was 0.40 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例６
スルホン酸アンモニウム化合物１に代えて、スルホン酸アンモニウム化合物５の２．２２ｇを用いたこと以外は実施例２と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物３の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．４０モル％であった。
Example 6
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was prepared in the same manner as in Example 2 except that 2.22 g of ammonium sulfonate compound 5 was used instead of ammonium sulfonate compound 1. Obtained. The ratio of the charged amount of the ammonium sulfonate compound 3 was 0.40 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例７
スルホン酸アンモニウム化合物１に代えて、スルホン酸アンモニウム化合物６の０．６２ｇを用いたこと以外は実施例２と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物６の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．４０モル％であった。
Example 7
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was prepared in the same manner as in Example 2 except that 0.62 g of ammonium sulfonate compound 6 was used instead of the ammonium sulfonate compound 1. Obtained. The ratio of the charged amount of the ammonium sulfonate compound 6 was 0.40 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例８
スルホン酸アンモニウム化合物１の量を２．７３ｇに変更したこと以外は実施例１と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物６の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．７２モル％であった。
Example 8
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was obtained in the same manner as in Example 1 except that the amount of ammonium sulfonate compound 1 was changed to 2.73 g. The ratio of the charged amount of the ammonium sulfonate compound 6 was 0.72 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例９
スルホン酸アンモニウム化合物１の量を１．７４ｇに変更したこと以外は実施例１と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物６の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．４６モル％であった。
Example 9
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was obtained in the same manner as in Example 1 except that the amount of ammonium sulfonate compound 1 was changed to 1.74 g. The ratio of the charged amount of the ammonium sulfonate compound 6 was 0.46 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例１０
スルホン酸アンモニウム化合物１の量を１．５１ｇに変更したこと以外は実施例１と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物６の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．４０モル％であった。
Example 10
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was obtained in the same manner as in Example 1 except that the amount of the ammonium sulfonate compound 1 was changed to 1.51 g. The ratio of the charged amount of the ammonium sulfonate compound 6 was 0.40 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例１１
スルホン酸アンモニウム化合物１の量を０．４１ｇに変更したこと以外は実施例１と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物６の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．１１モル％であった。
Example 11
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was obtained in the same manner as in Example 1 except that the amount of ammonium sulfonate compound 1 was changed to 0.41 g. The ratio of the charged amount of the ammonium sulfonate compound 6 was 0.11 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
実施例１２
スルホン酸アンモニウム化合物１の量を０．２０ｇに変更したこと以外は実施例１と同様にして、スルホネート基を有する固形の変性ポリオレフィン系共重合体を含む変性ポリオレフィン材料を得た。スルホン酸アンモニウム化合物６の仕込み量の比率は、エチレン単位及びＮ，Ｎ―ジエチルアミノエチルアクリレート単位の合計量に対して０．０６モル％であった。
Example 12
A modified polyolefin material containing a solid modified polyolefin-based copolymer having a sulfonate group was obtained in the same manner as in Example 1 except that the amount of ammonium sulfonate compound 1 was changed to 0.20 g. The ratio of the charged amount of the ammonium sulfonate compound 6 was 0.06 mol% with respect to the total amount of the ethylene unit and the N, N-diethylaminoethyl acrylate unit.
比較例１
低密度ポリエチレン（ＬＤＰＥ）（スミカセンＬ７０５、住友化学株式会社製、密度：９１９ｋｇ／ｍ３、ＭＦＲ：７ｇ／１０分）を、比較例１のポリエチレンとして準備した。
Comparative Example 1
Low-density polyethylene (LDPE) (Sumikasen L705, manufactured by Sumitomo Chemical Co., Ltd., density: 919 kg / m 3 , MFR: 7 g / 10 minutes) was prepared as the polyethylene of Comparative Example 1.
比較例２
合成例１で使用したエチレン−メチルアクリレート共重合体を、比較例２として評価した。
Comparative Example 2
The ethylene-methyl acrylate copolymer used in Synthesis Example 1 was evaluated as Comparative Example 2.
比較例３
合成例２で使用したエチレン−メチルメタクリレート共重合体を、比較例３として評価した。
Comparative Example 3
The ethylene-methylmethacrylate copolymer used in Synthesis Example 2 was evaluated as Comparative Example 3.
３．水蒸気透過性の評価
各変性ポリオレフィン材料を、プレス成形によって成形して、１００μｍの厚さの樹脂フィルムを得た。得られた樹脂フィルムの水蒸気透過率を、水蒸気透過率測定装置（ＭＯＣＯＮ社製「ＰＥＲＭＡＴＲＡＮ−Ｗ ３／３３」）を用いて、ＪＩＳ Ｋ７１２９ Ｂ法に準じた４０℃、９０％ＲＨの条件下で測定した。結果を表１、表２及び表３に示す。
3. 3. Evaluation of Water Vapor Permeability Each modified polyolefin material was molded by press molding to obtain a resin film having a thickness of 100 μm. The water vapor transmittance of the obtained resin film was measured using a water vapor transmittance measuring device (“PERMATRAN-W 3/33” manufactured by MOCON) under the conditions of 40 ° C. and 90% RH according to the JIS K7129B method. It was measured. The results are shown in Table 1, Table 2 and Table 3.
Claims (6)
前記スルホネート単位が有する前記スルホネート基、及び前記スルホネート化合物が有する前記スルホネート基の合計の割合が、前記変性ポリオレフィン系共重合体中の全モノマー単位の量に対して、０．１〜２．０モル％である、請求項１に記載の変性ポリオレフィン材料。 The modified polyolefin material may further contain a sulfonate compound which has a sulfonate group which is a salt formed by a sulfonic acid group and a nitrogen-containing group and is different from the modified polyolefin-based copolymer.
The total ratio of the sulfonate group contained in the sulfonate unit and the sulfonate group contained in the sulfonate compound is 0.1 to 2.0 mol with respect to the amount of all monomer units in the modified polyolefin-based copolymer. %, The modified polyolefin material according to claim 1.
で表される単位であり、
Ｒ１、Ｒ２及びＲ３は、それぞれ独立に、水素原子、又は、非イオン性の有機基を示し、互いに結合して環状基を形成していてもよく、
Ｚは非イオン性の有機基を示し、
Ｘは、直接結合、又は、非イオン性の有機基を示す、
請求項１又は２に記載の変性ポリオレフィン材料。 The sulfonate unit is the following formula (1):
It is a unit represented by
R 1 , R 2 and R 3 each independently represent a hydrogen atom or a nonionic organic group, and may be bonded to each other to form a cyclic group.
Z represents a nonionic organic group
X represents a directly bonded or nonionic organic group,
The modified polyolefin material according to claim 1 or 2.
変性ポリオレフィン材料を製造する方法。 A modified polyolefin-based copolymer having an olefin unit and a nitrogen-containing monomer unit having a nitrogen-containing group is reacted with a sulfonate compound having a sulfonate group which is a salt of a sulfonic acid group and a nitrogen-containing group, whereby the sulfonate is described. A step of forming a modified polyolefin-based copolymer having a sulfonate unit having a sulfonate group, which is a salt formed by the sulfonic acid group of the compound and the nitrogen-containing group of the nitrogen-containing monomer unit, is provided.
A method for producing a modified polyolefin material.
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