JP2016187933A - Multilayer film - Google Patents
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- JP2016187933A JP2016187933A JP2015069167A JP2015069167A JP2016187933A JP 2016187933 A JP2016187933 A JP 2016187933A JP 2015069167 A JP2015069167 A JP 2015069167A JP 2015069167 A JP2015069167 A JP 2015069167A JP 2016187933 A JP2016187933 A JP 2016187933A
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- 229920005989 resin Polymers 0.000 claims abstract description 141
- 239000011347 resin Substances 0.000 claims abstract description 141
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 31
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 60
- 239000005977 Ethylene Substances 0.000 claims description 60
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000005227 gel permeation chromatography Methods 0.000 claims description 9
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 72
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 239000004711 α-olefin Substances 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 17
- -1 polypropylene Polymers 0.000 description 13
- 229920005604 random copolymer Polymers 0.000 description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 229920001155 polypropylene Polymers 0.000 description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- 101000573151 Arabidopsis thaliana Probable pectinesterase 8 Proteins 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 229940106006 1-eicosene Drugs 0.000 description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 description 2
- BWEKDYGHDCHWEN-UHFFFAOYSA-N 2-methylhex-2-ene Chemical compound CCCC=C(C)C BWEKDYGHDCHWEN-UHFFFAOYSA-N 0.000 description 2
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 2
- JTXUVHFRSRTSAT-UHFFFAOYSA-N 3,5,5-trimethylhex-1-ene Chemical compound C=CC(C)CC(C)(C)C JTXUVHFRSRTSAT-UHFFFAOYSA-N 0.000 description 2
- AUJLDZJNMXNESO-UHFFFAOYSA-N 3-ethylhex-3-ene Chemical compound CCC=C(CC)CC AUJLDZJNMXNESO-UHFFFAOYSA-N 0.000 description 2
- KNIRLWRQSSLZCZ-UHFFFAOYSA-N 3-ethyloct-3-ene Chemical compound CCCCC=C(CC)CC KNIRLWRQSSLZCZ-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- AAUHUDBDDBJONC-UHFFFAOYSA-N 3-methylhept-3-ene Chemical compound CCCC=C(C)CC AAUHUDBDDBJONC-UHFFFAOYSA-N 0.000 description 2
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical compound CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 2
- KZJIOVQKSAOPOP-UHFFFAOYSA-N 5,5-dimethylhex-1-ene Chemical compound CC(C)(C)CCC=C KZJIOVQKSAOPOP-UHFFFAOYSA-N 0.000 description 2
- 229920003355 Novatec® Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 2
- GVRWIAHBVAYKIZ-UHFFFAOYSA-N dec-3-ene Chemical compound CCCCCCC=CCC GVRWIAHBVAYKIZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- RGTDIFHVRPXHFT-UHFFFAOYSA-N 3-methylnon-3-ene Chemical compound CCCCCC=C(C)CC RGTDIFHVRPXHFT-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- BSJOLASGNWRVEH-UHFFFAOYSA-N 7,7-dimethyloct-1-ene Chemical compound CC(C)(C)CCCCC=C BSJOLASGNWRVEH-UHFFFAOYSA-N 0.000 description 1
- 101001094880 Arabidopsis thaliana Pectinesterase 4 Proteins 0.000 description 1
- CHZURPLULAEAHS-UHFFFAOYSA-N CC(C=C)CC.CC(CC=C)(C)C Chemical compound CC(C=C)CC.CC(CC=C)(C)C CHZURPLULAEAHS-UHFFFAOYSA-N 0.000 description 1
- 108700018427 F 327 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940038553 attane Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IYYGCUZHHGZXGJ-UHFFFAOYSA-N but-1-ene;ethene;prop-1-ene Chemical compound C=C.CC=C.CCC=C IYYGCUZHHGZXGJ-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- GJTGYNPBJNRYKI-UHFFFAOYSA-N hex-1-ene;prop-1-ene Chemical compound CC=C.CCCCC=C GJTGYNPBJNRYKI-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QAXLLGNKYJQIQK-UHFFFAOYSA-N oct-1-ene;prop-1-ene Chemical compound CC=C.CCCCCCC=C QAXLLGNKYJQIQK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明は多層フィルムに関する。 The present invention relates to a multilayer film.
プロピレン単独重合体は剛性、耐熱性、耐油性等に優れるため、ポリプロピレンフィルムは食品包装分野や産業資材分野などにおいて広く使用されている。また、ポリプロピレンフィルムを延伸したフィルム（ＯＰＰフィルム）は、剛性、引張強度に優れ、また伸びも小さいことから印刷特性にも優れる。 Since propylene homopolymers are excellent in rigidity, heat resistance, oil resistance, etc., polypropylene films are widely used in the food packaging field, the industrial material field, and the like. In addition, a film obtained by stretching a polypropylene film (OPP film) is excellent in rigidity and tensile strength, and is excellent in printing characteristics because of its small elongation.
しかしながら、ＯＰＰフィルムは低温での耐ピンホール性が劣る。また、ヒートシールのためには別途接着層が必要であり、加工コストが高く、焼却時に有害物質が発生することが懸念されている。 However, the OPP film has poor pinhole resistance at low temperatures. In addition, a separate adhesive layer is required for heat sealing, and the processing cost is high, and there is a concern that harmful substances are generated during incineration.
特許文献１には、低密度ポリエチレンの延伸フィルムと、ポリプロピレンフィルムとの積層体が、耐ピンホール性等に優れることが記載されている。また、特許文献２には、引裂バランスに優れる二軸延伸可能なポリエチレン系フィルムが記載されている。特許文献３には、表面が荒れていて少なくとも外層の１層がメタロセンにより製造されたポリエチレン層であって、その厚みが全体の２〜７％であり、片側がコロナ放電により荒らされたインクがのりやすい二軸延伸フィルムが記載されている。 Patent Document 1 describes that a laminate of a low-density polyethylene stretched film and a polypropylene film is excellent in pinhole resistance and the like. Patent Document 2 describes a biaxially stretchable polyethylene film excellent in tear balance. Patent Document 3 discloses an ink whose surface is rough and at least one outer layer is a polyethylene layer made of metallocene, the thickness of which is 2 to 7% of the whole, and one side is roughened by corona discharge. A biaxially stretched film that is easy to paste is described.
しかしながら、特許文献１記載の積層体ではヒートシールのためには接着層が必要である。また、特許文献２記載のフィルムは十分に薄くすることができず、ＯＰＰフィルムと積層した際にＯＰＰフィルムの物性を損なう場合がある。また、特許文献３には、ヒートシール性に関する記載がなく、またどのような物性を示すフィルムが製造されているのか記載がなく不明である。 However, the laminate described in Patent Document 1 requires an adhesive layer for heat sealing. In addition, the film described in Patent Document 2 cannot be made sufficiently thin, and the physical properties of the OPP film may be impaired when laminated with the OPP film. Further, Patent Document 3 has no description regarding heat-sealability, and it is unclear because there is no description of what physical properties are produced.
本発明は、引張強度および引裂バランスが高く、耐ピンホール性に優れ、低温にてヒートシールを行うことができ、成形時、延伸時の安定性が高い多層フィルムを提供することを目的とする。 An object of the present invention is to provide a multilayer film having high tensile strength and tear balance, excellent pinhole resistance, heat sealing at low temperature, and high stability during molding and stretching. .
本発明は以下の［１］〜［４］である。 The present invention includes the following [1] to [4].
［１］下記要件（Ａ１）〜（Ａ５）を満たすエチレン系樹脂（Ａ）を含む樹脂層（Ｉ）と、プロピレン系樹脂（Ｂ）を含む樹脂層（ＩＩ）と、を含み、
前記樹脂層（Ｉ）と前記樹脂層（ＩＩ）との厚みの比（樹脂層（Ｉ）／樹脂層（ＩＩ））が１／１４〜１／３である多層フィルム。
要件（Ａ１）：ＡＳＴＭ Ｄ１２３８に準じて１９０℃、２．１６ｋｇ荷重で測定したメルトフローレート（ＭＦＲ）が０．５〜５０．０ｇ／１０分である。
要件（Ａ２）：ＪＩＳ Ｋ６９２２に準じて測定した密度が８９０〜９４０ｋｇ／ｍ３である。
要件（Ａ３）：示差走査熱量測定（ＤＳＣ）で測定した融点が８０〜１３５℃である。
要件（Ａ４）：ゲル浸透クロマトグラフィ（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）と、数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が２．０〜９．０である。
要件（Ａ５）：ＪＩＳ Ｋ６９２１に準じて１０ｋｇ荷重、１９０℃で測定したメルトフローレート（ｇ／１０分）（ＭＦＲ１０）と、ＪＩＳ Ｋ６９２１に準じて２．１６ｋｇ荷重、１９０℃で測定したメルトフローレート（ｇ／１０分）（ＭＦＲ２．１６）との比（ＭＦＲ１０／ＭＦＲ２．１６）が４．０〜９．５である。
[1] A resin layer (I) containing an ethylene resin (A) that satisfies the following requirements (A1) to (A5), and a resin layer (II) containing a propylene resin (B),
The multilayer film whose ratio (resin layer (I) / resin layer (II)) of the resin layer (I) and the resin layer (II) is 1/14 to 1/3.
Requirement (A1): Melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238 is 0.5 to 50.0 g / 10 min.
Requirement (A2): The density measured according to JIS K6922 is 890 to 940 kg / m 3 .
Requirement (A3): Melting point measured by differential scanning calorimetry (DSC) is 80 to 135 ° C.
Requirement (A4): The ratio (Mw / Mn) between the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) and the number average molecular weight (Mn) is 2.0 to 9.0.
Requirement (A5): Melt flow rate measured at 190 ° C with a load of 10 kg according to JIS K6921 (g / 10 min) (MFR10) and Melt flow rate measured at 190 ° C with a load of 2.16 kg according to JIS K6921 The ratio (MFR10 / MFR2.16) to (g / 10 minutes) (MFR2.16) is 4.0 to 9.5.
［２］前記エチレン系樹脂（Ａ）が、さらに下記要件（Ａ６）を満たす［１］に記載の多層フィルム。
要件（Ａ６）：前記ＭＦＲ１０／ＭＦＲ２．１６が５．０以上の場合、前記Ｍｗ／Ｍｎが２．５以上である。
[2] The multilayer film according to [1], wherein the ethylene resin (A) further satisfies the following requirement (A6).
Requirement (A6): When the MFR10 / MFR2.16 is 5.0 or more, the Mw / Mn is 2.5 or more.
［３］前記多層フィルムの少なくとも一方の表面に、前記樹脂層（Ｉ）が配置されている［１］又は［２］に記載の多層フィルム。 [3] The multilayer film according to [1] or [2], wherein the resin layer (I) is disposed on at least one surface of the multilayer film.
［４］前記多層フィルムが延伸多層フィルムである［１］から［３］のいずれかに記載の多層フィルム。 [4] The multilayer film according to any one of [1] to [3], wherein the multilayer film is a stretched multilayer film.
本発明によれば、引張強度および引裂バランスが高く、耐ピンホール性に優れ、低温にてヒートシールを行うことができ、成形時、延伸時の安定性が高い多層フィルムを提供することができる。 According to the present invention, it is possible to provide a multilayer film having high tensile strength and tear balance, excellent pinhole resistance, heat sealing at low temperature, and high stability during molding and stretching. .
本発明に係る多層フィルムは、下記要件（Ａ１）〜（Ａ５）を満たすエチレン系樹脂（Ａ）を含む樹脂層（Ｉ）と、プロピレン系樹脂（Ｂ）を含む樹脂層（ＩＩ）とを含み、前記樹脂層（Ｉ）と前記樹脂層（ＩＩ）との厚みの比（樹脂層（Ｉ）／樹脂層（ＩＩ））が１／１４〜１／３である。
要件（Ａ１）：ＡＳＴＭ Ｄ１２３８に準じて１９０℃、２．１６ｋｇ荷重で測定したメルトフローレート（ＭＦＲ）が０．５〜５０．０ｇ／１０分である。
要件（Ａ２）：ＪＩＳ Ｋ６９２２に準じて測定した密度が８９０〜９４０ｋｇ／ｍ３である。
要件（Ａ３）：示差走査熱量測定（ＤＳＣ）で測定した融点が８０〜１３５℃である。
要件（Ａ４）：ゲル浸透クロマトグラフィ（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）と、数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が２．０〜９．０である。
要件（Ａ５）：ＪＩＳ Ｋ６９２１に準じて１０ｋｇ荷重、１９０℃で測定したメルトフローレート（ｇ／１０分）（ＭＦＲ１０）と、ＪＩＳ Ｋ６９２１に準じて２．１６ｋｇ荷重、１９０℃で測定したメルトフローレート（ｇ／１０分）（ＭＦＲ２．１６）との比（ＭＦＲ１０／ＭＦＲ２．１６）が４．０〜９．５である。
The multilayer film according to the present invention includes a resin layer (I) containing an ethylene resin (A) that satisfies the following requirements (A1) to (A5) and a resin layer (II) containing a propylene resin (B). The ratio of the thickness of the resin layer (I) to the resin layer (II) (resin layer (I) / resin layer (II)) is 1/14 to 1/3.
Requirement (A1): Melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238 is 0.5 to 50.0 g / 10 min.
Requirement (A2): The density measured according to JIS K6922 is 890 to 940 kg / m 3 .
Requirement (A3): Melting point measured by differential scanning calorimetry (DSC) is 80 to 135 ° C.
Requirement (A4): The ratio (Mw / Mn) between the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) and the number average molecular weight (Mn) is 2.0 to 9.0.
Requirement (A5): Melt flow rate measured at 190 ° C with a load of 10 kg according to JIS K6921 (g / 10 min) (MFR10) and Melt flow rate measured at 190 ° C with a load of 2.16 kg according to JIS K6921 The ratio (MFR10 / MFR2.16) to (g / 10 minutes) (MFR2.16) is 4.0 to 9.5.
本発明に係る多層フィルムは、前記要件（Ａ１）〜（Ａ５）を全て満たすエチレン系樹脂（Ａ）を含む樹脂層（Ｉ）を備え、所定の厚みの比を満たすことにより、剛性、引張強度等に優れるプロピレン系樹脂（Ｂ）を含む樹脂層（ＩＩ）の性能を損なうことなく、良好な耐ピンホール性、ヒートシール性を付与することができ、かつ、成形時、延伸時の安定性も良好である。また、積層時に接着層が不要のため、加工コストが下がり、焼却時に有害物質も発生しない。また、ドライラミネートに比べてエチレン系樹脂を含む層を薄くできるため、プロピレン系樹脂を含む層の物性を損なわない。 The multilayer film according to the present invention includes a resin layer (I) containing an ethylene-based resin (A) that satisfies all of the requirements (A1) to (A5), and satisfies a predetermined thickness ratio, whereby rigidity and tensile strength are achieved. Good pinhole resistance and heat sealability can be imparted without impairing the performance of the resin layer (II) containing the excellent propylene-based resin (B), and stability during molding and stretching. Is also good. In addition, since no adhesive layer is required during lamination, processing costs are reduced and no harmful substances are generated during incineration. Further, since the layer containing the ethylene resin can be made thinner than the dry laminate, the physical properties of the layer containing the propylene resin are not impaired.
＜エチレン系樹脂（Ａ）＞
本発明に係るエチレン系樹脂（Ａ）は、前記要件（Ａ１）〜（Ａ５）を全て満たすエチレン系樹脂である。また、エチレン系樹脂（Ａ）は、さらに下記要件（Ａ６）を満たすことが好ましい。なお、エチレン系樹脂とはエチレン単位を５０質量％以上含む樹脂を示す。エチレン系樹脂（Ａ）としては、エチレン単独重合体、エチレン・α−オレフィン共重合体等が挙げられる。なお、エチレン系樹脂（Ａ）は、２種類以上のエチレン系樹脂を含む組成物であってもよい。
<Ethylene resin (A)>
The ethylene-based resin (A) according to the present invention is an ethylene-based resin that satisfies all the requirements (A1) to (A5). The ethylene resin (A) preferably further satisfies the following requirement (A6). In addition, ethylene-type resin shows resin containing 50 mass% or more of ethylene units. Examples of the ethylene resin (A) include an ethylene homopolymer, an ethylene / α-olefin copolymer, and the like. The ethylene resin (A) may be a composition containing two or more types of ethylene resins.
エチレン・α−オレフィン共重合体におけるα−オレフィンとしては、例えば炭素数３〜２０のα−オレフィンが挙げられる。具体的には、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン、１−ドデセン、１−テトラドデセン、１−ヘキサドデセン、１−オクタドデセン、１−エイコセン、４−メチル−１−ペンテン、２−メチル−１−ブテン、３−メチル−１−ブテン、３，３−ジメチル−１−ブテン、ジエチル−１−ブテン、トリメチル−１−ブテン、３−メチル−１−ペンテン、エチル−１−ペンテン、プロピル−１−ペンテン、ジメチル−１−ペンテン、メチルエチル−１−ペンテン、ジエチル−１−ヘキセン、トリメチル−１−ペンテン、３−メチル−１−ヘキセン、ジメチル−１−ヘキセン、３，５，５−トリメチル−１−ヘキセン、メチルエチル−１−ヘプテン、トリメチル−１−ヘプテン、エチル−１−オクテン、メチル−１−ノネンなどが挙げられる。これらの中では、炭素数３〜８のα−オレフィンが好ましく、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテンが好ましく、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−オクテンがより好ましい。エチレン系樹脂（Ａ）は、これらの単位を一種含んでもよく、二種以上含んでもよい。 Examples of the α-olefin in the ethylene / α-olefin copolymer include α-olefins having 3 to 20 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradodecene, 1-hexadodecene, 1-octadodecene 1-eicosene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl- 1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-hept Down, ethyl-1-octene, and the like methyl-1-nonene. Among these, an α-olefin having 3 to 8 carbon atoms is preferable, and propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferable, and propylene, 1-butene. 1-pentene, 1-hexene and 1-octene are more preferable. The ethylene resin (A) may contain one or more of these units.
エチレン・α−オレフィン共重合体としては、具体的には、エチレン・プロピレンランダム共重合体、エチレン・１−ブテンランダム共重合体等が挙げられる。 Specific examples of the ethylene / α-olefin copolymer include an ethylene / propylene random copolymer and an ethylene / 1-butene random copolymer.
（要件（Ａ１））
エチレン系樹脂（Ａ）の、ＡＳＴＭ Ｄ１２３８に準じて１９０℃、２．１６ｋｇ荷重で測定したメルトフローレート（ＭＦＲ）（以下、ＭＦＲ（１９０℃）とも示す）は、０．５〜５０．０ｇ／分であり、０．７〜２０．０ｇ／１０分が好ましく、１．０〜１２．０ｇ／１０分がより好ましく、１．５〜８．０ｇ／１０分がさらに好ましい。ＭＦＲ（１９０℃）が前記範囲外の場合、成形時の安定性が低い。
(Requirement (A1))
The melt flow rate (MFR) (hereinafter also referred to as MFR (190 ° C.)) of the ethylene-based resin (A) measured at 190 ° C. and a load of 2.16 kg according to ASTM D1238 is 0.5 to 50.0 g / Minutes, preferably 0.7 to 20.0 g / 10 minutes, more preferably 1.0 to 12.0 g / 10 minutes, and even more preferably 1.5 to 8.0 g / 10 minutes. When MFR (190 degreeC) is outside the said range, stability at the time of shaping | molding is low.
（要件（Ａ２））
エチレン系樹脂（Ａ）の、ＪＩＳ Ｋ６９２２に準じて測定した密度は、８９０〜９４０ｋｇ／ｍ３であり、８９５〜９３５ｋｇ／ｍ３が好ましく、８９７〜９３０ｋｇ／ｍ３がより好ましく、９００〜９２５ｋｇ／ｍ３がさらに好ましい。該密度が８９０ｋｇ／ｍ３未満である場合、縦延伸時にフィルムがロールに抱きつき、成形できない。また、該密度が９４０ｋｇ／ｍ３を超える場合、延伸時にフィルムが破断する。
(Requirement (A2))
Ethylenically resin (A), the density was measured in accordance with JIS K6922 is 890~940kg / m 3, preferably 895~935kg / m 3, more preferably 897~930kg / m 3, 900~925kg / m 3 is more preferable. When the density is less than 890 kg / m 3 , the film is stuck to the roll during longitudinal stretching and cannot be molded. When the density exceeds 940 kg / m 3 , the film breaks during stretching.
（要件（Ａ３））
エチレン系樹脂（Ａ）の、示差走査熱量測定（ＤＳＣ）で測定した融点は、８０〜１３５℃であり、８５〜１３０℃が好ましく、９０〜１２５℃がより好ましく、９５〜１２０℃がさらに好ましい。該融点が８０℃未満である場合、縦延伸時にフィルムがロールに抱きつき、成形できない。また、該融点が１３５℃を超える場合、延伸時にフィルムが破断する。なお、該融点は具体的には後述する方法により測定した値である。
(Requirement (A3))
Melting | fusing point measured by the differential scanning calorimetry (DSC) of ethylene-type resin (A) is 80-135 degreeC, 85-130 degreeC is preferable, 90-125 degreeC is more preferable, 95-120 degreeC is further more preferable. . When the melting point is less than 80 ° C., the film is stuck to the roll during longitudinal stretching and cannot be molded. On the other hand, when the melting point exceeds 135 ° C., the film breaks during stretching. The melting point is specifically a value measured by the method described later.
（要件（Ａ４））
エチレン系樹脂（Ａ）の、ゲル浸透クロマトグラフィ（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）と、数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）は、２．０〜９．０であり、２．１〜７．０が好ましく、２．２〜６．０がより好ましく、２．３〜５．５がさらに好ましい。該Ｍｗ／Ｍｎが２．０未満の場合、押出性、多層フィルムの外観および延伸性が低下する。また、該Ｍｗ／Ｍｎが９．０を超える場合、ヒートシール性、臭い及び味が低下する。なお、該Ｍｗ／Ｍｎは具体的には後述する方法により測定した値である。
(Requirement (A4))
The ratio (Mw / Mn) of the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) and the number average molecular weight (Mn) of the ethylene resin (A) is 2.0 to 9.0. 2.1-7.0 are preferable, 2.2-6.0 are more preferable, and 2.3-5.5 are further more preferable. When the Mw / Mn is less than 2.0, the extrudability, the appearance of the multilayer film and the stretchability are lowered. Moreover, when this Mw / Mn exceeds 9.0, heat-sealability, smell, and taste will fall. The Mw / Mn is specifically a value measured by the method described later.
（要件（Ａ５））
エチレン系樹脂（Ａ）の、ＪＩＳ Ｋ６９２１に準じて１０ｋｇ荷重、１９０℃で測定したメルトフローレート（ｇ／１０分）（ＭＦＲ１０）と、ＪＩＳ Ｋ６９２１に準じて２．１６ｋｇ荷重、１９０℃で測定したメルトフローレート（ｇ／１０分）（ＭＦＲ２．１６）との比（ＭＦＲ１０／ＭＦＲ２．１６）は、４．０〜９．５であり、４．５〜９．０が好ましく、５．０〜８．５がより好ましく、５．５〜８．０がさらに好ましい。該ＭＦＲ１０／ＭＦＲ２．１６が４．０未満の場合、押出性、多層フィルムの外観および延伸性が低下する。また、該ＭＦＲ１０／ＭＦＲ２．１６が９．５を超える場合、ヒートシール性、臭い及び味が低下する。
(Requirement (A5))
The melt flow rate (g / 10 minutes) (MFR10) of the ethylene-based resin (A) measured at 190 ° C. according to JIS K6921 was measured at 2.16 kg and 190 ° C. according to JIS K6921. The ratio (MFR10 / MFR2.16) to the melt flow rate (g / 10 minutes) (MFR2.16) is 4.0 to 9.5, preferably 4.5 to 9.0, and preferably 5.0 to 8.5 is more preferable, and 5.5 to 8.0 is even more preferable. When the MFR10 / MFR2.16 is less than 4.0, the extrudability, the appearance of the multilayer film and the stretchability are deteriorated. Moreover, when this MFR10 / MFR2.16 exceeds 9.5, heat-sealing property, smell, and taste will fall.
（要件（Ａ６））
前記ＭＦＲ１０／ＭＦＲ２．１６が５．０以上の場合、前記Ｍｗ／Ｍｎは２．５以上であることが好ましく、３．０以上であることがより好ましく、３．５以上であることがさらに好ましい。前記ＭＦＲ１０／ＭＦＲ２．１６が５．０以上の場合、前記Ｍｗ／Ｍｎは２．５以上であることにより、押出性、多層フィルムの外観および延伸性が向上する。前記ＭＦＲ１０／ＭＦＲ２．１６が５．０以上の場合、前記Ｍｗ／Ｍｎは８．０以下であることが好ましく、７．０以下であることがより好ましく、６．０以下であることがさらに好ましい。前記ＭＦＲ１０／ＭＦＲ２．１６が５．０以上の場合、前記Ｍｗ／Ｍｎは８．０以下であることにより、ヒートシール性が向上し、臭い及び味が良好となる。
(Requirement (A6))
When the MFR10 / MFR2.16 is 5.0 or more, the Mw / Mn is preferably 2.5 or more, more preferably 3.0 or more, and further preferably 3.5 or more. . When the MFR10 / MFR2.16 is 5.0 or more, the Mw / Mn is 2.5 or more, thereby improving the extrudability, the appearance of the multilayer film, and the stretchability. When MFR10 / MFR2.16 is 5.0 or more, the Mw / Mn is preferably 8.0 or less, more preferably 7.0 or less, and even more preferably 6.0 or less. . When the MFR10 / MFR2.16 is 5.0 or more, the Mw / Mn is 8.0 or less, so that the heat sealability is improved, and the odor and taste are improved.
エチレン系樹脂（Ａ）は、エチレンや、エチレンおよびα−オレフィンを原料として、チーグラー触媒やメタロセン触媒を用いて製造することができる。ＭＦＲ（要件（Ａ１）、（Ａ５）および（Ａ６））を調節するためには、触媒の種類や重合条件を変更することが有効である。また、連鎖移動剤を用いる場合、連鎖移動剤としては水素を用いることが好ましい。また、密度（要件（Ａ２））は、エチレン系樹脂（Ａ）がエチレン・α−オレフィン共重合体の場合、α−オレフィンの含有量により調節することができる。融点（要件（Ａ３））は、重量平均分子量や、エチレン系樹脂（Ａ）がエチレン・α−オレフィン共重合体の場合にはα−オレフィンの含有量により調節することができる。また、Ｍｗ／Ｍｎ（要件（Ａ４）および（Ａ６））は、２種類以上の触媒を用いたり、２種類以上のエチレン系樹脂を混合したり、多段重合を行う方法を採用したりすることで調節することができる。 The ethylene resin (A) can be produced using ethylene, ethylene and α-olefin as raw materials, using a Ziegler catalyst or a metallocene catalyst. In order to adjust the MFR (requirements (A1), (A5) and (A6)), it is effective to change the type of the catalyst and the polymerization conditions. Moreover, when using a chain transfer agent, it is preferable to use hydrogen as a chain transfer agent. The density (requirement (A2)) can be adjusted by the content of α-olefin when the ethylene resin (A) is an ethylene / α-olefin copolymer. The melting point (requirement (A3)) can be adjusted by the weight average molecular weight or the content of α-olefin when the ethylene resin (A) is an ethylene / α-olefin copolymer. In addition, Mw / Mn (requirements (A4) and (A6)) can be achieved by using two or more types of catalysts, mixing two or more types of ethylene resins, or adopting a method of performing multistage polymerization. Can be adjusted.
エチレン系樹脂（Ａ）としては、市販品では、エボリュー（商品名、（株）プライムポリマー社製）、ハーモレックス（商品名、日本ポリエチレン（株）社製）、カーネル（商品名、日本ポリエチレン（株）社製）、ノバテック（商品名、日本ポリエチレン（株）社製）、Ｅｌｉｔｅ，Ｄｏｗｌｅｘ，Ａｆｆｉｎｉｔｙ，Ａｔｔａｎｅ（商品名、ダウケミカル社製）、Ｅｘｃｅｅｄ，Ｅｎａｂｌｅ（商品名、エクソンケミカル社製）、ＳＰ０５４０、ＳＰ１５４０、ＳＰ１０７１Ｃ、ＳＰ３０２０（以上商品名、（株）プライムポリマー社製）、２０４５Ｇ、ＰＴ１４５０（以上商品名、ダウ社製）などが挙げられる。これらは一種を用いてもよく、二種以上を併用してもよい。 As the ethylene-based resin (A), commercially available products include Evolue (trade name, manufactured by Prime Polymer Co., Ltd.), Harmolex (trade name, manufactured by Nippon Polyethylene Co., Ltd.), kernel (trade name, Japanese polyethylene ( Co., Ltd.), Novatec (trade name, manufactured by Nippon Polyethylene Co., Ltd.), Elite, Dowlex, Affinity, Attane (trade name, manufactured by Dow Chemical Company), Exceed, Enable (trade name, manufactured by Exxon Chemical) SP0540, SP1540, SP1071C, SP3020 (above trade name, manufactured by Prime Polymer Co., Ltd.), 2045G, PT1450 (above trade name, manufactured by Dow) and the like. These may use 1 type and may use 2 or more types together.
＜プロピレン系樹脂（Ｂ）＞
本発明に係るプロピレン系樹脂（Ｂ）としては、例えばプロピレン単独重合体であるホモポリプロピレン（ホモＰＰ）、プロピレン・α−オレフィンランダム共重合体（ランダムＰＰ）、いわゆるブロックポリプロピレン（ブロックＰＰ）等が挙げられる。なお、プロピレン系樹脂とはプロピレン単位を５０質量％以上含む樹脂を示す。また、プロピレン系樹脂（Ｂ）は、２種類以上のプロピレン系樹脂を含む組成物であってもよい。
<Propylene resin (B)>
Examples of the propylene-based resin (B) according to the present invention include a homopolypropylene (homo PP) that is a propylene homopolymer, a propylene / α-olefin random copolymer (random PP), a so-called block polypropylene (block PP), and the like. Can be mentioned. In addition, a propylene-type resin shows resin which contains 50 mass% or more of propylene units. The propylene resin (B) may be a composition containing two or more types of propylene resins.
プロピレン・α−オレフィンランダム共重合体におけるα−オレフィンとしては、例えば、エチレン、炭素数４〜２０のα−オレフィンが挙げられる。炭素数４〜２０のα−オレフィンとしては、具体的には１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン、１−ドデセン、１−テトラドデセン、１−ヘキサドデセン、１−オクタドデセン、１−エイコセン、４−メチル−１−ペンテン、２−メチル−１−ブテン、３−メチル−１−ブテン、３，３−ジメチル−１−ブテン、ジエチル−１−ブテン、トリメチル−１−ブテン、３−メチル−１−ペンテン、エチル−１−ペンテン、プロピル−１−ペンテン、ジメチル−１−ペンテン、メチルエチル−１−ペンテン、ジエチル−１−ヘキセン、トリメチル−１−ペンテン、３−メチル−１−ヘキセン、ジメチル−１−ヘキセン、３，５，５−トリメチル−１−ヘキセン、メチルエチル−１−ヘプテン、トリメチル−１−ヘプテン、エチル−１−オクテン、メチル−１−ノネンなどが挙げられる。これらは一種を用いてもよく、二種以上を併用してもよい。これらの中でも、エチレンおよび炭素数４〜８のα−オレフィンが好ましく、エチレンがより好ましい。 Examples of the α-olefin in the propylene / α-olefin random copolymer include ethylene and an α-olefin having 4 to 20 carbon atoms. Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1- Tetradodecene, 1-hexadodecene, 1-octadodecene, 1-eicosene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl- 1-butene, trimethyl-1-butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl -1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-hept Emissions, trimethyl-1-heptene, ethyl-1-octene, and the like methyl-1-nonene. These may use 1 type and may use 2 or more types together. Among these, ethylene and an α-olefin having 4 to 8 carbon atoms are preferable, and ethylene is more preferable.
プロピレン・α−オレフィンランダム共重合体としては、具体的には、プロピレン・エチレンランダム共重合体、プロピレン・１−ブテンランダム共重合体、プロピレン・１−ペンテンランダム共重合体、プロピレン・１−ヘキセンランダム共重合体、プロピレン・１−オクテンランダム共重合体、プロピレン・エチレン・１−ブテンランダム共重合体等が挙げられる。これらは一種を用いてもよく、二種以上を併用してもよい。これらの中でも、プロピレン・エチレンランダム共重合体が好ましい。プロピレン・α−オレフィンランダム共重合体におけるα−オレフィン単位の含有量は、５質量％以下であることが好ましい。 Specific examples of the propylene / α-olefin random copolymer include propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / 1-pentene random copolymer, propylene / 1-hexene. Examples thereof include a random copolymer, a propylene / 1-octene random copolymer, and a propylene / ethylene / 1-butene random copolymer. These may use 1 type and may use 2 or more types together. Among these, a propylene / ethylene random copolymer is preferable. The content of α-olefin units in the propylene / α-olefin random copolymer is preferably 5% by mass or less.
ホモＰＰ、ランダムＰＰとしては、市販品では、ＰＭシリーズ、ＰＬシリーズ、ＰＣシリーズ（商品名、サンアロイ社製）、プライムポリプロ（商品名、プライムポリマー社製）、ノバテック（商品名、日本ポリプロ（株）製））、Ｅ−２００ＧＰ（商品名、プライムポリマー社製）、Ｅ−３３０ＧＶ（商品名、プライムポリマー社製）、Ｆ１０７ＤＪ（商品名、プライムポリマー社製）、Ｂ２４１（商品名、プライムポリマー社製）、Ｆ−３００ＳＰ（商品名、プライムポリマー社製）、Ｆ３２７（商品名、プライムポリマー社製）等が挙げられる。これらは一種を用いてもよく、二種以上を併用してもよい。 As homo PP and random PP, commercial products are PM series, PL series, PC series (trade name, manufactured by Sun Alloy), Prime Polypro (trade name, manufactured by Prime Polymer), Novatec (trade name, Nippon Polypro Co., Ltd.) ))), E-200GP (trade name, manufactured by Prime Polymer), E-330GP (trade name, manufactured by Prime Polymer), F107DJ (trade name, manufactured by Prime Polymer), B241 (trade name, Prime Polymer) Product), F-300SP (trade name, manufactured by Prime Polymer), F327 (trade name, manufactured by Prime Polymer), and the like. These may use 1 type and may use 2 or more types together.
ＪＩＳ Ｋ６９２１−１およびＪＩＳ Ｋ６９２１−２に準じて、２３０℃、２１．１８Ｎ荷重の条件下で測定したプロピレン系樹脂（Ｂ）のＭＦＲ（以下、ＭＦＲ（２３０℃）とも示す）は、フィルムの製造や延伸性の観点から、１〜２０ｇ／１０分が好ましく、２〜１０ｇ／１０分がより好ましい。該ＭＦＲがこの範囲内であることにより、延伸性が向上し、フィルム成形が容易になる。 According to JIS K6921-1 and JIS K6921-2, MFR of propylene-based resin (B) measured under conditions of 230 ° C. and 21.18 N load (hereinafter also referred to as MFR (230 ° C.)) From the viewpoint of stretchability, it is preferably 1 to 20 g / 10 minutes, more preferably 2 to 10 g / 10 minutes. When the MFR is within this range, stretchability is improved and film formation becomes easy.
＜樹脂層（Ｉ）＞
樹脂層（Ｉ）は前記エチレン系樹脂（Ａ）を含む。樹脂層（Ｉ）は前記エチレン系樹脂（Ａ）を８０質量％以上含むことが好ましく、９０質量％以上含むことがより好ましく、９５質量％以上含むことがさらに好ましい。特に、樹脂層（Ｉ）は前記エチレン系樹脂（Ａ）からなることが好ましい。樹脂層（Ｉ）の厚みは特に限定されないが、延伸前の厚みで例えば５〜１００μｍであることができる。なお、多層フィルムが複数の樹脂層（Ｉ）を含む場合には、該厚みは、複数の樹脂層（Ｉ）の厚みの合計を示す。
<Resin layer (I)>
The resin layer (I) contains the ethylene resin (A). The resin layer (I) preferably contains 80% by mass or more of the ethylene resin (A), more preferably 90% by mass or more, and further preferably 95% by mass or more. In particular, the resin layer (I) is preferably made of the ethylene resin (A). Although the thickness of the resin layer (I) is not particularly limited, the thickness before stretching can be, for example, 5 to 100 μm. In addition, when a multilayer film contains several resin layer (I), this thickness shows the sum total of the thickness of several resin layer (I).
樹脂層（Ｉ）は、前記エチレン系樹脂（Ａ）以外にも、例えば、ＩＲＧＡＮＯＸ １０１０およびＩＲＧＡＦＯＳ １６８（以上商品名、Ｃｉｂａ Ｓｐｅｃｉａｌｉｔｙ Ｃｈｅｍｉｃａｌｓ；Ｇｌａｔｔｂｒｕｇｇ、Ｓｗｉｔｚｅｒｌａｎｄ製）等の酸化防止剤、紫外線吸収剤、帯電防止剤、顔料、染料、核形成剤、充填剤、滑剤、難燃剤、可塑剤、加工助剤、潤滑剤、安定剤、煙抑制剤、粘度調整剤、表面改質剤、ならびにブロッキング防止剤等の添加剤を含んでもよい。樹脂層（Ｉ）は、これらの添加剤を一種含んでもよく、二種以上含んでもよい。樹脂層（Ｉ）は、該添加剤を例えば１０質量％以下含むことができる。 In addition to the ethylene resin (A), the resin layer (I) is made of, for example, an antioxidant such as IRGANOX 1010 and IRGAFOS 168 (above trade name, Ciba Specialty Chemicals; manufactured by Glattbrugg, Switzerland), an ultraviolet absorber, a charge Inhibitors, pigments, dyes, nucleating agents, fillers, lubricants, flame retardants, plasticizers, processing aids, lubricants, stabilizers, smoke suppressants, viscosity modifiers, surface modifiers, antiblocking agents, etc. The additive may be included. The resin layer (I) may contain one or more of these additives. The resin layer (I) can contain, for example, 10% by mass or less of the additive.
＜樹脂層（ＩＩ）＞
樹脂層（ＩＩ）は前記プロピレン系樹脂（Ｂ）を含む。樹脂層（ＩＩ）は前記プロピレン系樹脂（Ｂ）を８０質量％以上含むことが好ましく、９０質量％以上含むことがより好ましく、９５質量％以上含むことがさらに好ましい。特に、樹脂層（ＩＩ）は前記プロピレン系樹脂（Ｂ）からなることが好ましい。樹脂層（ＩＩ）の厚みは特に限定されないが、延伸前の厚みで例えば５〜１００μｍであることができる。なお、多層フィルムが複数の樹脂層（ＩＩ）を含む場合には、該厚みは、複数の樹脂層（ＩＩ）の厚みの合計を示す。
<Resin layer (II)>
The resin layer (II) contains the propylene resin (B). The resin layer (II) preferably contains 80% by mass or more of the propylene-based resin (B), more preferably 90% by mass or more, and further preferably 95% by mass or more. In particular, the resin layer (II) is preferably made of the propylene-based resin (B). Although the thickness of resin layer (II) is not specifically limited, It can be 5-100 micrometers by the thickness before extending | stretching. In addition, when a multilayer film contains several resin layer (II), this thickness shows the sum total of the thickness of several resin layer (II).
樹脂層（ＩＩ）は、前記樹脂層（Ｉ）における前記添加剤と同様の添加剤を含むことができる。樹脂層（ＩＩ）は、該添加剤を例えば１０質量％以下含むことができる。 The resin layer (II) can contain the same additive as the additive in the resin layer (I). The resin layer (II) can contain, for example, 10% by mass or less of the additive.
＜多層フィルム＞
本発明に係る多層フィルムは、前記エチレン系樹脂（Ａ）を含む樹脂層（Ｉ）と、前記プロピレン系樹脂（Ｂ）を含む樹脂層（ＩＩ）とを含む。該多層フィルムは、前記樹脂層（Ｉ）と、前記樹脂層（ＩＩ）とからなってもよい。該多層フィルムは、少なくとも一層の樹脂層（Ｉ）と、少なくとも一層の樹脂層（ＩＩ）とを備えていればよいが、樹脂層（Ｉ）および／または樹脂層（ＩＩ）を複数層備えてもよい。また、樹脂層（Ｉ）は高いヒートシール機能を有する樹脂層であり、高いヒートシール性が得られる観点から、該多層フィルムの少なくとも一方の表面に、樹脂層（Ｉ）が配置されていることが好ましく、該多層フィルムの両方の表面に、樹脂層（Ｉ）が配置されていることがより好ましい。例えば、樹脂層（Ｉ）／樹脂層（ＩＩ）／樹脂層（Ｉ）の順で積層されていることが好ましい。なお、樹脂層（Ｉ）は熱融着性も具備するため、該多層フィルムをヒートシールする場合には、樹脂層（Ｉ）をヒートシール面に積層することが好ましい。
<Multilayer film>
The multilayer film according to the present invention includes a resin layer (I) containing the ethylene resin (A) and a resin layer (II) containing the propylene resin (B). The multilayer film may be composed of the resin layer (I) and the resin layer (II). The multilayer film only needs to include at least one resin layer (I) and at least one resin layer (II), but includes a plurality of resin layers (I) and / or resin layers (II). Also good. In addition, the resin layer (I) is a resin layer having a high heat seal function, and from the viewpoint of obtaining high heat sealability, the resin layer (I) is disposed on at least one surface of the multilayer film. It is preferable that the resin layer (I) is disposed on both surfaces of the multilayer film. For example, it is preferable that the layers are laminated in the order of resin layer (I) / resin layer (II) / resin layer (I). In addition, since the resin layer (I) also has heat-fusibility, when heat-sealing the multilayer film, it is preferable to laminate the resin layer (I) on the heat-sealing surface.
樹脂層（Ｉ）と樹脂層（ＩＩ）との厚みの比（樹脂層（Ｉ）／樹脂層（ＩＩ））は、１／１４〜１／３であり、１／１３〜１／４が好ましく、１／１２〜１／５がより好ましい。該比が１／１４未満である場合、耐ピンホール性が低下する。また、該比が１／３を超える場合、引張強度、引裂バランス等が低下する。なお、多層フィルムが複数の樹脂層（Ｉ）および／または樹脂層（ＩＩ）を含む場合には、該厚みは、複数の樹脂層（Ｉ）および／または樹脂層（ＩＩ）の厚みの合計を示す。 The ratio of the thickness of the resin layer (I) to the resin layer (II) (resin layer (I) / resin layer (II)) is 1/14 to 1/3, preferably 1/13 to 1/4. 1/12 to 1/5 is more preferable. When the ratio is less than 1/14, pinhole resistance is lowered. Moreover, when this ratio exceeds 1/3, tensile strength, tear balance, etc. will fall. When the multilayer film includes a plurality of resin layers (I) and / or resin layers (II), the thickness is the sum of the thicknesses of the plurality of resin layers (I) and / or resin layers (II). Show.
多層フィルムの厚みは特に限定されないが、例えば５〜１００μｍであることができる。また、剛性、引張強度、耐ピンホール性の観点から、多層フィルムは延伸多層フィルムであることが好ましく、二軸延伸多層フィルムであることがより好ましい。 Although the thickness of a multilayer film is not specifically limited, For example, it can be 5-100 micrometers. Moreover, from the viewpoint of rigidity, tensile strength, and pinhole resistance, the multilayer film is preferably a stretched multilayer film, and more preferably a biaxially stretched multilayer film.
本発明に係る多層フィルムは、例えばタバコ包装、菓子包装等に好ましく用いることができる。 The multilayer film according to the present invention can be preferably used for tobacco packaging, confectionery packaging, and the like.
＜多層フィルムの製造方法＞
本発明に係る多層フィルムは、例えば各材料を溶融押出し、Ｔダイ等により賦形した後、冷却することで、共押出シートとして得られる。多層フィルムが二軸延伸多層フィルムである場合には、該共押出シートを作製した後に、例えばチューブラー方式やフラット方式（テンター方式）により、縦方向（流れ方向、ＭＤ方向）及び横方向（幅方向、ＴＤ方向）に二軸延伸することで二軸延伸多層フィルムが得られる。該二軸延伸は同時二軸延伸でも、逐次二軸延伸でもよい。これらの中でも、フラット方式により得られる二軸延伸多層フィルムが、透明性に優れるため好ましい。
<Method for producing multilayer film>
The multilayer film according to the present invention can be obtained as a co-extruded sheet by, for example, melt-extruding each material, shaping it with a T-die or the like, and then cooling. When the multilayer film is a biaxially stretched multilayer film, the longitudinal direction (flow direction, MD direction) and the lateral direction (width) are produced by, for example, a tubular method or a flat method (tenter method) after the coextruded sheet is produced. Direction, TD direction), a biaxially stretched multilayer film is obtained. The biaxial stretching may be simultaneous biaxial stretching or sequential biaxial stretching. Among these, a biaxially stretched multilayer film obtained by a flat method is preferable because of excellent transparency.
フラット方式による場合は、共押出シートを例えば９０〜１２５℃の温度範囲でＭＤ方向に延伸した後、例えば９０〜１３０℃の温度範囲でＴＤ方向に延伸することにより得ることができる。二軸延伸した後は、用途により、例えば８０〜１４０℃の温度範囲でヒートセットを行ってもよい。該ヒートセットの温度は目的とする熱収縮率に応じて変更することができる。延伸倍率は、ＭＤ方向およびＴＤ方向共に、３〜１４倍であることが好ましく、５〜１０倍であることがより好ましい。 In the case of the flat method, the coextruded sheet can be obtained by stretching in the MD direction in a temperature range of 90 to 125 ° C., for example, and then stretching in the TD direction in a temperature range of 90 to 130 ° C., for example. After biaxial stretching, heat setting may be performed in a temperature range of, for example, 80 to 140 ° C. depending on the application. The temperature of the heat set can be changed according to the desired heat shrinkage rate. The draw ratio is preferably 3 to 14 times, more preferably 5 to 10 times in both the MD direction and the TD direction.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。各物性の測定及び評価は以下の方法により行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to these. Each physical property was measured and evaluated by the following methods.
＜メルトフローレート（ＭＦＲ）＞
エチレン系樹脂のＭＦＲ（１９０℃）は、ＡＳＴＭ Ｄ１２３８に準じて、１９０℃、２．１６ｋｇ荷重の条件下で測定した。プロピレン系樹脂のＭＦＲ（２３０℃）は、ＪＩＳ Ｋ６９２１−１およびＪＩＳ Ｋ６９２１−２に準じて、２３０℃、２１．１８Ｎ荷重の条件下で測定した。エチレン系樹脂のＭＦＲ１０は、ＪＩＳ Ｋ６９２１に準じて、１０ｋｇ荷重、１９０℃の条件下で測定した。エチレン系樹脂のＭＦＲ２．１６は、ＪＩＳ Ｋ６９２１に準じて、２．１６ｋｇ荷重、１９０℃の条件下で測定した。
<Melt flow rate (MFR)>
The MFR (190 ° C.) of the ethylene resin was measured under the conditions of 190 ° C. and 2.16 kg load in accordance with ASTM D1238. The MFR (230 ° C.) of the propylene-based resin was measured under the conditions of 230 ° C. and 21.18 N load according to JIS K6921-1 and JIS K6921-2. The MFR10 of the ethylene resin was measured under the conditions of 10 kg load and 190 ° C. according to JIS K6921. The MFR 2.16 of the ethylene-based resin was measured under a condition of 2.16 kg load and 190 ° C. according to JIS K6921.
＜密度＞
エチレン系樹脂の密度は、ＪＩＳ Ｋ６９２２に従い、エチレン系樹脂を１００℃で３０分間加熱した後、２３℃で１時間保持し、密度勾配管法によって測定した。
<Density>
The density of the ethylene-based resin was measured by a density gradient tube method in accordance with JIS K6922, after heating the ethylene-based resin at 100 ° C. for 30 minutes and holding at 23 ° C. for 1 hour.
＜融点＞
エチレン系樹脂の融点（Ｔｍ）を、Ｐｙｒｉｓ １（商品名、ＰＥＲＫＩＮ ＥＬＭＥＲ社製）を用い、ＤＳＣで以下のように測定した。
<Melting point>
The melting point (Tm) of the ethylene-based resin was measured by DSC using Pyris 1 (trade name, manufactured by PERKIN ELMER) as follows.
エチレン系樹脂を、プレス成形機（神藤金属工業所製）を用い、予熱温度１９０℃、予熱時間５分間、加熱温度１９０℃、加熱時間２分間、加熱圧力１００ｋｇ／ｃｍ２、冷却温度２０℃、冷却時間５分間、冷却圧力１００ｋｇ／ｃｍ２の条件にて厚さ２ｍｍにプレス成形することで、測定サンプルを作製した。 Using a press molding machine (manufactured by Shinfuji Metal Industry), ethylene-based resin is subjected to a preheating temperature of 190 ° C., a preheating time of 5 minutes, a heating temperature of 190 ° C., a heating time of 2 minutes, a heating pressure of 100 kg / cm 2 , a cooling temperature of 20 ° C., A measurement sample was produced by press molding to a thickness of 2 mm under a cooling pressure of 100 kg / cm 2 for 5 minutes.
前記測定サンプル約５ｍｇをアルミパンに詰め、窒素雰囲気下（窒素：２０ｍｌ／分）で以下の（１）〜（３）の温度プロファイルにて測定を実施した。（１）３０℃から１０℃／分で２００℃まで昇温、（２）２００℃で５分間保持したのち１０℃／分で３０℃まで降温、（３）３０℃から１０℃／分で２００℃まで昇温。前記（３）の測定で得られた吸熱曲線における最大ピークの温度を融点（Ｔｍ）とした。 About 5 mg of the measurement sample was packed in an aluminum pan, and measurement was performed in the following temperature profiles (1) to (3) under a nitrogen atmosphere (nitrogen: 20 ml / min). (1) Temperature rise from 30 ° C. to 10 ° C./min to 200 ° C., (2) Hold at 200 ° C. for 5 minutes, then fall to 10 ° C./min to 30 ° C., (3) 200 ° C. from 30 ° C. to 10 ° C./min Heated up to ℃. The temperature of the maximum peak in the endothermic curve obtained by the measurement of (3) was defined as the melting point (Tm).
＜数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）＞
ＧＰＣ−粘度検出器（ＧＰＣ−ＶＩＳＣＯ）（商品名：ＧＰＣ／Ｖ２０００、ウォーターズ社製）を用い、以下のように測定した。
<Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw / Mn)>
Using a GPC-viscosity detector (GPC-VISCO) (trade name: GPC / V2000, manufactured by Waters), the measurement was performed as follows.
ガードカラムにはＡＴ−Ｇ（商品名、Ｓｈｏｄｅｘ製）を用いた。分析カラムにはＡＴ−８０６（商品名、Ｓｈｏｄｅｘ製）を２本用いた。検出器には示差屈折計および３キャピラリー粘度計を用いた。カラム温度は１４５℃とした。移動相としては、酸化防止剤としてジブチルヒドロキシトルエン（ＢＨＴ）を０．３質量％含むｏ−ジクロロベンゼンを用いた。流速を１．０ｍｌ／分とし、試料濃度は０．１質量％とした。標準ポリスチレンには、東ソー社製の標準ポリスチレンを用いた。粘度計および屈折計から実測粘度を計算し、実測ユニバーサルキャリブレーションより数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）、および分子量分布（Ｍｗ／Ｍｎ）を求めた。 AT-G (trade name, manufactured by Shodex) was used for the guard column. Two AT-806 (trade name, manufactured by Shodex) were used for the analytical column. A differential refractometer and a 3-capillary viscometer were used as detectors. The column temperature was 145 ° C. As the mobile phase, o-dichlorobenzene containing 0.3% by mass of dibutylhydroxytoluene (BHT) as an antioxidant was used. The flow rate was 1.0 ml / min, and the sample concentration was 0.1% by mass. As the standard polystyrene, standard polystyrene manufactured by Tosoh Corporation was used. The actually measured viscosity was calculated from a viscometer and a refractometer, and the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were determined from the actually measured universal calibration.
＜引張試験＞
多層フィルムから長さ方向がフィルムの流れ方向（ＭＤ）、幅方向（ＴＤ）となるように１５ｍｍ幅、２００ｍｍ長さの短冊状の試験片を切出した。該試験片について、テンシロンＲＴ１２２５型（商品名、オリエンテック社製）を使用して、ＪＩＳ Ｋ７１２７に準拠して破断点強度、破断点伸び、およびヤング率を測定した。
<Tensile test>
A strip-shaped test piece having a width of 15 mm and a length of 200 mm was cut out from the multilayer film so that the length direction was the film flow direction (MD) and the width direction (TD). About this test piece, Tensylon RT1225 type (trade name, manufactured by Orientec Co., Ltd.) was used, and the strength at break, elongation at break and Young's modulus were measured according to JIS K7127.
＜引裂試験＞
軽荷重引裂試験機（東洋精機製作所製：振り子の左端に容量ウェイトＢ：７９ｇを取り付け）を使用し、多層フィルムから引裂き方向に長さ６３．５ｍｍ（長辺）及び引裂き方向と垂直の方向に幅５０ｍｍ（短辺）の長方形の試験片を複数枚切出し、短辺の中央に端から１２．７ｍｍの切り込みを入れた。試験機の指針（置き針）が２０〜８０の範囲に収まるように、該試験片を複数枚重ねて予備テストを行い、測定に用いる試験片の枚数を調整した。その後、引裂試験を行い、以下の式によりＭＤ方向、ＴＤ方向における引裂強度（Ｎ／ｃｍ）を求めた。また、引裂バランス（ＭＤ方向における引裂強度／ＴＤ方向における引裂強度）を算出した。なお、試験機の測定レンジ（Ｒ）は２００とした。
<Tear test>
Using a light load tear tester (Toyo Seiki Seisakusho: capacity weight B: 79g attached to the left end of the pendulum), the length is 63.5mm (long side) in the tear direction from the multilayer film, and the direction perpendicular to the tear direction A plurality of rectangular test pieces having a width of 50 mm (short side) were cut out, and a 12.7 mm cut was made from the end in the center of the short side. A plurality of the test pieces were stacked and a preliminary test was performed so that the indicator (placement needle) of the test machine was within a range of 20 to 80, and the number of test pieces used for measurement was adjusted. Thereafter, a tear test was performed, and the tear strength (N / cm) in the MD direction and the TD direction was determined by the following formula. Moreover, the tear balance (Tear strength in MD direction / Tear strength in TD direction) was calculated. The measurement range (R) of the testing machine was 200.
Ｔ＝（Ａ×０．００１×９．８１×Ｒ／１００）／（ｔ）
Ｔ：引裂強度（Ｎ／ｃｍ）
Ａ：指針の指した値（ｇ）
ｔ：重ねた試験片の合計厚み（ｃｍ）。
T = (A × 0.001 × 9.81 × R / 100) / (t)
T: Tear strength (N / cm)
A: Value indicated by the pointer (g)
t: Total thickness (cm) of the stacked test pieces.
＜耐ピンホール性＞
ゲルボフレックス装置（テスター産業製）にて、ＡＳＴＭ Ｆ３９２：９３ 可撓性バリア材料の耐屈曲性標準試験法に基づいて、多層フィルムを３０００回屈曲させた。その後、ピンホール検出器（ウエッジ株式会社製）にてピンホール数を測定した。
<Pinhole resistance>
The multilayer film was bent 3000 times with a Gelboflex apparatus (manufactured by Tester Sangyo) based on the standard test method for bending resistance of ASTM F392: 93 flexible barrier material. Thereafter, the number of pinholes was measured with a pinhole detector (Wedge Corp.).
＜ヒートシール開始温度＞
１５ｍｍ巾に裁断した多層フィルム２枚を、外層−１同士が接するように重ねた。これに対し、熱盤式ヒートシーラー（東洋精機社製）にてシール圧力：０．１ＭＰａ、シール時間：１．０秒でヒートシールを行った。得られたサンプルについて、引張試験機にて２００ｍｍ／分でヒートシール強度を測定した。ヒートシール強度が２Ｎ／１５ｍｍとなる温度をヒートシール開始温度とした。
<Heat seal start temperature>
Two multilayer films cut to a width of 15 mm were stacked so that the outer layers -1 were in contact with each other. On the other hand, heat sealing was performed with a hot plate heat sealer (manufactured by Toyo Seiki Co., Ltd.) at a sealing pressure of 0.1 MPa and a sealing time of 1.0 second. About the obtained sample, the heat seal intensity | strength was measured at 200 mm / min with the tensile tester. The temperature at which the heat seal strength was 2 N / 15 mm was defined as the heat seal start temperature.
＜Ｔダイ成形時の安定性＞
Ｔダイ成形時に、ダイから押し出され冷却された溶融膜が安定に多層共押シートに成形可能かどうかを目視およびシートの断面観察により外観および層比から確認した。
良好：安定に多層フィルムが成形できる。
不良：面荒れが発生し、層比も安定していないため、安定に多層フィルムを成形できない。
<Stability during T-die molding>
At the time of T-die molding, whether or not the molten film extruded and cooled from the die can be stably formed into a multilayer co-pressed sheet was confirmed from the appearance and the layer ratio by visual observation and cross-sectional observation of the sheet.
Good: A multilayer film can be formed stably.
Defect: Surface roughness occurs and the layer ratio is not stable, so a multilayer film cannot be stably formed.
＜延伸時の安定性＞
フィルムを延伸した時に、破断するか否かを確認した。
良好：フィルムを延伸した時に破断しなかった。
不良：フィルムを延伸した時に破断した。
<Stability during stretching>
It was confirmed whether or not the film was broken when the film was stretched.
Good: Not broken when the film was stretched.
Bad: The film broke when it was stretched.
以下の実施例および比較例では、エチレン系樹脂およびプロピレン系樹脂として、表１に示される材料を用いた。 In the following examples and comparative examples, the materials shown in Table 1 were used as the ethylene resin and the propylene resin.
なお、表１におけるエチレン系樹脂（ＰＥ−１０）は、以下に示す方法により調製した。 In addition, the ethylene-type resin (PE-10) in Table 1 was prepared by the method shown below.
（固体状担体（Ｓ−１）の調製）
内容積２７０リットルの攪拌機付き反応器に、窒素雰囲気下、シリカゲル（富士シリシア社製：平均粒径７０μｍ、比表面積３４０ｍ２／ｇ、細孔容積１．３ｃｍ３／ｇ、２５０℃で１０時間乾燥）１０ｋｇを添加し、これを７７リットルのトルエンに懸濁させた後、０〜５℃に冷却した。この懸濁液にメチルアルミノキサンのトルエン溶液（Ａｌ原子換算で３．５ｍｍｏｌ／ｍＬ）１９．４リットルを３０分間かけて滴下した。この際、系内温度を０〜５℃に保った。引き続き０〜５℃で３０分間接触させた後、約１．５時間かけて系内温度を９５℃まで上げ、引き続き９５℃で４時間接触させた。その後常温まで降温して、上澄み液をデカンテーションにより除去し、さらにトルエンで２回洗浄した。これにより、全量１１５リットルの固体状担体（Ｓ−１）のトルエンスラリーを調製した。得られたスラリー成分の一部を採取し濃度を調べたところ、スラリー濃度：１２２．６ｇ／Ｌ、Ａｌ濃度：０．６２ｍｏｌ／Ｌであった。
(Preparation of solid carrier (S-1))
Silica gel (manufactured by Fuji Silysia Co., Ltd .: average particle size 70 μm, specific surface area 340 m 2 / g, pore volume 1.3 cm 3 / g, dried at 250 ° C. for 10 hours under a nitrogen atmosphere in a reactor equipped with a stirrer with an internal volume of 270 liters ) 10 kg was added and suspended in 77 liters of toluene, and then cooled to 0-5 ° C. To this suspension, 19.4 liters of a toluene solution of methylaluminoxane (3.5 mmol / mL in terms of Al atom) was added dropwise over 30 minutes. At this time, the system temperature was kept at 0 to 5 ° C. Subsequently, contact was performed at 0 to 5 ° C. for 30 minutes, and then the system temperature was raised to 95 ° C. over about 1.5 hours, followed by contact at 95 ° C. for 4 hours. Thereafter, the temperature was lowered to room temperature, the supernatant was removed by decantation, and further washed twice with toluene. As a result, a total amount of 115 liters of a solid slurry (S-1) toluene slurry was prepared. When a part of the obtained slurry component was sampled and the concentration was examined, the slurry concentration was 122.6 g / L and the Al concentration was 0.62 mol / L.
（予備重合触媒成分（ＸＰ−１）の調製）
内容積１１４リットルの撹拌機付き反応器に、上記で得られた固体状担体（Ｓ−１）のトルエンスラリー１０．０リットル（Ａｌ原子換算で６．２０ｍｏｌ）を窒素雰囲気下で装入し、全量が２８リットルになるようトルエンを添加した。
(Preparation of prepolymerization catalyst component (XP-1))
To a reactor with an internal volume of 114 liters equipped with a stirrer, 10.0 liters of toluene slurry (6.20 mol in terms of Al atom) of the solid support (S-1) obtained above was charged under a nitrogen atmosphere, Toluene was added to a total volume of 28 liters.
次に、５リットルのガラス製反応器に窒素雰囲気下、ビス（１，３−ブチルメチルシクロペンタジエニル）ジルコニウムジクロリド１９．１５ｇ（Ｚｒ原子換算で４４．３ｍｍｏｌ）を添加し、これをトルエン５．０リットルに溶解させ、固体状担体（Ｓ−１）の入った上記反応器に圧送した。 Next, 19.15 g (44.3 mmol in terms of Zr atom) of bis (1,3-butylmethylcyclopentadienyl) zirconium dichloride was added to a 5 liter glass reactor under a nitrogen atmosphere. It was dissolved in 0.0 liter and pumped to the reactor containing the solid support (S-1).
系内温度２０〜２５℃で１時間接触させた後、系内温度を７５℃に上げ、さらに２時間接触させた。降温後、上澄み液をデカンテーションにより除去し、さらにヘキサンを用いて３回洗浄した後、ヘキサンを加えて全量３０リットルとし、固体触媒成分のヘキサンスラリーを調製した。 After contact at an internal temperature of 20 to 25 ° C. for 1 hour, the internal temperature was raised to 75 ° C. and further contacted for 2 hours. After the temperature was lowered, the supernatant was removed by decantation, and further washed three times with hexane, and then hexane was added to make a total volume of 30 liters to prepare a solid catalyst component hexane slurry.
引き続き、上記で得られた固体触媒成分のヘキサンスラリーを１０℃まで冷却した後、ジイソブチルアルミニウムヒドリド（ＤｉＢＡｌ−Ｈ）３．３ｍｏｌを添加した。さらに常圧下でエチレンを系内に連続的に数分間供給した。この間系内の温度は１０〜１５℃に保持し、次いで１−ヘキセン０．４２リットルを添加した。１−ヘキセン添加後、エチレン供給を開始し、系内温度３２〜３７℃にて予備重合を行った。予備重合を開始してから３０分毎に計５回、１−ヘキセン０．１５リットルを添加し、予備重合開始から１８０分後、エチレン供給量が固体触媒成分質量の３倍に到達したところで、エチレン供給を停止した。その後、上澄み液をデカンテーションにより除去し、ヘキサンを用いて４回洗浄した後、ヘキサンを加えて全量を５０リットルとした。 Subsequently, after the hexane slurry of the solid catalyst component obtained above was cooled to 10 ° C., 3.3 mol of diisobutylaluminum hydride (DiBAl—H) was added. Further, ethylene was continuously fed into the system for several minutes under normal pressure. During this time, the temperature in the system was maintained at 10 to 15 ° C., and then 0.42 liter of 1-hexene was added. After the addition of 1-hexene, ethylene supply was started and prepolymerization was performed at a system temperature of 32 to 37 ° C. 0.15 liter of 1-hexene was added 5 times every 30 minutes after starting the prepolymerization, and after 180 minutes from the start of the prepolymerization, when the ethylene supply amount reached 3 times the mass of the solid catalyst component, The ethylene supply was stopped. Thereafter, the supernatant was removed by decantation, washed 4 times with hexane, and then hexane was added to make the total volume 50 liters.
次に、系内温度３４〜３６℃にて、ケミスタット２５００（商品名、三洋化成工業社製）４９．０ｇのヘキサン溶液を上記反応器に圧送し、引き続き、３４〜３６℃で２時間反応させた。その後、上澄み液をデカンテーションにより除去し、ヘキサンを用いて４回洗浄した。 Next, a hexane solution of 49.0 g of Chemistat 2500 (trade name, manufactured by Sanyo Kasei Kogyo Co., Ltd.) was pumped into the reactor at a system temperature of 34 to 36 ° C., and subsequently reacted at 34 to 36 ° C. for 2 hours. It was. Thereafter, the supernatant was removed by decantation and washed four times with hexane.
次に、内容積４３リットルの撹拌機付き蒸発乾燥機に、窒素雰囲気下、ヘキサンスラリーを挿入した後、乾燥機内を約６０分かけて−６８ｋＰａＧまで減圧し、−６８ｋＰａＧに到達したところで約４．３時間真空乾燥し、ヘキサンならびに予備重合触媒成分中の揮発分を除去した。さらに−１００ｋＰａＧまで減圧し、−１００ｋＰａＧに到達したところで８時間真空乾燥し、予備重合触媒成分（ＸＰ−１）４．９ｋｇを得た。得られた予備重合触媒成分の一部を採取し、組成を調べたところ、予備重合触媒成分１ｇ当たりＺｒ原子が０．５４ｍｇ含まれていた。 Next, a hexane slurry was inserted into a 43 liter evaporative dryer with a stirrer under a nitrogen atmosphere, and then the pressure in the dryer was reduced to −68 kPaG over about 60 minutes, and when the pressure reached −68 kPaG, about 4. Vacuum drying was performed for 3 hours to remove volatile components in hexane and the prepolymerized catalyst component. The pressure was further reduced to −100 kPaG, and when the pressure reached −100 kPaG, vacuum drying was performed for 8 hours to obtain 4.9 kg of a prepolymerized catalyst component (XP-1). A part of the obtained prepolymerization catalyst component was sampled and the composition was examined. As a result, 0.54 mg of Zr atom was contained per 1 g of the prepolymerization catalyst component.
（ＰＥ−１０の調製）
内容積１．０ｍ３の流動層型気相重合反応器において、予備重合触媒成分（ＸＰ−１）を用いて、エチレン・１−ヘキセン共重合体の製造を行った。表２に示す条件に従い、連続的に反応器内に予備重合触媒成分（ＸＰ−１）、エチレン、窒素、１−ヘキセンなどを供給した。重合反応物を反応器より連続的に抜き出し、乾燥装置にて乾燥し、エチレン系樹脂（ＰＥ−１０）のパウダーを得た。
(Preparation of PE-10)
In a fluidized bed gas phase polymerization reactor having an internal volume of 1.0 m 3 , an ethylene / 1-hexene copolymer was produced using a prepolymerization catalyst component (XP-1). According to the conditions shown in Table 2, the prepolymerization catalyst component (XP-1), ethylene, nitrogen, 1-hexene and the like were continuously supplied into the reactor. The polymerization reaction product was continuously withdrawn from the reactor and dried with a drying apparatus to obtain a powder of ethylene resin (PE-10).
〔実施例１〕
エチレン系樹脂（Ａ）としてＰＥ−１、プロピレン系樹脂（Ｂ）としてＨＰＰ−１を用いた。これらを、二軸延伸フィルム成形機を用いて、ＰＥ−１／ＨＰＰ−１／ＨＰＰ−１＝１／１０／１の厚みの比にて溶融押出し、Ｔダイで賦形した後、冷却ロール上にて急冷し、厚さ約０．８ｍｍの共押出シートを得た。該共押出シートを１１０℃に加熱し、フィルムの流れ方向（ＭＤ方向）に５倍延伸した。この５倍延伸したシートを１５０℃に加熱し、流れ方向に対して直交する方向（ＴＤ方向）に８倍延伸して、厚さ２０μｍの二軸延伸多層フィルムを得た。該二軸延伸多層フィルムについて、上記評価を行った。結果を表３に示す。
[Example 1]
PE-1 was used as the ethylene resin (A), and HPP-1 was used as the propylene resin (B). These were melt-extruded at a thickness ratio of PE-1 / HPP-1 / HPP-1 = 1/10/1 using a biaxially stretched film molding machine, shaped with a T-die, and then on a cooling roll. And a coextruded sheet having a thickness of about 0.8 mm was obtained. The coextruded sheet was heated to 110 ° C. and stretched 5 times in the film flow direction (MD direction). The sheet stretched 5 times was heated to 150 ° C. and stretched 8 times in the direction orthogonal to the flow direction (TD direction) to obtain a biaxially stretched multilayer film having a thickness of 20 μm. The above evaluation was performed on the biaxially stretched multilayer film. The results are shown in Table 3.
〔実施例２〜９、比較例１〜７〕
実施例１において、各層に含まれるエチレン系樹脂およびプロピレン系樹脂の種類、各層の厚みの比、並びに二軸延伸多層フィルムの厚みを表３のように変更した以外は、実施例１と同様に二軸延伸多層フィルムを作製し、評価した。結果を表３に示す。なお、比較例１、３および４においては、成形不良のため上記評価を行うことができなかった。
[Examples 2 to 9, Comparative Examples 1 to 7]
In Example 1, except that the types of ethylene resin and propylene resin contained in each layer, the ratio of the thickness of each layer, and the thickness of the biaxially stretched multilayer film were changed as shown in Table 3, the same as in Example 1. A biaxially stretched multilayer film was prepared and evaluated. The results are shown in Table 3. In Comparative Examples 1, 3, and 4, the above evaluation could not be performed due to molding defects.
〔比較例８〕
ＰＥ−４をＴダイで賦形した後、冷却ロール上にて急冷し、厚さ約１．２ｍｍのシートを得た。該シートを１００℃に加熱し、フィルムの流れ方向（ＭＤ方向）に５倍延伸した。この５倍延伸したシートを１２５℃に加熱し、流れ方向に対して直交する方向（ＴＤ方向）に８倍延伸し、厚さ３０μｍの二軸延伸エチレン系樹脂フィルム（１）を得た。次いで、該二軸延伸エチレン系樹脂フィルム（１）に、ドライラミ用接着剤を塗布した後、厚さ２０μｍの二軸延伸ポリプロピレンフィルム（商品名：ＯＰ Ｕ−１、三井化学東セロ社製）を貼り合わせて二軸延伸多層フィルムを得た。なお、該ドライラミ用接着剤としては、タケラックＡ−９６９ＶおよびタケネートＡ−５（以上商品名、三井化学製）を混合したものを使用した。該二軸延伸多層フィルムについて、上記評価を行った。結果を表３に示す。
[Comparative Example 8]
PE-4 was shaped with a T die and then rapidly cooled on a cooling roll to obtain a sheet having a thickness of about 1.2 mm. The sheet was heated to 100 ° C. and stretched 5 times in the film flow direction (MD direction). The sheet stretched 5 times was heated to 125 ° C. and stretched 8 times in the direction perpendicular to the flow direction (TD direction) to obtain a biaxially stretched ethylene resin film (1) having a thickness of 30 μm. Next, after applying an adhesive for dry lamination to the biaxially stretched ethylene-based resin film (1), a 20 μm thick biaxially stretched polypropylene film (trade name: OP U-1, manufactured by Mitsui Chemicals, Inc.) is attached. In addition, a biaxially stretched multilayer film was obtained. In addition, as the dry laminating adhesive, a mixture of Takelac A-969V and Takenate A-5 (trade name, manufactured by Mitsui Chemicals) was used. The above evaluation was performed on the biaxially stretched multilayer film. The results are shown in Table 3.
〔比較例９〕
前記二軸延伸エチレン重合体フィルム（１）上にアンカー剤を塗布した後、該アンカー剤上に押出しラミネート機を用いてＰＥ−８を溶融押出した。該ＰＥ−８上に、厚さ２０μｍの二軸延伸ポリプロピレンフィルム（商品名：ＯＰ Ｕ−１、三井化学東セロ社製）を積層し、多層フィルムを得た。なお、前記アンカー剤には、コロネートＬ、ニッポラン１１００（以上商品名、日本ポリウレタン工業）、および溶剤としての酢酸エチル（広島和光純薬製）を混合したものを使用した。また、ＰＥ−８を含む層の厚みは２０μｍであった。該多層フィルムについて、上記評価を行った。結果を表３に示す。
[Comparative Example 9]
After applying an anchor agent on the biaxially stretched ethylene polymer film (1), PE-8 was melt-extruded on the anchor agent using an extrusion laminator. A biaxially stretched polypropylene film (trade name: OP U-1, manufactured by Mitsui Chemicals, Inc.) was laminated on the PE-8 to obtain a multilayer film. The anchor agent used was a mixture of Coronate L, Nipponran 1100 (trade name, Nippon Polyurethane Industry) and ethyl acetate (manufactured by Hiroshima Wako Pure Chemical Industries) as a solvent. Moreover, the thickness of the layer containing PE-8 was 20 μm. The above evaluation was performed on the multilayer film. The results are shown in Table 3.
〔比較例１０〕
前記アンカー剤を塗布しなかったこと以外は、比較例９と同様に多層フィルムを作製し、評価した。結果を表３に示す。なお、本比較例ではＰＥ−８を含む層と二軸延伸ポリプロピレンフィルムとの間で剥離が生じ、上記評価を行うことができなかった。
[Comparative Example 10]
A multilayer film was prepared and evaluated in the same manner as Comparative Example 9 except that the anchor agent was not applied. The results are shown in Table 3. In this comparative example, peeling occurred between the layer containing PE-8 and the biaxially stretched polypropylene film, and the above evaluation could not be performed.
〔比較例１１〕
前記二軸延伸エチレン重合体フィルム（１）に代えて、厚さ８０μｍの線状低密度ポリエチレンフィルム（商品名：Ｔ．Ｕ．Ｘ ＦＣＤ、三井化学東セロ社製）を用いた以外は、比較例８と同様に多層フィルムを作製した。該多層フィルムについて、上記評価を行った。結果を表３に示す。
[Comparative Example 11]
A comparative example except that instead of the biaxially stretched ethylene polymer film (1), a 80 μm thick linear low density polyethylene film (trade name: TUX FCD, manufactured by Mitsui Chemicals, Inc.) is used. A multilayer film was prepared in the same manner as in Example 8. The above evaluation was performed on the multilayer film. The results are shown in Table 3.
Claims (4)
前記樹脂層（Ｉ）と前記樹脂層（ＩＩ）との厚みの比（樹脂層（Ｉ）／樹脂層（ＩＩ））が１／１４〜１／３である多層フィルム。
要件（Ａ１）：ＡＳＴＭ Ｄ１２３８に準じて１９０℃、２．１６ｋｇ荷重で測定したメルトフローレート（ＭＦＲ）が０．５〜５０．０ｇ／１０分である。
要件（Ａ２）：ＪＩＳ Ｋ６９２２に準じて測定した密度が８９０〜９４０ｋｇ／ｍ３である。
要件（Ａ３）：示差走査熱量測定（ＤＳＣ）で測定した融点が８０〜１３５℃である。
要件（Ａ４）：ゲル浸透クロマトグラフィ（ＧＰＣ）で測定した重量平均分子量（Ｍｗ）と、数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が２．０〜９．０である。
要件（Ａ５）：ＪＩＳ Ｋ６９２１に準じて１０ｋｇ荷重、１９０℃で測定したメルトフローレート（ｇ／１０分）（ＭＦＲ１０）と、ＪＩＳ Ｋ６９２１に準じて２．１６ｋｇ荷重、１９０℃で測定したメルトフローレート（ｇ／１０分）（ＭＦＲ２．１６）との比（ＭＦＲ１０／ＭＦＲ２．１６）が４．０〜９．５である。 A resin layer (I) containing an ethylene resin (A) that satisfies the following requirements (A1) to (A5), and a resin layer (II) containing a propylene resin (B),
The multilayer film whose ratio (resin layer (I) / resin layer (II)) of the resin layer (I) and the resin layer (II) is 1/14 to 1/3.
Requirement (A1): Melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg according to ASTM D1238 is 0.5 to 50.0 g / 10 min.
Requirement (A2): The density measured according to JIS K6922 is 890 to 940 kg / m 3 .
Requirement (A3): Melting point measured by differential scanning calorimetry (DSC) is 80 to 135 ° C.
Requirement (A4): The ratio (Mw / Mn) between the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) and the number average molecular weight (Mn) is 2.0 to 9.0.
Requirement (A5): Melt flow rate (g / 10 min) measured at 190 ° C. according to JIS K6921 (g / 10 min) (MFR10) and Melt flow rate measured at 190 ° C. under 2.16 kg load according to JIS K6921 The ratio (MFR10 / MFR2.16) to (g / 10 minutes) (MFR2.16) is 4.0 to 9.5.
要件（Ａ６）：前記ＭＦＲ１０／ＭＦＲ２．１６が５．０以上の場合、前記Ｍｗ／Ｍｎが２．５以上である。 The multilayer film according to claim 1, wherein the ethylene-based resin (A) further satisfies the following requirement (A6).
Requirement (A6): When the MFR10 / MFR2.16 is 5.0 or more, the Mw / Mn is 2.5 or more.
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