JP4711920B2 - Biaxially oriented multilayer polypropylene film - Google Patents
Biaxially oriented multilayer polypropylene film Download PDFInfo
- Publication number
- JP4711920B2 JP4711920B2 JP2006254847A JP2006254847A JP4711920B2 JP 4711920 B2 JP4711920 B2 JP 4711920B2 JP 2006254847 A JP2006254847 A JP 2006254847A JP 2006254847 A JP2006254847 A JP 2006254847A JP 4711920 B2 JP4711920 B2 JP 4711920B2
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- Prior art keywords
- propylene
- biaxially stretched
- polypropylene film
- multilayer polypropylene
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001155 polypropylene Polymers 0.000 title claims description 119
- -1 polypropylene Polymers 0.000 title claims description 71
- 239000004743 Polypropylene Substances 0.000 title claims description 66
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 47
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 47
- 239000004711 α-olefin Substances 0.000 claims description 38
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 29
- 229920005604 random copolymer Polymers 0.000 claims description 25
- 229920001384 propylene homopolymer Polymers 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000010410 layer Substances 0.000 description 67
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
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- 239000002585 base Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical group CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 6
- 239000004971 Cross linker Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 150000003505 terpenes Chemical class 0.000 description 5
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
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- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000013032 Hydrocarbon resin Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 235000009508 confectionery Nutrition 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 150000003097 polyterpenes Chemical class 0.000 description 3
- 239000012748 slip agent Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
- 229910000271 hectorite Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229910000275 saponite Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001595840 Margarites Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 241000269851 Sarda sarda Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 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
- 229910052630 margarite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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- 235000011888 snacks Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 230000002522 swelling effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
Description
本発明は、防湿性、印刷適性及びラミネート強度に優れた二軸延伸多層ポリプロピレンフィルムに関する。 The present invention relates to a biaxially stretched multilayer polypropylene film having excellent moisture resistance, printability and laminate strength.
二軸延伸ポリプロピレンフィルム（以下ＯＰＰフィルムと呼ぶことがある）は、その優れた透明性、機械的強度、剛性等を活かして包装材料をはじめ広い分野で使用されている。又、ＯＰＰフィルムの防湿性を改良するために、石油樹脂、テルペン樹脂等の粘着付与剤を添加する方法も多々提案されている。そして、石油樹脂がＯＰＰフィルムの表面にブリードアウトするのを防ぐ方法として、石油樹脂を含むＯＰＰフィルムの両面あるいは片面に、石油樹脂を含まないポリプロピレン層をラミネートすることが提案されている（例えば、特許文献１、特許文献２、特許文献３）。 Biaxially stretched polypropylene films (hereinafter sometimes referred to as OPP films) are used in a wide range of fields including packaging materials by taking advantage of their excellent transparency, mechanical strength, rigidity and the like. In order to improve the moisture resistance of the OPP film, many methods for adding a tackifier such as petroleum resin or terpene resin have been proposed. And as a method for preventing petroleum resin from bleeding out on the surface of the OPP film, it has been proposed to laminate a polypropylene layer not containing petroleum resin on both sides or one side of the OPP film containing petroleum resin (for example, Patent Document 1, Patent Document 2, Patent Document 3).
ＯＰＰフィルムの防湿性は、石油樹脂の添加量を増やすことにより、より改良されるが、石油樹脂量が増すとともに、ＯＰＰフィルムの表面に滲み出る石油樹脂の量が増し、表面がべたついたり、他の層と積層（ラミネート）した場合に、ラミネート強度が低下する虞がある。石油樹脂の滲み出る量を抑制するには、石油樹脂を含むＯＰＰフィルムの両側に積層するポリプロピレン層の厚さをある程度厚くすれば改良されるが、当該層を厚くすれば、ＯＰＰフィルムの防湿性が低下する虞がある等の問題点がある。
本発明は、石油樹脂等の粘着付与剤の添加量を増しても、フィルム表面への滲み出しを抑制でき、ラミネート強度に優れ、しかもその低下がない防湿性に優れる二軸延伸ポリプロピレンフィルムを得ることを目的とする。 The present invention provides a biaxially stretched polypropylene film that can suppress oozing to the film surface even when the amount of a tackifier such as a petroleum resin is increased, is excellent in laminate strength, and is excellent in moisture resistance without a decrease thereof. For the purpose.
本発明は、プロピレン単独重合体（Ａ）７５〜９０重量％及び粘着付与剤（Ｄ）２５〜１０重量％を含むプロピレン重合体組成物からなる二軸延伸フィルムの片面に、融点が１５５℃以上のプロピレン系重合体（Ｂ）からなる層を介して融点が１２５〜１４５℃の範囲のプロピレン・α−オレフィンランダム共重合体（Ｃ）からなる層を有し、前記二軸延伸フィルムの他の片面に、プロピレン系重合体（Ｅ）からなる層を有してなることを特徴とする二軸延伸多層ポリプロピレンフィルム及びかかる二軸延伸多層ポリプロピレンフィルムのプロピレン・α−オレフィンランダム共重合体（Ｃ）からなる層上に、ビニルアルコール系重合体（Ｆ）からなる層を有してなる二軸延伸多層ポリプロピレンフィルムに関する。 The present invention has a melting point of 155 ° C. or higher on one side of a biaxially stretched film comprising a propylene polymer composition containing 75 to 90% by weight of a propylene homopolymer (A) and 25 to 10% by weight of a tackifier (D). A layer made of a propylene / α-olefin random copolymer (C) having a melting point of 125 to 145 ° C. through a layer made of the propylene-based polymer (B). A biaxially stretched multilayer polypropylene film comprising a layer made of a propylene-based polymer (E) on one side, and a propylene / α-olefin random copolymer (C) of the biaxially stretched multilayer polypropylene film It is related with the biaxially-stretched multilayer polypropylene film which has the layer which consists of a vinyl alcohol-type polymer (F) on the layer which consists of.
本発明の二軸延伸多層ポリプロピレンフィルムは、防湿性、印刷適性、及びラミネート強度に優れる。又、ビニルアルコール系重合体層を積層してなる二軸延伸多層ポリプロピレンフィルムは、更に、ガスバリア性にも優れる。 The biaxially stretched multilayer polypropylene film of the present invention is excellent in moisture resistance, printability, and laminate strength. Moreover, the biaxially stretched multilayer polypropylene film formed by laminating a vinyl alcohol polymer layer is further excellent in gas barrier properties.
プロピレン単独重合体（Ａ）
本発明の二軸延伸多層ポリプロピレンフィルムの二軸延伸フィルムを形成する成分の一つであるプロピレン単独重合体（Ａ）は、プロピレンの単独重合体からなり、ＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）が、通常０．５〜１０ｇ／１０分、好ましくは２〜５ｇ／１０分の範囲にある。
Propylene homopolymer (A)
The propylene homopolymer (A), which is one of the components forming the biaxially stretched multilayer polypropylene film of the present invention, is composed of a propylene homopolymer and is MFR (melt flow rate; ASTM D-1238). Load 2160 g, temperature 230 ° C.) is usually in the range of 0.5 to 10 g / 10 min, preferably 2 to 5 g / 10 min.
本発明に係わるプロピレン単独重合体（Ａ）は、好ましくはアイソタクチックインデックスが９５％以上である。プロピレン単独重合体（Ａ）として、かかるアイソタクチックインデックスが９５％以上を用いることにより、より防湿性に優れる二軸延伸多層ポリプロピレンフィルムを得ることができる。 The propylene homopolymer (A) according to the present invention preferably has an isotactic index of 95% or more. By using 95% or more of the isotactic index as the propylene homopolymer (A), it is possible to obtain a biaxially stretched multilayer polypropylene film having more excellent moisture resistance.
粘着付与剤（Ｄ）
本発明の二軸延伸多層ポリプロピレンフィルムの二軸延伸フィルムを形成する他の成分である粘着付与剤（Ｄ）は、一般に粘着付与剤として製造・販売されている樹脂状物質で、具体的には、クマロン・インデン樹脂等のクマロン樹脂、フェノール・ホルムアルデヒド樹脂、テルペン・フェノール樹脂、ポリテルペン樹脂及びキシレン・ホルムアルデヒド樹脂等のフェノール，テルペン樹脂、合成ポリテルペン樹脂、芳香族系炭化水素樹脂、脂肪族系炭化水素樹脂、脂肪族系環状炭化水素樹脂、脂肪族・脂環族系石油樹脂、脂肪族・芳香族系石油樹脂、不飽和炭化水素重合体、水素添加炭化水素樹脂及び炭化水素系粘着化樹脂等の石油系炭化水素樹脂、ロジンのペンタエリスリトール・エステル、ロジンのグリセロール・エステル、水素添加ロジン、水素添加ロジンエステル、特殊ロジンエステル及びロジン系粘着付与剤等のロジン誘導体及びテルペン系粘着付与剤等を例示できる。
Tackifier (D)
The tackifier (D), which is another component that forms the biaxially stretched film of the biaxially stretched multilayer polypropylene film of the present invention, is a resinous substance that is generally manufactured and sold as a tackifier, specifically, Coumarone resins such as coumarone / indene resins, phenol / formaldehyde resins, terpenes / phenol resins, phenols such as polyterpene resins and xylene / formaldehyde resins, terpene resins, synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbons Resin, aliphatic cyclic hydrocarbon resin, aliphatic / alicyclic petroleum resin, aliphatic / aromatic petroleum resin, unsaturated hydrocarbon polymer, hydrogenated hydrocarbon resin, hydrocarbon-based tackifying resin, etc. Petroleum hydrocarbon resin, rosin pentaerythritol ester, rosin glycerol ester, hydrogenated Jin, hydrogenated rosin esters, rosin derivatives and terpene tackifiers such as special rosin ester and rosin-based tackifier may be exemplified.
これらの中では、軟化点が１１０℃以上、好ましくは１２５〜１４５℃の範囲にある水素添加率が９５％以上、更には９９％以上の水素添加炭化水素樹脂、水素添加脂肪族系環状炭化水素樹脂、水素添加脂肪族・脂環族系石油樹脂、水素添加テルペン樹脂、水素添加合成ポリテルペン樹脂等の水素添加樹脂が、プロピレン単独重合体（Ａ）との相溶性に優れるので好ましい。軟化点が１１０℃未満のものは成形時に発煙の問題が発生し、成形機を汚ごす虞が生ずる場合があり、一方、１４５℃を超えるものはプロピレン単独重合体（Ａ）と相溶しづらくなるため二軸延伸多層ポリプロピレンフィルムの外観が悪くなる虞がある。 Among these, hydrogenated hydrocarbon resins and hydrogenated aliphatic cyclic hydrocarbons having a softening point of 110 ° C. or higher, preferably a hydrogenation rate in the range of 125 to 145 ° C. of 95% or higher, more preferably 99% or higher. Hydrogenated resins such as resins, hydrogenated aliphatic / alicyclic petroleum resins, hydrogenated terpene resins, and hydrogenated synthetic polyterpene resins are preferred because of their excellent compatibility with the propylene homopolymer (A). If the softening point is less than 110 ° C, smoke may be generated during molding, and the molding machine may be contaminated. On the other hand, if it exceeds 145 ° C, it is compatible with the propylene homopolymer (A). Since it becomes difficult, there exists a possibility that the external appearance of a biaxially stretched multilayer polypropylene film may worsen.
プロピレン重合体組成物
本発明の二軸延伸フィルムを形成するプロピレン重合体組成物は、前記プロピレン単独重合体（Ａ）が７５〜９０重量％、好ましくは８０〜９０重量％及び前記粘着付与剤（Ｄ）を２５〜１０重量％、好ましくは１０〜２０重量％の範囲で含む組成物である。粘着付与剤（Ｄ）が１０重量％未満の組成物では、防湿性に優れる二軸延伸多層ポリプロピレンフィルムが得られず、一方、２５重量％を超える組成物は、得られる二軸延伸多層ポリプロピレンフィルムの透明性が損なわれ、防湿性の改善効果も少ない虞がある。
Propylene polymer composition The propylene polymer composition for forming the biaxially stretched film of the present invention comprises 75 to 90% by weight of the propylene homopolymer (A), preferably 80 to 90% by weight and the tackifier ( D) is a composition comprising 25 to 10% by weight, preferably 10 to 20% by weight. A biaxially stretched multilayer polypropylene film excellent in moisture resistance cannot be obtained with a composition having a tackifier (D) of less than 10% by weight, while a biaxially stretched multilayer polypropylene film with a composition exceeding 25% by weight is obtained. There is a risk that the transparency of the glass will be impaired, and the effect of improving moisture resistance will be small.
本発明に係わるプロピレン重合体組成物には、耐熱安定剤、耐候安定剤、紫外線吸収剤、滑剤、スリップ剤、核剤、ブロッキング防止剤、帯電防止剤、防曇剤、顔料、染料、無機または有機の充填剤等の通常ポリオレフィンに用いる各種添加剤を本発明の目的を損なわない範囲で添加しておいてもよい。 The propylene polymer composition according to the present invention includes a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a lubricant, a slip agent, a nucleating agent, an antiblocking agent, an antistatic agent, an antifogging agent, a pigment, a dye, an inorganic or Various additives such as organic fillers usually used for polyolefins may be added within a range not impairing the object of the present invention.
プロピレン系重合体（Ｂ）
本発明の二軸延伸多層ポリプロピレンフィルムに係わるプロピレン系重合体（Ｂ）層を形成するプロピレン系重合体（Ｂ）は、融点が１５５℃以上、好ましくは１５７〜１７０℃のプロピレンの単独重合体若しくはプロピレンと少量、例えば、２モル％以下のエチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等のα−オレフィンとのランダム共重合体である。かかるプロピレン系重合体としては、プロピレン単独重合体が好ましい。融点（Ｔｍ）が１５５℃未満のプロピレン系重合体は、前記プロピレン系重合体組成物に含まれる粘着付与剤（Ｄ）の滲み出しを抑制できない虞がある。
Propylene polymer (B)
The propylene polymer (B) for forming the propylene polymer (B) layer related to the biaxially stretched multilayer polypropylene film of the present invention has a melting point of 155 ° C. or higher, preferably 157 to 170 ° C. propylene homopolymer or A random copolymer of propylene and a small amount, for example, 2 mol% or less of an α-olefin such as ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene. As such a propylene polymer, a propylene homopolymer is preferable. The propylene polymer having a melting point (Tm) of less than 155 ° C. may not be able to suppress the bleeding of the tackifier (D) contained in the propylene polymer composition.
本発明に係わるプロピレン系重合体（Ｂ）のＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）は二軸延伸フィルムとすることができる限り特に限定はされないが、通常、０．５〜１０ｇ／１０分、好ましくは２〜５．０ｇ／１０分の範囲にある。 The MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) of the propylene polymer (B) according to the present invention is not particularly limited as long as it can be a biaxially stretched film. It is in the range of 5 to 10 g / 10 minutes, preferably 2 to 5.0 g / 10 minutes.
本発明に係わるプロピレン系重合体（Ｂ）は、前記プロピレン単独重合体（Ａ）と同一の範疇の重合体であってもよい。 The propylene polymer (B) according to the present invention may be a polymer in the same category as the propylene homopolymer (A).
また、本発明に係わるプロピレン系重合体（Ｂ）には、前記粘着付与剤（Ｄ）を、プロピレン系重合体（Ｂ）と粘着付与剤（Ｄ）の合計量に対して、１０重量％以下の量で添加しておいてもよい。粘着付与剤（Ｄ）の量が、１０重量％を超えると、粘着付与剤（Ｄ）の滲み出しを抑制することができなくなる虞がある。 In the propylene polymer (B) according to the present invention, the tackifier (D) is added in an amount of 10% by weight or less based on the total amount of the propylene polymer (B) and the tackifier (D). It may be added in an amount of. When the amount of the tackifier (D) exceeds 10% by weight, the oozing of the tackifier (D) may not be suppressed.
プロピレン・α−オレフィンランダム共重合体（Ｃ）
本発明の二軸延伸多層ポリプロピレンフィルムに係わるプロピレン・α−オレフィンランダム共重合体（Ｃ）層を形成するプロピレン・α−オレフィンランダム共重合体（Ｃ）は、融点が１２５〜１４５℃、好ましくは１３０〜１４３℃の範囲にあるプロピレンとα−オレフィンとのランダム共重合体である。融点が１４５℃を越えると、得られる二軸延伸多層ポリプロピレンフィルムのヒートシール性、ラミネート強度が改良されない虞があり、一方、１２５℃未満では得られる二軸延伸多層ポリプロピレンフィルムにべたが発生し、ブロッキングし易くなる虞がある。α―オレフィンとしては、エチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等が例示できる。具体的な共重合体としては、プロピレン・エチレ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、プロピレン・１−ブテンランダム共重合体等が挙げられる。これら共重合体は、単独で用いても良いし、二種以上を混合して用いても良い。
Propylene / α-olefin random copolymer (C)
The propylene / α-olefin random copolymer (C) forming the propylene / α-olefin random copolymer (C) layer related to the biaxially stretched multilayer polypropylene film of the present invention has a melting point of 125 to 145 ° C., preferably It is a random copolymer of propylene and α-olefin in the range of 130 to 143 ° C. If the melting point exceeds 145 ° C, the heat-sealability and laminate strength of the resulting biaxially stretched multilayer polypropylene film may not be improved, while if it is less than 125 ° C, the resulting biaxially stretched multilayer polypropylene film is sticky, There is a risk of blocking. Examples of the α-olefin include ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene and the like. Specific examples of the copolymer include a propylene / ethylene random copolymer, a propylene / ethylene / 1-butene random copolymer, and a propylene / 1-butene random copolymer. These copolymers may be used alone or in admixture of two or more.
本発明に係わるプロピレン・α−オレフィン共重合体（Ｃ）のＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）はフィルム形成能がある限り特に限定はされないが、通常０．５〜１５ｇ／１０分、好ましくは２〜１０ｇ／１０分の範囲にある。 The MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) of the propylene / α-olefin copolymer (C) according to the present invention is not particularly limited as long as it has film-forming ability, but usually 0.5 It is in the range of ˜15 g / 10 minutes, preferably 2 to 10 g / 10 minutes.
本発明に係るプロピレン・α−オレフィン共重合体（Ｃ）には耐熱安定剤、耐候安定剤、紫外線吸収剤、滑剤、スリップ剤、核剤、ブロッキング防止剤、帯電防止剤、防曇剤、顔料、染料、無機または有機の充填剤等の通常ポリオレフィンに用いる各種添加剤を本発明の目的を損なわない範囲で添加しておいてもよい。 The propylene / α-olefin copolymer (C) according to the present invention includes a heat resistance stabilizer, a weather resistance stabilizer, an ultraviolet absorber, a lubricant, a slip agent, a nucleating agent, an antiblocking agent, an antistatic agent, an antifogging agent, and a pigment. Various additives usually used in polyolefins such as dyes, inorganic or organic fillers, etc. may be added within the range not impairing the object of the present invention.
また、ブロッキング防止剤を０．０１〜３．０重量％、好ましくは０．０５〜１．０重量％を添加しておくと、透明性に優れ、且つブロッキング防止性を有する二軸延伸多層ポリプロピレンフィルムとすることができる。ブロッキング防止剤の量が０．０１重量％未満では、得られる二軸延伸多層ポリプロピレンフィルムのブロッキング防止効果が充分でなく、一方、３．０重量％を越えると、得られる二軸延伸多層ポリプロピレンフィルムの透明性が劣る傾向にある。かかるブロッキング防止剤としては、種々公知のもの、例えば、シリカ、タルク、雲母、ゼオライトや更には金属アルコキシドを焼成して得た金属酸化物等の無機化合物粒子、ポリメタクリル酸メチル、メラミンホルマリン樹脂、メラミン尿素樹脂、ポリエステル樹脂等の有機化合物粒子等を用い得る。これらの中でも、シリカ、ポリメタクリル酸メチルがアンチブロッキング性、透明性の面から特に好ましい。 In addition, when 0.01 to 3.0% by weight, preferably 0.05 to 1.0% by weight of an antiblocking agent is added, the biaxially stretched multilayer polypropylene has excellent transparency and antiblocking properties. It can be a film. When the amount of the anti-blocking agent is less than 0.01% by weight, the anti-blocking effect of the resulting biaxially stretched multilayer polypropylene film is not sufficient, while when it exceeds 3.0% by weight, the resulting biaxially stretched multilayer polypropylene film is obtained. Tends to be inferior in transparency. As such an anti-blocking agent, various known compounds such as silica, talc, mica, zeolite and further inorganic compound particles such as metal oxide obtained by firing metal alkoxide, polymethyl methacrylate, melamine formalin resin, Organic compound particles such as melamine urea resin and polyester resin can be used. Among these, silica and polymethyl methacrylate are particularly preferable in terms of antiblocking properties and transparency.
プロピレン系重合体（Ｅ）
本発明の二軸延伸多層ポリプロピレンフィルムに係わるプロピレン系重合体（Ｅ）層を形成するプロピレン系重合体は、融点が１５５℃以上、好ましくは１５７〜１７０℃のプロピレンの単独重合体若しくはプロピレンと少量、例えば、２モル％以下のエチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等のα−オレフィンとのランダム共重合体である。かかるプロピレン系重合体としては、プロピレン単独重合体とプロピレンランダム共重合体との組成物であってもよい。
Propylene polymer (E)
The propylene polymer forming the propylene polymer (E) layer related to the biaxially stretched multilayer polypropylene film of the present invention is a propylene homopolymer having a melting point of 155 ° C. or higher, preferably 157 to 170 ° C., or a small amount with propylene. For example, it is a random copolymer with 2 mol% or less of α-olefin such as ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene. Such a propylene polymer may be a composition of a propylene homopolymer and a propylene random copolymer.
本発明に係わるプロピレン系重合体（Ｅ）のＭＦＲ（メルトフローレート；ＡＳＴＭ Ｄ−１２３８ 荷重２１６０ｇ、温度２３０℃）はニ軸延伸フィルムとすることができる限り特に限定はされないが、通常０．５〜１０ｇ／１０分、好ましくは２〜５．０ｇ／１０分の範囲にある。 The MFR (melt flow rate; ASTM D-1238 load 2160 g, temperature 230 ° C.) of the propylene polymer (E) according to the present invention is not particularly limited as long as it can be a biaxially stretched film. It is in the range of 10 to 10 g / 10 minutes, preferably 2 to 5.0 g / 10 minutes.
本発明に係わるプロピレン系重合体（Ｅ）は、前記プロピレン単独重合体（Ｂ）と同一の範疇の重合体であってもよい。 The propylene polymer (E) according to the present invention may be a polymer in the same category as the propylene homopolymer (B).
本発明に係るプロピレン系重合体（Ｅ）には耐熱安定剤、耐候安定剤、紫外線吸収剤、滑剤、スリップ剤、核剤、ブロッキング防止剤、帯電防止剤、防曇剤、顔料、染料、無機または有機の充填剤等の通常ポリオレフィンに用いる各種添加剤を本発明の目的を損なわない範囲で添加しておいてもよい。 The propylene polymer (E) according to the present invention includes a heat resistance stabilizer, a weather resistance stabilizer, an ultraviolet absorber, a lubricant, a slip agent, a nucleating agent, an antiblocking agent, an antistatic agent, an antifogging agent, a pigment, a dye, and an inorganic material. Alternatively, various additives such as organic fillers that are usually used for polyolefins may be added within a range that does not impair the object of the present invention.
また、上記同様、ブロッキング防止剤を０．０１〜３．０重量％、好ましくは０．０５〜１．０重量％を添加しておくと、透明性に優れ、且つブロッキング防止性を有する二軸延伸多層ポリプロピレンフィルムとすることができる。ブロッキング防止剤の量が０．０１重量％未満では、得られる二軸延伸多層ポリプロピレンフィルムのブロッキング防止効果が充分でなく、一方、３．０重量％を越えると、得られる二軸延伸多層ポリプロピレンフィルムの透明性が劣る傾向にある。かかるブロッキング防止剤としては、種々公知のもの、例えば、シリカ、タルク、雲母、ゼオライトや更には金属アルコキシドを焼成して得た金属酸化物等の無機化合物粒子、ポリメタクリル酸メチル、メラミンホルマリン樹脂、メラミン尿素樹脂、ポリエステル樹脂等の有機化合物粒子等を用い得る。これらの中でも、シリカ、ポリメタクリル酸メチルがアンチブロッキング性、透明性の面から特に好ましい。 Further, as described above, when the antiblocking agent is added in an amount of 0.01 to 3.0% by weight, preferably 0.05 to 1.0% by weight, the biaxial compound has excellent transparency and antiblocking properties. It can be set as a stretched multilayer polypropylene film. When the amount of the anti-blocking agent is less than 0.01% by weight, the anti-blocking effect of the resulting biaxially stretched multilayer polypropylene film is not sufficient, while when it exceeds 3.0% by weight, the resulting biaxially stretched multilayer polypropylene film is obtained. Tends to be inferior in transparency. As such an antiblocking agent, various known compounds such as silica, talc, mica, zeolite, and further inorganic compound particles such as metal oxide obtained by firing metal alkoxide, polymethyl methacrylate, melamine formalin resin, Organic compound particles such as melamine urea resin and polyester resin can be used. Among these, silica and polymethyl methacrylate are particularly preferable in terms of antiblocking properties and transparency.
ビニルアルコール系重合体（Ｆ）
本発明に係わるビニルアルコール系重合体（Ｆ）は、酢酸ビニル系重合体をケン化して得られる分子内に水酸基を持つ、好ましくは水に可溶の重合体である。原料である酢酸ビニル系重合体は酢酸ビニルの単独重合体であってもよいし、他の共重合可能なモノマー、例えばエチレン、プロピレンまたは１−ブテン等のα―オレフィン等が３０モル％まで共重合されたものであってもよい。共重合のモノマーが３０モル％を越えると、ガスバリア性が低下して、バリア材としての性能が不十分になる。
Vinyl alcohol polymer (F)
The vinyl alcohol polymer (F) according to the present invention is a polymer having a hydroxyl group in a molecule obtained by saponifying a vinyl acetate polymer, preferably soluble in water. The raw material vinyl acetate polymer may be a homopolymer of vinyl acetate, or other copolymerizable monomers such as ethylene, propylene or α-olefins such as 1-butene may be added up to 30 mol%. It may be polymerized. When the copolymerization monomer exceeds 30 mol%, the gas barrier property is lowered and the performance as a barrier material becomes insufficient.
ビニルアルコール系重合体（Ｆ）のケン化度は通常９０％以上、好ましくは９９％以上であり、この範囲にあると高湿度下でのバリア性が維持される。重合度は特に制限されないが３００〜５０００、より好ましくは５００〜２０００の範囲が望ましい。重合度が３００以下ではガスバリア性が不充分な虞があり、５０００以上ではかかるビニルアルコール系重合体（Ｅ）を塗布する際の分散液の粘度が高くなりすぎて塗布加工が難しくなる。 The saponification degree of the vinyl alcohol polymer (F) is usually 90% or more, and preferably 99% or more. When it is within this range, the barrier property under high humidity is maintained. The degree of polymerization is not particularly limited, but is preferably in the range of 300 to 5000, more preferably 500 to 2000. When the degree of polymerization is 300 or less, the gas barrier property may be insufficient. When the degree of polymerization is 5000 or more, the viscosity of the dispersion when applying the vinyl alcohol polymer (E) becomes too high, and the coating process becomes difficult.
無機層状化合物
本発明に係わるビニルアルコール系重合体（Ｆ）には、無機層状化合物を添加しておいてもよい。かかる無機層状化合物は、極薄の単位結晶層が１枚または数枚重なった多層構造をもって板状の粒子を形成している無機化合物のことであり、粘土鉱物が好ましく用いられる。本発明における粘土鉱物とは極薄の単位結晶層間に水を配位、吸収する性質、特には水分子が配位することにより浸漬前より体積が増加する化合物を持つ粘土化合物であり、一般にはＳｉ４＋がＯ２−対して配位し４面体構造を構成する層とＡｌ２、Ｍｇ２＋、Ｆｅ２＋、Ｆｅ３＋、Ｌｉ＋等がＯ２−およびＯＨ−に対して配位し８面体構造を構成する層とが１対１あるいは２対１で結合し積み重なって層状構造を構成しており、天然のものであっても合成されたものでも良い。代表的なものとしては、モンモリロナイト、バイデライト、サポナイト、ヘクトライト、カオリナイト、ハロイサイト、バーミキュライト、ディッカイト、ナクライト、アンチゴライト、パイロフィライト、マーガライト、タルク、テトラシリリックマイカ、白雲母、金雲母、緑泥石等が挙げられる。中でも、スメクタイト群と呼ばれているモンモリロナイト、バイデライト、ヘクトライトやサポナイトが好ましく用いられ、更には不純物の少ない合成品が好ましく、その中でも結晶構造が成長し、アスペクト比を大きくできる溶融法で生成したナトリウム型テトラシリシックマイカが特に好ましい。
Inorganic layered compound An inorganic layered compound may be added to the vinyl alcohol polymer (F) according to the present invention. Such an inorganic layered compound is an inorganic compound that forms plate-like particles with a multilayer structure in which one or several ultrathin unit crystal layers overlap each other, and a clay mineral is preferably used. The clay mineral in the present invention is a clay compound having a property of coordinating and absorbing water between ultra-thin unit crystal layers, in particular, a compound whose volume increases from before immersion due to coordination of water molecules. Si 4+ is coordinated to O 2− to form a tetrahedral structure, and Al 2 , Mg 2+ , Fe 2+ , Fe 3+ , Li + and the like are coordinated to O 2− and OH − to form an octahedral structure. The layers constituting the layer are combined in a one-to-one or two-to-one manner and stacked to form a layered structure, which may be natural or synthesized. Typical examples include montmorillonite, beidellite, saponite, hectorite, kaolinite, halloysite, vermiculite, dickite, nacrite, antigolite, pyrophyllite, margarite, talc, tetrasilic mica, muscovite, phlogopite. Chlorite and the like. Of these, montmorillonite, beidellite, hectorite and saponite, which are called smectite groups, are preferably used, and synthetic products with less impurities are preferred. Sodium tetralithic mica is particularly preferred.
上記層状化合物の層と層との間には通常陽イオンが保持されている。このような層間イオンとしては、Ｋ＋、Ｎａ＋、Ｌｉ＋等のアルカリ金属イオンを例示することが出来る。特に陽イオンが膨潤性を向上させるためにＮａで置換されていることが好ましい。 Cations are usually held between the layers of the layered compound. Examples of such interlayer ions include alkali metal ions such as K +, Na +, and Li +. In particular, the cation is preferably substituted with Na in order to improve the swelling property.
二軸延伸多層ポリプロピレンフィルム
本発明の二軸延伸多層ポリプロピレンフィルムは、前記プロピレン単独重合体及び粘着付与剤（Ｄ）を含むプロピレン重合体組成物からなる二軸延伸フィルムの片面に、前記プロピレン系重合体（Ｂ）からなる層を介してプロピレン・α−オレフィンランダム共重合体（Ｃ）からなる層を有し、他の片面に、プロピレン系重合体（Ｅ）からなる層を有してなることを特徴とする二軸延伸多層ポリプロピレンフィルムである。
Biaxially Stretched Multilayer Polypropylene Film The biaxially stretched multilayer polypropylene film of the present invention has the propylene-based polymer on one side of a biaxially stretched film composed of a propylene polymer composition containing the propylene homopolymer and a tackifier (D). It has a layer made of a propylene / α-olefin random copolymer (C) through a layer made of a polymer (B) and a layer made of a propylene polymer (E) on the other side. Is a biaxially stretched multilayer polypropylene film.
本発明の二軸延伸多層ポリプロピレンフィルムの厚さは用途により種々決められるものであり、特に限定はされないが、通常、プロピレン重合体組成物からなる二軸延伸フィルムが１０〜１００μｍ、好ましくは１５〜５０μｍ、プロピレン系重合体（Ｂ）層が０．５〜１５μｍ、好ましくは１〜１０μｍ、プロピレン・α−オレフィン共重合体（Ｃ）層が０．５〜１５μｍ、好ましくは１〜１０μｍ、他の片面にあるプロピレン系重合体（Ｂ）層が０．５〜１５μｍ、好ましくは１〜１０μｍの範囲にある。 The thickness of the biaxially stretched multilayer polypropylene film of the present invention is variously determined depending on the application and is not particularly limited. Usually, the biaxially stretched film made of the propylene polymer composition is 10 to 100 μm, preferably 15 to 50 μm, propylene polymer (B) layer 0.5 to 15 μm, preferably 1 to 10 μm, propylene / α-olefin copolymer (C) layer 0.5 to 15 μm, preferably 1 to 10 μm, other The propylene polymer (B) layer on one side is in the range of 0.5 to 15 μm, preferably 1 to 10 μm.
本発明の二軸延伸多層ポリプロピレンフィルムは、ラミネート層となるプロピレン・α−オレフィンランダム共重合体（Ｃ）層と粘着付与剤（Ｄ）を含むプロピレン重合体組成物からなる二軸延伸フィルムとの間に、プロピレン系重合体（Ｂ）層を有するので、プロピレン・α−オレフィンランダム共重合体（Ｃ）層の表面に、粘着付与剤（Ｄ）が滲み出す虞が極めて少ないので、得られる二軸延伸多層ポリプロピレンフィルムの表面がべたつかず、また、プロピレン・α−オレフィンランダム共重合体（Ｃ）層の表面に、ビニルアルコール系重合体（Ｅ）を積層（ラミネート）した際にも、良好な接着強度（ラミネート強度）が得られる。 The biaxially stretched multilayer polypropylene film of the present invention is a biaxially stretched film comprising a propylene / α-olefin random copolymer (C) layer to be a laminate layer and a propylene polymer composition containing a tackifier (D). Since there is a propylene-based polymer (B) layer in between, there is very little possibility that the tackifier (D) will ooze out on the surface of the propylene / α-olefin random copolymer (C) layer. The surface of the axially stretched multilayer polypropylene film is not sticky, and it is also good when the vinyl alcohol polymer (E) is laminated (laminated) on the surface of the propylene / α-olefin random copolymer (C) layer. Adhesive strength (laminate strength) is obtained.
また、本発明の二軸延伸多層ポリプロピレンフィルムは、前記プロピレン単独重合体及び粘着付与剤（Ｄ）を含むプロピレン重合体組成物からなる二軸延伸フィルムの片面に、前記プロピレン系重合体（Ｂ）からなる層を介してプロピレン・α−オレフィンランダム共重合体（Ｃ）からなる層を有し、他の片面に、プロピレン系重合体（Ｅ）からなる層を有し、且つ、プロピレン・α−オレフィンランダム共重合体（Ｃ）からなる層上に、ビニルアルコール系重合体（Ｆ）からなる層を有してなる二軸延伸多層ポリプロピレンフィルムでもある。 Moreover, the biaxially stretched multilayer polypropylene film of the present invention has the propylene polymer (B) on one side of a biaxially stretched film comprising a propylene polymer composition containing the propylene homopolymer and a tackifier (D). A layer made of propylene / α-olefin random copolymer (C) through a layer made of, and a layer made of propylene polymer (E) on the other side, and propylene / α- It is also a biaxially stretched multilayer polypropylene film having a layer made of a vinyl alcohol polymer (F) on a layer made of an olefin random copolymer (C).
かかる二軸延伸多層ポリプロピレンフィルムの各層の厚さは、ビニルアルコール系重合体（Ｅ）層若しくは無機層状化合物を含むビニルアルコール系重合体（Ｅ）層が０．１〜１０μｍ、好ましくは０．２〜３μｍの範囲にある。 The thickness of each layer of the biaxially oriented multilayer polypropylene film is 0.1 to 10 μm, preferably 0.2, for the vinyl alcohol polymer (E) layer or the vinyl alcohol polymer (E) layer containing an inorganic layered compound. It is in the range of ~ 3 μm.
本発明の二軸延伸多層ポリプロピレンフィルムは、種々用途に応じ、他の層、例えば、低温ヒートシール性を付与するために、高圧法低密度ポリエチレン、線状低密度ポリエチレン、結晶性あるいは低結晶性のエチレンと炭素数３〜１０のα−オレフィンとのランダム共重合体あるいはプロピレンとエチレンもしくは炭素数４以上のα−オレフィンとのランダム共重合体、ポリブテン、エチレン・酢酸ビニル共重合体等の低融点のポリマーを単独あるいはそれらの組成物をプロピレン・α−オレフィンランダム共重合体（Ｃ）層上、あるいはプロピレン系重合体（Ｅ）からなる層上、若しくはビニルアルコール系重合体（Ｆ）若しくは無機層状化合物を含むビニルアルコール系重合体（Ｆ）層に積層してもよい。 The biaxially stretched multi-layer polypropylene film of the present invention can be applied to other layers, for example, low-temperature heat-sealability, high-pressure low-density polyethylene, linear low-density polyethylene, crystalline or low-crystallinity, depending on various applications. Random copolymers of ethylene and α-olefins having 3 to 10 carbon atoms, or random copolymers of propylene and ethylene or α-olefins having 4 or more carbon atoms, polybutene, ethylene / vinyl acetate copolymers, etc. A polymer having a melting point alone or a composition thereof on a propylene / α-olefin random copolymer (C) layer, a layer made of a propylene polymer (E), a vinyl alcohol polymer (F) or an inorganic material You may laminate | stack on the vinyl alcohol-type polymer (F) layer containing a layered compound.
また、更に、ガスバリア性を付与するために、エチレン・ビニルアルコール共重合体、ポリアミド、ポリエステル、塩化ビニリデン系重合体等を押出しコーティング、フィルムラミネート等で積層してもよいし、金属あるいはその酸化物、シリカ等を蒸着してもよい。勿論、他の物質との接着性を増すために、延伸フィルムの表面をイミン、ウレタン等の接着剤でアンカー処理してもよいし、無水マレイン酸変性ポリオレフィンを積層してもよい。 Further, in order to impart gas barrier properties, an ethylene / vinyl alcohol copolymer, polyamide, polyester, vinylidene chloride polymer, etc. may be laminated by extrusion coating, film lamination, etc., or a metal or its oxide Further, silica or the like may be deposited. Of course, in order to increase the adhesion to other substances, the surface of the stretched film may be anchored with an adhesive such as imine or urethane, or maleic anhydride-modified polyolefin may be laminated.
二軸延伸多層ポリプロピレンフィルムの製造方法
本発明の二軸延伸多層ポリプロピレンフィルムは、例えば、プロピレン単独重合体（Ａ）と粘着付与剤（Ｄ）を所定量含むプロピレン重合体組成物、プロピレン系重合体（Ｂ）及び（Ｅ）、及びプロピレン・α−オレフィン共重合体（Ｃ）とを共押出し成形して得たプロピレン系重合体（Ｅ）／プロピレン重合体組成物／プロピレン系重合体（Ｂ）／プロピレン・α−オレフィン共重合体（Ｃ）からなる多層シートを、公知の同時二軸延伸法あるいは逐次二軸延伸法等の二軸延伸フィルム製造方法を用いて製造し得る。二軸延伸の条件は、公知のＯＰＰフィルムの製造条件、例えば、逐次二軸延伸法では、縦延伸温度を１１５℃〜１４５℃、延伸倍率を４．５〜６倍の範囲、横延伸温度を１５０〜１９０℃、延伸倍率を９〜１１倍の範囲にすればよい。
Method for Producing Biaxially Stretched Multilayer Polypropylene Film The biaxially stretched multilayer polypropylene film of the present invention is, for example, a propylene polymer composition containing a predetermined amount of a propylene homopolymer (A) and a tackifier (D), and a propylene polymer. Propylene polymer (E) / propylene polymer composition / propylene polymer (B) obtained by coextrusion molding of (B) and (E), and propylene / α-olefin copolymer (C) / A multilayer sheet comprising a propylene / α-olefin copolymer (C) can be produced using a biaxially stretched film production method such as a known simultaneous biaxial stretching method or a sequential biaxial stretching method. The biaxial stretching conditions are known OPP film production conditions, for example, in the sequential biaxial stretching method, the longitudinal stretching temperature is 115 ° C. to 145 ° C., the stretching ratio is 4.5 to 6 times, and the transverse stretching temperature is What is necessary is just to make 150-190 degreeC and a draw ratio into the range of 9-11 times.
プロピレン・α−オレフィン共重合体（Ｃ）層上に、ビニルアルコール系重合体（Ｆ）からなる層を有してなる二軸延伸多層ポリプロピレンフィルムは、前記記載の製造方法で二軸延伸多層フィルムを得た後、ビニルアルコール系重合体（Ｆ）若しくは無機層状化合物を含むビニルアルコール系重合体（Ｆ）の分散液を塗布・乾燥する方法により製造し得る。又、ビニルアルコール系重合体（Ｆ）の分散液等を塗布する場合は、共押出し成形して得た多層シートに塗布した後、二軸延伸してもよいし、共押出し成形して得た多層シートを縦方向に延伸したシートに塗布した後、横方向に延伸して二軸延伸多層フィルムとしてもよい。 The biaxially stretched multilayer polypropylene film having a layer of the vinyl alcohol polymer (F) on the propylene / α-olefin copolymer (C) layer is obtained by the above-described production method. Then, a dispersion of vinyl alcohol polymer (F) or a vinyl alcohol polymer (F) containing an inorganic layered compound can be applied and dried. When applying a dispersion of vinyl alcohol polymer (F), etc., it may be applied to a multilayer sheet obtained by coextrusion molding and then biaxially stretched or obtained by coextrusion molding. A multilayer sheet may be applied to a sheet stretched in the longitudinal direction, and then stretched in the transverse direction to form a biaxially stretched multilayer film.
ビニルアルコール系重合体（Ｆ）等の分散液には、プロピレン・α−オレフィン共重合体（Ｃ）層との密着性向上、及び／または皮膜の強度向上のためにビニルアルコール系重合体（Ｆ）に架橋剤成分を添加しても良い。かかる架橋剤成分としては、シランカップリング剤、イソシアネート系架橋剤、エポキシ系架橋剤、メラミン系架橋剤、アミン系化合物などがあるが、高湿度下でも密着性低下しないことからイソシアネート系架橋剤が好ましく、特に水性の自己乳化タイプが水溶液中で安定であるので好ましい。その添加量はビニルアルコール系重合体（Ｆ）に対し重量比で１〜１０％の範囲にあることが好ましい。 In order to improve adhesion to the propylene / α-olefin copolymer (C) layer and / or to improve the strength of the film, a dispersion of vinyl alcohol polymer (F) or the like is used. ) May contain a crosslinking agent component. Such crosslinker components include silane coupling agents, isocyanate crosslinkers, epoxy crosslinkers, melamine crosslinkers, amine compounds, etc., but isocyanate crosslinkers do not deteriorate adhesion even under high humidity. The aqueous self-emulsifying type is particularly preferable because it is stable in an aqueous solution. The addition amount is preferably in the range of 1 to 10% by weight with respect to the vinyl alcohol polymer (F).
又、ビニルアルコール系重合体（Ｆ）等の分散液に架橋剤成分を添加する代りに、プロピレン・α−オレフィン共重合体（Ｃ）層の表面を種々公知のアンカー（ＡＣ）剤、例えば有機チタン系ＡＣ剤、ポリウレタン系ＡＣ剤、ポリエチレンイミン系ＡＣ剤、ポリブタジエン系ＡＣ剤等で処理しておいてもよい。 Further, instead of adding a crosslinking agent component to a dispersion of vinyl alcohol polymer (F) or the like, the surface of the propylene / α-olefin copolymer (C) layer is coated with various known anchor (AC) agents such as organic You may process by titanium AC agent, polyurethane AC agent, polyethyleneimine AC agent, polybutadiene AC agent, etc.
本発明に係わるビニルアルコール系重合体（Ｆ）には、本発明の目的を阻害しない範囲で濡れ性向上剤、帯電防止剤、その他各種添加剤を加えることが可能である。特に、アンチブロッキング剤として粒径が０．１〜１０μｍ程度の酸化珪素、カオリン等の無機系微粒子やポリメチルメタクリレート、メラミン等の有機系微粒子を好ましく用いることが出来る。 It is possible to add a wettability improver, an antistatic agent and other various additives to the vinyl alcohol polymer (F) according to the present invention as long as the object of the present invention is not impaired. In particular, as the antiblocking agent, inorganic fine particles such as silicon oxide and kaolin having a particle diameter of about 0.1 to 10 μm, and organic fine particles such as polymethyl methacrylate and melamine can be preferably used.
ビニルアルコール系重合体（Ｆ）の分散媒としては、コスト、作業環境面から水が好ましく用いられるが、水以外の溶媒、例えばメタノール、エタノール、イソプロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、或いはその他ジエチルエーテル、テトラヒドロフラン等を必要に応じて、１種または２種以上を組み合わせて加えることも可能である。 As a dispersion medium for the vinyl alcohol polymer (F), water is preferably used from the viewpoint of cost and working environment, but solvents other than water, for example, alcohols such as methanol, ethanol and isopropanol, and ketones such as acetone and methyl ethyl ketone. Alternatively, diethyl ether, tetrahydrofuran or the like can be added alone or in combination of two or more as required.
次に実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を越えない限りこれらの実施例に制約されるものではない。 EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.
実施例及び比較例における物性等は、以下の評価方法により求めた。
（１）アイソタクチックインデックス
プロピレン単独重合体の樹脂ペレットの重量をＷ１（ｍｇ）はかり取り、ソックスレー抽出器に入れ沸騰ｎ−ヘプタンで１２時間抽出する。抽出残渣をアセトンで洗浄した後、１３０℃で６時間乾燥する。その後室温まで冷却した後重量Ｗ２（ｍｇ）を測定し、次式より求める。
The physical properties and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
(1) Isotactic index The weight of propylene homopolymer resin pellets is weighed out by W 1 (mg), placed in a Soxhlet extractor, and extracted with boiling n-heptane for 12 hours. The extraction residue is washed with acetone and then dried at 130 ° C. for 6 hours. Then, after cooling to room temperature, the weight W 2 (mg) is measured and determined from the following formula.
アイソタクチックインデックス（％）＝（Ｗ２／Ｗ１）×１００
（２）融点
ＤＳＣ（示差走査熱量計）として、ティー・エイ・インスツルメント社製 Ｑ１００を用い、試料約５ｍｇを精秤し、ＪＩＳ Ｋ ７１２１に準拠し、窒素ガス流入量：５０ｍｌ／分の条件下で、２５℃から加熱速度：１０℃／分で２００℃まで昇温し、当該温度に１０分間保った後、冷却速度：１０℃／分で２５℃まで冷却し、当該温度に１０分間保った後、再度加熱速度：１０℃／分で２００℃まで昇温し、その際得られたＤＳＣ曲線の最大融解ピークの温度を融点とした。
（３）濡れ張力
二軸延伸多層ポリプロピレンフィルムのプロピレン・α−オレフィンランダム共重合体層の表面を１１０℃、３０秒間熱処理し、コロナ処理面を和光純薬製濡れ張力試験用混合液（標準液）にて測定した。単位はｍＮ／ｍである。
（４）水蒸気透過度
ＪＩＳＺ０２０８（カップ法）に準じて測定（４０℃、９０％ＲＨ）を行った。単位はｇ／ｍ２・ｄａｙである。
（５）ラミネート強度
二軸延伸多層ポリプロピレンフィルムのポリビニルアルコール系重合体層に５０μｍの無延伸ポリエチレンフィルム（東セロ製Ｌ−ＬＤＰＥ ＦＣＳ）をドライラミネートした後１５ｍｍ幅に切り出し、オリエンテック製引張り試験機（型式ＲＴＣ−１２２５Ａ）に於いて３００ｍｍ／ｍｉｎの引張り速度で引き剥がし、その際の強度（単位はＮ／１５ｍｍ）をラミネート強度とした。
Isotactic index (%) = (W 2 / W 1 ) × 100
(2) Melting point As DSC (Differential Scanning Calorimeter), Q100 manufactured by TA Instruments Co., Ltd. was used. About 5 mg of sample was precisely weighed, and in accordance with JIS K 7121, nitrogen gas inflow: 50 ml / min Under the conditions, the temperature was raised from 25 ° C. to 200 ° C. at a heating rate of 10 ° C./min, kept at the temperature for 10 minutes, then cooled to 25 ° C. at a cooling rate of 10 ° C./min, and then kept at the temperature for 10 minutes Then, the temperature was raised again to 200 ° C. at a heating rate of 10 ° C./min, and the temperature of the maximum melting peak of the DSC curve obtained at that time was taken as the melting point.
(3) Wetting tension The surface of the propylene / α-olefin random copolymer layer of the biaxially stretched multilayer polypropylene film was heat-treated at 110 ° C. for 30 seconds, and the corona-treated surface was mixed with a Wako Pure Chemicals wetting tension test mixture (standard solution). ). The unit is mN / m.
(4) Water vapor permeability Measurement (40 ° C., 90% RH) was performed according to JISZ0208 (cup method). The unit is g / m 2 · day.
(5) Laminating strength A 50 μm unstretched polyethylene film (L-LDPE FCS manufactured by Tosero) was dry laminated on a polyvinyl alcohol polymer layer of a biaxially stretched multilayer polypropylene film, cut out to a width of 15 mm, and an orientec tensile tester ( In the case of model RTC-1225A), peeling was performed at a pulling speed of 300 mm / min, and the strength (unit: N / 15 mm) at that time was defined as the laminate strength.
実施例１
＜プロピレン重合体組成物（Ａ＋Ｄ）層＞
二軸延伸フィルム用の原料として、プロピレン単独重合体（融点；１６６℃、アイソタクチックインデックス；９９．２％、ＭＦＲ；３．０ｇ／１０分）に軟化点１３５℃のジシクロペンタジエン系粘着付与剤を１０％添加したプロピレン重合体組成物を用意した。
＜プロピレン系重合体層（Ｂ層、Ｅ層）＞
プロピレン系重合体層の原料として、融点；１６２℃、ＭＦＲ；３．０ｇ／１０分のプロピレン系重合体を用意した。
＜プロピレン・α−オレフィン共重合体（Ｃ）層＞
プロピレン・α−オレフィン共重合体層の原料として、エチレンから導かれる単位の含有量；４．０モル％、ブテン−１から導かれる単位の含有量；１．１モル％、融点；１３８℃、ＭＦＲ；７．０ｇ／１０分のプロピレン・α−オレフィン共重合体を用意した。
＜ビニルアルコール系重合体（F層）＞
ビニルアルコール系重合体層の原料として、ケン化度；９９．５％、重合度；１７００のポリビニルアルコールを水に溶解し、５％濃度の水溶液を得た。この水溶液に無機膨潤性無機層状化合物（トピー工業製合成マイカ）を固形分比で６％添加し、更に物水性ウレタン（三井武田ケミカル製 ＷＤ７２６）を固形分比で３％、及び塗れ向上剤としてアニオン系界面活性剤（花王製ネオペレックスＧ１５）を０．５％添加し、ビニルアルコール系重合体組成物を用意した。
＜二軸延伸多層ポロプロピレンフィルムの製造＞
前記、プロピレン系重合体（Ｅ）、プロピレン重合体組成物（Ａ＋Ｄ）、プロピレン系重合体（Ｂ）、及びプロピレン・α−オレフィン共重合体（Ｃ）を押出量比１／１８／２／１になるよう各々スクリュー押出機を用いて溶融押出しマルチマニホールドＴ−ダイを用いて賦形し、冷却ロール上にて急冷し厚さ約１．０ｍｍの共押出多層シートを得た。この多層シートを約１２０℃に加熱しシートの流れ方向（縦方向）に５倍に延伸した。この５倍延伸したシートを１５５℃に加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸し、次いで、二軸延伸ポリプロピレンフィルムのプロピレン・α−オレフィン共重合体層面にコロナ処理を施し、合計の厚さ２２μｍの二軸延伸多層ポリプロピレンフィルム（基材フィルム）を得た。
Example 1
<Propylene polymer composition (A + D) layer>
Propylene homopolymer (melting point: 166 ° C., isotactic index; 99.2%, MFR; 3.0 g / 10 min) as a raw material for a biaxially stretched film, dicyclopentadiene-based tackifier having a softening point of 135 ° C. A propylene polymer composition to which 10% of an agent was added was prepared.
<Propylene polymer layer (B layer, E layer)>
As a raw material of the propylene polymer layer, a propylene polymer having a melting point: 162 ° C., MFR: 3.0 g / 10 min was prepared.
<Propylene / α-olefin copolymer (C) layer>
As a raw material of the propylene / α-olefin copolymer layer, the content of units derived from ethylene: 4.0 mol%, the content of units derived from butene-1; 1.1 mol%, melting point: 138 ° C., MFR: A propylene / α-olefin copolymer of 7.0 g / 10 min was prepared.
<Vinyl alcohol polymer (F layer)>
As a raw material for the vinyl alcohol polymer layer, polyvinyl alcohol having a saponification degree of 99.5% and a polymerization degree of 1700 was dissolved in water to obtain a 5% aqueous solution. To this aqueous solution, an inorganic swellable inorganic layered compound (synthetic mica manufactured by Topy Industries, Ltd.) is added at a solid content ratio of 6%, and further, an aqueous urethane (WD 726, manufactured by Mitsui Takeda Chemical Co., Ltd.) is added at a solid content ratio of 3%. An anionic surfactant (Naoperex G15 manufactured by Kao) was added at 0.5% to prepare a vinyl alcohol polymer composition.
<Manufacture of biaxially oriented multilayer polypropylene film>
Extrusion ratio 1/18/2/1 of the propylene polymer (E), propylene polymer composition (A + D), propylene polymer (B), and propylene / α-olefin copolymer (C). Each was then melt extruded using a screw extruder and shaped using a multi-manifold T-die and quenched on a chill roll to obtain a coextruded multilayer sheet having a thickness of about 1.0 mm. The multilayer sheet was heated to about 120 ° C. and stretched 5 times in the sheet flow direction (longitudinal direction). This 5-fold stretched sheet is heated to 155 ° C. and stretched 10 times in the direction orthogonal to the flow direction (transverse direction), and then the propylene / α-olefin copolymer layer surface of the biaxially stretched polypropylene film is corona-treated. And a biaxially stretched multilayer polypropylene film (base material film) having a total thickness of 22 μm was obtained.
二軸延伸多層ポリプロピレンフィルムのプロピレン・α−オレフィン共重合体層面にポリビニルアルコール重合体組成物をバーコート法（メイヤーバー＃１４）にて塗布し、１１０℃で３０秒間乾燥した。塗膜の厚みは０．５μｍであった。
得られた二軸延伸多層ポリプロピレンフィルムを４０℃で１日エージングした後、水蒸気透過度、ラミネート強度を測定した。評価結果を表１に示す。
得られた二軸延伸多層ポリプロピレンフィルムは、優れた水蒸気透過度と高い塗れ性、十分なラミネート強度を示している。
The polyvinyl alcohol polymer composition was applied to the surface of the propylene / α-olefin copolymer layer of the biaxially stretched multilayer polypropylene film by a bar coating method (Meyer bar # 14) and dried at 110 ° C. for 30 seconds. The thickness of the coating film was 0.5 μm.
After the obtained biaxially stretched multilayer polypropylene film was aged at 40 ° C. for 1 day, the water vapor permeability and the laminate strength were measured. The evaluation results are shown in Table 1.
The obtained biaxially stretched multilayer polypropylene film exhibits excellent water vapor permeability, high paintability, and sufficient laminate strength.
比較例１
実施例１においてジシクロペンタジエン系粘着付与剤の添加量を５％とする以外は実施例１同様に実施した。高い塗れ性と十分なラミネート強度を有しているが、水蒸気透過度は十分では無い。
Comparative Example 1
The same procedure as in Example 1 was performed except that the amount of the dicyclopentadiene-based tackifier added in Example 1 was 5%. Although it has high spreadability and sufficient laminate strength, the water vapor permeability is not sufficient.
比較例２
実施例１で用いた二軸延伸多層ポリプロピレンフィルム（基材フィルム）に換えて、プロピレン系重合体（Ｅ）、プロピレン重合体組成物（Ａ＋Ｄ）及びプロピレン系重合体（Ｂ）の三層からなる二軸延伸多層ポリプロピレンフィルム（基材フィルム）を用いる以外は実施例１と同様に行い、プロピレン系重合体（Ｂ）層の表面にポリビニルアルコール重合体組成物を形成してなる二軸延伸多層ポリプロピレンフィルムを得た。
Comparative Example 2
Instead of the biaxially stretched multilayer polypropylene film (base film) used in Example 1, it consists of a propylene polymer (E), a propylene polymer composition (A + D), and a propylene polymer (B). A biaxially stretched multilayer polypropylene formed by forming a polyvinyl alcohol polymer composition on the surface of the propylene polymer (B) layer except that a biaxially stretched multilayer polypropylene film (base film) is used. A film was obtained.
得られた二軸延伸多層ポリプロピレンフィルムは、水蒸気透過度は優れ、基材フィルムは高い塗れ性を維持しているが、ラミネート強度は十分では無い。 The obtained biaxially stretched multilayer polypropylene film has excellent water vapor permeability and the base film maintains high coatability, but the laminate strength is not sufficient.
比較例３
実施例１で用いた二軸延伸多層ポリプロピレンフィルム（基材フィルム）に換えて、プロピレン系重合体（Ｅ）、プロピレン重合体組成物（Ａ＋Ｄ）及びプロピレン・α−オレフィン共重合体（Ｃ）の三層からなる二軸延伸多層ポリプロピレンフィルム（基材フィルム）を用いる以外は実施例１と同様に行い、プロピレン・α−オレフィン共重合体（Ｃ）層の表面にポリビニルアルコール重合体組成物を形成してなる二軸延伸多層ポリプロピレンフィルムを得た。
Comparative Example 3
Instead of the biaxially stretched multilayer polypropylene film (base film) used in Example 1, a propylene polymer (E), a propylene polymer composition (A + D), and a propylene / α-olefin copolymer (C) A polyvinyl alcohol polymer composition is formed on the surface of the propylene / α-olefin copolymer (C) layer except that a biaxially stretched multilayer polypropylene film (base film) consisting of three layers is used. A biaxially stretched multilayer polypropylene film was obtained.
得られた二軸延伸多層ポリプロピレンフィルムは、水蒸気透過度は優れているが、基材フィルムの塗れ性は低下し、ラミネート強度も十分では無い。 The obtained biaxially stretched multilayer polypropylene film has excellent water vapor permeability, but the coatability of the base film is lowered and the laminate strength is not sufficient.
本発明の二軸延伸多層ポリプロピレンフィルムは、透明性、水蒸気透過度に優れ、フィルム表面の高い塗れ性を維持し、またポリビニルアルコール系樹脂積層体との十分なラミネート強度を有するので、ラミネート原反として使用し得る、また、ビニルアルコール系重合体層を有してなる二軸延伸多層ポリプロピレンフィルムは、さらにガスバリア性に優れるので、特に食品包装材料としてスナック菓子、米菓、ビスケット、ピーナッツ等の乾燥食品に使用し得るし、また、無機層状化合物を含んでなるビニルアルコール重合体層を有する二軸延伸多層ポリプロピレンフィルムは、さらに高いガスバリア性を有しているので前記乾燥菓子はもちろんのこと含水率の多い饅頭やカステラ、切り餅、鰹節、各種珍味等の広範囲な用途にも使用し得る。
The biaxially stretched multilayer polypropylene film of the present invention is excellent in transparency and water vapor permeability, maintains high paintability on the film surface, and has a sufficient laminate strength with the polyvinyl alcohol-based resin laminate. As the biaxially stretched multilayer polypropylene film having a vinyl alcohol polymer layer is further excellent in gas barrier properties, it is a dry food such as snack confectionery, rice confectionery, biscuit, peanut, etc. In addition, the biaxially stretched multilayer polypropylene film having a vinyl alcohol polymer layer containing an inorganic layered compound has a higher gas barrier property, so that it has a moisture content as well as the dried confectionery. Can be used for a wide range of purposes such as many buns, castella, chopped rice cake, bonito, various delicacies .
Claims (4)
It has a layer which consists of a vinyl alcohol polymer (F) on a layer which consists of a propylene * alpha olefin random copolymer (C) of a biaxial stretching multilayer polypropylene film in any one of Claims 1-3. A biaxially oriented multilayer polypropylene film.
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