JP5047493B2 - Film and multilayer biaxially stretched film - Google Patents
Film and multilayer biaxially stretched film Download PDFInfo
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- JP5047493B2 JP5047493B2 JP2005343926A JP2005343926A JP5047493B2 JP 5047493 B2 JP5047493 B2 JP 5047493B2 JP 2005343926 A JP2005343926 A JP 2005343926A JP 2005343926 A JP2005343926 A JP 2005343926A JP 5047493 B2 JP5047493 B2 JP 5047493B2
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- propylene
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- 229920005604 random copolymer Polymers 0.000 claims description 53
- 239000010410 layer Substances 0.000 claims description 50
- 230000035699 permeability Effects 0.000 claims description 41
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 26
- 239000011342 resin composition Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 239000002344 surface layer Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 14
- 229920001384 propylene homopolymer Polymers 0.000 claims description 14
- 235000012055 fruits and vegetables Nutrition 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 229920006280 packaging film Polymers 0.000 claims description 2
- 239000012785 packaging film Substances 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 2
- -1 polypropylene Polymers 0.000 description 41
- 238000000034 method Methods 0.000 description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- 229920001155 polypropylene Polymers 0.000 description 26
- 239000004743 Polypropylene Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 24
- 239000004711 α-olefin Substances 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 239000001569 carbon dioxide Substances 0.000 description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- ISSYTHPTTMFJKL-UHFFFAOYSA-N 1-ethenylcyclopentene Chemical compound C=CC1=CCCC1 ISSYTHPTTMFJKL-UHFFFAOYSA-N 0.000 description 3
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 description 3
- UIIMVYYDGLHIAO-UHFFFAOYSA-N 2-methylnon-2-ene Chemical compound CCCCCCC=C(C)C UIIMVYYDGLHIAO-UHFFFAOYSA-N 0.000 description 3
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 3
- AUJLDZJNMXNESO-UHFFFAOYSA-N 3-ethylhex-3-ene Chemical compound CCC=C(CC)CC AUJLDZJNMXNESO-UHFFFAOYSA-N 0.000 description 3
- KNIRLWRQSSLZCZ-UHFFFAOYSA-N 3-ethyloct-3-ene Chemical compound CCCCC=C(CC)CC KNIRLWRQSSLZCZ-UHFFFAOYSA-N 0.000 description 3
- RITONZMLZWYPHW-UHFFFAOYSA-N 3-methylhex-1-ene Chemical compound CCCC(C)C=C RITONZMLZWYPHW-UHFFFAOYSA-N 0.000 description 3
- RGTDIFHVRPXHFT-UHFFFAOYSA-N 3-methylnon-3-ene Chemical compound CCCCCC=C(C)CC RGTDIFHVRPXHFT-UHFFFAOYSA-N 0.000 description 3
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 3
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 3
- BSJOLASGNWRVEH-UHFFFAOYSA-N 7,7-dimethyloct-1-ene Chemical compound CC(C)(C)CCCCC=C BSJOLASGNWRVEH-UHFFFAOYSA-N 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229940069096 dodecene Drugs 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 3
- 230000029058 respiratory gaseous exchange Effects 0.000 description 3
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-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
- 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
- AAUHUDBDDBJONC-UHFFFAOYSA-N 3-methylhept-3-ene Chemical compound CCCC=C(C)CC AAUHUDBDDBJONC-UHFFFAOYSA-N 0.000 description 2
- UNUVUYPEOAILGM-UHFFFAOYSA-N 4-ethenylbicyclo[2.2.1]heptane Chemical compound C1CC2CCC1(C=C)C2 UNUVUYPEOAILGM-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- GVRWIAHBVAYKIZ-UHFFFAOYSA-N dec-3-ene Chemical compound CCCCCCC=CCC GVRWIAHBVAYKIZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- UQBYRKFLCZTMAM-UHFFFAOYSA-N CC(=C)CC.CC(CC=C)C Chemical compound CC(=C)CC.CC(CC=C)C UQBYRKFLCZTMAM-UHFFFAOYSA-N 0.000 description 1
- KXYVMCOHUSUTQJ-UHFFFAOYSA-N CC(=CCCC)CC.CC(=CCCC)C Chemical compound CC(=CCCC)CC.CC(=CCCC)C KXYVMCOHUSUTQJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- LMHUKLLZJMVJQZ-UHFFFAOYSA-N but-1-ene;prop-1-ene Chemical group CC=C.CCC=C LMHUKLLZJMVJQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Description
本発明は青果物および花卉の鮮度保持包装に適したフィルムおよび多層二軸延伸フィルムに関する。 The present invention relates to a film and a multilayer biaxially stretched film suitable for freshness-keeping packaging of fruits and vegetables.
一般にポリオレフィン系樹脂フィルムは成形性、透明性、機械物性に優れることより食品、日用品、工業製品など各種の包装資材として広く普及している。しかしながら、青果物や花卉類をフィルムで密封包装すると、初期においては水分の蒸散や呼吸速度が低下するので、一定の鮮度保持効果が得られるものの、呼吸により包装内部の酸素濃度が低下し、二酸化炭素濃度が増加すると、嫌気呼吸による腐敗が始まり急速に鮮度が低下するという問題があった。 In general, polyolefin resin films are widely used as various packaging materials such as foods, daily necessities, and industrial products because of their excellent moldability, transparency, and mechanical properties. However, when vegetables and fruits and flowers are sealed and packaged with a film, the transpiration and respiration rate of the water are reduced in the initial stage, so that a certain freshness retention effect can be obtained, but the oxygen concentration inside the package decreases due to respiration, and carbon dioxide When the concentration increased, there was a problem that the freshness rapidly declined due to decay by anaerobic breathing.
このため、比較的ガス透過度が高い低密度ポリエチレン（ＬＤＰＥおよびＬＬＤＰＥ）製フィルムが青果物や花卉類の包装にしばしば使用されているが、ポリプロピレン製やポリスチレン製フィルムに比較すると、透明性と剛性が不足するという問題があった。また、ポリスチレン製フィルムは透明性と剛性があり、ガス透過度も比較的高いのでやはり同目的の包装に使用されているが、ポリプロピレン製や低密度ポリエチレン製フィルムに比較すると、伸びが小さいので破れやすく、またシール強度が低いという問題があった。 For this reason, low density polyethylene (LDPE and LLDPE) films with relatively high gas permeability are often used for packaging fruits and vegetables, but they are more transparent and rigid than polypropylene and polystyrene films. There was a problem of shortage. Polystyrene films are transparent and rigid, and have a relatively high gas permeability, so they are also used for packaging for the same purpose, but they are broken because they are less stretched than polypropylene or low-density polyethylene films. There was a problem that it was easy and the seal strength was low.
一方、ポリプロピレン製フィルムも透明性と剛性が優れているので、例えば防曇性を付与した二軸延伸ポリプロピレン系フィルムが青果物や花卉類の包装用として使用されている（例えば特許文献１参照）。しかしながら、ポリプロピレン製フィルムは低密度ポリエチレン製やポリスチレン製フィルムに比較すると、ガス透過度が低いので青果物や花卉類を密封包装する場合の鮮度保持性が劣っていた。 On the other hand, since a polypropylene film is also excellent in transparency and rigidity, for example, a biaxially stretched polypropylene film imparted with antifogging properties is used for packaging fruits and vegetables and flowers (see, for example, Patent Document 1). However, the film made of polypropylene has a lower gas permeability than the film made of low density polyethylene or polystyrene, so that the freshness retention in the case of hermetically wrapping fruits and vegetables and flowers is inferior.
そこで、微小な穴を開けてガス透過性を付与したフィルムで、青果物を密封包装する技術が提案されている（例えば特許文献２参照）。しかし、この方法は穴開けを行なうための設備や加工の費用が発生し、かつフィルムの生産性が低下する問題に加えて、穴を通して外部から汚染物質が侵入する可能性があった。 Therefore, a technique has been proposed in which fruits and vegetables are sealed and packaged with a film provided with gas permeability by opening minute holes (see, for example, Patent Document 2). However, in this method, equipment and processing costs for punching are generated, and in addition to the problem that the productivity of the film is lowered, there is a possibility that contaminants may enter from the outside through the hole.
また、アイソタクチックポリプロピレンとエチレン−オクテン−１共重合体からなるオレフィン系樹脂製フィルムが提案されている（特許文献３参照）。しかし、本提案はエチレン−オクテン−１共重合体からなる層が０．０３〜０．２ｍｍの厚みを有する厚手の表面化粧用フィルムであり、実施例でも全て炭酸カルシウムを１０％含み、厚みも０．１ｍｍの厚手フィルムが示されており、透明性が重視される青果物や花卉類の包装に適するものではなかった。 In addition, an olefin-based resin film made of isotactic polypropylene and an ethylene-octene-1 copolymer has been proposed (see Patent Document 3). However, the present proposal is a thick surface cosmetic film having a thickness of 0.03 to 0.2 mm and a layer made of an ethylene-octene-1 copolymer. A thick film with a thickness of 0.1 mm is shown, and it was not suitable for packaging fruits and vegetables and flowers that emphasize transparency.
また、特定のシンジオタクティックポリプロピレンとエチレン-オクテン共重合体からなる樹脂組成物をアイソタクティックポリプロピレンよりなる基材層に積層してなる積層フィルムが提案されている（特許文献４参照）。しかし、シンジオタクティックポリプロピレンは一般に結晶化度が低く、軟らかいので主要な用途は従来よりヒートシール材であり、本提案の組成物もヒートシール性の改良を目的とするものであった。 Further, there has been proposed a laminated film obtained by laminating a resin composition made of a specific syndiotactic polypropylene and an ethylene-octene copolymer on a base material layer made of isotactic polypropylene (see Patent Document 4). However, since syndiotactic polypropylene generally has a low crystallinity and is soft, its main application has been a heat seal material conventionally, and the proposed composition has also been aimed at improving heat sealability.
また、エチレン-１-オクテン系共重合体とエチレン-プロピレン系共重合体からなる樹脂層を含む共押出積層フィルムが提案されている（特許文献５参照）。しかし、本提案においても当該樹脂層の機能はあくまでヒートシール性であり、共押出積層フィルムに占める厚み割合は最大でも４０％である。
本発明は酸素透過度と二酸化炭素透過度、および二酸化炭素透過度／酸素透過度の比が大きく、青果物や花卉類を包装した際の鮮度保持性に優れたフィルムを提供することを課題とする。さらに本発明は、シール性と透明性に優れ、適度な剛性と高い酸素透過度を有する、青果物や花卉類の鮮度保持包装に適した積層フィルムを提供することを課題とする。 An object of the present invention is to provide a film having a large ratio of oxygen permeability, carbon dioxide permeability, and carbon dioxide permeability / oxygen permeability, and excellent in freshness retention when packaging fruits and vegetables and flowers. . Furthermore, this invention makes it a subject to provide the laminated | multilayer film suitable for the freshness maintenance packaging of fruits and vegetables and flowers which are excellent in sealing performance and transparency, and have moderate rigidity and high oxygen permeability.
本発明者は、上記課題を解決するため鋭意検討した結果、ポリプロピレン（Ａ）：５５〜９５ｗｔ％およびエチレン-１-オクテンランダム共重合体（Ｂ）：５〜４５ｗｔ％からなるフィルムが、ポリプロピレンはもとより、ポリプロピレンとエチレン-１-オクテンランダム共重合体以外のポリオレフィン系エラストマーからなるフィルムに比べても、酸素透過度と二酸化炭素透過度、および二酸化炭素透過度／酸素透過度の比が格段に大きく、青果物や花卉類の鮮度保持包装に極めて好適であることを見出して本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventor has found that a film composed of polypropylene (A): 55 to 95 wt% and ethylene-1-octene random copolymer (B): 5 to 45 wt% is polypropylene. Of course, the ratios of oxygen permeability, carbon dioxide permeability, and carbon dioxide permeability / oxygen permeability are much larger than films made of polyolefin elastomers other than polypropylene and ethylene-1-octene random copolymers. The present invention has been completed by finding that it is extremely suitable for packaging for maintaining the freshness of fruits and vegetables.
本発明のポリプロピレン（Ａ）はプロピレン単独重合体（Ａ１）およびまたはプロピレン-α-オレフィン共重合体（Ａ２）であり、エチレン-１-オクテンランダム共重合体（Ｂ）に含まれる１-オクテンの量は２〜２０モル％であることが好ましい。本発明のフィルムは単層でも多層でもよいが、多層の場合は全体の厚みに対する本発明の組成からなるフィルム層の厚みが５０％以上を占めることが好ましい。また、本発明の組成からなるフィルムないしフィルム層は、少なくとも一軸方向に延伸されていることが望ましい。また、本発明のガス透過制御フィルムのヘイズ値は１０％未満であることが好ましい。 The polypropylene (A) of the present invention is a propylene homopolymer (A1) and / or a propylene-α-olefin copolymer (A2), which is a 1-octene copolymer contained in the ethylene-1-octene random copolymer (B). The amount is preferably 2 to 20 mol%. The film of the present invention may be a single layer or a multilayer, but in the case of a multilayer, it is preferable that the thickness of the film layer comprising the composition of the present invention accounts for 50% or more with respect to the total thickness. The film or film layer having the composition of the present invention is desirably stretched at least in a uniaxial direction. The haze value of the gas permeation control film of the present invention is preferably less than 10%.
また本発明者は、鋭意検討をした結果、特定の樹脂組成物（Ｃ）からなる基材層と、特定のプロピレン系樹脂（Ｄ）からなる少なくとも１層の表層からなり、表層の厚さが１層について基材層の厚さの１〜２０％であることを特徴とする多層二軸延伸フィルムが、適度な剛性と高い酸素透過度を有することを見出し、本発明を完成させるに到った。
すなわち、本発明は、下記樹脂組成物（Ｃ）からなる基材層と、下記プロピレン系樹脂（Ｄ）からなる少なくとも１層の表層からなり、表層の厚さが１層について基材層の厚さの１〜２０％であることを特徴とする多層二軸延伸フィルムに係わるものである。
In addition, as a result of intensive studies, the inventor has a base material layer made of a specific resin composition (C) and at least one surface layer made of a specific propylene-based resin (D). The multilayer biaxially stretched film characterized by being 1 to 20% of the thickness of the base material layer per layer has been found to have appropriate rigidity and high oxygen permeability, and the present invention has been completed. It was.
That is, this invention consists of the base material layer which consists of the following resin composition (C), and the surface layer of at least 1 layer which consists of the following propylene-type resin (D), and the thickness of a base material layer is the thickness of one surface layer. 1 to 20% of the thickness, and relates to a multilayer biaxially stretched film.
＜樹脂組成物（Ｃ）＞
２３０℃で測定したＭＦＲが１〜１０ｇ／１０分であり、ＤＳＣの融解ピークから求めた融点Ｔｍが１５５℃以上であるプロピレン単独重合体（ＣＡ−１）および／またはプロピレン系ランダム共重合体（ＣＡ−２）７５〜９５重量部と、１９０℃で測定したＭＦＲが０．５〜３０ｇ／１０分であり、１−オクテン含有量が５〜２０モル％であるエチレン−１−オクテンランダム共重合体（ＣＢ−１）５〜２５重量部、からなる樹脂組成物。
<Resin composition (C)>
Propylene homopolymer (CA-1) and / or propylene-based random copolymer having a MFR measured at 230 ° C. of 1 to 10 g / 10 min and a melting point Tm determined from the melting peak of DSC of 155 ° C. or higher ( CA-2) An ethylene-1-octene random copolymer having 75 to 95 parts by weight, an MFR measured at 190 ° C. of 0.5 to 30 g / 10 min, and a 1-octene content of 5 to 20 mol% A resin composition comprising 5 to 25 parts by weight of combined (CB-1).
＜プロピレン系樹脂（Ｄ）＞
２３０℃で測定したＭＦＲが１〜２０ｇ／１０分であり、ＤＳＣの融解ピークから求めた融点Ｔｍが１２０〜１５０℃であるプロピレン単独重合体（Ｄ１）および／またはプロピレン系ランダム共重合体（Ｄ２）。
成分ＣＡ−１と成分ＣＡ−２は、合計量が樹脂組成物（Ｃ）中７５〜９５重量部の範囲にあれば、どちらか一方でも両者を混合して用いても構わない。エチレン−１−オクテンランダム共重合体ＣＢ−１は、樹脂組成物（Ｃ）の５〜２５重量部を占める。
<Propylene resin (D)>
Propylene homopolymer (D1) and / or propylene random copolymer (D2) having an MFR measured at 230 ° C. of 1 to 20 g / 10 min and a melting point Tm determined from the melting peak of DSC of 120 to 150 ° C. ).
As long as the total amount of component CA-1 and component CA-2 is in the range of 75 to 95 parts by weight in the resin composition (C), either one may be used in combination. The ethylene-1-octene random copolymer CB-1 occupies 5 to 25 parts by weight of the resin composition (C).
本発明のガス透過制御フィルムは、従来のポリプロピレン系フィルムに比べて酸素透過度と二酸化炭素透過度、および二酸化炭素透過度／酸素透過度の比が格段に大きいので、青果物や花卉類を密封包装した場合の鮮度保持期間を延長することができる。
さらに本発明の多層二軸延伸フィルムは、シール性と透明性に優れ、適度な剛性と高い酸素透過度を有するので、青果物や花卉類の鮮度保持包装に最適である。さらに本発明のフィルムには、物理的な穴を設けなくとも良いので、外部からの汚染物質侵入を防ぐことができる。
The gas permeation control film of the present invention has significantly higher ratios of oxygen permeability, carbon dioxide permeability, and carbon dioxide permeability / oxygen permeability than conventional polypropylene films. In this case, the freshness retention period can be extended.
Furthermore, since the multilayer biaxially stretched film of the present invention is excellent in sealing properties and transparency, has an appropriate rigidity and high oxygen permeability, it is optimal for packaging for maintaining freshness of fruits and vegetables. Furthermore, since it is not necessary to provide a physical hole in the film of the present invention, entry of contaminants from the outside can be prevented.
（ガス透過制御フィルム）
本発明に係るガス透過制御フィルムは、ポリプロピレン（Ａ）：５５〜９５ｗｔ％およびエチレン-１-オクテンランダム共重合体（Ｂ）：５〜４５ｗｔ％からなる。
本発明で使用するポリプロピレン（Ａ）はプロピレン単独重合体（Ａ１）およびまたはプロピレン-α-オレフィン共重合体（Ａ２）である。また、本発明で使用するポリプロピレン（Ａ）は基本的にアイソタクティックポリプロピレンであることが望ましい。プロピレン-α-オレフィン共重合体（Ａ２）で用いられるα-オレフィンとしては、たとえば、
エチレン、１-ブテン、１-ペンテン、１-ヘキセン、１-ヘプテン、１-オクテン、１-デセン、１-ドデセン、１-ヘキサドデセン、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-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、ジメチルオクテン、エチル-１- オクテン、メチル-１- ノネン、ビニルシクロペンテン、ビニルシクロヘキサン、ビニルノルボルナン
などが挙げられる。これらのα-オレフィンはプロピレン-α-オレフィン共重合体（Ａ２）中に一種類以上、合計１０モル％以下の量で含有することができる。
(Gas permeation control film)
The gas permeation control film according to the present invention comprises polypropylene (A): 55 to 95 wt% and ethylene-1-octene random copolymer (B): 5 to 45 wt%.
The polypropylene (A) used in the present invention is a propylene homopolymer (A1) and / or a propylene-α-olefin copolymer (A2). Moreover, it is desirable that the polypropylene (A) used in the present invention is basically isotactic polypropylene. As the α-olefin used in the propylene-α-olefin copolymer (A2), for example,
Ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-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-heptene, dimethyloctene, ethyl-1-octene, methyl-1-nonene, vinylcyclopentene, vinylcyclohexane, vinylnorvo For example, Renan. One or more of these α-olefins can be contained in the propylene-α-olefin copolymer (A2) in an amount of 10 mol% or less in total.
また、本発明で使用するポリプロピレン（Ａ）のメルトフローレート（ＡＳＴＭ Ｄ１２３８、２３０℃、荷重２．１６ｋｇ）は通常０．５〜１０ｇ／１０分、好ましくは１〜４ｇ／１０分、より好ましくは１．５〜３．５ｇ／分の範囲にある。メルトフローレートがこの範囲にあると、フィルムの成形性および機械的強度が良好であるため好ましい。 The melt flow rate (ASTM D1238, 230 ° C., load 2.16 kg) of the polypropylene (A) used in the present invention is usually 0.5 to 10 g / 10 minutes, preferably 1 to 4 g / 10 minutes, more preferably It is in the range of 1.5 to 3.5 g / min. A melt flow rate in this range is preferable because the moldability and mechanical strength of the film are good.
本発明で使用するエチレン-１-オクテンランダム共重合体（Ｂ）は１-オクテンから誘導される構成単位を２〜２０モル％の量で含有することが好ましい。１-オクテンの量がこの範囲にあると、フィルムの剛性とガス透過度が良好であるため好ましい。 The ethylene-1-octene random copolymer (B) used in the present invention preferably contains a structural unit derived from 1-octene in an amount of 2 to 20 mol%. When the amount of 1-octene is within this range, the film has good rigidity and gas permeability, which is preferable.
また、本発明で使用するエチレン-１-オクテンランダム共重合体（Ｂ）は、デカリン中、１３５℃で測定される極限粘度[η]が好ましくは１．５〜３．５ｄｌ／ｇ、さらに好ましくは２．０〜３．０ｄｌ／ｇである。このようなエチレン-１-オクテンランダム共重合体（Ｂ）は、公知のバナジウム系触媒またはメタロセン系触媒を用いて製造することができる。 The ethylene-1-octene random copolymer (B) used in the present invention preferably has an intrinsic viscosity [η] measured at 135 ° C. in decalin of 1.5 to 3.5 dl / g, more preferably Is 2.0 to 3.0 dl / g. Such an ethylene-1-octene random copolymer (B) can be produced using a known vanadium catalyst or metallocene catalyst.
本発明のガス透過制御フィルムは、必要に応じて一般的に使用される耐熱安定剤、酸化防止剤、スリップ剤、ブロッキング防止剤、可塑剤、着色剤、核剤、耐候安定剤、紫外線吸収剤などのほか、防曇剤、防霧剤、抗菌剤、エチレン除去剤などを含有することができる。 The gas permeation control film of the present invention includes heat stabilizers, antioxidants, slip agents, antiblocking agents, plasticizers, colorants, nucleating agents, weathering stabilizers, and UV absorbers that are generally used as necessary. In addition to these, an antifogging agent, an antifogging agent, an antibacterial agent, an ethylene removing agent and the like can be contained.
本発明のガス透過制御フィルムの厚みは、包装される青果物や花卉類の種類と使用方法にもよるので特に限定されないが、通常１０〜１００μｍであり、好ましくは１０〜６０μｍである。さらに好ましい厚みは、１０μｍ以上３０μｍ未満である。また、ヒートシール層や強化層、表面保護層などと積層して多層フィルムとする場合には、本発明のガス透過制御フィルムからなる層の厚みが、全体の厚みの少なくとも５０％以上、好ましくは６０％以上、より好ましくは７０％以上である。 The thickness of the gas permeation control film of the present invention is not particularly limited because it depends on the type and usage of the fruits and flowers to be packaged, but is usually 10 to 100 μm, preferably 10 to 60 μm. A more preferable thickness is 10 μm or more and less than 30 μm. In addition, when a multilayer film is formed by laminating with a heat seal layer, a reinforcing layer, a surface protective layer, etc., the thickness of the layer made of the gas permeation control film of the present invention is at least 50% of the total thickness, preferably 60% or more, more preferably 70% or more.
積層に使用する樹脂は特に限定されないが、例えばポリエチレン、エチレン-α-オレフィン共重合体、エチレン-酢酸ビニル共重合体、エチレン-アクリル酸エステル共重合体、エチレン-メタアクリル酸エステル共重合体、アイオノマー樹脂、ポリプロピレン、プロピレン-α-オレフィン共重合体、ポリメチルペンテン、ポリブテン、ポリブタジエン、ポリスチレン等を挙げることができる。 The resin used for lamination is not particularly limited. For example, polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, Examples include ionomer resins, polypropylene, propylene-α-olefin copolymers, polymethylpentene, polybutene, polybutadiene, and polystyrene.
本発明のガス透過制御フィルムは、Ｔダイ法、インフレーション法、カレンダー法などにより成形される。多層フィルムの場合には、共押出により多層成形するか、基材フィルムに押出ラミネート法、またはドライラミネート法で別の樹脂層を積層することにより成形される。 The gas permeation control film of the present invention is formed by a T-die method, an inflation method, a calendar method, or the like. In the case of a multilayer film, the multilayer film is formed by coextrusion or by laminating another resin layer on the base film by an extrusion lamination method or a dry lamination method.
また本発明のガス透過制御フィルムは、少なくとも一軸方向、より好ましくは二軸方向に延伸されていることが望ましい。延伸により、強度、光学性、外観に優れたフィルムが得られる。延伸の方法としては、ロール方式、テンター方式、チューブラー方式などあり、さらに二軸延伸の場合には逐次二軸延伸または同時二軸延伸することができる。延伸倍率は一軸延伸の場合で３〜８倍、二軸延伸の場合で面倍率１０〜６０倍の範囲が好ましい。 The gas permeation control film of the present invention is desirably stretched in at least a uniaxial direction, more preferably in a biaxial direction. By stretching, a film excellent in strength, optical properties and appearance can be obtained. Examples of the stretching method include a roll method, a tenter method, and a tubular method. Further, in the case of biaxial stretching, sequential biaxial stretching or simultaneous biaxial stretching can be performed. The stretching ratio is preferably in the range of 3 to 8 times in the case of uniaxial stretching and in the range of 10 to 60 times in the case of biaxial stretching.
本発明のガス透過制御フィルムのＪＩＳ Ｋ７１０５に準じて測定されるヘイズ値は、１０％未満が好ましく、より好ましくは７％未満である。ヘイズ値がこの範囲であると包装された野菜や花卉の視認性が損なわれず、見栄えも良い。 The haze value measured according to JIS K7105 of the gas permeation control film of the present invention is preferably less than 10%, more preferably less than 7%. When the haze value is within this range, the visibility of the packaged vegetables and florets is not impaired, and the appearance is good.
本発明のガス透過制御フィルムを製造するにあたってはドライブレンド法やメルトブレンド法を用いることが出来る。すなわち、ポリプロピレン（Ａ）およびエチレン-１-オクテンランダム共重合体（Ｂ）をペレットや粉体等固体の状態で混合して組成物とし、成型時に溶融混錬しても良いし、（Ａ）（Ｂ）をあらかじめ溶融混錬した組成物を用いることもできる。 In producing the gas permeation control film of the present invention, a dry blend method or a melt blend method can be used. That is, polypropylene (A) and ethylene-1-octene random copolymer (B) may be mixed in a solid state such as pellets or powder to form a composition, which may be melt-kneaded at the time of molding. A composition obtained by melt-kneading (B) in advance can also be used.
（多層二軸延伸フィルム）
本発明の多層二軸延伸フィルムについて説明する。樹脂組成物（Ｃ）からなる基材層と、プロピレン系樹脂（Ｄ）からなる少なくとも１層の表層からなり、表層の厚さが１層について基材層の厚さの１〜２０％の範囲にある。
(Multilayer biaxially stretched film)
The multilayer biaxially stretched film of the present invention will be described. It consists of a base material layer composed of the resin composition (C) and at least one surface layer composed of the propylene-based resin (D), and the thickness of the surface layer is in the range of 1 to 20% of the thickness of the base material layer per layer It is in.
＜樹脂組成物（Ｃ）＞
２３０℃で測定したＭＦＲが１〜１０ｇ／１０分であり、ＤＳＣの融解ピークから求めた融点Ｔｍが１５５℃以上であるプロピレン単独重合体（ＣＡ−１）およびまたはプロピレン系ランダム共重合体（ＣＡ−２）７５〜９５重量部および１９０℃で測定したＭＦＲが０．５〜３０ｇ／１０分であり、１−オクテン含有量が５〜２０モル％であるエチレン−１−オクテンランダム共重合体（ＣＢ−１）５〜２５重量部からなる樹脂組成物。
成分ＣＡ−１と成分ＣＡ−２は、合計量が樹脂組成物（Ｃ）中７５〜９５重量部の範囲にあれば、どちらか一方でも両者を混合して用いても構わない。エチレン−１−オクテンランダム共重合体ＣＢ−１は、樹脂組成物（Ｃ）の５〜２５重量部を占める。
＜プロピレン系樹脂（Ｄ）＞
２３０℃で測定したＭＦＲが１〜２０ｇ／１０分であり、ＤＳＣの融解ピークから求めた融点Ｔｍが１２０〜１５０℃であるプロピレン単独重合体（Ｄ１）およびまたはプロピレン系ランダム共重合体（Ｄ２）。
<Resin composition (C)>
Propylene homopolymer (CA-1) and / or propylene random copolymer (CA) having an MFR measured at 230 ° C. of 1 to 10 g / 10 min and a melting point Tm determined from the melting peak of DSC of 155 ° C. or higher. -2) An ethylene-1-octene random copolymer having an MFR measured at 75 to 95 parts by weight and 190 ° C. of 0.5 to 30 g / 10 min and a 1-octene content of 5 to 20 mol% ( CB-1) A resin composition comprising 5 to 25 parts by weight.
As long as the total amount of component CA-1 and component CA-2 is in the range of 75 to 95 parts by weight in the resin composition (C), either one may be used in combination. The ethylene-1-octene random copolymer CB-1 occupies 5 to 25 parts by weight of the resin composition (C).
<Propylene resin (D)>
Propylene homopolymer (D1) and / or propylene-based random copolymer (D2) having an MFR measured at 230 ° C. of 1 to 20 g / 10 min and a melting point Tm determined from the melting peak of DSC of 120 to 150 ° C. .
基材層に使用するプロピレン系ランダム共重合体（ＣＡ−２）はプロピレン−α−オレフィン共重合体であり、α−オレフィンとしては、たとえば、エチレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン、１−ドデセン、１−ヘキサドデセン、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−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、ジメチルオクテン、エチル−１− オクテン、メチル−１− ノネン、ビニルシクロペンテン、ビニルシクロヘキサン、ビニルノルボルナンなどが挙げられる。これらのα−オレフィンはプロピレン−α−オレフィン共重合体中に一種類以上、合計１０モル％以下の量で含有することができる。 The propylene random copolymer (CA-2) used for the base material layer is a propylene-α-olefin copolymer, and examples of the α-olefin include ethylene, 1-butene, 1-pentene, and 1-hexene. 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-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, , 5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, dimethyloctene, ethyl-1-octene, methyl-1-nonene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane and the like. It is done. One or more of these α-olefins can be contained in the propylene-α-olefin copolymer in a total amount of 10 mol% or less.
また、本発明の基材層に使用するプロピレン単独重合体（ＣＡ−１）およびまたはプロピレン系ランダム共重合体（ＣＡ−２）の２３０℃で測定したＭＦＲは通常１〜１０ｇ／１０分、好ましくは２〜７ｇ／１０分、さらに好ましくは２〜５ｇ／１０分の範囲にある。ＭＦＲがこの範囲にあると、フィルムの成形性と機械的強度のバランスが良好であるため好ましい。 The MFR measured at 230 ° C. of the propylene homopolymer (CA-1) and / or propylene random copolymer (CA-2) used for the base material layer of the present invention is usually 1 to 10 g / 10 min, preferably Is in the range of 2-7 g / 10 min, more preferably in the range of 2-5 g / 10 min. When the MFR is within this range, it is preferable because the balance between the moldability of the film and the mechanical strength is good.
本発明の基材層に使用するプロピレン単独重合体（ＣＡ−１）およびまたはプロピレン系ランダム共重合体（ＣＡ−２）の示差走査型熱量計（ＤＳＣ）によって測定される融解曲線のピーク温度から定義される融点（Ｔｍ、単位：℃）は１５５℃以上、好ましくは１５５℃以上１７０℃以下である。融点Ｔｍが１５５℃以上であると、フィルムに適度の剛性を付与することができるので好ましい。 From the peak temperature of the melting curve measured by a differential scanning calorimeter (DSC) of the propylene homopolymer (CA-1) and / or the propylene random copolymer (CA-2) used for the base material layer of the present invention. The defined melting point (Tm, unit: ° C) is 155 ° C or higher, preferably 155 ° C or higher and 170 ° C or lower. It is preferable for the melting point Tm to be 155 ° C. or higher, since an appropriate rigidity can be imparted to the film.
本発明の基材層に使用するエチレン−１−オクテンランダム共重合体（ＣＢ−１）の１９０℃で測定したＭＦＲは通常０．５〜３０ｇ／１０分、好ましくは０．５〜５ｇ／分、さらに好ましくは１〜５ｇ／１０分の範囲にある。ＭＦＲがこの範囲にあると、フィルムの透明性が良好であるため好ましい。 MFR measured at 190 degreeC of the ethylene-1-octene random copolymer (CB-1) used for the base material layer of this invention is 0.5-30 g / 10min normally, Preferably it is 0.5-5 g / min. More preferably, it is in the range of 1 to 5 g / 10 minutes. When the MFR is in this range, it is preferable because the transparency of the film is good.
また、本発明の基材層に使用するエチレン−１−オクテンランダム共重合体（ＣＢ−１）の１−オクテン含有量は５〜２０モル％、好ましくは１０〜２０モル％、さらに好ましくは１２〜１８モル％の範囲にある。１−オクテンの量がこの範囲にあると、フィルムの剛性とガス透過度のバランスが良好になるので好ましい。 Moreover, 1-octene content of the ethylene-1-octene random copolymer (CB-1) used for the base material layer of this invention is 5-20 mol%, Preferably it is 10-20 mol%, More preferably, it is 12 It is in the range of ˜18 mol%. When the amount of 1-octene is within this range, the balance between the rigidity of the film and the gas permeability is good, which is preferable.
本発明の基材層を構成する樹脂組成物（Ｃ）はプロピレン単独重合体（ＣＡ−１）およびまたはプロピレン系ランダム共重合体（ＣＡ−２）７５〜９５重量部、好ましくは８０〜９０重量部と、エチレン−１−オクテンランダム共重合体（ＣＢ−１）５〜２５重量部、好ましくは１０〜２０重量部からなる。組成がこの範囲にあると、フィルムの透明性、剛性、ガス透過性のバランスが良好になるので好ましい。 The resin composition (C) constituting the substrate layer of the present invention is 75 to 95 parts by weight, preferably 80 to 90 parts by weight, of propylene homopolymer (CA-1) and / or propylene random copolymer (CA-2). Parts and 5 to 25 parts by weight, preferably 10 to 20 parts by weight of ethylene-1-octene random copolymer (CB-1). When the composition is within this range, the balance of transparency, rigidity, and gas permeability of the film is improved, which is preferable.
本発明の表層に使用するプロピレン系ランダム共重合体（Ｄ２）は、前記の基材層に使用するプロピレン系ランダム共重合体（ＣＡ−２）と同様にプロピレン−α−オレフィン共重合体であり、α−オレフィンとしては、たとえば、エチレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−デセン、１−ドデセン、１−ヘキサドデセン、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−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、ジメチルオクテン、エチル−１− オクテン、メチル−１− ノネン、ビニルシクロペンテン、ビニルシクロヘキサン、ビニルノルボルナンなどが挙げられる。これらのα−オレフィンはプロピレン−α−オレフィン共重合体中に一種類以上、合計１０モル％以下の量で含有することができる。 The propylene random copolymer (D2) used for the surface layer of the present invention is a propylene-α-olefin copolymer similar to the propylene random copolymer (CA-2) used for the base material layer. As the α-olefin, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4-methyl-1-pentene 2-methyl-1-butene, 3-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, tri Tyl-1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, dimethyloctene, ethyl- Examples include 1-octene, methyl-1-nonene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane. One or more of these α-olefins can be contained in the propylene-α-olefin copolymer in a total amount of 10 mol% or less.
本発明の表層に使用するプロピレン単独重合体（Ｄ１）およびまたはプロピレン系ランダム共重合体（Ｄ２）の２３０℃で測定したＭＦＲは通常１〜２０ｇ／１０分、好ましくは２〜１０ｇ／１０分、さらに好ましくは４〜１０ｇ／１０分の範囲にある。ＭＦＲがこの範囲にあると、フィルムの成形性および外観が良好であるため好ましい。 The MFR measured at 230 ° C. of the propylene homopolymer (D1) and / or propylene random copolymer (D2) used for the surface layer of the present invention is usually 1 to 20 g / 10 minutes, preferably 2 to 10 g / 10 minutes. More preferably, it exists in the range of 4-10 g / 10min. An MFR in this range is preferable because the moldability and appearance of the film are good.
また、本発明の表層に使用するプロピレン単独重合体（Ｄ１）およびまたはプロピレン系ランダム共重合体（Ｄ２）の融点Ｔｍは１２０〜１５０℃、好ましくは１３０〜１４５℃の範囲にある。融点Ｔｍがこの範囲にあると、フィルムのベタツキがなく、透明性とシール性が良好で、ガス透過度も高くなるので好ましい。 The melting point Tm of the propylene homopolymer (D1) and / or the propylene random copolymer (D2) used for the surface layer of the present invention is in the range of 120 to 150 ° C, preferably 130 to 145 ° C. When the melting point Tm is in this range, there is no stickiness of the film, transparency and sealing properties are good, and gas permeability is high, which is preferable.
本発明の多層二軸延伸フィルムの表層は基材層の片面または両面に積層される。表層を両面に積層する場合は、表層用のプロピレン単独重合体（Ｄ１）およびまたはプロピレン系ランダム共重合体（Ｄ２）は同一のものでも異なるものでもよい。表層の厚さは、１層について基材層の厚さの１〜２０％、好ましくは２〜１０％、さらに好ましくは４〜７％である。表層の厚さがこの範囲にあると、得られる多層二軸延伸フィルムのシール性と剛性が良好になるので好ましい。両面に積層する場合は、各層の厚さが前記範囲にあればよく、各層の厚さは同一でも異なっていてもよいが、プロピレン系ランダム共重合体（Ｄ２）を両面に積層することが好ましい。 The surface layer of the multilayer biaxially stretched film of the present invention is laminated on one side or both sides of the base material layer. When the surface layer is laminated on both surfaces, the propylene homopolymer (D1) and / or the propylene random copolymer (D2) for the surface layer may be the same or different. The thickness of the surface layer is 1 to 20%, preferably 2 to 10%, more preferably 4 to 7% of the thickness of the base material layer for one layer. When the thickness of the surface layer is within this range, the resulting multilayer biaxially stretched film is preferable in terms of sealing properties and rigidity. When laminating on both surfaces, the thickness of each layer may be in the above range, and the thickness of each layer may be the same or different, but it is preferable to laminate the propylene random copolymer (D2) on both surfaces. .
また、本発明の多層二軸延伸フィルムのヘイズ値は５％以下が好ましい。ヘイズ値が５％以下であれば、包装した内容物の視認性が損なわれないので好ましい。 The haze value of the multilayer biaxially stretched film of the present invention is preferably 5% or less. A haze value of 5% or less is preferable because the visibility of the packaged contents is not impaired.
本発明の多層二軸延伸フィルムのＭＤ方向の引張弾性率は１８００Ｍｐａ以上が好ましく、さらに好ましくは２０００ＭＰａ以上である。引張弾性率がこの範囲にあると、得られる多層二軸延伸フィルムの剛性が十分で、腰が不足することがないので好ましい。 The tensile elastic modulus in the MD direction of the multilayer biaxially stretched film of the present invention is preferably 1800 Mpa or more, more preferably 2000 MPa or more. When the tensile elastic modulus is in this range, the resulting multilayer biaxially stretched film has sufficient rigidity, and is not insufficient.
また、本発明の多層二軸延伸フィルムの酸素透過度は１．６×１０−１１ｍｏｌ／ｍ２・ｓ・Ｐａ以上が好ましく、より好ましくは１．８×１０−１１ｍｏｌ／ｍ２・ｓ・Ｐａ以上、とりわけ好ましくは２．０×１０−１１ｍｏｌ／ｍ２・ｓ・Ｐａ以上である。酸素透過度がこの範囲にあると、鮮度保持効果が高まるので好ましい。 Further, the oxygen permeability of the multilayer biaxially stretched film of the present invention is preferably 1.6 × 10 −11 mol / m 2 · s · Pa or more, more preferably 1.8 × 10 −11 mol / m 2 · s. -Pa or more, Especially preferably, it is 2.0 * 10 < -11 > mol / m < 2 > * s * Pa or more. When the oxygen permeability is within this range, the effect of maintaining freshness is enhanced, which is preferable.
本発明で使用するプロピレン単独重合体（Ａ１、ＣＡ−１およびＤ１）とプロピレン系ランダム共重合体（ＣＡ−２およびＤ２）、プロピレン-α-オレフィン共重合体（Ａ２）の製造方法としては、公知の重合触媒を用いて、公知の重合方法によって製造する方法が挙げられる。
公知の重合触媒としては、例えば、マグネシウム、チタンおよびハロゲンを必須とする固体触媒成分と、有機アルミニウム化合物と、必要に応じて用いられる電子供与性化合物等の第３成分とからなる触媒系、シクロペンタジエニル環を有する周期表第ＩＶ族の遷移金属化合物とアルキルアルミノキサンからなる触媒系、またはシクロペンタジエニル環を有する周期表第ＩＶ族の遷移金属化合物とそれと反応してイオン性の錯体を形成する化合物および有機アルミニウム化合物からなる触媒系等が挙げられる。
As a manufacturing method of the propylene homopolymer (A1, CA-1 and D1) and the propylene-based random copolymer (CA-2 and D2) and the propylene-α-olefin copolymer (A2) used in the present invention, The method of manufacturing by a well-known polymerization method using a well-known polymerization catalyst is mentioned.
Known polymerization catalysts include, for example, a catalyst system comprising a solid catalyst component essentially containing magnesium, titanium and halogen, an organoaluminum compound, and a third component such as an electron-donating compound used as necessary. A catalyst system comprising a transition metal compound of group IV of the periodic table having a pentadienyl ring and an alkylaluminoxane, or an ionic complex by reacting with a transition metal compound of group IV of the periodic table having a cyclopentadienyl ring. Examples thereof include a catalyst system composed of a compound to be formed and an organoaluminum compound.
公知の重合方法としては、例えば、不活性炭化水素溶媒によるスラリー重合法、溶液重合法、無溶媒による液相重合法、気相重合法等が挙げられる。さらに、前記の重合法を組み合わせ、それらを連続的に行なう方法、例えば、液相−気相重合法等が挙げられる。
また、本発明で使用するエチレン−１−オクテンランダム共重合体（Ｂ）は、公知のバナジウム系触媒またはメタロセン系触媒を用いて、公知の重合方法により製造することができる。
Known polymerization methods include, for example, a slurry polymerization method using an inert hydrocarbon solvent, a solution polymerization method, a liquid phase polymerization method using no solvent, and a gas phase polymerization method. Furthermore, a method of combining the above-described polymerization methods and continuously performing them, for example, a liquid phase-gas phase polymerization method and the like can be mentioned.
The ethylene-1-octene random copolymer (B) used in the present invention can be produced by a known polymerization method using a known vanadium catalyst or metallocene catalyst.
本発明の多層二軸延伸フィルムは、必要に応じて一般的に使用される耐熱安定剤、酸化防止剤、スリップ剤、ブロッキング防止剤、可塑剤、着色剤、核剤、耐候安定剤、紫外線吸収剤などのほか、防曇剤、防霧剤、抗菌剤、エチレン除去剤などを含有することができる。特に防曇剤は、包装フィルムの内面に青果物や花卉類の蒸散水分が結露して内容物を濡らしたり、フィルムの透視性を悪くすることを防ぐ効果があるので、有用である。防曇剤としては公知のグリセリン脂肪酸エステル、ジグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、アルキルアミンのエチレンオキサイド付加物、脂肪族アミドのエチレンオキサイド付加物等が挙げられる。防曇剤の含有量は通常０．５〜２．０重量％である。 The multi-layer biaxially stretched film of the present invention is a heat stabilizer, antioxidant, slip agent, anti-blocking agent, plasticizer, colorant, nucleating agent, weathering stabilizer, UV absorber, which are generally used as necessary. In addition to the agent, it may contain an antifogging agent, an antifogging agent, an antibacterial agent, an ethylene removing agent, and the like. In particular, the anti-fogging agent is useful because it has an effect of preventing the moisture content of the fruits and flowers from condensing on the inner surface of the packaging film to wet the contents or to deteriorate the transparency of the film. Examples of the antifogging agent include known glycerin fatty acid esters, diglycerin fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts of alkylamines, ethylene oxide adducts of aliphatic amides, and the like. The content of the antifogging agent is usually 0.5 to 2.0% by weight.
本発明の多層二軸延伸フィルムを製造する際に使用する樹脂や添加剤などを混合する方法としては、タンブラーミキサー、ヘンシェルミキサー、リボンブレンダーなどで混合するドライブレンド法や、押出機で溶融混練するメルトブレンド法が挙げられる。 As a method of mixing the resin and additives used when producing the multilayer biaxially stretched film of the present invention, a dry blend method of mixing with a tumbler mixer, a Henschel mixer, a ribbon blender or the like, or melt-kneading with an extruder A melt blending method is mentioned.
本発明の多層二軸延伸フィルムの製膜、延伸加工方法には特に制限はない。例えば多層Ｔダイ成形機で成形したシートを、ロールやテンターを使用して、逐次二軸延伸や同時二軸延伸する方法がある。また、環状ダイを用いて成形したチューブを、加圧空気で膨らませるチューブラー二軸延伸方式がある。さらに、縦に一軸延伸した基材層に、表層を積層した後、横延伸することもできる。 There is no restriction | limiting in particular in the film forming of the multilayer biaxially stretched film of this invention, and the extending | stretching processing method. For example, there is a method of sequentially biaxially stretching or simultaneously biaxially stretching a sheet molded by a multilayer T-die molding machine using a roll or a tenter. Further, there is a tubular biaxial stretching method in which a tube molded using an annular die is expanded with pressurized air. Furthermore, after a surface layer is laminated on a base material layer that has been uniaxially stretched vertically, it can be stretched laterally.
本発明の多層二軸延伸フィルムの厚みには特に制限はないが、通常１０〜１００μｍ、好ましくは１０〜６０μｍである。さらに好ましくは１０μｍ以上３０μｍ未満である。厚みがこの範囲にあると透明性、剛性、酸素透過性のバランスに優れ好ましい。 Although there is no restriction | limiting in particular in the thickness of the multilayer biaxially stretched film of this invention, Usually, 10-100 micrometers, Preferably it is 10-60 micrometers. More preferably, it is 10 μm or more and less than 30 μm. When the thickness is within this range, the balance of transparency, rigidity and oxygen permeability is excellent and preferable.
以下、実施例により本発明をさらに説明するが、本発明はこれに限定されるものではない。物性試験は、次の方法で行なった。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. The physical property test was conducted by the following method.
（１）融点Ｔｍ
サンプル約５ｍｇを秤量し、セイコーインスツルメンツ(株)製 示差走査熱量計 ＤＳＣ６２００を用いて、昇温速度１０℃／分で２００℃まで昇温し、２００℃で１０分間保持した後、降温速度１０℃／分で３０℃まで冷却し、３０℃で１分間保持した後、再度、昇温速度１０℃／分で２００℃まで昇温したときの融解熱量曲線から、最大ピーク温度を融点Ｔｍとして求めた。
（２）引張弾性率
ＪＩＳ Ｋ６７８１のダンベルを用いて、チャック間距離８０ｍｍ、引張速度５０ｍｍ／ｍｉｎでＳ−Ｓ曲線を描き、初期弾性率を測定した。
（３）ガス透過度
(株)東洋精機製作所製 ガス透過率測定装置 ＭＴ−Ｃ３型を使用して、ＪＩＳ Ｋ７１２６のＡ法に準拠して、２３℃、０％ＲＨの条件にて測定した。
（４）ヘイズ
ＪＩＳ Ｋ７１０５に準拠して、フィルム１枚のヘイズを測定した。
(1) Melting point Tm
About 5 mg of a sample was weighed and heated to 200 ° C. at a heating rate of 10 ° C./min using a differential scanning calorimeter DSC6200 manufactured by Seiko Instruments Inc. After cooling to 30 ° C./minute and holding at 30 ° C. for 1 minute, the maximum peak temperature was determined as the melting point Tm from the heat of fusion curve when the temperature was raised again to 200 ° C. at a temperature increase rate of 10 ° C./minute. .
(2) Tensile Elastic Modulus Using an JIS K6781 dumbbell, an SS curve was drawn at a distance between chucks of 80 mm and a tensile speed of 50 mm / min, and the initial elastic modulus was measured.
(3) Gas permeability
Using a gas permeability measuring device MT-C3 type manufactured by Toyo Seiki Seisakusho Co., Ltd., measurement was performed under the conditions of 23 ° C. and 0% RH in accordance with A method of JIS K7126.
(4) Haze The haze of one film was measured according to JIS K7105.
（単層ガス透過フィルム）
［参考例１］
ポリプロピレン（ＰＰ-１）[三井ポリプロ（登録商標）Ｆ１１３Ｇ 三井化学(株)製、ＭＦＲ（ＪＩＳ Ｋ７２１０、２３０℃）＝３ｇ／１０分]（ＰＰ-１）７５重量部と、１-オクテンの量が１５モル％でＭＦＲ（ＪＩＳ Ｋ７２１０、１９０℃）＝１ｇ／１０分のエチレン-１-オクテンランダム共重合体（ＥＯＲ-１）２５重量部を、ヘンシェルミキサーで混合（ドライブレンド）して樹脂組成物を得た。
(Single layer gas permeable film)
[ Reference Example 1]
Polypropylene (PP-1) [Mitsui Polypro (registered trademark) F113G, manufactured by Mitsui Chemicals, MFR (JIS K7210, 230 ° C.) = 3 g / 10 min] (PP-1) 75 parts by weight and the amount of 1-octene Is 15 mol% and MFR (JIS K7210, 190 ° C.) = 1 g / 10 min of ethylene-1-octene random copolymer (EOR-1) 25 parts by weight is mixed (dry blended) with a Henschel mixer to obtain a resin composition I got a thing.
次にこの樹脂組成物をＴダイ成形機（ダイリップ幅：２００ｍｍ、押出機：３０ｍｍφ、Ｌ／Ｄ＝２５）を使用して、押出機設定温度：２３０℃、ダイ設定温度：２３０℃、チルロール温度：３０℃、引取速度：１ｍ／分、片面エアー冷却の条件で成形して、厚み５００μｍの原反フィルムを得た。次にこの原反フィルムを、１４５℃の熱風を循環させたテンター内で、延伸速度１０ｍ／ｍｉｎで縦方向５倍、横方向５倍に同時延伸を行い、厚み２０μｍの二軸延伸フィルムを得た。このフィルムの酸素透過度[ＧＴＲ（Ｏ２）]と二酸化炭素透過度[ＧＴＲ（ＣＯ２）]を測定するとともに、その比を算出した。結果を表１に示す。 Next, using this resin composition, a T-die molding machine (die lip width: 200 mm, extruder: 30 mmφ, L / D = 25), extruder set temperature: 230 ° C., die set temperature: 230 ° C., chill roll temperature : 30 ° C., take-up speed: 1 m / min, molded on the condition of single-sided air cooling to obtain a 500 μm-thick original film. Next, this original film was simultaneously stretched 5 times in the longitudinal direction and 5 times in the transverse direction at a stretching speed of 10 m / min in a tenter in which hot air at 145 ° C. was circulated to obtain a biaxially stretched film having a thickness of 20 μm. It was. The oxygen permeability [GTR (O2)] and carbon dioxide permeability [GTR (CO2)] of this film were measured, and the ratio was calculated. The results are shown in Table 1.
［比較例１〜６］
樹脂組成物の内容を表１に示したものに変更したほかは、参考例１と同様にして厚み２０μｍの二軸延伸フィルムを得た。このフィルムの酸素透過度と二酸化炭素透過度を測定するともに、その比を算出した。結果を表１に示す。エチレン-１-オクテンランダム共重合体の代わりに用いた重合体を以下に示す：
ＰＥＲ：プロピレン-エチレンランダム共重合体[エチレン量＝４２モル％、ＭＦＲ（ＪＩＳ Ｋ７２１０、１９０℃）＝２ｇ／１０分]
ＥＰＲ：エチレン-プロピレンランダム共重合体[プロピレン量＝２２モル％、ＭＦＲ（ＪＩＳ Ｋ７２１０、２３０℃）＝２ｇ／１０分]
ＢＰＲ：１-ブテン-プロピレンランダム共重合体[プロピレン量＝２８モル％、ＭＦＲ（ＪＩＳ Ｋ７２１０、１９０℃）＝２ｇ／１０分]
ＥＢＲ：エチレン-１-ブテンランダム共重合体[１-ブテン量＝１５モル％、ＭＦＲ（ＪＩＳ Ｋ７２１０、１９０℃）＝４ｇ／１０分]
ＰＢ：ポリ-１-ブテン[ＭＦＲ（ＪＩＳ Ｋ７２１０、１９０℃）＝２ｇ／１０分]
[Comparative Examples 1-6]
A biaxially stretched film having a thickness of 20 μm was obtained in the same manner as in Reference Example 1, except that the content of the resin composition was changed to that shown in Table 1. The oxygen permeability and carbon dioxide permeability of this film were measured and the ratio was calculated. The results are shown in Table 1. The polymer used in place of the ethylene-1-octene random copolymer is shown below:
PER: propylene-ethylene random copolymer [ethylene content = 42 mol%, MFR (JIS K7210, 190 ° C.) = 2 g / 10 min]
EPR: ethylene-propylene random copolymer [propylene content = 22 mol%, MFR (JIS K7210, 230 ° C.) = 2 g / 10 min]
BPR: 1-butene-propylene random copolymer [propylene content = 28 mol%, MFR (JIS K7210, 190 ° C.) = 2 g / 10 min]
EBR: ethylene-1-butene random copolymer [1-butene amount = 15 mol%, MFR (JIS K7210, 190 ° C.) = 4 g / 10 min]
PB: Poly-1-butene [MFR (JIS K7210, 190 ° C.) = 2 g / 10 min]
［比較例７］
二軸延伸フィルムとして、二村化学工業(株)製のガス通気性ＯＰＰフィルム ＰＯＲＯ ＰＲＥＳＨ Ｆ＃２５（厚み２５μｍ）の酸素透過度と二酸化炭素透過度を測定するともに、その比を算出した。結果を表１に示す。
[Comparative Example 7]
As a biaxially stretched film, the oxygen permeability and carbon dioxide permeability of a gas-permeable OPP film PORO PRESH F # 25 (thickness 25 μm) manufactured by Nimura Chemical Industry Co., Ltd. were measured, and the ratio was calculated. The results are shown in Table 1.
（多層二軸延伸フィルム）
［実施例２］
エチレンの量が１．２モル％でＤＳＣの融解ピークから求めた融点Ｔｍが１５９．８℃であり、ＭＦＲ（ＪＩＳ Ｋ７２１０、２３０℃）が３ｇ／１０分であるプロピレン−エチレンランダム共重合体９５重量部と、１−オクテンの量が１５モル％でＭＦＲ（ＪＩＳ Ｋ７２１０、１９０℃）が１ｇ／１０分のエチレン−１−オクテンランダム共重合体５重量部を、二軸押出機（スクリュー径３６ｍｍ、Ｌ／Ｄ＝３１）を使用して、押出機設定温度：２３０℃で溶融混練することにより、基材層用の樹脂組成物を得た。
(Multilayer biaxially stretched film)
[Example 2]
A propylene-ethylene random copolymer 95 having an ethylene amount of 1.2 mol%, a melting point Tm determined from a DSC melting peak of 159.8 ° C., and an MFR (JIS K7210, 230 ° C.) of 3 g / 10 min. 2 parts by weight of an ethylene-1-octene random copolymer having an amount of 1-octene of 15 mol% and an MFR (JIS K7210, 190 ° C.) of 1 g / 10 min. , L / D = 31), and melt kneading at an extruder set temperature: 230 ° C. to obtain a resin composition for a base material layer.
次に二種三層Ｔダイ成形機（ダイリップ幅：２００ｍｍ）の基材層用押出機（３０ｍｍφ、Ｌ／Ｄ＝２５）に上で得た樹脂組成物を投入し、表層用押出機（２５ｍｍφ、Ｌ／Ｄ＝２５）にはエチレンの量が３．３モル％、１−ブテンの量が１．５モル％で融点Ｔｍが１３８．４℃、ＭＦＲ（ＪＩＳ Ｋ７２１０、２３０℃）が７ｇ／１０分であるプロピレン−エチレン−１−ブテンランダム共重合体を投入して、押出機設定温度：２３０℃、ダイ設定温度：２３０℃、チルロール温度：３０℃、片面エアー冷却の条件で、表層の厚さが１層について基材層の厚さの５．５％となる押出量設定で、基材層の両面に表層を有する、全層厚み５００μｍの原反フィルムを得た。次にこの原反フィルムを、１５０℃の熱風を循環させたテンター内で、はじめにＭＤ方向に５倍、次にＴＤ方向に５倍、それぞれ
延伸速度１０ｍ／ｍｉｎで逐次延伸することにより、厚み２０μｍの多層二軸延伸フィルムを得た。この多層二軸延伸フィルムのＭＤ方向の引張弾性率と酸素透過度およびヘイズを測定した。結果を表２に示す。
Next, the resin composition obtained above was put into a substrate layer extruder (30 mmφ, L / D = 25) of a two-type three-layer T-die molding machine (die lip width: 200 mm), and a surface layer extruder (25 mmφ). L / D = 25), the amount of ethylene is 3.3 mol%, the amount of 1-butene is 1.5 mol%, the melting point Tm is 138.4 ° C., and the MFR (JIS K7210, 230 ° C.) is 7 g / The propylene-ethylene-1-butene random copolymer that is 10 minutes is charged, the extruder set temperature: 230 ° C., the die set temperature: 230 ° C., the chill roll temperature: 30 ° C., under the conditions of single-sided air cooling, An original film having a total layer thickness of 500 μm having a surface layer on both surfaces of the base material layer was obtained with an extrusion rate setting of 5.5% of the thickness of the base material layer for one layer. Next, this raw film was first stretched 5 times in the MD direction and then 5 times in the TD direction in a tenter in which hot air at 150 ° C. was circulated. A multilayer biaxially stretched film was obtained. The tensile elastic modulus, oxygen permeability and haze in the MD direction of this multilayer biaxially stretched film were measured. The results are shown in Table 2.
［実施例３］
基材層用の樹脂組成物に含まれるプロピレン−エチレンランダム共重合体が９０重量部、エチレン−１−オクテンランダム共重合体が１０重量部であること以外は、実施例２と同様にして厚み２０μｍの多層二軸延伸フィルムを得た。
[Example 3]
The thickness is the same as in Example 2 except that the propylene-ethylene random copolymer contained in the resin composition for the base layer is 90 parts by weight and the ethylene-1-octene random copolymer is 10 parts by weight. A 20 μm multilayer biaxially stretched film was obtained.
［実施例４］
基材層用の樹脂組成物に含まれるプロピレン−エチレンランダム共重合体が８５重量部、エチレン−１−オクテンランダム共重合体が１５重量部であること以外は、実施例２と同様にして厚み２０μｍの多層二軸延伸フィルムを得た。
[Example 4]
The thickness is the same as in Example 2 except that the propylene-ethylene random copolymer contained in the resin composition for the base layer is 85 parts by weight and the ethylene-1-octene random copolymer is 15 parts by weight. A 20 μm multilayer biaxially stretched film was obtained.
［実施例５］
実施例４において、原反フィルムの全層厚みを３２０μｍとして、延伸倍率をＭＤ方向に４倍、ＴＤ方向に４倍とする以外は、実施例４と同様にして、厚み２０μｍの多層二軸延伸フィルムを得た。
[Example 5]
In Example 4, a multilayer biaxial stretching of 20 μm in thickness was performed in the same manner as in Example 4 except that the total thickness of the raw film was 320 μm and the stretching ratio was 4 times in the MD direction and 4 times in the TD direction. A film was obtained.
［実施例６］
実施例４において、原反フィルムの全層厚みを７２０μｍとして、延伸倍率をＭＤ方向に６倍、ＴＤ方向に６倍とする以外は、実施例４と同様にして、厚み２０μｍの多層二軸延伸フィルムを得た。
[Example 6]
In Example 4, multilayer biaxial stretching of 20 μm in thickness was performed in the same manner as in Example 4 except that the total thickness of the raw film was 720 μm and the stretching ratio was 6 times in the MD direction and 6 times in the TD direction. A film was obtained.
［実施例７］
基材層用の樹脂組成物に含まれるプロピレン−エチレンランダム共重合体が８０重量部、エチレン−１−オクテンランダム共重合体が２０重量部であること以外は、実施例２と同様にして厚み２０μｍの多層二軸延伸フィルムを得た。
[Example 7]
The thickness is the same as in Example 2 except that the propylene-ethylene random copolymer contained in the resin composition for the base material layer is 80 parts by weight and the ethylene-1-octene random copolymer is 20 parts by weight. A 20 μm multilayer biaxially stretched film was obtained.
［実施例８］
基材層用の樹脂組成物に含まれるプロピレン−エチレンランダム共重合体が７５重量部、エチレン−１−オクテンランダム共重合体が２５重量部であること以外は、実施例６と同様にして、厚み２０μｍの多層二軸延伸フィルムを得た。
[Example 8]
Except that the propylene-ethylene random copolymer contained in the resin composition for the base layer is 75 parts by weight and the ethylene-1-octene random copolymer is 25 parts by weight, the same as in Example 6, A multilayer biaxially stretched film having a thickness of 20 μm was obtained.
［比較例８］
基材層用の樹脂としてプロピレン−エチレンランダム共重合体のみを使用すること以外は、実施例２と同様にして厚み２０μｍの多層二軸延伸フィルムを得た。
[Comparative Example 8]
A multilayer biaxially stretched film having a thickness of 20 μm was obtained in the same manner as in Example 2 except that only a propylene-ethylene random copolymer was used as the resin for the base material layer.
［比較例９］
基材層用の樹脂組成物に含まれるプロピレン−エチレンランダム共重合体が７０重量部、エチレン−１−オクテンランダム共重合体が３０重量部であること以外は、実施例６と同様にして、厚み２０μｍの多層二軸延伸フィルムを得た。
[Comparative Example 9]
Except that the propylene-ethylene random copolymer contained in the resin composition for the base layer is 70 parts by weight and the ethylene-1-octene random copolymer is 30 parts by weight, the same as in Example 6, A multilayer biaxially stretched film having a thickness of 20 μm was obtained.
本発明により提供されるガス透過制御フィルムは、従来のポリプロピレン系フィルムに比べて酸素透過度と二酸化炭素透過度、および二酸化炭素透過度／酸素透過度の比が大きい。本発明により提供される多層二軸延伸フィルムは、透明性に優れ、適度な剛性と高い酸素透過度を有し、良好なシール性も備える。さらに本発明のフィルムには、物理的な穴が存在しないので、外部からの汚染物質侵入を防ぐことができる。これにより本発明により提供されるガス透過制御フィルムならびに多層二軸延伸フィルムは青果物や花卉類の鮮度保持包装材料として最適である。
The gas permeation control film provided by the present invention has a larger ratio of oxygen permeability, carbon dioxide permeability, and carbon dioxide permeability / oxygen permeability than conventional polypropylene films. The multilayer biaxially stretched film provided by the present invention is excellent in transparency, has an appropriate rigidity and high oxygen permeability, and also has a good sealing property. Furthermore, since no physical hole exists in the film of the present invention, entry of contaminants from the outside can be prevented. As a result, the gas permeation control film and multilayer biaxially stretched film provided by the present invention are optimal as packaging materials for maintaining the freshness of fruits and vegetables.
Claims (6)
樹脂組成物（Ｃ）：
２３０℃で測定したメルトフローレート（ＡＳＴＭ Ｄ１２３８、荷重２．１６ｋｇ、以下ＭＦＲと略す）が１〜１０ｇ／１０分であり、ＤＳＣの融解ピークから求めた融点Ｔｍが１５５℃以上であるプロピレン単独重合体（ＣＡ−１）および／またはプロピレン系ランダム共重合体（ＣＡ−２）７５〜９５重量部と、１９０℃で測定したＭＦＲが０．５〜３０ｇ／１０分であり、１−オクテン含有量が５〜２０モル％であるエチレン−１−オクテンランダム共重合体（ＣＢ−１）５〜２５重量部からなる樹脂組成物。
プロピレン系樹脂（Ｄ）：
２３０℃で測定したＭＦＲが１〜２０ｇ／１０分であり、ＤＳＣの融解ピークから求めた融点Ｔｍが１２０〜１５０℃であるプロピレン単独重合体（Ｄ１）および／またはプロピレン系ランダム共重合体（Ｄ２）。 In a multilayer biaxially stretched film comprising a substrate layer and at least one surface layer, the substrate layer is composed of the following resin composition (C), the surface layer is composed of the following propylene-based resin (D), and the thickness of the surface layer is 1. A multilayer biaxially stretched film characterized in that the layer is 1 to 20% of the thickness of the base material layer.
Resin composition (C):
Propylene single weight having a melt flow rate (ASTM D1238, load 2.16 kg, hereinafter abbreviated as MFR) measured at 230 ° C. of 1 to 10 g / 10 min and a melting point Tm determined from a melting peak of DSC of 155 ° C. or more 75-95 parts by weight of coalescence (CA-1) and / or propylene random copolymer (CA-2), MFR measured at 190 ° C. is 0.5-30 g / 10 min, and 1-octene content The resin composition which consists of 5-25 weight part of ethylene-1-octene random copolymer (CB-1) whose is 5-20 mol%.
Propylene resin (D):
Propylene homopolymer (D1) and / or propylene random copolymer (D2) having an MFR measured at 230 ° C. of 1 to 20 g / 10 min and a melting point Tm determined from the melting peak of DSC of 120 to 150 ° C. ).
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| JP5224840B2 (en) * | 2008-02-08 | 2013-07-03 | 三井化学株式会社 | Gas permeable film |
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