JP2004017615A - Polypropylene-based laminated film, its production method and packaging material - Google Patents
Polypropylene-based laminated film, its production method and packaging material Download PDFInfo
- Publication number
- JP2004017615A JP2004017615A JP2002179828A JP2002179828A JP2004017615A JP 2004017615 A JP2004017615 A JP 2004017615A JP 2002179828 A JP2002179828 A JP 2002179828A JP 2002179828 A JP2002179828 A JP 2002179828A JP 2004017615 A JP2004017615 A JP 2004017615A
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- JP
- Japan
- Prior art keywords
- polypropylene
- laminated film
- layer
- based laminated
- resin
- 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.)
- Granted
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 138
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 133
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 133
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000005022 packaging material Substances 0.000 title claims description 15
- 239000010410 layer Substances 0.000 claims abstract description 105
- 229920005989 resin Polymers 0.000 claims abstract description 98
- 239000011347 resin Substances 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000012792 core layer Substances 0.000 claims abstract description 51
- 239000003208 petroleum Substances 0.000 claims abstract description 35
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 230000009477 glass transition Effects 0.000 claims abstract description 8
- 230000005540 biological transmission Effects 0.000 claims abstract description 6
- 239000011247 coating layer Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052717 sulfur Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 150000003505 terpenes Chemical class 0.000 claims description 20
- 235000007586 terpenes Nutrition 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 12
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 10
- 239000002216 antistatic agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003125 aqueous solvent Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002734 clay mineral Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000005001 laminate film Substances 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 abstract description 53
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 10
- 238000010586 diagram Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000903 blocking effect Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000003475 lamination Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920005673 polypropylene based resin Polymers 0.000 description 8
- 235000013305 food Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000002981 blocking agent Substances 0.000 description 6
- 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 6
- 230000001771 impaired effect Effects 0.000 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
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- 230000000694 effects Effects 0.000 description 5
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- 239000003112 inhibitor Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000005026 oriented polypropylene 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
- 239000000654 additive Substances 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
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- 238000007639 printing Methods 0.000 description 3
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- 239000002344 surface layer Substances 0.000 description 3
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
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- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 239000011229 interlayer Substances 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
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
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- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
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Abstract
【課題】ポリプロピレン系フィルムの優れた特性を維持しつつ、水蒸気バリア性と酸素ガスバリア性を改善したポリプロピレン系積層フィルムを提供すること。
【解決手段】結晶性ポリプロピレン７５〜９４重量％と石油樹脂等２５〜６重量％を含むコア層（Ｃ）と、コア層（Ｃ）の裏面に共重合型のポリプロピレンを含むスキン層（Ｓ）を有する少なくとも二層の積層フィルムであって、コア層（Ｃ）中の結晶性ポリプロピレンは、融点が１６０℃以上、アイソタクチック指数が９７％以上であり、一方、石油樹脂等は、ガラス転移温度が６０℃以上であり、さらに、積層フィルムの水蒸気透過度と厚みの積は、７５ｇ・μｍ／（ｍ２・２４ｈ）以下であり、かつ積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係（Ｒ）が特定の式（１）を満足することを特徴とするポリプロピレン系積層フィルム等を提供した。
【選択図】 なしAn object of the present invention is to provide a polypropylene-based laminated film having improved water vapor barrier properties and oxygen gas barrier properties while maintaining excellent properties of the polypropylene-based films.
A core layer (C) containing 75 to 94% by weight of crystalline polypropylene and 25 to 6% by weight of petroleum resin and the like, and a skin layer (S) containing copolymerized polypropylene on the back surface of the core layer (C) Wherein the crystalline polypropylene in the core layer (C) has a melting point of 160 ° C. or more and an isotactic index of 97% or more, while a petroleum resin or the like has a glass transition The temperature is 60 ° C. or more, and the product of the water vapor transmission rate and the thickness of the laminated film is 75 g · μm / (m 2 · 24 h) or less, and the crystallinity (X c ) of the laminated film is A polypropylene-based laminated film or the like characterized in that the relationship (R) between the partial density (d a ) and the degree of orientation (F) satisfies the specific formula (1).
[Selection diagram] None
Description
【０００１】
【発明の属する技術分野】
本発明は、水蒸気バリア性とガスバリア性に優れたポリプロピレン系積層フィルム、その製造方法及び包装材に関し、更に詳しくは、防湿性、酸素ガスバリア性がよく、食品包装材料等として適しているポリプロピレン系積層フィルム、その製造方法及びそれを用いる包装材に関する。
【０００２】
【従来の技術】
ポリプロピレン系フィルムは、優れた透明性、光沢性等の光学特性、引張特性、ヤング率に代表される機械特性、実質上の無毒性及び無臭性等の特性を備えているため、特に食品用の包装材料として広く用いられている。食品用の包装材料として適用するとき、食品の種類によっては、吸湿を防止する防湿性と乾燥（脱湿）を防止する耐脱湿性の観点から水蒸気バリア性を具備することが要求される場合があるが、ポリプロピレン系フィルムに対して、ポリビニルアルコール系重合体単独、エチレン−ビニルアルコール系重合体、シロキサン系重合体をコーティングする方法では、酸素ガスバリア性は付与されるものの、水蒸気バリア性はほとんど向上しない。また、アルミやシリカ等の金属又は金属酸化物を蒸着する方法は、水蒸気バリア性を改善することはできるが、フィルムを包装材として用いた場合に中身が見えないし、一方、透明蒸着ポリエチレンテレフタレート（ＰＥＴ）では、中身が見えるものの加工時にクラックを発生し、バリア劣化を起こす可能性があり、二軸延伸ポリプロピレン（ＯＰＰ）ベースで高い水蒸気バリア性を具備したものが望まれている。
【０００３】
ポリプロピレン樹脂に石油樹脂およびテルペン樹脂を添加すると、ヤング率が高くなったり、防湿性が向上することが知られている。例えば、特開昭５８−２１３０３７号公報や特開昭６０−２１０６４７号公報には、水蒸気バリア性が改良されたポリプロピレンフィルムが開示されているが、これらはいずれもテルペン樹脂又は石油樹脂を添加することのみによって水蒸気バリア性を向上させている。これらの技術では、テルペン樹脂や石油樹脂が表面にブリードして透明性が悪化したり、ラミネート強度、印刷インキのにじみ、外観や触感不良を起こすという不具合があった。さらに、石油樹脂やテルペン樹脂がポリプロピレンおよび帯電防止剤との相溶性に優れ、低軟化点であるため、これらを添加したフイルムは熱寸法安定性に劣り、また帯電防止剤の効果の発現性に劣るために加工時の工程安定性に劣るという問題もあった。
【０００４】
また、内容物保護性としての各種ガスバリア性は、食品の保存性を左右する大切な性質であり、一般プラスチック材料の弱点でもある。食品の変質要因としては、酸素、光、熱、水分等があげられ、とりわけ酸素は、その起因物質として重要である。バリア材は、酸素を有効に遮断すると同時にガス充填や真空包装などの食品の変質を制御する手段にとってもなくてはならない材料である。
ガスバリア性を有するバリア性フィルムとして、ポリ塩化ビニリデン系樹脂（ＰＶＤＣ）やポリビニルアルコールをコートした透明ポリプロピレンフィルム、シリカやアルミナなどを透明蒸着したポリエステルフィルムなどが数多く使用されてきた。例えば、特開昭６４−０４３５５４号公報には、エチレン／ビニルアルコール共重合体のメタノール水溶液に、平均長さ７μｍで、アスペクト比１４０のマイカを添加し、これを冷水中に注入して沈殿させ、濾過、乾燥し、ペレットとし、次いでフィルムを得る方法が記載されている。
しかし、ガスバリア性の樹脂をコーティングして、さらに防湿性を付与させようとしたときに、コーティング後の乾燥時の熱でフイルムが収縮してコーティング樹脂層に亀裂が入ったり、またポリプロピレンフイルムとの界面接着力が低下して、防湿性が向上しないという問題があった。また、これら従来の技術において得られるフィルムは、ガスバリア性について未だ充分なものではないという問題があった。
【０００５】
【発明が解決しようとする課題】
従って、本発明の目的は、ポリプロピレン系フィルムの優れた特性を維持しつつ、水蒸気バリア性と酸素ガスバリア性を改善したポリプロピレン系積層フィルムを提供することにある。なお、本発明において「フィルム」は、実質的に二次元的構造を有する「シート」も含む。
【０００６】
【課題を解決するための手段】
本発明者らは、前記目的を達成するために、積層フィルムのコア層（基材層）に、石油樹脂やテルペン樹脂を添加した結晶化度の高いポリプロピレン系樹脂を用い、コア層の少なくとも一面のスキン層（表面層）に、共重合型のポリプロピレン系樹脂を用い、或いはさらに、コロナ放電処理したスキン層に、塗布層としてポリビニルアルコールなどを積層したポリプロピレン系積層フィルムにおいて、水蒸気バリア性を改善すべく、鋭意種々検討した結果、塗布されていない積層フィルムの水蒸気透過度と厚みの積は、７５ｇ・μｍ／（ｍ２・２４ｈ）以下がよいこと、かつ、水蒸気バリア性は、積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の３者の関係パラメータ（Ｒ）に影響され、さらに、その関係パラメータ（Ｒ）を特定範囲にすることにより、積層フィルムの水蒸気透過度と成形性を適性にすることができることを見出し、本発明を完成するに至ったものである。
【０００７】
すなわち、本発明の第１の発明によれば、結晶性ポリプロピレン７５〜９４重量％と石油樹脂又はテルペン樹脂の少なくとも１種の樹脂２５〜５重量％を含むコア層（Ｃ）と、コア層（Ｃ）の裏面に共重合型のポリプロピレンを含むスキン層（Ｓ）を有する少なくとも二層の積層フィルムであって、コア層（Ｃ）中の結晶性ポリプロピレンは、融点が１６０℃以上、アイソタクチック指数が９７％以上であり、一方、石油樹脂又はテルペン樹脂は、ガラス転移温度が６０℃以上であり、さらに、積層フィルムの水蒸気透過度と厚みの積は、７５ｇ・μｍ／（ｍ２・２４ｈ）以下であり、かつ積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係（Ｒ）が下記の式（１）を満足することを特徴とするポリプロピレン系積層フィルムが提供される。
式（１）：
０．３６＜［（１−Ｘｃ）／（ｄａ／０．８５４）−０．１２５Ｆ］＜０．４４
【０００８】
本発明の第２の発明によれば、第１の発明において、さらに、コア層（Ｃ）の表面に単独重合型のポリプロピレンを含むスキン層（Ｓ’）を形成し、三層であることを特徴とするポリプロピレン系積層フィルムが提供される。
また、本発明の第３の発明によれば、第１の発明において、裏面側のスキン層（Ｓ）は、エチレンを０．１〜５重量％含有するランダム共重合型のポリプロピレンであることを特徴とするポリプロピレン系積層フィルムが提供される。
【０００９】
本発明の第４の発明によれば、第１〜３のいずれかの発明において、スキン層（Ｓ又はＳ’）の厚みは、１．５μｍ以下であることを特徴とするポリプロピレン系積層フィルムが提供される。
また、本発明の第５の発明によれば、第１〜４のいずれかの発明において、スキン層（Ｓ又はＳ’）には、ブロッキング防止剤として、シリカ又はポリメタクリル酸メチル（ＰＭＭＡ）を１００〜４０００ｐｐｍ配合することを特徴とするポリプロピレン系積層フィルムが提供される。
さらに、本発明の第６の発明によれば、第１の発明において、コア層（Ｃ）には、ブロッキング防止剤又は帯電防止剤を配合しないことを特徴とするポリプロピレン系積層フィルムが提供される。
【００１０】
本発明の第７の発明によれば、第１の発明において、表面処理を施した裏面側のスキン層（Ｓ）に、塗布層（Ｂ）としてポリビニルアルコール又はポリビニルアルコールと無機層状化合物の混合物を形成することを特徴とするポリプロピレン系積層フィルムが提供される。
また、本発明の第８の発明によれば、第７の発明において、無機層状化合物は、水溶媒に膨潤又はへき開する粘土鉱物であることを特徴とするポリプロピレン系積層フィルムが提供される。
さらに、本発明の第９の発明によれば、第７の発明において、無機層状化合物（ａ）とポリビニルアルコール（ｂ）の混合重量比（ａ／ｂ）は、１５／８５〜２５／７５であることを特徴とするポリプロピレン系積層フィルムが提供される。
【００１１】
また、本発明の第１０の発明によれば、第７の発明において、全厚みは、４０μｍ以下であることを特徴とするポリプロピレン系積層フィルムが提供される。さらに、本発明の第１１の発明によれば、第１〜１０のいずれかの発明において、ラミネート強度は、１００ｇ／１５ｍｍ幅以上であることを特徴とするポリプロピレン系積層フィルムが提供される。
【００１２】
一方、本発明の第１２の発明によれば、表面処理を施した裏面側のスキン層（Ｓ）に塗布層（Ｂ）の形成は、溶媒に溶解又は分散して塗布液とした塗布層（Ｂ）の構成素材を、スキン層（Ｓ）の表面に塗布することにより行われることを特徴とする第７の発明のポリプロピレン系積層フィルムの製造方法が提供される。また、本発明の第１３の発明によれば、無機層状化合物とポリビニルアルコールとの混合は、水溶媒に膨潤又はへき開した状態での無機層状化合物をポリビニルアルコールへ高圧分散法を用いて分散させることにより行われることを特徴とする第７〜９のいずれかの発明のポリプロピレン系積層フィルムの製造方法が提供される。
さらに、本発明の第１４の発明によれば、ポリプロピレン系積層フィルムの製造工程において、３０〜５５℃で１２時間以上の熱処理が施されることを特徴とする第１〜１１のいずれかの発明のポリプロピレン系積層フィルムの製造方法が提供される。
【００１３】
本発明の第１５の発明によれば、第１〜１１のいずれかの発明のポリプロピレン系積層フィルムを使用することを特徴とする包装材が提供される。
【００１４】
本発明は、上記した如く、結晶性ポリプロピレン７５〜９４重量％と石油樹脂又はテルペン樹脂の少なくとも１種の樹脂２５〜６重量％を含むコア層（Ｃ）と、コア層（Ｃ）の裏面に共重合型のポリプロピレンを含むスキン層（Ｓ）を有する少なくとも二層の積層フィルム、或いはさらに、ポリビニルアルコール又はポリビニルアルコールと無機層状化合物の混合物である塗布層（Ｂ）を有することを特徴とする水蒸気バリア性に優れたポリプロピレン系積層フィルムに係るものであるが、その好ましい態様としては、次のものが包含される。
（１）本発明の第５の発明において、裏面側のスキン層（Ｓ）に、ブロッキング防止剤として、ポリメタクリル酸メチル（ＰＭＭＡ）を１００〜４０００ｐｐｍ含有することを特徴とするポリプロピレン系積層フィルム。
（２）本発明の第６の発明において、表面側のスキン層（Ｓ’）に、ブロッキング防止剤として、シリカを１００〜４０００ｐｐｍ含有することを特徴とするポリプロピレン系積層フィルム。
（３）本発明の第５の発明において、スキン層（Ｓ又はＳ’）には、帯電防止剤と有機系滑剤（粒子型を除く）を配合しないことを特徴とするポリプロピレン系積層フィルム。
【００１５】
【発明の実施の形態】
以下、本発明のポリプロピレン系積層フィルムについて、詳細に説明する。
本発明のポリプロピレン系積層フィルムは、結晶性ポリプロピレン７５〜９４重量％と石油樹脂又はテルペン樹脂の少なくとも１種の樹脂２５〜６重量％を含むコア層（Ｃ）と、コア層（Ｃ）の裏面に共重合型のポリプロピレンを含むスキン層（Ｓ）を有する少なくとも二層の積層フィルムであって、コア層（Ｃ）中の結晶性ポリプロピレンは、融点が１６０℃以上、アイソタクチック指数が９７％以上であり、一方、石油樹脂又はテルペン樹脂は、ガラス転移温度が６０℃以上であり、さらに、積層フィルムの水蒸気透過度と厚みの積は、７５ｇ・μｍ／（ｍ２・２４ｈ）以下であり、かつ積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係パラメータ（Ｒ）が下記の式（１）を満足するものである。
式（１）：
０．３６＜［（１−Ｘｃ）／（ｄａ／０．８５４）−０．１２５Ｆ］＜０．４４
【００１６】
上記の式（１）に係るポリプロピレン系積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係パラメータ（Ｒ）は、ポリプロピレン系積層フィルムの水蒸気バリア性と成形性の指標となるものである。
積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係パラメータ（Ｒ）が、０．３６＜Ｒ＜０．４４を満足することにより、積層フィルムの水蒸気バリア性と成形性の両性能をバランスよく、適性なものにすることができる。
【００１７】
本発明においては、結晶化度（Ｘｃ）は、走査型熱量計（パーキンエルマー社製 ＤＳＣ−７Ｃ）を用い、昇温速度２０℃／分で測定して求めた融解熱より、ポリプロピレンの結晶融解熱を２０９Ｊ／ｇとして、結晶化度を算出したものを用いている。尚、この結晶化度の算出には、添加した石油樹脂などの重量を除くポリプロピレンに対する割合として求めた。
また、非晶部密度（ｄａ）は、（１／ｄ）＝（１−Ｘｃ）／ｄａ＋（Ｘｃ／ｄｃ）の関係式から算出したものを用いている。ここでｄは、ニ軸延伸ポリプロピレン（ＯＰＰ）の平均密度であり、その測定は、島津製作所社製のガス置換式密度計（アキュピック１３３０）で１ｃｍ２のセルを用い２５℃で行った。また、Ｘｃは、上記の走査型熱量計で求めた結晶化度であり、ｄｃは、結晶部密度であり、０．９４３ｇ／ｍ３とした。
さらに、配向度（Ｆ）は、Ｆ＝〔ｎｘ−（ｎｙ＋ｎｚ）／２〕／０．０４の関係式から算出したものを用いている。ここで、ポリプロピレン（ＰＰ）の固有複屈折を０．０４とし、また、ｎｘ、ｎｙ、ｎｚは、ｘ（ＴＤ方向に近い主屈折率の軸）、ｙ（ＭＤ方向に近い主屈折率の軸）、ｚ（厚み方向に近い主屈折率の軸）方向の屈折率であり、その測定は、王子計測機器株式会社製の自動複屈折計（ＫＯＢＲＡ−２１ＨＤ）を用いて行い、その屈折率の算出ではフィルムの平均屈折率を１．５１とした。
【００１８】
この関係パラメータの値（Ｒ）が小さいと、積層フィルムの水蒸気バリア性がよくなり、すなわち水蒸気透過度が小さくなる。言い替えると、関係パラメータの値（Ｒ）が小さいほど、水蒸気透過度が小さくなって、水蒸気バリア性を向上させることができるが、関係パラメータの値（Ｒ）が小さすぎると、例えば、結晶化度（Ｘｃ）や非晶部密度（ｄａ）が大きくなりすぎると、積層フィルムの成形性に問題が生じてくる。
すなわち、本発明のポリプロピレン系積層フィルムの構成において、積層フィルムの結晶化度（Ｘｃ）や非晶部密度（ｄａ）が大きい値をとることは、一義的ではないが、例えば、コア層の石油樹脂又はテルペン樹脂の配合量が多いことを意味し、石油樹脂などの配合量が多すぎると、水蒸気バリア性が良好となるものの、結晶化度（Ｘｃ）や非晶部密度（ｄａ）が大きくなりすぎ、その結果、関係パラメータの値（Ｒ）が小さくなりすぎて、積層フィルムの成形性に問題が生じ、成形の際には、発煙が多くなったり、耐熱性の脆さの点で配向が掛け難くなるなどの問題が生じる恐れがある。
このようにして、本発明のポリプロピレン系積層フィルムは、積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係パラメータ（Ｒ）が、０．３６＜Ｒ＜０．４４の適性な範囲を満足することにより、水蒸気バリア性と成形性の両性能をバランスよく、適性なものにすることができる。
【００１９】
また、本発明のポリプロピレン系積層フィルムは、結晶性ポリプロピレン７５〜９４重量％と石油樹脂又はテルペン樹脂の少なくとも１種の樹脂２５〜６重量％を含むコア層（Ｃ）と、コア層（Ｃ）の裏面に共重合型のポリプロピレンを含むスキン層（Ｓ）を有する少なくとも二層の積層フィルムであって、積層フィルムの水蒸気透過度と厚みの積は、７５ｇ・μｍ／（ｍ２・２４ｈ）以下であることを特徴とする。
ポリプロピレン系積層フィルムにおいて、防湿性の指標として、その水蒸気透過度がフィルム厚さに逆比例するために、積層フィルムの水蒸気透過度と厚みの積で表したものであり、その水蒸気透過度としては、例えば、フィルム厚さが２０μｍのときに、３．７５ｇ／（ｍ２・２４ｈ）以下であり、好ましくは３ｇ／（ｍ２・２４ｈ）以下であり、さらに好ましくは２．５ｇ／（ｍ２・２４ｈ）以下である。
【００２０】
以下、項目毎に説明する。
１．コア層（Ｃ）
コア層（基材層）は、ポリプロピレン系樹脂又はポリプロピレン系樹脂を好ましくは７０重量％以上、より好ましくは８０重量％以上含有する樹脂組成物からなる。ポリプロピレン系樹脂は、高結晶の結晶性ポリプロピレンが好ましい。また、プロピレンと、エチレン、ブテン−１、３−メチルペンテン、４−メチルペンテン等との共重合体でもよいが、プロピレン以外の構成単位の含有率は１重量％以下がよく、好ましくは０．５重量％未満、より好ましくは０．３重量％未満である。
【００２１】
望ましいポリプロピレン系樹脂は、高結晶ポリプロピレン系樹脂であり、防湿性の点から規則性は高い方がよく、すなわち高立体規則性ポリプロピレン樹脂が好ましく、ポリプロピレン系樹脂のアイソタクチック指数は、積層フィルムの特性を損なわない範囲である限り特に制限されないが、好ましくは９７％以上がよく、より好ましくは９９％以上である。一方、アイソタクチック指数が９７％未満では、フィルムの熱収縮率が大きくなって熱寸法安定性に劣るために印刷やコーティングおよびラミネート加工などの二次加工性に劣る。
尚、アイソタクチック指数及びその測定条件としては、対象となる物質をｎ−ヘキサン還流下で３０分抽出後の残留物の重量％を表す。
【００２２】
また、コア層（基材層）に用いられるポリプロピレン系樹脂の融点は、好ましくは１６０℃以上、より好ましくは１６２℃以上である。２３０℃でのメルトフローレート（ＡＳＴＭ Ｄ１２３８、以下ＭＦＲと略す）は、成形のしやすさの点から、好ましくは０．５〜２０ｇ／１０分、より好ましくは１〜４ｇ／１０分である。
【００２３】
コア層には、石油樹脂又はテルペン樹脂から選ばれる１種以上の樹脂を配合することが望ましい。石油樹脂又はテルペン樹脂を含有することにより、本発明のポリプロピレン系積層フィルムの水蒸気に対するバリア性が向上する。
石油樹脂としては、シクロペンタジエン系や高級オレフィン系炭化水素を主原料とする樹脂又はこれらに８０％以上の水添率で水素添加したものを挙げることができる。この石油樹脂は、極性基を含まないものであることが好ましい。このような石油樹脂としては、具体的に、例えば荒川化学製の商品名「アルコンＰ−１２０」、トーネックス社製の商品名「エスコレッツＥ５３２０ＨＣ」が挙げられる。
石油樹脂は、軟化点が１２５℃以上のものが望ましく、また、ガラス転移温度は、６０℃以上が望ましく、６５〜８５℃のものがより望ましい。
【００２４】
テルペン樹脂としては、ピネン、カレン、ミルセン、オシメン、リモネン、テルピノレン、テルピネン、サビネン、トリシクレン、ピサボレン、ジンギペレン、サンタレン、カンホレン、ミレン、トタレン等又はこれらに８０％以上の水添率で水素添加したものを挙げることができる。これらのテルペン樹脂は、極性基を含まないものであることが好ましい。
【００２５】
コア層中における石油樹脂又はテルペン樹脂の少なくとも１種の樹脂の含有量は、６〜２５重量％、好ましくは６〜２０重量％、より好ましくは１０〜２０重量％である。すなわち、結晶性ポリプロピレンの含有量は、９４〜７５重量％、好ましくは９４〜８０重量％、より好ましくは９０〜８０重量％である。
石油樹脂などの含有量が６重量％未満であると、コア層に高結晶性ポリプロピレンを使用しているために、延伸性が悪く、破断が起こり易くなったり、厚薄精度が悪くなる。さらに、水蒸気バリア性に影響を及ぼす配向がかかり難くなり、得られたフィルムの水蒸気バリア性（水蒸気透過度）は、フィルム厚さ２０μｍのときに、４ｇ／（ｍ２・２４ｈ）を超えるものとなり、悪化する。
一方、石油樹脂などの含有量が２５重量％を超えると、押出加工時に発煙が多く発生し、成形を行う上でいろいろと不具合が発生するようになる。さらに、延伸後のフィルムにおいても、石油樹脂などがブリードアウトし易くなることにより、フィルムのすべり性の阻害やブロッキング等の悪影響も懸念されるようになる。
【００２６】
コア層には、本発明の目的を損なわない限り、さらに紫外線吸収剤、帯電防止剤、結晶核成長剤、スチレン系樹脂、ジシクロペンタジエン樹脂、クマロニンデン樹脂等のクマロン樹脂、フェノール樹脂、ロジンとその誘導体やそれらの水添樹脂等の炭化水素系重合体、可塑剤、充填剤を配合することができる。なお、フィルムを、後加工の工程に供する場合には、これらの添加剤のブリード等によってコーティング層、蒸着層、ラミネート層、インキ層等との適性を損なわないように条件設定する必要がある。また、コア層には、ラミネート強度の点から帯電防止剤と、透明性の点からブロッキング防止剤を含有しないことが望ましい。
【００２７】
また、コア層は単層であってもよく、２層以上のポリプロピレン系樹脂層が積層されたものであってもよい。コア層の厚みは、特に制限されず、好ましくは１〜１００μｍ、より好ましくは５〜５０μｍ、さらに好ましくは１５〜４０μｍである。
【００２８】
２．スキン層（Ｓ又はＳ’）
スキン層（表面層）（Ｓ又はＳ’）は、主としてコア層に含有された石油樹脂又はテルペン樹脂のブリードアウトを防止する目的、及び密着力向上、すべり性向上のためであって、コア層と同じポリプロピレン系樹脂又はポリプロピレン系樹脂を含む樹脂組成物からなるものである。スキン層を構成するポリプロピレン系樹脂は、望ましい態様として、コア層（Ｃ）の表面処理される裏面側のスキン層（Ｓ）には、エチレンを０．１〜５重量％含有するランダム共重合型のポリプロピレンを使用するが、加工適正の観点から好ましくはエチレン含量が０．５〜４％、さらに好ましくは１〜３％である。ここでいう加工適正とは、塗布時のロールとのすべり性を指し、エチレン含量が多くなると高温時のすべり性が悪くなり、加工適正が低下することをいう。
そして、コア層（Ｃ）の表面側のスキン層（Ｓ’）には、単独重合型のポリプロピレン、すなわちホモポリプロピレンである。但し、０．５％以下のエチレンを含有するプロピレンについても、ホモポリプロピレンの範疇と考える。
【００２９】
上記のエチレンを０．１〜５重量％含有するランダム共重合型のポリプロピレンとしては、例えばエチレンとプロピレンのランダムコポリマー、エチレン−プロピレン−ブチレンターポリマーなどが挙げられ、特にエチレンとプロピレンのランダムコポリマーが好ましい。さらに、このようなポリプロピレンランダムコポリマーのコモノマー成分としては、エチレン、１−ブテン、２−ブテン、１−ペンテン、１−ヘキセン、３−メチルペンテン、４−メチルペンテンなどの炭素数２〜６程度のアルケン等が挙げられる。さらに好ましくは、プロピレンをポリプロピレン系コポリマー全体の８４重量％以上、特に好ましくは８４〜９９重量％含み、エチレンを０．１〜３重量％含有し、エチレンおよび／またはブテンをポリプロピレン系コポリマー全体の１６重量％以下、特に好ましくは１６〜１重量％含むコポリマーであるのがよい。なお、スキン層（Ｓ）を構成するポリプロピレン系コポリマーには、本発明の作用を阻害しない範囲で、添加剤等の他の成分を含有していても良い。
【００３０】
スキン層（Ｓ又はＳ’）に用いられるポリプロピレン系樹脂のＭＦＲは、３ｇ／１０分以上、好ましくは３〜２０ｇ／１０分、さらに好ましくは３〜１６ｇ／１０分である。なお、スキン層を構成するポリプロピレン系樹脂のＭＦＲは、コア層を構成するポリプロピレン系樹脂のＭＦＲよりも大きくする方が、メルトフラクチャーを起こし難くなるので好ましい。
【００３１】
コア層及びスキン層を構成するポリプロピレン系樹脂には、酸化防止剤を配合することができる。
酸化防止剤としては、フェノール系、リン系、硫黄系等が挙げられるが、フェノール系としては２，６−ジ−ｔ−ブチル−ｐ−クレゾール（ＢＨＴ）、テトラキス〔メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕メタン（例えば、日本チバガイギー社、イルガノックス１０１０）等が好ましい。
【００３２】
スキン層を構成するポリプロピレン系樹脂には、ブロッキング防止剤（アンチブロッキング剤）を配合することが望ましい。ブロッキング防止剤としては、シリカ、アルミナ、合成ゼオライト、カオリン、タルク、酸化亜鉛、酸化マグネシウム、酸化ジルコニウム、酸化チタン、水酸化アルミニウム、石英粉、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム等の無機系微粉末、ポリエステル、ナイロン、ポリカーボネート、ポリエーテルスルホン、ポリエーテルイミド、ポリフェニレンスルフィド、ポリエーテルエーテルケトン、ポリアミドイミド等の熱可塑性樹脂、架橋アクリル樹脂、架橋メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、アミノ樹脂、フラン樹脂、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ビニルエステル樹脂、ジアリルフタレート樹脂、ポリイミド等の熱硬化性樹脂等から選ばれる１種以上が挙げられる。中でも、適切にすべり性を付与する観点から、シリカやＰＭＭＡ（ポリメタクリル酸メチル）が好ましく、好ましい実施態様として、コア層（Ｃ）の裏面側のスキン層（Ｓ）には、ＰＭＭＡが、一方、表面側のスキン層（Ｓ’）には、シリカが挙げられる。なお、ブロッキング防止剤は、フィルム成形時に加えられる熱によっても変形することなく形状を保持するために、フィルム成形時の温度より高い融点又は軟化点を有するものが好ましい。
【００３３】
ブロッキング防止剤は、真球状でも不定形でもよいが、真球状のブロッキング防止剤を用いると、透明性を低下させることなく、高い耐ブロッキング性を付与できるため好ましい。シリカなどのブロッキング防止剤の平均粒子径は、表面層の厚みに応じて、耐ブロッキング性、すべり性、透明性を損なわない範囲で選択でき、好ましくは０．１〜７．５μｍ、より好ましくは０．５〜５μｍ、さらに好ましくは１〜４μｍである。
また、耐ブロッキング性やすべり性を良くするために、スキン層を構成するポリプロピレン系樹脂には、ブロッキング防止剤と類似の無機系滑剤や粒子型の有機系滑剤などを配合してもよい。
【００３４】
ブロッキング防止剤の含有量は、ポリプロピレン系樹脂１００重量部に対して、好ましくは０．０１〜０．５重量部がよく、より好ましくは０．０２〜０．４重量部、さらに好ましくは０．０３〜０．３重量部である。ブロッキング防止剤の含有量が０．０１重量部以上であると巻取時におけるフィルムのブロッキングを防止でき、また、０．５重量部以下であると透明性の低下を防止できる。
【００３５】
また、コア層（Ｃ）に対する表面処理される裏面側のスキン層（Ｓ）のラミネート強度は、１５０ｇ／１５ｍｍ幅以上あることが望ましい。
【００３６】
さらに、ポリプロピレン系積層フィルムの裏面側のスキン層（Ｓ）には、通常、表面処理が施され、その表面処理としては、慣用の表面処理、例えばコロナ放電処理、火炎処理、プラズマ処理、オゾンや紫外線照射処理等を採用できるが、コロナ放電処理が好ましい。表面処理は、フィルムの延伸処理に先立って行ってもよいが、延伸後に行うことが望ましい。
【００３７】
本発明のポリプロピレン系積層フィルムは、スキン層の上にコーティング層、蒸着層、ラミネート層、インキ層等を形成する場合には、スキン層には前記（すなわち酸化防止剤とブロッキング防止剤）以外の成分を含まないことが好ましいが、すなわち、塗布層の密着強度を安定化するために帯電防止剤や有機系滑剤（粒子型を除く）を配合しないことが望ましいが、層間の密着性が損なわれない範囲であれば、紫外線吸収剤、帯電防止剤、可塑剤、ワックス等を少量含んでいてもよい。また、このような表面処理は、密着性を向上させるため、好ましくは３６ｄｙｎｅ／ｃｍ以上、より好ましくは３７〜４５ｄｙｎｅ／ｃｍ、さらに好ましくは３８〜４２ｄｙｎｅ／ｃｍの表面張力となるように行うことが望ましい。
【００３８】
３．塗布層（Ｂ）
本発明のポリプロピレン系積層フィルムは、コア層（Ｃ）の表面処理される裏面側のスキン層（Ｓ）に、所望によりアンカー層無しに或いはアンカー層を介して、ポリビニルアルコール又はポリビニルアルコールと無機層状化合物の混合物からなる塗布層（バリア層）（Ｂ）を少なくとも１層有することができる。
【００３９】
所望により、アンカー層を介する場合、アンカー層としては、密着性を高めるものであれば特に限定されず、例えばウレタン系、ポリエチレンイミン系、ポリブタジエン系、ポリエステル系等の公知あるいは慣用のアンカーコート剤などを使用できる。また、これらの中でも、接着強度及び耐水性の観点から、ポリエチレンイミン系、ウレタン系、ポリエステル系のアンカーコート剤が好ましい。なお、アンカー層には、本発明の作用を阻害しない範囲で、添加剤等の他の成分を含有していても良い。
【００４０】
また、アンカー層の厚みも特に限定されず、スキン層（Ｓ）や塗布層（Ｂ）の構成、所望の接着強度等により適宜設定すればよいが、好ましくは、乾燥時の厚みで０．０５〜１ｇ／ｍ２となるようにするのがよい。
【００４１】
アンカー層は、スキン層（Ｓ）の形成後、例えば、必要に応じて溶媒に溶解あるいは分散して塗布液としたアンカー層の構成素材を、スキン層（Ｓ）の表面に塗布する方法により形成できる。上記塗布液は、溶媒が水性あるいは有機溶剤のいずれであっても良い。なお、アンカー層の形成時には、スキン層（Ｓ）の表面に、慣用の表面処理、例えば、コロナ放電処理、火炎処理、プラズマ処理、紫外線照射処理、電子線照射処理などを施すことが望ましい。
【００４２】
本発明のポリプロピレン系積層フィルムは、表面処理面側のスキン層（Ｓ）に対する塗布層（Ｂ）の密着強度（ラミネート強度）が３００ｇ／１５ｍｍ幅以上であることが望ましい。密着強度が３００ｇ／１５ｍｍ幅未満であると、塗布層が剥離しやすく、本発明のポリプロピレン系積層フィルムを用いた包装材の形成時などに、塗布層側に他のフィルムを積層した場合のラミネート強度が低下したり、塗布層側に他のヒートシール性フィルムを積層して封筒貼り形態などにヒートシールした場合のヒートシール強度が低下したりする。
また、本発明のポリプロピレン系積層フィルムは、スキン層（Ｓ）に塗布層（Ｂ）が積層された後のラミネート強度が、１００ｇ／１５ｍｍ幅以上であることが望ましい。
【００４３】
本発明において、塗布層（Ｂ）として、ポリビニルアルコール又はポリビニルアルコールと無機層状化合物の混合物を用いることができる。
上記のポリビニルアルコールとしては、ビニルアルコールを主たるモノマー成分とするビニルアルコール共重合体が挙げられ、このビニルアルコール共重合体を使用することにより、塗布層は、酸素ガスへのバリア性に優れる。好ましくは、主たるモノマー成分であるビニルアルコールが、ビニルアルコール共重合体中の全モノマー成分に対し７０〜９９モル％、さらに好ましくは８０〜９８モル％であるのがよい。上記ビニルアルコール以外のモノマー成分としては、酢酸ビニルやエチレンが挙げられる。なお、塗布層には、本発明の作用を阻害しない範囲で、添加剤等の他の成分を含有していても良い。
【００４４】
また、上記の無機層状化合物は、単位結晶層が互いに積み重なって層状構造を有している無機化合物であって、無機層状化合物の具体例としては、グラファイト、リン酸塩系誘導体型化合物（リン酸ジルコニウム系化合物）、カルコゲン化物〔ＩＶ族（Ｔｉ、Ｚｒ、Ｈｆ）、Ｖ族（Ｖ、Ｎｂ、Ｔａ）およびＶＩ族（Ｍｏ、Ｗ）のジカルコゲン化物であり、式ＭＸ２で表わされる。ここで、Ｘはカルコゲン（Ｓ、Ｓｅ、Ｔｅ）を示す。〕、粘土系鉱物などを挙げることができる。中でも、溶媒に膨潤又はへき開する無機層状化合物が好ましく用いられる。
【００４５】
溶媒に膨潤又はへき開する無機層状化合物としては、溶媒に膨潤又はへき開性を有する粘土鉱物が好ましく用いることができる。粘土系鉱物は、一般に、シリカの四面体層の上部に、アルミニウムやマグネシウム等を中心金属にした８面体層を有する２層構造よりなるタイプと、シリカの４面体層が、アルミニウムやマグネシウム等を中心金属にした８面体層を両側から挟んだ３層構造よりなるタイプに分類される。前者としてはカオリナイト族、アンチゴライト族等を挙げることができ、後者としては層間カチオンの数によってスメクタイト族、バーミキュライト族、マイカ族等を挙げることができる。具体的には、カオリナイト、ディッカイト、ナクライト、ハロイサイト、アンチゴライト、クリソタイル、パイロフィライト、モンモリロナイト、ヘクトライト、テトラシリリックマイカ、ナトリウムテニオライト、白雲母、マーガライト、タルク、バーミキュライト、金雲母、ザンソフィライト、緑泥石等をあげることができる。これらの鉱物は、天然のクレー中より産するもの、天然品より抽出したものの層間イオン交換処理を行った半合成品、及び天然品と類似構造を有するごとく合成した純合成品などが挙げられる。中でも、溶媒、例えば水に膨潤またはへき開する層状珪酸塩が好ましく用いられ、純度が９９％以上である天然物のモンモリロナイトなどが挙げられる。
【００４６】
溶媒としては、無機層状化合物の密度より小さい密度を有する溶媒を用いる。無機層状化合物が天然の膨潤性粘土鉱物である場合、該溶媒としては、水を用いることが好ましい。他の溶媒として、例えばメタノールやエタノ−ル等のアルコール類が挙げられる。
【００４７】
無機層状化合物の大きさとしては、フィルムとした際の製膜性ないし成形性の点から、粒径が５μｍ以下であることが好ましい。さらに、透明性の点からは、粒径が３μｍ以下であることが好ましい。本発明のポリプロピレン系積層フィルムを透明性が重視される用途（例えば食品用途）に用いる場合には、この粒径は１μｍ以下であることが、特に好ましい。
【００４８】
ポリビニルアルコールと無機層状化合物の混合方法としては、均一に混合、分散する限り特に限定されないが、例えば、先ず、溶媒としての水に膨潤又はへき開した状態での無機層状化合物を作製し、次に、そのような状態の無機層状化合物を水に溶解させたポリビニルアルコール溶液へ高圧分散法にて、例えば高圧ホモジナイザーを用いて分散させることにより行われる方法などが挙げられる。
その溶媒としての水に膨潤またはへき開した状態での無機層状化合物の作製方法としては、水に混合分散させた無機層状化合物を高圧ホモジナイザーを用いて５００ｋｇｆ／ｃｍ２以上の圧力条件下で２パス以上処理させ、水溶媒に膨潤またはへき開した分散状態にする方法などが挙げられる。
さらに、無機層状化合物（ａ）とポリビニルアルコール（ｂ）の混合重量比（ａ／ｂ）は、１５／８５〜２５／７５であることが望ましい。
【００４９】
塗布層（Ｂ）は、スキン層（Ｓ）の形成後、例えば、必要に応じて溶媒に溶解あるいは分散して塗布液とした塗布層の構成素材を、スキン層（Ｓ）の表面に塗布する方法により形成できる。上記塗布液は、溶媒が水性あるいは有機溶剤のいずれであっても良いが、好ましくは水あるいは水と親水性溶媒の混合液であるのがよい。
また、塗布層の厚みは、特に限定されず、所望のバリア性等により適宜設定すればよいが、好ましくは０．３〜３μｍ、さらに好ましくは０．３〜２μｍである。
さらに、塗布層を複数有する場合は、塗布層同士の間にアンカー層を有していても良い。
【００５０】
４．ポリプロピレン系積層フィルム（製造方法）
本発明のポリプロピレン系積層フィルムの製造方法は、特に限定されず、通常一般に使用されるフィルムの成形方法および積層方法を使用できる。好ましくは、コア層（Ｃ）、スキン層（Ｓ又はＳ’）および塗布層（Ｂ）を共押出し法により同時に成形するのがよい。例えば、コア層とスキン層の形成に使用する樹脂等を、それぞれ個別の押出機に供給し、樹脂温度２００〜２６０℃の範囲で融解混合させた後、スリット上の口金から共押出し法により積層することにより得られる。尚、各押出機の温度設定は、ＭＦＲ及び融点によりそれぞれ別の温度設定にしても構わない。コア層（Ｃ）或いはスキン層（Ｓ又はＳ’）が多層構成であっても、同様の共押出し法を使用することができる。また、口金から押出された溶融樹脂が接触するチルロールの温度は、２５〜６５℃、好ましくは３０〜６０℃、さらに好ましくは３０〜５５℃に設定すると、シートの冷却が徐冷になり好ましい。また、好ましくは共押出し後、少なくとも一軸方向に延伸、さらに好ましくは二軸方向に延伸するのがよい。二軸延伸条件は、特に制約はないが、逐次二軸延伸が好ましい。逐次二軸延伸の際、縦方向の延伸倍率は４〜７倍、好ましくは４．５〜６倍で、横方向の延伸倍率は７〜１２倍、好ましくは８〜１１倍である。また、横方向の延伸時の予熱温度設定は、出来るだけ低く設定することが好ましく、設定温度範囲は１５０〜１８０℃で、好ましくは１５５〜１７５℃で、フィルムに配向がかかることが望ましい。延伸することにより、水蒸気バリア性発現効果があがる。押出し条件および延伸条件は、使用する各層の素材や厚み、所望の物性等に応じて適宜設定できる。
【００５１】
上述の製造工程において、３０〜５５℃の比較的低温で１２時間以上の熱エージング等の熱処理を施すことにより、積層フィルムの水蒸気バリア性が向上する。
【００５２】
本発明のポリプロピレン系積層フィルムは、フィルムの全厚み（Ｔｆ）が好ましくは４０μｍ以下であり、コア層の厚み（Ｔｃ）は、好ましくは１０〜２５μｍであり、スキン層の厚み（Ｔｓ）（両側にスキン層がある場合はそれらの合計）が好ましくは０．５〜１．５μｍである。また、塗布層の厚み（Ｔｂ）は、前述したように特に限定されず、所望のバリア性等により適宜選定される。
【００５３】
また、本発明のポリプロピレン系積層フィルムのスキン層の厚み（Ｔｓ）と、フィルムの総厚みＴｆとの比（Ｔｓ／Ｔｆ）は、０．０４〜０．６０がよく、好ましくは０．０５〜０．５である。Ｔｓ／Ｔｆが０．０４以上であるとスキン層による防湿性を十分に向上させることができ、また０．６０以下であるとフィルムとしての外観や触感に不具合が生じることもない。
【００５４】
本発明のポリプロピレン系積層フィルムは、単独で包装材として使用可能であるが、例えばヒートシール性を有する無延伸透明ポリプロピレン系樹脂（ＣＰＰ）フィルムや無延伸ポリエチレン系樹脂フィルムなどの他の素材と積層し、包装材として使用することもできる。該包装材の構成や積層方法は特に限定されない。無延伸透明ポリプロピレン系樹脂フィルムや無延伸ポリエチレン系樹脂フィルムは、本発明のポリプロピレン系積層フィルムの塗布層側に積層することにより、両面にヒートシール性を有し、計量で、塗布層の基材との密着性にも優れた包装材を得ることができる。また、本発明のポリプロピレン系積層フィルムには、印刷等により着色処理や画像形成処理を施しても良い。
【００５５】
本発明のポリプロピレン系積層フィルムは、水蒸気バリア性と酸素ガス等のガスバリア性に優れているために、キャンディ、チョコレート、米菓、ビスケット、クッキー等の各種菓子類、海苔等の個別包装及び全体包装用として好適である。
【００５６】
【実施例】
以下、実施例に基づいて本発明を更に詳しく説明するが、本発明は、これらの実施例に限定されるものではない。なお、実施例及び比較例において、各種性状や性能の測定、評価は下記の試験方法により評価した。
【００５７】
（１）フィルムの全厚み（Ｔｆ）
実施例／比較例のポリプロピレン系積層フィルムの全厚み（Ｔｆ）をデジタル厚み計により測定した。
【００５８】
（２）ラミネート強度
実施例／比較例のポリプロピレン系積層フィルムに対し、ラミネート用接着剤（東洋モートン社製、ＴＭ３２９）とラミネート用接着剤（東洋モートン社製、ＣＡＴ−８Ｂ）と酢酸エチルとをそれぞれ重量比で４．８：４．８：１０．４となるように混合したラミネート接着剤を、乾燥後の厚みで２〜２．５ｇ／ｍ２となるように上記フィルムのスキン層又は塗布層表面に塗布し、乾燥後、ラミネート接着剤塗布面と、表面にコロナ処理３８ｄｙｎｅ／ｃｍ以上の処理度）を施した厚さ２０μｍの透明ポリプロピレン系樹脂（ＯＰＰ）フィルムのコロナ処理面とを圧着させた。圧着後２４時間、４０℃、３０％ＲＨの条件下で保存した。接着されたフィルムを、１５ｍｍ幅の短冊状に裁断して試験片を作成し、ＪＩＳ Ｋ ７１２７に準じて、試験片の一方の端部側のポリプロピレン系積層フィルムとＯＰＰフィルムのそれぞれ端部を保持して、ポリプロピレン系積層フィルムとＯＰＰフィルムが剥離する方向に３００ｍｍ／ｍｉｎの速度で引張った時の強度を測定し、密着強度とした。
【００５９】
（３）水蒸気バリア性
水蒸気バリア性は、温度４０℃、相対湿度９０％の条件で、水蒸気過率測定装置（ＰＥＲＭＡＴＲＡＮ Ｗ２００、ＭＯＣＯＮ社製）により水蒸気透過速度を測定、評価した。
【００６０】
（４）酸素ガスバリア性
酸素ガスバリア性は、酸素透過度測定装置（ＯＸ−ＴＲＡＮ２／２０、ＭＯＣＯＮ社製）を用いて、２０℃、６０％ＲＨの条件下での酸素透過率を測定、評価した。
【００６１】
［実施例１］
コア層（Ｃ）として、アイソタクチック指数（Ｉ．Ｉ．）が９９％の結晶性ポリプロピレン（ＭＦＲ：２ｇ／１０分、融点：１６６℃）８５重量％に、ガラス転移温度が７０℃の水添石油樹脂（エスコレッツ５３２０ＨＣ）１５重量％を添加した組成物を用い、また、表面処理面（裏面）側のスキン層（Ｓ）として、エチレン含量が２重量％のランダム共重合型ポリプロピレン（ＭＦＲ：１５ｇ／１０分、融点：１５０℃）に、ブロッキング防止剤としてのポリメタクリル酸メチル（ＰＭＭＡ）を１５００ｐｐｍ添加したものを用いた。さらに、非処理面側のスキン層（Ｓ’）として結晶性プロピレン（ＭＦＲ：８ｇ／１０分、融点：１６０℃）に、ブロッキング防止剤としてシリカを２５００ｐｐｍ添加したものを用いた。コア層樹脂の温度は２５０℃に設定し、両スキン層樹脂については２３０℃に設定し、各押出機からダイ内部へ供給され積層された溶融樹脂が、内部を５５℃の温度が循環しているチルロールに接触、反対面は空気接触する方法で冷却された多層シートを、縦５．５倍、横９．５倍、製膜速度１００ｍ／分で逐次二軸延伸することにより、厚さ２０μｍの積層フィルムを得た。さらに製造工程において、温度４５℃で２４時間の熱エージングを施した。
得られたフィルムの諸物性を評価し、その結果などを表１に示す。
【００６２】
［実施例２］
実施例１と同様の組成で、逐次二軸延伸を行い、３０μｍの厚みのフィルムを得、実施例１と同様に熱エージングを実施した。得られたフィルムの諸物性を評価し、その結果などを表１に示す。
【００６３】
［比較例１］
コア層（Ｃ）として、アイソタクチック指数（Ｉ．Ｉ．）が９９％の結晶性ポリプロピレン（ＭＦＲ：２ｇ／１０分、融点：１６６℃）９５重量％に、ガラス転移温度が７０℃の水添石油樹脂（エスコレッツ５３２０ＨＣ）５重量％を添加すること以外は、実施例１と同条件にて製膜を実施したところ、延伸時に破断が起こり、成形できなかった。その組成を表１に示す。
【００６４】
［比較例２］
コア層（Ｃ）として、アイソタクチック指数（Ｉ．Ｉ．）が９７％の結晶性ポリプロピレン（ＭＦＲ：３ｇ／１０分、融点：１６１℃）９５重量％に、ガラス転移温度が７０℃の水添石油樹脂（エスコレッツ５３２０ＨＣ）５重量％を添加した組成とした以外は、実施例１と同じ条件にて、成形及び熱処理を実施し、厚み２０μｍの二軸延伸フィルムを得た。得られたフィルムの諸物性を評価し、その結果などを表１に示す。
【００６５】
［比較例３］
表面処理面側のスキン層（Ｓ）として、エチレンを含有していないホモポリプロピレンを用いた以外は、比較例１と同じ条件にて、成形及び熱処理を実施し、厚み２０μｍの二軸延伸フィルムを得た。得られたフィルムの諸物性を評価し、その結果などを表１に示す。
【００６６】
［比較例４］
製造工程において、温度４５℃で２時間の熱エージングを施した以外は、実施例１と同じ条件にて、成形及び熱処理を実施し、厚み２０μｍの二軸延伸フィルムを得た。得られたフィルムの諸物性を評価し、その結果などを表１に示す。
【００６７】
［実施例３］
実施例１と同じ条件にて、厚み２０μｍの二軸延伸フィルムを得た後、塗布層（Ｂ）として、ポリビニルアルコール（ＰＶＡ）の水溶液に、無機層状化合物であるモンモリロナイトを高圧ホモジナイザーによる高圧分散法にて分散したもの（ＰＶＡ：モンモリロナイト＝８０：２０重量％）を、厚み１μｍで表面処理面側のスキン層（Ｓ）に塗布、乾燥を実施し、全厚みが２１μｍである積層フィルムを作製した。得られた積層フィルムの諸物性を評価し、その結果などを表１に示す。
【００６８】
［実施例４］
ＰＶＡの水溶液を塗付した以外は、実施例３と同様の条件にて実施し、全厚みが２１μｍである積層フィルムを作製した。得られた積層フィルムの諸物性を評価し、その結果などを表１に示す。
【００６９】
［比較例５］
比較例２と同様にして、厚み２０μｍの二軸延伸フィルムを得た後、塗布層（Ｂ）として、ＰＶＡの水溶液に、無機層状化合物であるモンモリロナイトを高圧ホモジナイザーによる高圧分散法にて分散したもの（ＰＶＡ：モンモリロナイト＝８０：２０重量％）を、厚み１μｍで表面処理面側のスキン層（Ｓ）に塗布、乾燥を実施し、全厚みが２１μｍである積層フィルムを作製した。得られた積層フィルムの諸物性を評価し、その結果などを表１に示す。
【００７０】
【表１】
実施例１、２は、コア層にアイソタクチック指数が９７％以上の結晶性ポリプロピレンと水添石油樹脂の混合物（８５：１５重量％）を用い、また、スキン層にエチレン含量が２重量％のランダム共重合型ポリプロピレンにＰＭＭＡを配合しているため、さらに、積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係（Ｒ）が特定範囲内であるために、水蒸気バリア性とラミネート強度に優れている。一方、比較例１は、コア層として、アイソタクチック指数が９７％以上（９９％）の結晶性ポリプロピレンに、水添石油樹脂を配合しているものの、配合割合が６重量％未満（５重量％）であること等から延伸ができなかった。また、比較例２、３は、コア層に水添石油樹脂を配合しているものの、配合割合が６重量％未満（５重量％）であるため、さらに、積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係（Ｒ）が特定範囲外であるために、水蒸気バリア性が悪い。さらに、比較例３は、スキン層にランダム共重合型ポリプロピレンを用いていないため、ラミネート強度が低い。また、比較例４は、実施例１と対比すると、温度４５℃で２時間（実施例１では２４時間）の熱エージングを施しているため、水蒸気バリア性が悪い。
実施例３、４は、実施例１のものに塗布層を塗布したものであるために、水蒸気バリア性とラミネート強度及び酸素ガスバリア性にも優れている。一方、比較例５は、比較例３のものに塗布層を塗布したものであるために、水蒸気バリア性と酸素ガスバリア性に優れているものの、ラミネート強度が悪い。
【００７２】
【発明の効果】
本発明のポリプロピレン系積層フィルムは、本来ポリプロピレン系フィルムが持つ特性を損なうことなく、水蒸気バリア性と酸素ガスバリア性に優れているので、食品分野、医薬品分野、精密電子部品分野等の各種包装用材料として好適に用いることができ、内容物の長期保存に効果を発揮する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polypropylene-based laminated film having excellent water vapor barrier properties and gas barrier properties, a method for producing the same, and a packaging material. The present invention relates to a film, a method for producing the film, and a packaging material using the same.
[0002]
[Prior art]
Polypropylene-based film has excellent optical properties such as transparency and gloss, tensile properties, mechanical properties represented by Young's modulus, and properties such as substantial non-toxicity and odorlessness. Widely used as packaging material. When applied as a packaging material for food, depending on the type of food, it may be required to have a water vapor barrier property from the viewpoint of moisture proofing to prevent moisture absorption and dehumidification resistance to prevent drying (dehumidification). However, in the method of coating a polypropylene film with a polyvinyl alcohol polymer alone, an ethylene-vinyl alcohol polymer, or a siloxane polymer, the oxygen gas barrier property is provided, but the water vapor barrier property is almost improved. do not do. In addition, a method of vapor-depositing a metal or metal oxide such as aluminum or silica can improve the water vapor barrier property. However, when a film is used as a packaging material, the content is not visible, while a transparent vapor-deposited polyethylene terephthalate ( In PET, although the contents can be seen, cracks may occur during processing and barrier deterioration may occur, and a biaxially oriented polypropylene (OPP) base having high water vapor barrier properties is desired.
[0003]
It is known that when a petroleum resin and a terpene resin are added to a polypropylene resin, the Young's modulus increases and the moisture resistance improves. For example, JP-A-58-213037 and JP-A-60-210647 disclose polypropylene films having improved water vapor barrier properties, all of which contain a terpene resin or a petroleum resin. This alone improves the water vapor barrier properties. In these techniques, terpene resin or petroleum resin bleeds on the surface to deteriorate transparency, laminating strength, bleeding of printing ink, and poor appearance and tactile sensation. Furthermore, since petroleum resins and terpene resins have excellent compatibility with polypropylene and antistatic agents, and have a low softening point, films to which these are added are inferior in thermal dimensional stability. There was also a problem that the process stability during processing was poor due to the inferiority.
[0004]
In addition, various gas barrier properties as content protection properties are important properties that affect the preservability of foods, and are also weak points of general plastic materials. Deterioration factors of food include oxygen, light, heat, moisture, etc., and oxygen is particularly important as a causative substance thereof. Barrier materials are indispensable materials for effectively blocking oxygen and simultaneously controlling deterioration of foods such as gas filling and vacuum packaging.
As a barrier film having a gas barrier property, a transparent polypropylene film coated with polyvinylidene chloride resin (PVDC) or polyvinyl alcohol, a polyester film formed by transparently depositing silica, alumina, or the like have been used in many cases. For example, JP-A-64-043554 discloses that mica having an average length of 7 μm and an aspect ratio of 140 is added to an aqueous methanol solution of an ethylene / vinyl alcohol copolymer, which is poured into cold water to precipitate. Filtration, drying, pelletizing and then obtaining a film are described.
However, when coating with a gas barrier resin to further impart moisture resistance, the film shrinks due to the heat of drying after coating, causing cracks in the coating resin layer, or with the polypropylene film. There was a problem that the interfacial adhesive strength was reduced and the moisture resistance was not improved. In addition, there is a problem that the films obtained by these conventional techniques are not yet sufficient in terms of gas barrier properties.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a polypropylene-based laminated film having improved water vapor barrier properties and oxygen gas barrier properties while maintaining excellent properties of the polypropylene-based films. In the present invention, the “film” includes a “sheet” having a substantially two-dimensional structure.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the present inventors use a highly crystalline polypropylene resin to which a petroleum resin or a terpene resin is added for a core layer (base layer) of a laminated film, and at least one surface of the core layer. The water vapor barrier property is improved in a polypropylene-based laminated film in which a copolymer type polypropylene resin is used for the skin layer (surface layer), or a polyvinyl alcohol or the like is laminated as a coating layer on the skin layer that has been subjected to corona discharge treatment. As a result of intensive studies, the product of the water vapor transmission rate and the thickness of the uncoated laminated film is 75 g · μm / (m 2 ・ 24h) The following is preferred, and the water vapor barrier property is determined by the crystallinity (X c ) And the amorphous part density (d a ) And the degree of orientation (F) are affected by the three related parameters (R), and by setting the related parameters (R) to a specific range, the water vapor permeability and moldability of the laminated film are made appropriate. And found that the present invention was completed.
[0007]
That is, according to the first aspect of the present invention, a core layer (C) containing 75 to 94% by weight of crystalline polypropylene and 25 to 5% by weight of at least one kind of resin such as a petroleum resin or a terpene resin; A crystalline film in the core layer (C), which is a laminated film of at least two layers having a skin layer (S) containing copolymerized polypropylene on the back surface of C), and has a melting point of 160 ° C. or more, and is isotactic. The index is 97% or more, while the petroleum resin or terpene resin has a glass transition temperature of 60 ° C. or more, and the product of the water vapor permeability and the thickness of the laminated film is 75 g · μm / (m 2 24h) or less, and the crystallinity (X c ) And the amorphous part density (d a ) And the relationship (R) between the degree of orientation (F) and the following formula (1) are provided.
Equation (1):
0.36 <[(1-X c ) / (D a /0.854)-0.125F]<0.44
[0008]
According to a second aspect of the present invention, in the first aspect, a skin layer (S ′) containing a homopolymerized polypropylene is further formed on the surface of the core layer (C) to form a three-layer. A characteristic polypropylene-based laminated film is provided.
According to a third aspect of the present invention, in the first aspect, the back side skin layer (S) is a random copolymer type polypropylene containing 0.1 to 5% by weight of ethylene. A characteristic polypropylene-based laminated film is provided.
[0009]
According to a fourth aspect of the present invention, in any one of the first to third aspects, the thickness of the skin layer (S or S ′) is 1.5 μm or less. Provided.
According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the skin layer (S or S ′) contains silica or polymethyl methacrylate (PMMA) as a blocking inhibitor. A polypropylene-based laminated film characterized by being blended in an amount of 100 to 4000 ppm is provided.
Further, according to a sixth aspect of the present invention, there is provided the polypropylene-based laminated film according to the first aspect, wherein the core layer (C) does not contain an antiblocking agent or an antistatic agent. .
[0010]
According to a seventh aspect of the present invention, in the first aspect, polyvinyl alcohol or a mixture of polyvinyl alcohol and an inorganic layered compound is applied as the coating layer (B) to the skin layer (S) on the back side after the surface treatment. A polypropylene-based laminated film characterized by being formed is provided.
According to an eighth aspect of the present invention, there is provided the polypropylene-based laminated film according to the seventh aspect, wherein the inorganic layered compound is a clay mineral which swells or cleaves in an aqueous solvent.
Further, according to a ninth aspect of the present invention, in the seventh aspect, the mixing weight ratio (a / b) of the inorganic layered compound (a) and the polyvinyl alcohol (b) is 15/85 to 25/75. A polypropylene-based laminate film is provided.
[0011]
According to a tenth aspect of the present invention, there is provided the polypropylene-based laminated film according to the seventh aspect, wherein the total thickness is 40 μm or less. Further, according to an eleventh aspect of the present invention, there is provided the polypropylene-based laminated film according to any one of the first to tenth aspects, wherein the laminate strength is 100 g / 15 mm or more in width.
[0012]
On the other hand, according to the twelfth aspect of the present invention, the formation of the coating layer (B) on the surface-treated skin layer (S) on the rear surface side is performed by dissolving or dispersing in a solvent to form a coating liquid A method for producing a polypropylene-based laminated film according to a seventh aspect of the present invention, which is performed by applying the constituent material (B) to the surface of the skin layer (S). According to the thirteenth aspect of the present invention, the mixing of the inorganic layered compound and polyvinyl alcohol is performed by dispersing the inorganic layered compound in a state of being swollen or cleaved in an aqueous solvent into polyvinyl alcohol using a high-pressure dispersion method. The method for producing a polypropylene-based laminated film according to any one of the seventh to ninth aspects of the present invention is provided.
Further, according to a fourteenth aspect of the present invention, in the process for producing a polypropylene-based laminated film, a heat treatment at 30 to 55 ° C for 12 hours or more is performed. A method for producing a polypropylene-based laminated film is provided.
[0013]
According to a fifteenth aspect of the present invention, there is provided a packaging material characterized by using the polypropylene-based laminated film of any one of the first to eleventh aspects.
[0014]
The present invention provides, as described above, a core layer (C) containing 75 to 94% by weight of crystalline polypropylene and at least 25 to 6% by weight of at least one resin such as a petroleum resin or a terpene resin, and a back layer of the core layer (C). Water vapor having a laminated film of at least two layers having a skin layer (S) containing copolymerized polypropylene, or a coating layer (B) which is polyvinyl alcohol or a mixture of polyvinyl alcohol and an inorganic layered compound. The present invention relates to a polypropylene-based laminated film having excellent barrier properties. Preferred embodiments thereof include the following.
(1) The polypropylene-based laminated film according to the fifth aspect of the present invention, wherein the back skin layer (S) contains 100 to 4000 ppm of polymethyl methacrylate (PMMA) as a blocking inhibitor.
(2) The polypropylene-based laminated film according to the sixth aspect of the present invention, wherein the skin layer (S ′) on the surface side contains 100 to 4000 ppm of silica as a blocking inhibitor.
(3) The polypropylene-based laminated film according to the fifth aspect of the present invention, wherein the skin layer (S or S ′) does not contain an antistatic agent and an organic lubricant (excluding a particle type).
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the polypropylene-based laminated film of the present invention will be described in detail.
The polypropylene-based laminated film of the present invention comprises a core layer (C) containing 75 to 94% by weight of crystalline polypropylene and 25 to 6% by weight of at least one resin such as a petroleum resin or a terpene resin, and a back surface of the core layer (C). A laminated film of at least two layers having a skin layer (S) containing copolymerized polypropylene, wherein the crystalline polypropylene in the core layer (C) has a melting point of 160 ° C. or more and an isotactic index of 97%. On the other hand, the petroleum resin or the terpene resin has a glass transition temperature of 60 ° C. or higher, and the product of the water vapor transmission rate and the thickness of the laminated film is 75 g · μm / (m 2 24h) or less, and the crystallinity (X c ) And the amorphous part density (d a ) And the relationship parameter (R) between the degree of orientation (F) satisfies the following equation (1).
Equation (1):
0.36 <[(1-X c ) / (D a /0.854)-0.125F]<0.44
[0016]
The crystallinity (X) of the polypropylene-based laminated film according to the above formula (1) c ) And the amorphous part density (d a ) And the relative parameter (R) of the degree of orientation (F) are indicators of the water vapor barrier property and moldability of the polypropylene-based laminated film.
Crystallinity of laminated film (X c ) And the amorphous part density (d a ) And the degree of orientation (F) satisfy 0.36 <R <0.44, so that both the water vapor barrier property and the moldability of the laminated film are well-balanced and suitable. can do.
[0017]
In the present invention, the crystallinity (X c ) Is determined from the heat of fusion determined by using a scanning calorimeter (DSC-7C manufactured by PerkinElmer) at a heating rate of 20 ° C./min, with the crystal heat of fusion of polypropylene being 209 J / g. Is calculated. The crystallinity was calculated as a ratio to polypropylene excluding the weight of the added petroleum resin and the like.
In addition, the amorphous portion density (d a ) Is (1 / d) = (1-X c ) / D a + (X c / D c ) Is used. Here, d is the average density of biaxially-stretched polypropylene (OPP), and the measurement was performed using a gas displacement type densitometer (Acupic 1330) manufactured by Shimadzu Corporation for 1 cm. 2 Was performed at 25 ° C. using the above cell. Also, X c Is the crystallinity determined by the above scanning calorimeter, and d c Is the density of crystal parts, and is 0.943 g / m 3 And
Further, the degree of orientation (F) is F = [n x − (N y + N z ) / 2] /0.04. Here, the intrinsic birefringence of polypropylene (PP) is set to 0.04, and n x , N y , N z Are the refractive indices in x (the axis of the main refractive index close to the TD direction), y (the axis of the main refractive index close to the MD direction), and z (the axis of the main refractive index close to the thickness direction). The measurement was performed using an automatic birefringence meter (KOBRA-21HD) manufactured by Oji Scientific Instruments, and the average refractive index of the film was set to 1.51 in the calculation of the refractive index.
[0018]
When the value (R) of the relation parameter is small, the water vapor barrier property of the laminated film is improved, that is, the water vapor permeability is reduced. In other words, as the value of the related parameter (R) is smaller, the water vapor permeability is smaller, and the water vapor barrier property can be improved. However, if the value of the related parameter (R) is too small, for example, the crystallinity (X c ) And amorphous part density (d a If) is too large, problems arise in the moldability of the laminated film.
That is, in the structure of the polypropylene-based laminated film of the present invention, the crystallinity (X c ) And amorphous part density (d a A large value of) is not unique, but means, for example, that the amount of the petroleum resin or the terpene resin in the core layer is large, and if the amount of the petroleum resin or the like is too large, the water vapor barrier property becomes poor. Although good, the crystallinity (X c ) And amorphous part density (d a ) Becomes too large, and as a result, the value (R) of the related parameter becomes too small, which causes a problem in the formability of the laminated film. There is a possibility that problems such as difficulty in orientation at points may occur.
In this manner, the polypropylene-based laminated film of the present invention has a crystallinity (X c ) And the amorphous part density (d a ) And the degree of orientation (F) satisfy a suitable range of 0.36 <R <0.44, so that both the water vapor barrier property and the moldability are well-balanced and suitable. Can be
[0019]
Further, the polypropylene-based laminated film of the present invention comprises a core layer (C) containing 75 to 94% by weight of crystalline polypropylene and 25 to 6% by weight of at least one resin such as a petroleum resin or a terpene resin, and a core layer (C). Is a laminated film of at least two layers having a skin layer (S) containing copolymerized polypropylene on the back surface of the laminated film, wherein the product of the water vapor transmission rate and the thickness of the laminated film is 75 g · μm / (m 2 ・ 24h) It is characterized by the following.
In the polypropylene-based laminated film, as a moisture-proof index, because the water vapor permeability is inversely proportional to the film thickness, it is expressed by the product of the water vapor permeability and the thickness of the laminated film, as the water vapor permeability For example, when the film thickness is 20 μm, 3.75 g / (m 2 .24h) or less, preferably 3 g / (m 2 .24h) or less, more preferably 2.5 g / (m 2 -24h) or less.
[0020]
Hereinafter, each item will be described.
1. Core layer (C)
The core layer (base layer) is made of a polypropylene resin or a resin composition containing preferably 70% by weight or more, more preferably 80% by weight or more. The polypropylene-based resin is preferably a highly crystalline crystalline polypropylene. Further, a copolymer of propylene with ethylene, butene-1, 3-methylpentene, 4-methylpentene, or the like may be used, but the content of structural units other than propylene is preferably 1% by weight or less, and preferably 0.1% by weight or less. It is less than 5% by weight, more preferably less than 0.3% by weight.
[0021]
Desirable polypropylene-based resin is a high-crystalline polypropylene-based resin, the higher the regularity is better from the viewpoint of moisture resistance, that is, a high stereoregularity polypropylene resin is preferable, the isotactic index of the polypropylene-based resin is, There is no particular limitation as long as the characteristics are not impaired, but it is preferably 97% or more, and more preferably 99% or more. On the other hand, when the isotactic index is less than 97%, the thermal shrinkage of the film becomes large and the thermal dimensional stability is poor, so that the secondary workability such as printing, coating and laminating is poor.
The isotactic index and the measurement conditions thereof represent the weight% of the residue after extracting the target substance under reflux of n-hexane for 30 minutes.
[0022]
Further, the melting point of the polypropylene resin used for the core layer (base layer) is preferably 160 ° C. or higher, more preferably 162 ° C. or higher. The melt flow rate at 230 ° C. (ASTM D1238, hereinafter abbreviated as MFR) is preferably 0.5 to 20 g / 10 min, more preferably 1 to 4 g / 10 min, from the viewpoint of ease of molding.
[0023]
The core layer desirably contains one or more resins selected from petroleum resins and terpene resins. By containing a petroleum resin or a terpene resin, the barrier property against water vapor of the polypropylene-based laminated film of the present invention is improved.
Examples of the petroleum resin include a resin containing a cyclopentadiene-based or higher olefin-based hydrocarbon as a main raw material or a resin obtained by hydrogenating the resin at a hydrogenation ratio of 80% or more. This petroleum resin preferably does not contain a polar group. Specific examples of such a petroleum resin include, for example, a trade name “ALCON P-120” manufactured by Arakawa Chemical Co., Ltd. and a trade name “ESCOLETZ E5320HC” manufactured by Tonex.
The petroleum resin preferably has a softening point of 125 ° C. or higher, and has a glass transition temperature of 60 ° C. or higher, more preferably 65 to 85 ° C.
[0024]
Examples of the terpene resin include pinene, kalen, myrcene, ocimene, limonene, terpinolene, terpinene, sabinene, tricyclene, pisabolene, gingiperene, santalen, camphorene, millen, and totalen, or a hydrogenated product of these at 80% or more. Can be mentioned. It is preferable that these terpene resins do not contain a polar group.
[0025]
The content of at least one petroleum resin or terpene resin in the core layer is 6 to 25% by weight, preferably 6 to 20% by weight, more preferably 10 to 20% by weight. That is, the content of the crystalline polypropylene is 94 to 75% by weight, preferably 94 to 80% by weight, and more preferably 90 to 80% by weight.
If the content of petroleum resin or the like is less than 6% by weight, since the core layer is made of highly crystalline polypropylene, the stretchability is poor, the breakage is liable to occur, and the thickness accuracy is poor. Further, the orientation that affects the water vapor barrier property is less likely to be applied, and the water vapor barrier property (water vapor permeability) of the obtained film is 4 g / (m) when the film thickness is 20 μm. 2 -Exceeds 24h) and deteriorates.
On the other hand, if the content of the petroleum resin or the like exceeds 25% by weight, a large amount of smoke is generated at the time of extrusion processing, and various problems occur during molding. Furthermore, even in the stretched film, the petroleum resin and the like are likely to bleed out, which may cause an adverse effect such as inhibition of the slipperiness of the film and blocking.
[0026]
As long as the purpose of the present invention is not impaired, the core layer further contains an ultraviolet absorber, an antistatic agent, a crystal nucleus growth agent, a styrene resin, a dicyclopentadiene resin, a cumarone resin such as a coumaloninden resin, a phenol resin, a rosin and the like. A hydrocarbon polymer such as a derivative or a hydrogenated resin thereof, a plasticizer, and a filler can be blended. When the film is subjected to a post-processing step, it is necessary to set conditions so that the bleeding of these additives does not impair the suitability for the coating layer, the vapor deposition layer, the laminate layer, the ink layer, and the like. It is desirable that the core layer does not contain an antistatic agent from the viewpoint of lamination strength and does not contain an antiblocking agent from the viewpoint of transparency.
[0027]
Further, the core layer may be a single layer or a laminate of two or more polypropylene resin layers. The thickness of the core layer is not particularly limited, and is preferably 1 to 100 μm, more preferably 5 to 50 μm, and further preferably 15 to 40 μm.
[0028]
2. Skin layer (S or S ')
The skin layer (surface layer) (S or S ′) is mainly for the purpose of preventing the bleed-out of the petroleum resin or terpene resin contained in the core layer, and for improving the adhesion and the slipperiness. And a resin composition containing the same polypropylene resin or polypropylene resin. In a desirable mode, the polypropylene resin constituting the skin layer is a random copolymer type containing 0.1 to 5% by weight of ethylene in the skin layer (S) on the back surface side of the core layer (C) to be surface-treated. The ethylene content is preferably 0.5 to 4%, more preferably 1 to 3% from the viewpoint of processability. Here, the workability refers to the slipperiness with a roll at the time of application, and means that when the ethylene content increases, the slipperiness at high temperatures deteriorates, and the workability decreases.
The skin layer (S ′) on the surface side of the core layer (C) is a homopolymerized polypropylene, that is, a homopolypropylene. However, propylene containing 0.5% or less of ethylene is also considered as a category of homopolypropylene.
[0029]
Examples of the random copolymerized polypropylene containing 0.1 to 5% by weight of ethylene include a random copolymer of ethylene and propylene, and an ethylene-propylene-butylene terpolymer. preferable. Further, as the comonomer component of such a polypropylene random copolymer, ethylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 3-methylpentene, 4-methylpentene and the like having about 2 to 6 carbon atoms Alkenes and the like. More preferably, propylene is contained in an amount of 84% by weight or more, particularly preferably 84 to 99% by weight of the entire polypropylene-based copolymer, ethylene is contained in an amount of 0.1 to 3% by weight, and ethylene and / or butene is contained in 16% of the entire polypropylene-based copolymer. It is preferable that the copolymer contains not more than 16% by weight, particularly preferably 16 to 1% by weight. The polypropylene-based copolymer constituting the skin layer (S) may contain other components such as additives as long as the effects of the present invention are not impaired.
[0030]
The MFR of the polypropylene resin used for the skin layer (S or S ′) is 3 g / 10 min or more, preferably 3 to 20 g / 10 min, more preferably 3 to 16 g / 10 min. In addition, it is preferable that the MFR of the polypropylene-based resin constituting the skin layer is larger than the MFR of the polypropylene-based resin constituting the core layer because melt fracture hardly occurs.
[0031]
An antioxidant can be added to the polypropylene resin constituting the core layer and the skin layer.
Examples of the antioxidant include a phenol type, a phosphorus type, a sulfur type, and the like. Examples of the phenol type include 2,6-di-t-butyl-p-cresol (BHT) and tetrakis [methylene-3- (3 ′). , 5'-Di-t-butyl-4'-hydroxyphenyl) propionate] methane (for example, Irganox 1010, Ciba-Geigy Japan).
[0032]
It is desirable to blend an anti-blocking agent (anti-blocking agent) with the polypropylene resin constituting the skin layer. As an anti-blocking agent, inorganic fine powders such as silica, alumina, synthetic zeolite, kaolin, talc, zinc oxide, magnesium oxide, zirconium oxide, titanium oxide, aluminum hydroxide, quartz powder, calcium carbonate, magnesium carbonate, and barium sulfate Thermoplastic resins such as polyester, nylon, polycarbonate, polyether sulfone, polyetherimide, polyphenylene sulfide, polyetheretherketone, polyamideimide, crosslinked acrylic resin, crosslinked melamine resin, benzoguanamine resin, urea resin, amino resin, furan resin And at least one selected from thermosetting resins such as epoxy resin, phenol resin, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, and polyimide. Among them, silica and PMMA (polymethyl methacrylate) are preferred from the viewpoint of imparting appropriate slip properties. In a preferred embodiment, PMMA is contained in the skin layer (S) on the back surface side of the core layer (C). The surface side skin layer (S ′) includes silica. The blocking inhibitor preferably has a melting point or a softening point higher than the temperature at the time of film formation in order to maintain the shape without being deformed by the heat applied at the time of film formation.
[0033]
Although the anti-blocking agent may be spherical or amorphous, it is preferable to use a spherical anti-blocking agent because high anti-blocking properties can be imparted without lowering the transparency. The average particle size of the anti-blocking agent such as silica can be selected within a range that does not impair the blocking resistance, the sliding property, and the transparency according to the thickness of the surface layer, and is preferably 0.1 to 7.5 μm, more preferably. It is 0.5-5 μm, more preferably 1-4 μm.
Further, in order to improve the blocking resistance and the sliding property, the polypropylene resin constituting the skin layer may contain an inorganic lubricant similar to the antiblocking agent or a particle-type organic lubricant.
[0034]
The content of the antiblocking agent is preferably 0.01 to 0.5 part by weight, more preferably 0.02 to 0.4 part by weight, and still more preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the polypropylene resin. 03 to 0.3 parts by weight. When the content of the antiblocking agent is 0.01 part by weight or more, blocking of the film at the time of winding can be prevented, and when it is 0.5 part by weight or less, a decrease in transparency can be prevented.
[0035]
Further, the lamination strength of the skin layer (S) on the back surface side to be subjected to the surface treatment with respect to the core layer (C) is desirably 150 g / 15 mm width or more.
[0036]
Further, the skin layer (S) on the back side of the polypropylene-based laminated film is usually subjected to a surface treatment, and the surface treatment includes a conventional surface treatment such as a corona discharge treatment, a flame treatment, a plasma treatment, an ozone or the like. Ultraviolet irradiation treatment or the like can be employed, but corona discharge treatment is preferred. The surface treatment may be performed before the film is stretched, but is preferably performed after the film is stretched.
[0037]
In the case of forming a coating layer, a vapor-deposited layer, a laminate layer, an ink layer, etc. on the skin layer, the polypropylene-based laminated film of the present invention has a skin layer other than the above (that is, an antioxidant and an antiblocking agent). It is preferable not to contain any components, that is, it is desirable not to add an antistatic agent or an organic lubricant (except for a particle type) in order to stabilize the adhesion strength of the coating layer, but the adhesion between the layers is impaired. If it is not in the range, a small amount of an ultraviolet absorber, an antistatic agent, a plasticizer, a wax, or the like may be contained. In addition, such a surface treatment is preferably performed to have a surface tension of 36 dyne / cm or more, more preferably 37 to 45 dyne / cm, and still more preferably 38 to 42 dyne / cm, in order to improve adhesion. desirable.
[0038]
3. Coating layer (B)
The polypropylene-based laminated film of the present invention comprises a polyvinyl alcohol or polyvinyl alcohol and an inorganic layer on the skin layer (S) on the back side of the core layer (C) to be surface-treated, if desired, without or through an anchor layer. At least one coating layer (barrier layer) (B) composed of a mixture of compounds can be provided.
[0039]
If desired, when an anchor layer is interposed, the anchor layer is not particularly limited as long as it enhances adhesiveness. Examples thereof include known or commonly used anchor coating agents such as urethane, polyethyleneimine, polybutadiene, and polyester. Can be used. Among these, from the viewpoints of adhesive strength and water resistance, polyethyleneimine-based, urethane-based, and polyester-based anchor coating agents are preferred. The anchor layer may contain other components such as additives as long as the action of the present invention is not impaired.
[0040]
The thickness of the anchor layer is not particularly limited, and may be appropriately set depending on the configuration of the skin layer (S) and the coating layer (B), a desired adhesive strength, and the like. ~ 1g / m 2 It is better to be.
[0041]
After the formation of the skin layer (S), the anchor layer is formed, for example, by a method of applying a constituent material of the anchor layer as a coating solution by dissolving or dispersing it in a solvent as necessary on the surface of the skin layer (S). it can. The solvent of the coating liquid may be either an aqueous solvent or an organic solvent. At the time of forming the anchor layer, it is desirable to perform a conventional surface treatment, for example, a corona discharge treatment, a flame treatment, a plasma treatment, an ultraviolet irradiation treatment, an electron beam irradiation treatment, or the like on the surface of the skin layer (S).
[0042]
In the polypropylene-based laminated film of the present invention, the adhesion strength (lamination strength) of the coating layer (B) to the skin layer (S) on the surface-treated side is desirably 300 g / 15 mm width or more. When the adhesion strength is less than 300 g / 15 mm width, the coating layer is easily peeled off, and when forming a packaging material using the polypropylene-based laminated film of the present invention, a laminate in which another film is laminated on the coating layer side. The strength may be reduced, or the heat sealing strength may be reduced when another heat-sealing film is laminated on the coating layer side and heat-sealed in an envelope-attached form or the like.
Further, in the polypropylene-based laminated film of the present invention, the lamination strength after the coating layer (B) is laminated on the skin layer (S) is desirably 100 g / 15 mm width or more.
[0043]
In the present invention, polyvinyl alcohol or a mixture of polyvinyl alcohol and an inorganic layered compound can be used as the coating layer (B).
Examples of the polyvinyl alcohol include a vinyl alcohol copolymer containing vinyl alcohol as a main monomer component. By using this vinyl alcohol copolymer, the coating layer has excellent barrier properties against oxygen gas. Preferably, vinyl alcohol, which is the main monomer component, accounts for 70 to 99 mol%, more preferably 80 to 98 mol%, based on all monomer components in the vinyl alcohol copolymer. Examples of the monomer components other than the vinyl alcohol include vinyl acetate and ethylene. The coating layer may contain other components such as additives as long as the effects of the present invention are not impaired.
[0044]
The above-mentioned inorganic layered compound is an inorganic compound in which unit crystal layers are stacked on each other to have a layered structure, and specific examples of the inorganic layered compound include graphite, a phosphate-based derivative type compound (phosphate A zirconium compound), a chalcogenide [a dichalcogenide of a group IV (Ti, Zr, Hf), a group V (V, Nb, Ta) and a group VI (Mo, W); 2 Is represented by Here, X represents chalcogen (S, Se, Te). And clay-based minerals. Among them, an inorganic layered compound which swells or cleaves in a solvent is preferably used.
[0045]
As the inorganic layered compound which swells or cleaves in a solvent, a clay mineral which swells or cleaves in a solvent can be preferably used. Clay-based minerals are generally of a two-layer structure having an octahedral layer with aluminum or magnesium as the central metal on top of a silica tetrahedral layer, and a silica tetrahedral layer with aluminum or magnesium. It is classified into a type having a three-layer structure in which an octahedron layer serving as a central metal is sandwiched from both sides. The former include kaolinites and antigolites, and the latter include smectites, vermiculites and micas depending on the number of interlayer cations. Specifically, kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, hectorite, tetrasilyl mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite , Zansophyllite, chlorite and the like. Examples of these minerals include those produced from natural clay, semi-synthetic products obtained by performing interlayer ion exchange treatment on those extracted from natural products, and pure synthetic products synthesized to have a structure similar to that of natural products. Among them, a layered silicate which swells or cleaves in a solvent, for example, water, is preferably used, and examples thereof include natural montmorillonite having a purity of 99% or more.
[0046]
As the solvent, a solvent having a density smaller than the density of the inorganic layered compound is used. When the inorganic layered compound is a natural swellable clay mineral, it is preferable to use water as the solvent. Other solvents include, for example, alcohols such as methanol and ethanol.
[0047]
As the size of the inorganic layered compound, the particle size is preferably 5 μm or less from the viewpoint of film formability or moldability when formed into a film. Further, from the viewpoint of transparency, the particle size is preferably 3 μm or less. When the polypropylene-based laminated film of the present invention is used for applications where transparency is important (for example, food applications), the particle size is particularly preferably 1 μm or less.
[0048]
The method of mixing the polyvinyl alcohol and the inorganic layered compound is not particularly limited as long as they are uniformly mixed and dispersed.For example, first, an inorganic layered compound in a state of being swollen or cleaved in water as a solvent is prepared, A method in which the inorganic layered compound in such a state is dispersed in a polyvinyl alcohol solution obtained by dissolving in water by a high-pressure dispersion method, for example, using a high-pressure homogenizer, may be used.
As a method for producing an inorganic layered compound in a state of being swollen or cleaved in water as a solvent, an inorganic layered compound mixed and dispersed in water is mixed with a high-pressure homogenizer to 500 kgf / cm. 2 A method in which the treatment is carried out for two or more passes under the above pressure conditions to obtain a dispersed state which is swollen or cleaved in an aqueous solvent.
Further, the mixing weight ratio (a / b) of the inorganic layered compound (a) and the polyvinyl alcohol (b) is desirably 15/85 to 25/75.
[0049]
After forming the skin layer (S), for example, the coating layer (B) is formed by coating or dissolving or dispersing in a solvent as needed to form a coating liquid on the surface of the skin layer (S). It can be formed by a method. The solvent of the coating liquid may be either an aqueous solvent or an organic solvent, but is preferably water or a mixture of water and a hydrophilic solvent.
The thickness of the coating layer is not particularly limited and may be appropriately set depending on the desired barrier properties and the like, but is preferably 0.3 to 3 μm, and more preferably 0.3 to 2 μm.
Further, when a plurality of coating layers are provided, an anchor layer may be provided between the coating layers.
[0050]
4. Polypropylene-based laminated film (production method)
The method for producing the polypropylene-based laminated film of the present invention is not particularly limited, and a generally used film forming method and laminating method can be used. Preferably, the core layer (C), the skin layer (S or S ') and the coating layer (B) are formed simultaneously by a co-extrusion method. For example, a resin and the like used for forming the core layer and the skin layer are supplied to respective extruders, and melted and mixed at a resin temperature of 200 to 260 ° C., and then laminated by a co-extrusion method from a die on a slit. It is obtained by doing. The temperature of each extruder may be set differently depending on the MFR and the melting point. The same coextrusion method can be used even when the core layer (C) or the skin layer (S or S ′) has a multilayer structure. When the temperature of the chill roll with which the molten resin extruded from the die comes into contact is set at 25 to 65 ° C, preferably 30 to 60 ° C, and more preferably 30 to 55 ° C, the cooling of the sheet becomes slower, which is preferable. Preferably, after co-extrusion, the film is stretched in at least one direction, more preferably in the direction of two axes. The biaxial stretching conditions are not particularly limited, but sequential biaxial stretching is preferred. In the successive biaxial stretching, the stretching ratio in the machine direction is 4 to 7 times, preferably 4.5 to 6 times, and the stretching ratio in the transverse direction is 7 to 12 times, preferably 8 to 11 times. Further, it is preferable to set the preheating temperature at the time of stretching in the transverse direction as low as possible. The set temperature range is 150 to 180 ° C, preferably 155 to 175 ° C, and it is desirable that the film is oriented. By stretching, the effect of expressing the water vapor barrier property is increased. Extrusion conditions and stretching conditions can be appropriately set according to the material and thickness of each layer used, desired physical properties, and the like.
[0051]
In the above-described manufacturing process, by performing a heat treatment such as heat aging at a relatively low temperature of 30 to 55 ° C. for 12 hours or more, the water vapor barrier property of the laminated film is improved.
[0052]
In the polypropylene-based laminated film of the present invention, the total thickness (Tf) of the film is preferably 40 μm or less, the thickness (Tc) of the core layer is preferably 10 to 25 μm, and the thickness (Ts) of the skin layer (both sides). (If there is a skin layer), it is preferably 0.5 to 1.5 μm. Further, the thickness (Tb) of the coating layer is not particularly limited as described above, and is appropriately selected depending on a desired barrier property and the like.
[0053]
The ratio (Ts / Tf) of the thickness (Ts) of the skin layer of the polypropylene-based laminated film of the present invention to the total thickness Tf of the film is preferably 0.04 to 0.60, and more preferably 0.05 to 0.60. 0.5. When Ts / Tf is 0.04 or more, the moisture resistance of the skin layer can be sufficiently improved, and when Ts / Tf is 0.60 or less, there is no problem in appearance and touch feeling as a film.
[0054]
The polypropylene-based laminated film of the present invention can be used alone as a packaging material, but may be laminated with another material such as a non-oriented transparent polypropylene-based resin (CPP) film or a non-oriented polyethylene-based resin film having heat sealing properties. It can also be used as a packaging material. The configuration of the packaging material and the lamination method are not particularly limited. The unstretched transparent polypropylene-based resin film and unstretched polyethylene-based resin film are laminated on the coating layer side of the polypropylene-based laminated film of the present invention to have heat sealing properties on both sides, and to measure the base material of the coating layer. A packaging material having excellent adhesion to the packaging material can be obtained. Further, the polypropylene-based laminated film of the present invention may be subjected to a coloring treatment or an image forming treatment by printing or the like.
[0055]
Since the polypropylene-based laminated film of the present invention is excellent in water vapor barrier properties and gas barrier properties such as oxygen gas, individual wrapping of candy, chocolate, rice confectionery, biscuits, cookies and other confectionery, seaweed and other individual packaging and overall packaging. It is suitable for use.
[0056]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, measurement and evaluation of various properties and performances were evaluated by the following test methods.
[0057]
(1) Total thickness of film (Tf)
The total thickness (Tf) of the polypropylene-based laminated films of Examples / Comparative Examples was measured with a digital thickness gauge.
[0058]
(2) Lamination strength
The adhesives for lamination (TM329, manufactured by Toyo Morton Co., Ltd.), the adhesives for lamination (CAT-8B, manufactured by Toyo Morton Co., Ltd.) and ethyl acetate were added to the polypropylene-based laminated films of Examples / Comparative Examples in a weight ratio of 4 respectively. .8: 4.8: 10.4, the laminated adhesive was mixed in a dry thickness of 2 to 2.5 g / m2. 2 A transparent polypropylene resin having a thickness of 20 μm, which is applied to the surface of a skin layer or a coating layer of the above-mentioned film, dried, and then subjected to a laminating adhesive application surface and a surface having a corona treatment of at least 38 dyne / cm). The (OPP) film was pressed against the corona-treated surface. It was stored under the conditions of 40 ° C. and 30% RH for 24 hours after the pressure bonding. The bonded film is cut into a strip having a width of 15 mm to prepare a test piece, and each end of the polypropylene-based laminated film and the OPP film on one end side of the test piece is held according to JIS K 7127. Then, the strength when pulled at a speed of 300 mm / min in the direction in which the polypropylene-based laminated film and the OPP film were peeled off was measured and defined as the adhesion strength.
[0059]
(3) Water vapor barrier properties
The water vapor barrier property was evaluated by measuring the water vapor transmission rate with a water vapor excess ratio measuring device (PERMATRAN W200, manufactured by MOCON) under the conditions of a temperature of 40 ° C. and a relative humidity of 90%.
[0060]
(4) Oxygen gas barrier properties
The oxygen gas barrier property was measured and evaluated using an oxygen permeability measuring device (OX-TRAN 2/20, manufactured by MOCON) under the conditions of 20 ° C. and 60% RH.
[0061]
[Example 1]
As the core layer (C), 85% by weight of a crystalline polypropylene (MFR: 2 g / 10 min, melting point: 166 ° C.) having an isotactic index (II) of 99% and water having a glass transition temperature of 70 ° C. A random copolymerized polypropylene (MFR: ethylene content: 2% by weight) was used as the skin layer (S) on the surface-treated side (back side) side, using a composition to which 15% by weight of an added petroleum resin (Escolets 5320HC) was added. 15 g / 10 min, melting point: 150 ° C.) and 1500 ppm of polymethyl methacrylate (PMMA) as an antiblocking agent were added. Further, as the skin layer (S ′) on the non-treated surface side, crystalline propylene (MFR: 8 g / 10 min, melting point: 160 ° C.) was used in which 2500 ppm of silica was added as a blocking inhibitor. The temperature of the core layer resin was set at 250 ° C., and the temperature of both the skin layer resins was set at 230 ° C., and the molten resin supplied from each extruder to the inside of the die was circulated through the inside at a temperature of 55 ° C. The multilayer sheet cooled by the method of contacting with the chill roll and contacting with the air on the opposite side is successively biaxially stretched at 5.5 times in length and 9.5 times in width at a film forming speed of 100 m / min to have a thickness of 20 μm. Was obtained. Further, in the manufacturing process, heat aging was performed at a temperature of 45 ° C. for 24 hours.
Various physical properties of the obtained film were evaluated, and the results are shown in Table 1.
[0062]
[Example 2]
With the same composition as in Example 1, sequential biaxial stretching was performed to obtain a film having a thickness of 30 μm, and heat aging was performed as in Example 1. Various physical properties of the obtained film were evaluated, and the results are shown in Table 1.
[0063]
[Comparative Example 1]
As the core layer (C), 95% by weight of crystalline polypropylene (MFR: 2 g / 10 min, melting point: 166 ° C.) having an isotactic index (II) of 99% and water having a glass transition temperature of 70 ° C. A film was formed under the same conditions as in Example 1 except that 5% by weight of an added petroleum resin (ESCOLETS 5320HC) was added. The composition is shown in Table 1.
[0064]
[Comparative Example 2]
As the core layer (C), 95% by weight of a crystalline polypropylene having an isotactic index (II) of 97% (MFR: 3 g / 10 minutes, melting point: 161 ° C.) and water having a glass transition temperature of 70 ° C. Molding and heat treatment were performed under the same conditions as in Example 1 except that the composition was such that 5% by weight of an added petroleum resin (ESCOLETS 5320HC) was added to obtain a biaxially stretched film having a thickness of 20 μm. Various physical properties of the obtained film were evaluated, and the results are shown in Table 1.
[0065]
[Comparative Example 3]
Molding and heat treatment were performed under the same conditions as in Comparative Example 1 except that a homopolypropylene containing no ethylene was used as the skin layer (S) on the surface-treated side, and a biaxially stretched film having a thickness of 20 μm was obtained. Obtained. Various physical properties of the obtained film were evaluated, and the results are shown in Table 1.
[0066]
[Comparative Example 4]
In the manufacturing process, molding and heat treatment were performed under the same conditions as in Example 1 except that heat aging was performed at a temperature of 45 ° C. for 2 hours to obtain a biaxially stretched film having a thickness of 20 μm. Various physical properties of the obtained film were evaluated, and the results are shown in Table 1.
[0067]
[Example 3]
After obtaining a biaxially stretched film having a thickness of 20 μm under the same conditions as in Example 1, as a coating layer (B), montmorillonite as an inorganic layered compound was dispersed in an aqueous solution of polyvinyl alcohol (PVA) by a high-pressure homogenizer using a high-pressure homogenizer. (PVA: montmorillonite = 80: 20% by weight) was applied to the skin layer (S) having a thickness of 1 μm on the surface-treated side and dried to prepare a laminated film having a total thickness of 21 μm. . Various physical properties of the obtained laminated film were evaluated, and the results are shown in Table 1.
[0068]
[Example 4]
A laminated film having a total thickness of 21 μm was produced under the same conditions as in Example 3 except that an aqueous solution of PVA was applied. Various physical properties of the obtained laminated film were evaluated, and the results are shown in Table 1.
[0069]
[Comparative Example 5]
After obtaining a biaxially stretched film having a thickness of 20 μm in the same manner as in Comparative Example 2, a coating layer (B) in which montmorillonite, which is an inorganic layered compound, is dispersed in an aqueous PVA solution by a high-pressure dispersion method using a high-pressure homogenizer. (PVA: montmorillonite = 80: 20% by weight) was applied to the skin layer (S) on the surface-treated surface side with a thickness of 1 μm and dried to prepare a laminated film having a total thickness of 21 μm. Various physical properties of the obtained laminated film were evaluated, and the results are shown in Table 1.
[0070]
[Table 1]
In Examples 1 and 2, a mixture of crystalline polypropylene having an isotactic index of 97% or more and a hydrogenated petroleum resin (85: 15% by weight) was used for the core layer, and an ethylene content of 2% by weight was used for the skin layer. Because PMMA is blended with the random copolymerized polypropylene of the above, the crystallinity (X c ) And the amorphous part density (d a ) And the relationship (R) between the degree of orientation (F) and the degree of orientation (F) are within a specific range, so that the water vapor barrier property and the laminate strength are excellent. On the other hand, in Comparative Example 1, as the core layer, a hydrogenated petroleum resin was blended with crystalline polypropylene having an isotactic index of 97% or more (99%), but the blending ratio was less than 6% by weight (5% by weight). %) Could not be stretched. In Comparative Examples 2 and 3, although the hydrogenated petroleum resin was blended in the core layer, the blending ratio was less than 6% by weight (5% by weight). c ) And the amorphous part density (d a ) And the relationship (R) between the degree of orientation (F) and the degree of orientation (F) are out of the specific range, so that the water vapor barrier property is poor. Furthermore, in Comparative Example 3, since the random copolymerization type polypropylene was not used for the skin layer, the laminate strength was low. Further, Comparative Example 4 has a poor water vapor barrier property because heat aging is performed at a temperature of 45 ° C. for 2 hours (24 hours in Example 1) as compared with Example 1.
In Examples 3 and 4, since the coating layer was applied to that of Example 1, the water vapor barrier property, the laminate strength, and the oxygen gas barrier property were also excellent. On the other hand, Comparative Example 5 is obtained by applying a coating layer to that of Comparative Example 3, and thus has excellent water vapor barrier properties and oxygen gas barrier properties, but has poor laminating strength.
[0072]
【The invention's effect】
The polypropylene-based laminated film of the present invention is excellent in water vapor barrier properties and oxygen gas barrier properties without impairing the properties inherent in polypropylene-based films, so that it can be used for various packaging materials in the fields of foods, pharmaceuticals, precision electronic parts, etc. And is effective for long-term storage of the contents.
Claims (15)
コア層（Ｃ）中の結晶性ポリプロピレンは、融点が１６０℃以上、アイソタクチック指数が９７％以上であり、一方、石油樹脂又はテルペン樹脂は、ガラス転移温度が６０℃以上であり、さらに、
積層フィルムの水蒸気透過度と厚みの積は、７５ｇ・μｍ／（ｍ２・２４ｈ）以下であり、かつ積層フィルムの結晶化度（Ｘｃ）と非晶部密度（ｄａ）及び配向度（Ｆ）の関係（Ｒ）が下記の式（１）を満足することを特徴とするポリプロピレン系積層フィルム。
式（１）：
０．３６＜［（１−Ｘｃ）／（ｄａ／０．８５４）−０．１２５Ｆ］＜０．４４A core layer (C) containing 75 to 94% by weight of crystalline polypropylene and at least 25 to 6% by weight of at least one resin such as a petroleum resin or a terpene resin; and a skin containing copolymerized polypropylene on the back surface of the core layer (C). A laminated film having at least two layers having a layer (S),
The crystalline polypropylene in the core layer (C) has a melting point of 160 ° C. or more and an isotactic index of 97% or more, while a petroleum resin or a terpene resin has a glass transition temperature of 60 ° C. or more.
The product of the water vapor transmission rate and the thickness of the laminated film is 75 g · μm / (m 2 · 24 h) or less, and the crystallinity (X c ), the amorphous part density (d a ), and the orientation degree ( A polypropylene-based laminated film, wherein the relationship (R) of F) satisfies the following expression (1).
Equation (1):
0.36 <[(1-X c ) / (d a /0.854)-0.125F]<0.44
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| JP2004043538A (en) * | 2002-07-09 | 2004-02-12 | Daicel Chem Ind Ltd | Moisture-proof laminated film, laminate and package |
| JP2005349769A (en) * | 2004-06-11 | 2005-12-22 | Daicel Chem Ind Ltd | Laminated film |
| JP2007062753A (en) * | 2005-08-30 | 2007-03-15 | Dainippon Printing Co Ltd | Paper cup having ink permeation preventive layer |
| JP2008073926A (en) * | 2006-09-20 | 2008-04-03 | Tohcello Co Ltd | Biaxially oriented multilayer polypropylene film |
| JP2008132614A (en) * | 2006-11-27 | 2008-06-12 | Daicel Chem Ind Ltd | Polypropylene-based laminated film and gas barrier film |
| JP2014065199A (en) * | 2012-09-25 | 2014-04-17 | Sumitomo Bakelite Co Ltd | Multilayer film and package |
| JP2018167487A (en) * | 2017-03-30 | 2018-11-01 | 三井化学東セロ株式会社 | Packaging film for food and package for food |
| WO2022224647A1 (en) * | 2021-04-23 | 2022-10-27 | 東洋紡株式会社 | Laminated film and packaging material |
| JP7616593B1 (en) | 2023-09-28 | 2025-01-17 | 大日本印刷株式会社 | Laminate and packaging bag |
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| JP2006316279A (en) * | 2006-06-16 | 2006-11-24 | Daicel Chem Ind Ltd | Moisture-proof laminated film, laminate and package |
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| JP2022167664A (en) * | 2021-04-23 | 2022-11-04 | 東洋紡株式会社 | Laminated film and packaging material |
| WO2025070674A1 (en) * | 2023-09-27 | 2025-04-03 | 大日本印刷株式会社 | Multilayer body, packaging bag, and heat sterilization pouch |
| JP7616593B1 (en) | 2023-09-28 | 2025-01-17 | 大日本印刷株式会社 | Laminate and packaging bag |
| JP2025058861A (en) * | 2023-09-28 | 2025-04-09 | 大日本印刷株式会社 | Laminate and packaging bag |
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