JP2005288996A - Laminated film - Google Patents
Laminated film Download PDFInfo
- Publication number
- JP2005288996A JP2005288996A JP2004111093A JP2004111093A JP2005288996A JP 2005288996 A JP2005288996 A JP 2005288996A JP 2004111093 A JP2004111093 A JP 2004111093A JP 2004111093 A JP2004111093 A JP 2004111093A JP 2005288996 A JP2005288996 A JP 2005288996A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- film
- laminated film
- temperature
- laminated
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Links
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 104
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 238000002844 melting Methods 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 34
- 238000005259 measurement Methods 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 238000000235 small-angle X-ray scattering Methods 0.000 claims description 3
- 230000004308 accommodation Effects 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 84
- 229920005989 resin Polymers 0.000 description 26
- 239000011347 resin Substances 0.000 description 26
- 229920000139 polyethylene terephthalate Polymers 0.000 description 20
- 239000005020 polyethylene terephthalate Substances 0.000 description 20
- -1 polyethylene Polymers 0.000 description 19
- 238000000034 method Methods 0.000 description 14
- 238000012545 processing Methods 0.000 description 11
- 230000003068 static effect Effects 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- 229920001707 polybutylene terephthalate Polymers 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000003475 lamination Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 102220534965 Trafficking regulator of GLUT4 1_F20S_mutation Human genes 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 238000007666 vacuum forming Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N 1,5-Pentadiol Natural products OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
本発明は、積層フィルムに関するものである。 The present invention relates to a laminated film.
熱可塑性樹脂フィルムは、包装材料をはじめ、ラベル・グラフィック・ＯＨＰ・離型・インクリボン・電気絶縁・感熱孔版・スタンピングなどの種々の工業材料や、オーディオ・ビデオ・データストレージなどの磁気材料などとして幅広く利用されている。これら種々の用途において、一般的には高剛性でかつ高温下での寸法安定性にすぐれた材料が必要とされている。 Thermoplastic resin films are used as packaging materials, various industrial materials such as labels, graphics, OHP, mold release, ink ribbons, electrical insulation, heat sensitive stencils, stamping, and magnetic materials such as audio, video, and data storage. Widely used. In these various applications, a material having high rigidity and excellent dimensional stability at high temperatures is generally required.
これらの用途においては、一般に、フィルムは支持体として用いられており、フィルムに印刷、蒸着、スパッタ、メッキ、ラミネート、コーティング、成形加工などの種々の加工が高温下にて施されるため、その処理工程おいて高剛性であることが、支持体であるフィルムの腰が強くなりハンドリングがよくなるという点から重要であるとともに、寸法安定性が高いことは加工時の変形を抑制できるため精度良く加工を施せるために重要である。この中で特に、高温下での寸法安定性にも優れ、成形加工性や表面加工特性にも優れたフィルム（例えば特許文献１参照）が存在する。 In these applications, the film is generally used as a support, and various processes such as printing, vapor deposition, sputtering, plating, laminating, coating, and molding are applied to the film at a high temperature. High rigidity in the processing process is important from the viewpoint that the support film becomes firm and handling is good, and that high dimensional stability can suppress deformation during processing, so it can be processed accurately. It is important to apply. Among them, there is a film (see, for example, Patent Document 1) that is particularly excellent in dimensional stability at high temperatures and excellent in molding processability and surface processing characteristics.
一方、熱可塑性樹脂を多層に積層したフィルムとしては、種々提案されており、例えば、耐引裂性に優れた多層に積層したフィルムをガラス表面に貼りつけることにより、ガラスの破損および飛散を大幅に防止できるもの（特許文献２、）、屈折率の異なる樹脂層を交互に多層に積層することより、選択的に特定の波長を反射するフィルム（特許文献３）等が存在する。 On the other hand, various films have been proposed as multilayered thermoplastic resins. For example, by attaching a multilayered film excellent in tear resistance to the glass surface, glass breakage and scattering are greatly reduced. There are films that can be prevented (Patent Document 2), films that selectively reflect a specific wavelength by alternately laminating resin layers having different refractive indexes (Patent Document 3), and the like.
しかし、これらのフィルムは高温下での寸法安定性が不十分であったり、成形加工性についても満足すべきものではなかった。
本発明は上記した背景技術の問題点に鑑み、高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムを提供することを課題とするものである。 In view of the problems of the background art described above, the present invention provides a film having high rigidity, excellent dimensional stability at high temperatures, and excellent transparency after heating and moldability in a wide temperature range. It is an object to do.
上記課題を解決するため、本発明の積層フィルムは以下の構成からなる。すなわち、熱可塑性樹脂Ａからなる層と、熱可塑性樹脂Ｂからなる層によって形成される５０層以上の積層フィルムであって、動的粘弾性測定におけるα緩和温度が、（熱可塑性樹脂Ｂのα緩和温度＋１０）℃〜（熱可塑性樹脂Ａのα緩和温度−１０）℃の間に観察され、かつ融点が２つ以上存在することを特徴とする。 In order to solve the above problems, the laminated film of the present invention has the following constitution. That is, it is a laminated film of 50 layers or more formed by a layer made of thermoplastic resin A and a layer made of thermoplastic resin B, and the α relaxation temperature in dynamic viscoelasticity measurement is (α of thermoplastic resin B It is observed between relaxation temperature + 10) ° C. to (α relaxation temperature of thermoplastic resin A−10) ° C., and has two or more melting points.
本発明の積層フィルムは、熱可塑性樹脂Ａからなる層と、熱可塑性樹脂Ｂからなる層によって形成される５０層以上の積層フィルムであって、動的粘弾性測定における積層フィルムのα緩和の温度が、（熱可塑性樹脂Ｂのα緩和温度＋１０）℃〜（熱可塑性樹脂Ａのα緩和温度−１０）℃の間に少なくとも観察され、かつ融点が２つ以上存在することを特徴とする積層フィルムであるため、高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムを得ることができる。 The laminated film of the present invention is a laminated film of 50 layers or more formed by a layer made of thermoplastic resin A and a layer made of thermoplastic resin B, and the α relaxation temperature of the laminated film in dynamic viscoelasticity measurement. Is observed at least between (α relaxation temperature of thermoplastic resin B + 10) ° C. to (α relaxation temperature of thermoplastic resin A−10) ° C., and has two or more melting points. Therefore, it is possible to obtain a film having high rigidity and excellent dimensional stability at high temperatures, and further excellent transparency after heating and molding processability in a wide temperature range.
また積層フィルムの熱膨張係数が１１０ｐｐｍ以下とすることにより、高温下での寸法安定性に優れ、高温下での高精度な成形が可能となるものである。 Further, when the thermal expansion coefficient of the laminated film is 110 ppm or less, the dimensional stability at high temperature is excellent, and high-precision molding at high temperature is possible.
さらに、加熱試験後のヘイズ上昇値が１５％以下とすることにより、加熱後の透明性に優れ、成形体とした場合光沢のある外観の優れたものとなるものである。 Furthermore, by setting the haze increase value after the heating test to 15% or less, the transparency after heating is excellent, and when it is formed into a molded body, the glossy appearance is excellent.
以下、本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明の積層フィルムは、熱可塑性樹脂Ａからなる層と、熱可塑性樹脂Ｂからなる層によって形成される５０層以上の積層フィルムである。より好ましくは、厚みが３０ｎｍ未満である層を５０層以上含んでおり、さらに好ましくは厚みが３０ｎｍ未満である層を５００層以上含んでおり、最も好ましくは厚みが３０ｎｍ未満である層を１０００層以上含んでいることである。層が５０層より少ない場合には、フィルム中に占める微細構造制御が達成された部位の割合が極端に低下するため、高温下での寸法安定性および成型加工性の効果が十分ではなくなる。 The laminated film of the present invention is a laminated film of 50 layers or more formed by a layer made of thermoplastic resin A and a layer made of thermoplastic resin B. More preferably, it includes 50 or more layers having a thickness of less than 30 nm, more preferably 500 or more layers having a thickness of less than 30 nm, and most preferably 1000 layers having a thickness of less than 30 nm. It is to include the above. When the number of layers is less than 50, the ratio of the portion where the fine structure control in the film is achieved is extremely reduced, and the effects of dimensional stability and moldability at high temperatures are not sufficient.
また、ここで層厚みが３０ｎｍ未満の場合、サイズ効果による層間の相互作用のために従来の方法では達することができなかった結晶部および非晶部の微細構造制御が達成され、熱可塑性樹脂の特徴を損なうことなく、高温下での寸法安定性を飛躍的に向上するため好ましい。より好ましくは、１５ｎｍ未満である。１５ｎｍ未満の場合、さらに高温下での寸法安定性が向上するものである。また、厚みが３０ｎｍ未満の層が５００層以上の場合には高温下での寸法安定性と成形性がさらに向上する。また、厚みが３０ｎｍ未満の層が１０００層以上の場合には、高温下での寸法安定性と成型加工性がさらに向上する。上限値は特に限定されないが、５００００層以下であることが好ましい。また、本発明の効果を阻害しない範囲で、他の層、例えば熱可塑性樹脂Ｃを有していても良い。例えば、熱可塑性樹脂Ａ、熱可塑性樹脂Ｂ、熱可塑性樹脂Ｃの３種からなる場合には、Ａ（ＢＣＡ）ｎ、Ａ（ＢＣＢＡ）ｎ、Ａ（ＢＡＢＣＢＡ）ｎなどの規則的順列で積層されることがより好ましい。ここでｎは繰り返しの単位数であり、例えばＡ（ＢＣＡ）ｎにおいてｎ＝３の場合、厚み方向にＡＢＣＡＢＣＡＢＣＡの順列で積層されているものを表す。また、２種類の熱可塑性樹脂からなる場合、それらが交互に積層された構造を有することがより好ましい。 Further, when the layer thickness is less than 30 nm, the fine structure control of the crystal part and the amorphous part, which could not be achieved by the conventional method due to the interaction between layers due to the size effect, is achieved, and the thermoplastic resin This is preferable because the dimensional stability at high temperatures is dramatically improved without impairing the characteristics. More preferably, it is less than 15 nm. When the thickness is less than 15 nm, the dimensional stability at a higher temperature is further improved. Further, when the number of layers having a thickness of less than 30 nm is 500 or more, the dimensional stability and moldability at a high temperature are further improved. Further, when the number of layers having a thickness of less than 30 nm is 1000 or more, the dimensional stability and molding processability at a high temperature are further improved. Although an upper limit is not specifically limited, It is preferable that it is 50000 layers or less. Moreover, you may have another layer, for example, the thermoplastic resin C, in the range which does not inhibit the effect of this invention. For example, in the case of three types of thermoplastic resin A, thermoplastic resin B, and thermoplastic resin C, they are laminated in a regular permutation such as A (BCA) n, A (BCBA) n, A (BABCBA) n. More preferably. Here, n is the number of repeating units. For example, in the case of A (BCA) n where n = 3, this indicates that the layers are stacked in a permutation of ABCABCABCA in the thickness direction. Moreover, when it consists of two types of thermoplastic resins, it is more preferable to have the structure where they were laminated alternately.
ここで、本発明における熱可塑性樹脂としては、たとえば、ポリエチレン、ポリプロピレン、ポリメチルペンテンなどのポリオレフィン樹脂、ナイロン６、ナイロン６６などのポリアミド樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチルサクシネート、ポリエチレン−２，６−ナフタレートなどのポリエステル樹脂、ポリカーボネート樹脂、ポリアリレート樹脂、ポリアセタール樹脂、ポリフェニレンスルフィド樹脂、アクリル樹脂、ポリグリコール酸樹脂、ポリ乳酸樹脂などを用いることができる。この中で、強度・耐熱性・透明性の観点から、特にポリエステルであることがより好ましい。 Here, examples of the thermoplastic resin in the present invention include polyolefin resins such as polyethylene, polypropylene and polymethylpentene, polyamide resins such as nylon 6 and nylon 66, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate and polybutyl succinate. Polyester resin such as polyethylene-2,6-naphthalate, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, acrylic resin, polyglycolic acid resin, polylactic acid resin, and the like can be used. Among these, polyester is particularly preferable from the viewpoint of strength, heat resistance, and transparency.
本発明における熱可塑性樹脂として好ましいポリエステルとは、ジカルボン酸成分とジオール成分との重縮合体でのことを言う。ジカルボン酸成分としては、テレフタル酸、イソフタル酸、フタル酸、１，４−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、２，６−ナフタレンジカルボン酸、４，４’−ジフェニルジカルボン酸、４，４’−ジフェニルスルホンジカルボン酸、アジピン酸、セバシン酸、ダイマー酸、シクロヘキサンジカルボン酸などが挙げられ、またこれらのエステル誘導体も含まれる。グリコール成分としては、エチレングリコール、１，３−プロパンジオール、１，２−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，５−ペンタジオール、ジエチレングリコール、ポリアルキレングリコール、２，２−ビス（４’−β−ヒドロキシエトキシフェニル）プロパン、１，４−シクロヘキサンジメタノールなどが挙げられる。特に、ポリエステル樹脂の中でも、ポリエチレン−２，６−ナフタレートやポリエチレンテレフタレートが好ましく、特にポリエチレンテレフタレートがさらに好ましい。またこれらの熱可塑性樹脂としてはホモ樹脂であってもよく、共重合または２種類以上のブレンドであってもよい。また、各層中には、各種添加剤、例えば、酸化防止剤、帯電防止剤、結晶核剤、無機粒子、有機粒子、減粘剤、熱安定剤、滑剤、赤外線吸収剤、紫外線吸収剤などが添加されていてもよい。 The polyester preferable as the thermoplastic resin in the present invention refers to a polycondensate of a dicarboxylic acid component and a diol component. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, Examples thereof include 4′-diphenylsulfone dicarboxylic acid, adipic acid, sebacic acid, dimer acid, cyclohexane dicarboxylic acid, and the like, and ester derivatives thereof are also included. Examples of the glycol component include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentadiol, diethylene glycol, polyalkylene glycol, 2 , 2-bis (4′-β-hydroxyethoxyphenyl) propane, 1,4-cyclohexanedimethanol and the like. In particular, among polyester resins, polyethylene-2,6-naphthalate and polyethylene terephthalate are preferable, and polyethylene terephthalate is more preferable. Further, these thermoplastic resins may be homo resins, copolymerized or blends of two or more. In each layer, various additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, inorganic particles, organic particles, a thinning agent, a heat stabilizer, a lubricant, an infrared absorber, and an ultraviolet absorber are included. It may be added.
本発明の積層フィルムは、動的粘弾性測定における積層フィルムのα緩和温度が、（熱可塑性樹脂Ｂのα緩和温度＋１０）℃〜（熱可塑性樹脂Ａのα緩和温度−１０）℃の間に観察され、かつ融点が２つ以上存在することが必要である。α緩和温度がこのような範囲となるためには、厚みが３０ｎｍ未満で熱可塑性樹脂Ａと熱可塑性樹脂Ｂからなる層が５０層以上積層されていることが好ましい。ここで、α緩和温度の高い方を熱可塑性樹脂Ａと定める。本発明の積層フィルムは、本来動的粘弾性測定において異なるα緩和温度をもつ熱可塑性樹脂Ａと熱可塑性樹脂Ｂを積層しているにもかかわらず、非常に微細な層構造となるため、積層フィルム自体のα緩和温度は、（熱可塑性樹脂Ｂのα緩和温度＋１０）℃〜（熱可塑性樹脂Ａのα緩和温度−１０）℃の間に単一の樹脂であるかのように一つ観察されるものである。これに対し、ＤＳＣによる融点測定においては、熱可塑性樹脂Ａと熱可塑性樹脂Ｂ個々の融点のピークが存在し、それぞれの樹脂の熱的性質が損なわれないことが必要である。このような場合に結晶部および非晶部の微細構造制御が達成され、各熱可塑性樹脂の特徴を損なうことなく、高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や広い温度範囲での成形加工性にも優れたフィルムを得ることができる。ここで、本発明におけるα緩和とは、動的粘弾性測定において、フィルム非晶部の比較的長い分子鎖の運動に起因するものであり、延伸フィルムのガラス転移温度に相当するものである（村上謙吉著 レオロジー基礎論 第１３２頁参照）。本発明積層フィルムのα緩和温度はより好ましくは（熱可塑性樹脂Ｂのα緩和温度＋１２）℃〜（熱可塑性樹脂Ａのα緩和温度−１２）℃である。この場合上述の効果のうち加熱後の透明性がさらに向上するため好ましい。α緩和温度をこのような温度範囲にするためには積層フィルム内での熱可塑性樹脂Ａの重量比率を２０ｗｔ％〜８０ｗｔ％にすることが好ましい。またさらに好ましくは（熱可塑性樹脂Ｂのα緩和温度＋１５）℃〜（熱可塑性樹脂Ａのα緩和温度−１５）℃である。この場合上述の効果のうち高温下での寸法安定性と加熱後の透明性がさらに向上するため、より好ましい。α緩和温度をこのような温度範囲にするためには積層フィルム内での熱可塑性樹脂Ａの重量比率を３５ｗｔ％〜６５ｗｔ％にすることが好ましい。熱可塑性樹脂Ａの重量比率が２０ｗｔ％未満の場合、一方の結晶制御が十分でなく、高温下での寸法安定性の効果が低減する場合がある。また８０ｗｔ％より大きい場合も同様である。 In the laminated film of the present invention, the α relaxation temperature of the laminated film in dynamic viscoelasticity measurement is between (α relaxation temperature of thermoplastic resin B + 10) ° C. to (α relaxation temperature of thermoplastic resin A−10) ° C. It must be observed and there must be at least two melting points. In order for the α relaxation temperature to be in such a range, it is preferable that 50 or more layers of thermoplastic resin A and thermoplastic resin B are laminated with a thickness of less than 30 nm. Here, the higher α relaxation temperature is defined as the thermoplastic resin A. The laminated film of the present invention has a very fine layer structure even though the thermoplastic resin A and the thermoplastic resin B, which originally have different α relaxation temperatures in the dynamic viscoelasticity measurement, are laminated. The α relaxation temperature of the film itself is observed as if it was a single resin between (α relaxation temperature of thermoplastic resin B + 10) ° C. to (α relaxation temperature of thermoplastic resin A−10) ° C. It is what is done. On the other hand, in the melting point measurement by DSC, it is necessary that the melting point peaks of the thermoplastic resin A and the thermoplastic resin B exist and the thermal properties of the respective resins are not impaired. In such a case, fine structure control of the crystal part and the amorphous part is achieved, without impairing the characteristics of each thermoplastic resin, high rigidity and excellent dimensional stability at high temperature, and transparency after heating In addition, it is possible to obtain a film excellent in moldability in a wide temperature range. Here, the α relaxation in the present invention is caused by the motion of a relatively long molecular chain in the film amorphous part in the dynamic viscoelasticity measurement, and corresponds to the glass transition temperature of the stretched film ( Murakami Kenkichi, Rheology Basics, page 132). The α relaxation temperature of the laminated film of the present invention is more preferably (α relaxation temperature of thermoplastic resin B + 12) ° C. to (α relaxation temperature of thermoplastic resin A−12) ° C. In this case, among the above effects, the transparency after heating is further improved, which is preferable. In order to set the α relaxation temperature in such a temperature range, the weight ratio of the thermoplastic resin A in the laminated film is preferably 20 wt% to 80 wt%. More preferably, it is (α relaxation temperature of thermoplastic resin B + 15) ° C. to (α relaxation temperature of thermoplastic resin A−15) ° C. In this case, among the above effects, the dimensional stability at high temperature and the transparency after heating are further improved, which is more preferable. In order to set the α relaxation temperature in such a temperature range, the weight ratio of the thermoplastic resin A in the laminated film is preferably 35 wt% to 65 wt%. When the weight ratio of the thermoplastic resin A is less than 20 wt%, one crystal control is not sufficient, and the effect of dimensional stability at high temperature may be reduced. The same applies to the case where it is greater than 80 wt%.
本発明に用いる熱可塑性樹脂は特に限定されるものではないが、熱可塑性樹脂Ａの融点が熱可塑性樹脂Ｂの融点より５℃以上高いことが好ましい。このような樹脂を用いると、３０ｎｍ未満の層が５０層以上である場合、両樹脂の結晶からなるラメラの周期構造が層内に形成されるため、高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や広い温度範囲での成形加工性にも優れたフィルムが得られるため好ましい。融点に５℃以上差がある２種類の熱可塑性樹脂は特に限定されるものではないが、熱可塑性樹脂Ａをポリエチレンテレフタレートとした場合には、熱可塑性樹脂Ｂには次のような樹脂が好ましく用いられる。例えばポリブチレンテレフタレートやポリプロピレンテレフタレートなどのポリエステル樹脂、ポリエチレン、ポリプロピレン、ポリメチルペンテンなどのポリオレフィン樹脂、ナイロン６やナイロン６６などのポリアミド樹脂、またポリエチレンテレフタレートにイソフタル酸、アジピン酸、セバシン酸、ダイマー酸、シクロヘキサンジカルボン酸などを共重合したものが挙げられるが、これに限るものではない。 The thermoplastic resin used in the present invention is not particularly limited, but the melting point of the thermoplastic resin A is preferably higher by 5 ° C. or more than the melting point of the thermoplastic resin B. When such a resin is used, when the number of layers less than 30 nm is 50 or more, a lamellar periodic structure composed of crystals of both resins is formed in the layer, so that the rigidity is high and the dimensional stability under high temperature is high. In addition, it is preferable because a film excellent in transparency after heating and excellent in moldability in a wide temperature range can be obtained. The two types of thermoplastic resins having a difference of 5 ° C. or more in the melting point are not particularly limited, but when the thermoplastic resin A is polyethylene terephthalate, the following resins are preferable for the thermoplastic resin B: Used. For example, polyester resins such as polybutylene terephthalate and polypropylene terephthalate, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, polyamide resins such as nylon 6 and nylon 66, polyethylene terephthalate, isophthalic acid, adipic acid, sebacic acid, dimer acid, Although what copolymerized cyclohexane dicarboxylic acid etc. is mentioned, it is not restricted to this.
また、熱可塑性樹脂Ａおよび熱可塑性樹脂Ｂに起因するα緩和以外に、第３の熱可塑性樹脂や各種添加剤に起因するα緩和および／または融点のピークが観察されてもよいものである。 Further, in addition to the α relaxation caused by the thermoplastic resin A and the thermoplastic resin B, α relaxation and / or melting point peaks caused by the third thermoplastic resin and various additives may be observed.
本発明の積層フィルムは、雰囲気温度を５０℃から６５℃まで変化させたときの長手方向および／または幅方向の熱膨張係数が１１０ｐｐｍ以下であることが好ましい。より好ましくは１００ｐｐｍ以下である。１１０ｐｐｍ以下の膨張の場合、加工時等に問題なく使用することができる。さらに延伸倍率を高めフィルムの配向を高めることで１００ｐｐｍ以下とすることができ、この場合ではさらに膨張の影響が少なく寸法安定性が向上するため好ましい。熱膨張係数の下限は特に定めるものではなく、低いほど好ましい。特に限定されないが、一般的には９０ｐｐｍ程度である。また熱膨張係数が１１０ｐｐｍより高いと、高温下での寸法安定性が低下し、たるみが発生したり皺が入りやすくなるため好ましくない。 The laminated film of the present invention preferably has a thermal expansion coefficient of 110 ppm or less in the longitudinal direction and / or the width direction when the atmospheric temperature is changed from 50 ° C. to 65 ° C. More preferably, it is 100 ppm or less. In the case of expansion of 110 ppm or less, it can be used without problems during processing. Further, by increasing the draw ratio and increasing the orientation of the film, it can be reduced to 100 ppm or less. In this case, the influence of expansion is further reduced and the dimensional stability is improved, which is preferable. The lower limit of the thermal expansion coefficient is not particularly defined, and the lower the better. Although not particularly limited, it is generally about 90 ppm. On the other hand, if the thermal expansion coefficient is higher than 110 ppm, the dimensional stability at a high temperature is lowered, and sagging or wrinkles easily occurs.
本発明の積層フィルムは２１０℃の雰囲気中で３０分加熱試験を実施した後のヘイズ上昇値が１５％以下であることが好ましい。ここでいうヘイズの上昇値とは、加熱後のヘイズ（％）と加熱前のヘイズ（％）の差である。より好ましくは１０％以下、さらに好ましくは５％以下、最も好ましくは２％以下である。熱可塑性樹脂Ａと熱可塑性樹脂Ｂを５０層以上積層することにより、ヘイズ上昇値を１５％以下にすることができ、この場合光線の透過性の観点から問題ない範囲であり、成形体等に用いるのに適している。さらにフィルム製膜時の熱処理温度を熱可塑性樹脂Ｂの融点Ｔｍ以下（ここで融点は熱可塑性樹脂Ａ＞熱可塑性樹脂Ｂとする）にすることにより、ヘイズ上昇値を１０％以下にすることができ、この場合透過光の散乱がより少なり、成形体としたとき外観が白く濁って見えることがないため好ましい。ここで融点Ｔｍとは、ＤＳＣにて試料を一定速度で昇温したとき、融解による吸熱が最も大きくなる温度のことである。また、積層精度を３０％以下にすることにより、ヘイズ上昇値を５％以下にすることができ、この場合透過光の散乱がさらに少なく、透明性に優れたフィルムを得ることができ、成形体とした場合、光沢のあるものとなるため好ましい。積層精度を３０％以下にするためには、製膜時に異なる種類の熱可塑性樹脂を積層させるユニットとして２００層〜２０００層のスリットを有し、かつそのスリットの加工精度が±１０μｍ以下であるフィードブロックとを用いることが好ましく、加えて積層数を増加させるために用いるスタティックミキサーは、その流路長Ｌが次に示す式に当てはまるものであることが好ましい。すなわちＬ≧Ｑ／（４０√Ａ）である（ここでＬ：スタティックミキサーの流路長[ｍ]、Ｑ：ポリマー押出量[ｔ／ｈ]、Ａ：総流路断面積[ｍ2]である）。またさらに製膜時の熱可塑性樹脂ＢのＴｍ以下とし、なおかつ上述のような、フィードブロックおよびスタティックミキサーを用いた場合には、ヘイズ上昇値を２％以下にすることができ、この場合透過光の散乱が非常に少なく、透明性に非常に優れたフィルムを得ることができ、成形体とした場合さらに光沢感のあるものとなるため好ましい。ヘイズ上昇値の下限は特に定めるものではなく、上昇値が低いほど散乱が少なくなるため好ましい。 The laminated film of the present invention preferably has a haze increase value of 15% or less after a 30-minute heating test in an atmosphere at 210 ° C. The increase value of haze here is a difference between haze (%) after heating and haze (%) before heating. More preferably, it is 10% or less, more preferably 5% or less, and most preferably 2% or less. By laminating 50 or more layers of the thermoplastic resin A and the thermoplastic resin B, the haze increase value can be reduced to 15% or less. In this case, there is no problem from the viewpoint of light transmittance, and the molded body or the like can be used. Suitable for use. Furthermore, by setting the heat treatment temperature during film formation to the melting point Tm or less of the thermoplastic resin B (where the melting point is thermoplastic resin A> thermoplastic resin B), the haze increase value can be 10% or less. In this case, the scattered light is less scattered, and it is preferable because the molded article does not appear white and cloudy. Here, the melting point Tm is a temperature at which the endotherm due to melting is maximized when the sample is heated at a constant rate by DSC. Further, by setting the lamination accuracy to 30% or less, the haze increase value can be made 5% or less. In this case, it is possible to obtain a film having less transparency of transmitted light and excellent transparency. Is preferable because it is glossy. In order to reduce the lamination accuracy to 30% or less, a feed having 200 to 2000 slits as a unit for laminating different types of thermoplastic resins during film formation, and the processing accuracy of the slits is ± 10 μm or less. In addition, it is preferable to use a block, and it is preferable that the static mixer used for increasing the number of stacked layers has a flow path length L that satisfies the following formula. That is, L ≧ Q / (40√A) (where, L: static mixer channel length [m], Q: polymer extrusion rate [t / h], A: total channel cross-sectional area [m 2 ]) is there). Further, when Tm or less of the thermoplastic resin B at the time of film formation is used, and the above-described feed block and static mixer are used, the haze increase value can be 2% or less. The film has a very low scattering and can be obtained with a very excellent transparency, and when it is formed into a molded product, it is preferable because it has a more glossy appearance. The lower limit of the haze increase value is not particularly defined, and the lower the increase value, the better the scattering.
本発明の積層フィルムは小角Ｘ線散乱測定において、ｅｎｄ方向および／あるいはｅｄｇｅ方向において、スポット状の散乱が観察されることが好ましい。本発明において、スポット状の散乱とは、ラメラ構造の厚みが大きいということを指している。このような構造とするためには、厚みが３０ｎｍ未満の層を５０層以上とすることが好ましく、またさらに長手方向と幅方向の物性の差が少なくなるように、延伸倍率を調整することがより好ましい。このような場合、隣り合う層との相互作用が強まり、高温下での寸法安定性と成形性を向上させるため好ましい。 In the laminated film of the present invention, it is preferable that spot-like scattering is observed in the end direction and / or the edge direction in the small-angle X-ray scattering measurement. In the present invention, spot-like scattering means that the thickness of the lamellar structure is large. In order to obtain such a structure, it is preferable that the thickness of the layer having a thickness of less than 30 nm is 50 or more, and the stretching ratio can be adjusted so that the difference in physical properties between the longitudinal direction and the width direction is reduced. More preferred. In such a case, the interaction with adjacent layers is strengthened, which is preferable because the dimensional stability and moldability at high temperatures are improved.
本発明の積層フィルムは熱可塑性樹脂Ａもしくは熱可塑性樹脂ＢのΔＴｍが６０℃以下であることが好ましい。ここでいうΔＴｍとはＤＳＣにて求まる、融点Ｔｍと降温結晶化温度Ｔｍｃの差である。降温結晶化温度Ｔｍｃとは、融点以上まで昇温して熱履歴を取り去った試料を一定速度で降温した時に、結晶化による放熱が最も大きくなる温度のことである。熱可塑性樹脂Ａもしくは熱可塑性樹脂ＢのΔＴｍが６０℃以下で、３０ｎｍ未満の層が５０層以上含まれる場合であれば、層内で両樹脂の結晶からなるラメラの周期構造が形成されるために適切な結晶化速度となり、高温下での寸法安定性と成形性が向上するため好ましい。 In the laminated film of the present invention, ΔTm of the thermoplastic resin A or the thermoplastic resin B is preferably 60 ° C. or less. Here, ΔTm is the difference between the melting point Tm and the cooling crystallization temperature Tmc, as determined by DSC. The temperature-falling crystallization temperature Tmc is a temperature at which the heat release due to crystallization becomes maximum when the temperature of a sample that has been raised to the melting point or higher and removed the thermal history is lowered at a constant rate. If ΔTm of thermoplastic resin A or thermoplastic resin B is 60 ° C. or lower and 50 or more layers of less than 30 nm are included, a lamellar periodic structure composed of crystals of both resins is formed in the layer. Therefore, it is preferable because the crystallization speed is suitable and the dimensional stability and moldability at high temperature are improved.
本発明の積層フィルムは、その厚みが１μｍ以上６００μｍ以下であることが好ましい。厚みが１μｍより小さい場合、皺が入りやすいなど取り扱い性が悪くなるため好ましくなく、さらに積層数が１０００層以上の場合には１層あたりの厚みが小さくなりすぎるため好ましくない。また６００μｍより大きい場合製膜が困難であったり、層の数が多くなりすぎるため生産効率が悪くなったり、厚みが大きすぎるため加工時等に取り扱い性が悪いため好ましくない。 The laminated film of the present invention preferably has a thickness of 1 μm or more and 600 μm or less. When the thickness is smaller than 1 μm, the handling property is deteriorated because it is easy to cause wrinkles, and when the number of laminated layers is 1000 layers or more, the thickness per layer becomes too small. On the other hand, when it is larger than 600 μm, it is not preferable because film formation is difficult, the number of layers becomes too large, the production efficiency is deteriorated, and the thickness is too large, so that the handleability is poor at the time of processing.
本発明の積層フィルムは二軸延伸フィルムであることが好ましい。二軸延伸されたフィルムは、高剛性でかつ高温下での寸法安定性に優れるためである。 The laminated film of the present invention is preferably a biaxially stretched film. This is because the biaxially stretched film has high rigidity and excellent dimensional stability at high temperatures.
本発明の積層フィルムは長手方向と幅方向の物性の差が小さく、縦横にバランス化されていることが好ましい。具体的には長手方向の破断伸度（％）と幅方向の破断伸度（％）の値の差が５０％以内である。このような構造にすることにより、高温下での寸法安定性や広い温度範囲での成形加工性が向上するだけでなく、加熱後の透明性も優れたフィルムを得ることができるため好ましい。縦横にバランス化された構造を持つためには、未延伸フィルムの幅方向の厚みにおいて、フィルムエッジ部分の厚みがフィルム中心部分の厚みの２．５倍以内であることが好ましい。未延伸フィルムがこのような厚みである場合、ニ軸延伸後の幅方向の厚みムラが少なく、製膜性が良好となるため好ましい。また延伸前に施す予熱工程の時間は２０秒以内であることが好ましい。予熱時間が２０秒より長いとフィルムの結晶化が進み、延伸性が悪くなるため好ましくない。さらに縦延伸および横延伸時の予熱工程で予熱温度と延伸温度は、熱可塑性樹脂Ａのガラス転移温度と熱可塑性樹脂Ｂのガラス転移温度の間の温度とすることが好ましく、延伸倍率は、２．８倍〜３．５倍の間とすることが好ましい。このような延伸条件で製膜した場合、熱可塑性樹脂Ａおよび熱可塑性樹脂Ｂ両方の樹脂の結晶化が制御されるため、加熱後の透明性が優れたフィルムになるとともに、長手方向・幅方向の配向が同程度となり縦横にバランス化されるため、高温下での寸法安定性や広い温度範囲での成形加工性が向上するものである。一方従来の積層フィルムではこのような温度条件で延伸すると、破れが多発するなどの問題があった。本発明の構成とすることにより、このような温度条件で延伸が可能となったものである。 The laminated film of the present invention has a small difference in physical properties between the longitudinal direction and the width direction, and is preferably balanced vertically and horizontally. Specifically, the difference between the breaking elongation (%) in the longitudinal direction and the breaking elongation (%) in the width direction is within 50%. Such a structure is preferable because not only the dimensional stability at high temperature and the molding processability in a wide temperature range can be improved, but also a film having excellent transparency after heating can be obtained. In order to have a vertically and horizontally balanced structure, it is preferable that the thickness of the film edge portion is within 2.5 times the thickness of the center portion of the film in the thickness in the width direction of the unstretched film. It is preferable that the unstretched film has such a thickness because the thickness unevenness in the width direction after biaxial stretching is small and the film forming property is improved. Moreover, it is preferable that the time of the preheating process performed before extending | stretching is less than 20 second. When the preheating time is longer than 20 seconds, the crystallization of the film proceeds and the stretchability is deteriorated, which is not preferable. Further, in the preheating step during longitudinal stretching and transverse stretching, the preheating temperature and the stretching temperature are preferably set between the glass transition temperature of the thermoplastic resin A and the glass transition temperature of the thermoplastic resin B, and the stretching ratio is 2 It is preferably between 8 times and 3.5 times. When the film is formed under such stretching conditions, since the crystallization of both the thermoplastic resin A and the thermoplastic resin B is controlled, it becomes a film having excellent transparency after heating, and in the longitudinal direction / width direction. Therefore, the dimensional stability at a high temperature and the molding processability in a wide temperature range are improved. On the other hand, when the conventional laminated film is stretched under such temperature conditions, there are problems such as frequent tearing. By adopting the configuration of the present invention, stretching can be performed under such temperature conditions.
本発明の積層構造としては、少なくとも熱可塑性樹脂Ａを主成分とする層と熱可塑性樹脂Ｂを主成分とする層とを厚み方向に規則的に積層した構造を有していることが好ましい。すなわち、本発明において、積層フィルム中の熱可塑性樹脂Ａを主成分とする層と熱可塑性樹脂Ｂを主成分とする層との厚み方向における配置の序列がランダムな状態ではないことが好ましく、熱可塑性樹脂Ａを主成分とする層と熱可塑性樹脂Ｂを主成分とする層以外の第３の層以上についてはその配置の序列については特に限定されるものではない。 本発明の積層フィルムにおいては、熱機械試験機を用い、本発明の測定条件にて測定した際、少なくとも長手方向の１８０℃における変形率が−１％以上３％以下であることが好ましい。より好ましくは、−０．３％以上１．５％以下である。すなわち、このようなフィルムは高温下での寸法安定性に優れたフィルムと言えるものであり、従来は制御することが困難であった長手方向の寸法安定性が大幅に向上したものである。一方、変形率が−１．０％未満の場合、収縮が大きく、成形加工の際に高度な寸法安定性を要求される場合には使用が困難となる。また、変形率が３より大きい場合には、膨張量が大きいために、同様に使用が困難となる。また、さらに好ましくは長手方向および幅方向の１８０℃における変形率が−１％以上３％以下であることが好ましい。 The laminated structure of the present invention preferably has a structure in which at least a layer mainly composed of the thermoplastic resin A and a layer mainly composed of the thermoplastic resin B are regularly laminated in the thickness direction. That is, in the present invention, it is preferable that the arrangement order in the thickness direction of the layer mainly composed of the thermoplastic resin A and the layer mainly composed of the thermoplastic resin B in the laminated film is not in a random state. The order of arrangement of the third and higher layers other than the layer mainly composed of the plastic resin A and the layer mainly composed of the thermoplastic resin B is not particularly limited. In the laminated film of the present invention, when measured under the measurement conditions of the present invention using a thermomechanical tester, it is preferable that at least the deformation rate at 180 ° C. in the longitudinal direction is −1% or more and 3% or less. More preferably, it is -0.3% or more and 1.5% or less. That is, such a film can be said to be a film excellent in dimensional stability at high temperatures, and the dimensional stability in the longitudinal direction, which has conventionally been difficult to control, is greatly improved. On the other hand, when the deformation rate is less than −1.0%, the shrinkage is large, and it becomes difficult to use when a high degree of dimensional stability is required during molding. Further, when the deformation rate is larger than 3, the expansion amount is large, so that the use is similarly difficult. More preferably, the deformation rate at 180 ° C. in the longitudinal direction and the width direction is from −1% to 3%.
本発明の積層フィルムでは、長手方向と幅方向の少なくとも一方向の降伏点応力が１００ＭＰａ以下であり、かつ破断伸度が１８０％以上であることがこのましい。このようなフィルムは、低応力で変形しかつ大変形にも追従できるため、成型加工性に優れたフィルムといえる。より好ましくは、少なくとも一方向の破断伸度が２００％以上である。破断伸度が１８０％未満の場合、大変形を要求される成型加工ではフィルム切れが生じるため好ましくない。 In the laminated film of the present invention, it is preferable that the yield point stress in at least one of the longitudinal direction and the width direction is 100 MPa or less and the elongation at break is 180% or more. Such a film can be said to be a film excellent in molding processability because it deforms with low stress and can follow large deformation. More preferably, the elongation at break in at least one direction is 200% or more. When the elongation at break is less than 180%, the film breakage occurs in the molding process requiring large deformation, which is not preferable.
本発明の積層フィルムは、長手方向と幅方向の合計のヤング率が７ＧＰａ以上であることが好ましい。このようなフィルムは、剛性に優れており、加工工程でのハンドリング性に優れる。また、より好ましくは７．５ＧＰａ以上である。 The laminated film of the present invention preferably has a total Young's modulus of 7 GPa or more in the longitudinal direction and the width direction. Such a film is excellent in rigidity and excellent in handling properties in a processing step. More preferably, it is 7.5 GPa or more.
本発明の積層フィルムには、易滑層、易接着層、粘着層、反射防止膜、ハードコート層、近赤外線遮蔽層、電磁波遮蔽層、帯電防止層、導電層、防汚層、結露防止層などが内部や表層に形成されていてもよい。これらの層としては、特に限定されず各種の従来から知られている技術等を用いることができる。 The laminated film of the present invention includes an easy-slip layer, an easy-adhesion layer, an adhesive layer, an antireflection film, a hard coat layer, a near-infrared shielding layer, an electromagnetic wave shielding layer, an antistatic layer, a conductive layer, an antifouling layer, and a dew condensation prevention layer. Etc. may be formed inside or on the surface layer. These layers are not particularly limited, and various conventionally known techniques can be used.
次に、本発明の積層フィルムの好ましい製造方法を以下に説明する。
熱可塑性樹脂Ａおよび熱可塑性樹脂Ｂをペレットなどの形態で用意する。ペレットは、必要に応じて、事前乾燥を熱風中あるいは真空下で行い、押出機に供給される。押出機内において、融点以上に加熱溶融された樹脂は、ギヤポンプ等で樹脂の押出量を均一化され、フィルタ等を介して異物や変性した樹脂をろ過される。さらに、樹脂はダイにて目的の形状に成形された後、吐出される。
Next, the preferable manufacturing method of the laminated | multilayer film of this invention is demonstrated below.
A thermoplastic resin A and a thermoplastic resin B are prepared in the form of pellets. If necessary, the pellets are pre-dried in hot air or under vacuum and supplied to an extruder. In the extruder, the resin melted by heating to the melting point or higher is made uniform in the amount of resin extruded by a gear pump or the like, and foreign matter or modified resin is filtered through a filter or the like. Further, the resin is formed into a desired shape with a die and then discharged.
多層フィルムを得るための方法としては、２台以上の押出機を用いて異なる流路から送り出された熱可塑性樹脂を、マルチマニホールドダイやフィールドブロックやスタティックミキサー等を用いて多層に積層する方法等を使用することができる。また、これらを任意に組み合わせても良い。ここで本発明の効果を効率よく得るためには、５００層以上のフィードブロックを少なくとも用いることが好ましい。また、さらにこのフィードブロック部での圧力損失が３ＭＰａ以上１０ＭＰａ以下であることがより好ましい。少なくとも５００層以上のフィードブロックを用いると、積層精度が良好となるため好ましい。また、フィードブロック部での圧力損出が３ＭＰａ以上１０ＭＰａ以下であると、さらに積層精度が高い積層フィルムを得られやすくなり好ましい。 As a method for obtaining a multilayer film, a method of laminating thermoplastic resins sent from different flow paths using two or more extruders in multiple layers using a multi-manifold die, a field block, a static mixer, etc. Can be used. Moreover, you may combine these arbitrarily. Here, in order to efficiently obtain the effect of the present invention, it is preferable to use at least a feed block having 500 layers or more. Furthermore, it is more preferable that the pressure loss in the feed block portion is 3 MPa or more and 10 MPa or less. It is preferable to use a feed block having at least 500 layers because stacking accuracy is improved. In addition, it is preferable that the pressure loss at the feed block portion is 3 MPa or more and 10 MPa or less because it is easy to obtain a laminated film with higher lamination accuracy.
ダイから吐出された多層に積層されたシートは、キャスティングドラム等の冷却体上に押し出され、冷却固化され、キャスティングフィルムが得られる。この際、ワイヤー状、テープ状、針状あるいはナイフ状等の電極を用いて、静電気力によりキャスティングドラム等の冷却体に密着させ急冷固化させる方法や、スリット状、スポット状の装置からエアーを吹き出してキャスティングドラム等の冷却体に密着させ急冷固化させる方法が好ましい。このようにして得られたキャスティングフィルムは、必要に応じて二軸延伸することが好ましい。二軸延伸とは、縦方向および横方向に延伸することをいう。二軸延伸されたフィルムは、高剛性でかつ高温下での寸法安定性に優れるため好ましい。延伸は、逐次二軸延伸しても良いし、同時に二方向に延伸してもよい。また、さらに縦および／または横方向に再延伸を行ってもよい。 The multi-layered sheets discharged from the die are extruded onto a cooling body such as a casting drum, and cooled and solidified to obtain a casting film. At this time, air is blown out from a slit-like or spot-like device by using a wire-like, tape-like, needle-like, or knife-like electrode to bring it into close contact with a cooling body such as a casting drum by electrostatic force and rapidly solidify it. Thus, a method in which the material is brought into close contact with a cooling body such as a casting drum and rapidly solidified is preferable. The casting film thus obtained is preferably biaxially stretched as necessary. Biaxial stretching refers to stretching in the longitudinal direction and the transverse direction. A biaxially stretched film is preferred because it is highly rigid and excellent in dimensional stability at high temperatures. Stretching may be performed sequentially biaxially or simultaneously in two directions. Further, re-stretching may be performed in the longitudinal and / or transverse direction.
ここで、縦方向への延伸とは、フィルムに長手方向の分子配向を与えるための延伸を言い、通常は、ロールの周速差により施される。この延伸は１段階で行ってもよく、また、複数本のロール対を使用して多段階に行っても良い。延伸の倍率としては樹脂の種類により異なるが、通常、２〜１５倍が好ましく、積層フィルムを構成する樹脂の過半量がポリエチレンテレフタレートを用いた場合には、２〜７倍が特に好ましく用いられる。さらに長手方向と幅方向の物性の差を小さくして、寸法安定性や成形性を向上させたい場合には、２．８倍〜３．５倍が好ましく用いられる。また、延伸温度としては積層フィルムを構成する樹脂のガラス転移温度〜ガラス転移温度＋１００℃が好ましい。また長手方向と幅方向の物性の差を小さくして、寸法安定性や成形性を向上させたい場合には、熱可塑性樹脂Ａのガラス転移温度と熱可塑性樹脂Ｂのガラス転移温度の間の温度で予熱・延伸することが好ましい。 Here, the stretching in the longitudinal direction refers to stretching for imparting molecular orientation in the longitudinal direction to the film, and is usually performed by a difference in peripheral speed between rolls. This stretching may be performed in one stage, or may be performed in multiple stages using a plurality of roll pairs. Although it changes with kinds of resin as a magnification of extending | stretching, 2 to 15 times is preferable normally, and when the majority of resin which comprises a laminated | multilayer film uses a polyethylene terephthalate, 2 to 7 times is used especially preferable. Furthermore, when it is desired to reduce the difference in physical properties between the longitudinal direction and the width direction to improve dimensional stability and formability, 2.8 to 3.5 times is preferably used. Moreover, as extending | stretching temperature, the glass transition temperature-glass transition temperature +100 degreeC of resin which comprises a laminated | multilayer film are preferable. Further, when it is desired to improve the dimensional stability and formability by reducing the difference between the physical properties in the longitudinal direction and the width direction, the temperature between the glass transition temperature of the thermoplastic resin A and the glass transition temperature of the thermoplastic resin B. It is preferable to preheat and stretch with.
このようにして得られた一軸延伸されたフィルムに、必要に応じてコロナ処理やフレーム処理、プラズマ処理などの表面処理を施した後、易滑性、易接着性、帯電防止性などの機能をインラインコーティングにより付与してもよい。 The uniaxially stretched film thus obtained is subjected to surface treatment such as corona treatment, flame treatment, and plasma treatment as necessary, and then functions such as slipperiness, easy adhesion, and antistatic properties are provided. It may be applied by in-line coating.
また、横方向の延伸とは、フィルムに幅方向の配向を与えるための延伸を言い、通常は、テンターを用いて、フィルムの両端をクリップで把持しながら搬送して、幅方向に延伸する。延伸の倍率としては樹脂の種類により異なるが、通常、２〜１５倍が好ましく、積層フィルムを構成する樹脂の過半量がポリエチレンテレフタレートを用いた場合には、２〜７倍が特に好ましく用いられる。さらに長手方向と幅方向の物性の差を小さくして、寸法安定性や成形性を向上させたい場合には、２．８倍〜３．５倍が好ましく用いられる。また、延伸温度としては積層フィルムを構成する樹脂のガラス転移温度〜ガラス転移温度＋１２０℃が好ましい。さらに長手方向と幅方向の物性の差を小さくして、寸法安定性や成形性を向上させたい場合には、熱可塑性樹脂Ａのガラス転移温度と熱可塑性樹脂Ｂのガラス転移温度の間の温度で予熱・延伸することが好ましい。 The stretching in the transverse direction refers to stretching for imparting the orientation in the width direction to the film. Usually, the film is stretched in the width direction by using a tenter while conveying both ends of the film with clips. Although it changes with kinds of resin as a magnification of extending | stretching, 2 to 15 times is preferable normally, and when the majority of resin which comprises a laminated | multilayer film uses a polyethylene terephthalate, 2 to 7 times is used especially preferable. Furthermore, when it is desired to reduce the difference in physical properties between the longitudinal direction and the width direction to improve dimensional stability and formability, 2.8 to 3.5 times is preferably used. Moreover, as extending | stretching temperature, the glass transition temperature-glass transition temperature +120 degreeC of resin which comprises a laminated | multilayer film are preferable. Furthermore, when it is desired to improve the dimensional stability and moldability by reducing the difference in physical properties between the longitudinal direction and the width direction, the temperature between the glass transition temperature of the thermoplastic resin A and the glass transition temperature of the thermoplastic resin B. It is preferable to preheat and stretch with.
こうして二軸延伸されたフィルムは、平面性、寸法安定性を付与するために、テンター内で延伸温度以上融点以下の熱処理を行うのが好ましい。より好ましくは熱可塑性樹脂Ａの融点以下、熱可塑性樹脂Ｂの融点以上（ここでは熱可塑性樹脂Ａの融点＞熱可塑性樹脂Ｂの融点）である。このように熱可塑性樹脂Ａの融点以下、熱可塑性樹脂Ｂの融点以上で熱処理された場合、前述の層内に周期構造が形成されるようになり、より高い寸法安定性と成形加工性が得られるようになるものである。このようにして熱処理された後、均一に徐冷後、室温まで冷やして巻き取られる。また、必要に応じて、熱処理から徐冷の際に弛緩処理などを併用してもよい。 The biaxially stretched film is preferably subjected to a heat treatment at a temperature not lower than the stretching temperature and not higher than the melting point in the tenter in order to impart flatness and dimensional stability. More preferably, it is below the melting point of the thermoplastic resin A and above the melting point of the thermoplastic resin B (here, the melting point of the thermoplastic resin A> the melting point of the thermoplastic resin B). Thus, when heat treatment is performed below the melting point of the thermoplastic resin A and above the melting point of the thermoplastic resin B, a periodic structure is formed in the aforementioned layer, and higher dimensional stability and moldability are obtained. It comes to be able to be. After being heat-treated in this way, it is gradually cooled down uniformly, then cooled to room temperature and wound up. Moreover, you may use a relaxation process etc. together in the case of annealing from heat processing as needed.
そして、このようにして得られた本発明の積層フィルムは、成形体として、各種成形加工などに好適に用いられる。加工方法は特に限定されないが、例えば表面加工、エンボス加工、サンドマット加工、絞り加工、真空成形、真空圧空成形、インモールドラミ、冷間延伸、インモールドスタンピング、インサート成形などの易成形性が求められる加工方法において、製品または支持体として用いられるとき、必要な形状に成形加工できるものである。また本発明の積層フィルムは転写箔の材料に好適である。転写箔はベースフィルム上に剥離層・インキ・接着層などが重なった構成であり、熱や圧力を用いて成形済み製品に絵柄を転写する際に用いられる。本発明の積層フィルムは広い温度範囲での成形加工性に優れるため、転写箔のベースフィルムとして用いて、複雑な形状の製品に絵柄を転写するのに好適である。さらに本発明の積層フィルムは携帯電話用のリチウムイオン電池等の外装材に好適である。リチウムイオン電池の外装材用途では深いしぼり比での成形が要求され、その構成としては未延伸ポリプロピレンフィルム、アルミ箔に加え、ナイロンフィルム、ＰＥＴフィルムなどを貼り合わせたものとなっている。本発明の積層フィルムは従来に比べて深いしぼりや複雑な形状にも加工でき、さらに高剛性であり透明性が高く外観の点で優れ、耐薬品性にも優れる特徴を有している。よって本発明の積層フィルムを未延伸ポリプロピレンフィルム、アルミ箔と貼り合わせてリチウムイオン電池の外装材として好適に用いることができる。 And the laminated | multilayer film of this invention obtained by doing in this way are used suitably for various shaping | molding processes etc. as a molded object. The processing method is not particularly limited, but easy formability such as surface processing, embossing, sand mat processing, drawing processing, vacuum forming, vacuum / pressure forming, in-mold lamination, cold drawing, in-mold stamping, insert molding is required. In a processing method to be used, when used as a product or a support, it can be formed into a required shape. The laminated film of the present invention is suitable as a material for transfer foil. The transfer foil has a structure in which a release layer, an ink, an adhesive layer, and the like overlap on a base film, and is used when a pattern is transferred to a molded product using heat or pressure. Since the laminated film of the present invention is excellent in moldability in a wide temperature range, it can be used as a base film for a transfer foil and is suitable for transferring a pattern to a product having a complicated shape. Furthermore, the laminated film of the present invention is suitable for exterior materials such as lithium ion batteries for mobile phones. In the case of exterior materials for lithium ion batteries, molding with a deep squeezing ratio is required, and the configuration is a laminate of an unstretched polypropylene film, an aluminum foil, a nylon film, a PET film, and the like. The laminated film of the present invention can be processed into deep squeezing and complex shapes as compared with the conventional ones, and further has characteristics of high rigidity, high transparency, excellent appearance, and excellent chemical resistance. Therefore, the laminated film of the present invention can be suitably used as an exterior material of a lithium ion battery by laminating with an unstretched polypropylene film and an aluminum foil.
本発明に使用した物性値の評価法を記載する。
（物性値の評価法）
（１）積層数
フィルムの層構成は、ミクロトームを用いて断面を切り出したサンプルについて、電子顕微鏡観察により求めた。すなわち、透過型電子顕微鏡ＨＵ−１２型（（株）日立製作所製）を用い、フィルムの断面を３０００〜５０００００倍に拡大観察し、断面写真を撮影、層構成および層数を測定した。なお本測定では２０００００倍に拡大し、ＲｕＯ４で染色して観察を行なった。
An evaluation method of physical property values used in the present invention will be described.
(Method for evaluating physical properties)
(1) Number of layers The layer structure of the film was determined by observation with an electron microscope for a sample obtained by cutting out a cross section using a microtome. That is, using a transmission electron microscope HU-12 type (manufactured by Hitachi, Ltd.), the cross section of the film was magnified to 3000 to 500,000 times, a cross-sectional photograph was taken, and the layer configuration and the number of layers were measured. In this measurement, the image was magnified 200000 times and stained with RuO4 for observation.
（２）動的粘弾性
動的粘弾性はセイコーインスツルメンツ（株）社製ＥＸＳＴＲＡ６０００＆ＤＭＳ６１００を用いて評価した。長手方向について、昇温速度２℃／ｍｉｎで−１５０℃から２２０℃まで昇温し、そのｔａｎδからα緩和のピーク温度を読みとり、α緩和温度とした。周波数は１Ｈｚ、試料形状は長さ２０ｍｍ、幅１０ｍｍとした。
(2) Dynamic Viscoelasticity Dynamic viscoelasticity was evaluated using EXSTRA6000 & DMS6100 manufactured by Seiko Instruments Inc. In the longitudinal direction, the temperature was increased from −150 ° C. to 220 ° C. at a rate of temperature increase of 2 ° C./min, and the α relaxation peak temperature was read from the tan δ to obtain the α relaxation temperature. The frequency was 1 Hz, the sample shape was 20 mm long and 10 mm wide.
（３）融点・降温結晶化温度
試料の融点は、示差熱量分析（ＤＳＣ）を用い、ＪＩＳ−Ｋ−７１２２（１９８７年）に従って測定・算出した。装置はセイコー電子工業（株）製”ロボットＤＳＣ−ＲＤＣ２２０”、またデータ解析は”ディスクセッションＳＳＣ／５２００”を用いて評価を行なった。サンプル質量は５ｍｇ、昇温および降温速度は２０℃／ｍｉｎとした。
(3) Melting point / cooling crystallization temperature The melting point of the sample was measured and calculated according to JIS-K-7122 (1987) using differential calorimetry (DSC). Evaluation was performed using “Robot DSC-RDC220” manufactured by Seiko Denshi Kogyo Co., Ltd., and “Disk Session SSC / 5200” for data analysis. The sample mass was 5 mg, and the temperature increase and decrease rate was 20 ° C./min.
（４）熱膨張係数
熱膨張係数は、熱機械試験機セイコーインスツルメンス（株）社製ＥＸＴＡＲ６０００＆ＴＭＡ／ＳＳ６０００を用いて評価した。試料は長さ２０ｍｍ、幅４ｍｍとし、長手方向、幅方向それぞれについて、定荷重伸び量試験機のチャック間（距離Ｌ＝１５０ｍｍ）にフィルムを把持した。昇温速度１０℃／ｍｉｎで３０℃から１５０℃まで昇温し、続いて降温速度１０℃／ｍｉｎで１５０℃から３０℃まで降温した。この降温過程での６５℃から５０℃までの変形量を平均傾きから求めた。測定中の荷重は３６７．５ｋＰａに一定になるようにした。
(4) Thermal expansion coefficient The thermal expansion coefficient was evaluated using EXTAR6000 & TMA / SS6000 manufactured by Seiko Instruments Inc. The sample had a length of 20 mm and a width of 4 mm, and the film was held between the chucks of the constant load elongation tester (distance L = 150 mm) in each of the longitudinal direction and the width direction. The temperature was increased from 30 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C./min, and then the temperature was decreased from 150 ° C. to 30 ° C. at a rate of temperature decrease of 10 ° C./min. The amount of deformation from 65 ° C. to 50 ° C. in the temperature lowering process was determined from the average slope. The load during measurement was made constant at 367.5 kPa.
（５）ヘイズ
２３℃、相対湿度６５％において、フィルムを２時間放置した後、スガ試験機（株）製全自動直読ヘイズコンピューター「ＨＧＭ−２ＤＰ」を用いて、波長５９０ｎｍにおけるヘイズを測定した。３回の測定値の平均値を該サンプルのヘイズとした。また加熱試験後のヘイズの上昇値を測定する方法としては、試料を収縮変形しないように金属製の枠に貼りつけ、２１０℃に設定したＴＡＢＡＩ製ギアオーブンＧＨＰＳ−２２２中で３０分間加熱し取り出した。この加熱後の試料のヘイズを上述の方法で測定し、加熱試験後のヘイズ上昇値を求めた。
加熱後のヘイズ上昇値＝加熱後のヘイズ（％）− 加熱前のヘイズ（％）
（６）小角Ｘ線散乱測定による結晶構造
理学電機（株）社製Ｘ線発生装置ＲＵ−２００を用いて行った。Ｘ線源はＣｕＫα線（Ｎｉフィルター使用）、出力５０ｋＶ ２００ｍＡ、スリット系０．５ｍｍφ、カメラ半径４０５ｍｍ、露出時間６０ｍｉｎとした。得られた結果を表２に示す。
(5) Haze The film was allowed to stand for 2 hours at 23 ° C. and a relative humidity of 65%, and then the haze at a wavelength of 590 nm was measured using a fully automatic direct reading haze computer “HGM-2DP” manufactured by Suga Test Instruments Co., Ltd. The average value of three measurements was taken as the haze of the sample. As a method of measuring the increase in haze after the heating test, the sample was attached to a metal frame so as not to be deformed by deformation, and heated for 30 minutes in a TABAI gear oven GHPS-222 set at 210 ° C. It was. The haze of the sample after heating was measured by the method described above, and the haze increase value after the heating test was determined.
Increase in haze after heating = haze after heating (%)-haze before heating (%)
(6) Crystal structure by small-angle X-ray scattering measurement This was performed using an X-ray generator RU-200 manufactured by Rigaku Corporation. The X-ray source was CuKα ray (using Ni filter), output 50 kV 200 mA, slit system 0.5 mmφ, camera radius 405 mm, and exposure time 60 min. The obtained results are shown in Table 2.
（７）寸法安定性
寸法安定性は、熱機械試験機セイコーインスツルメンス（株）社製ＥＸＴＡＲ６０００＆ＴＭＡ／ＳＳ６０００を用いて評価した。試料は長さ２０ｍｍ、幅４ｍｍとし、長手方向、幅方向それぞれについて、定荷重伸び量試験機のチャック間（距離Ｌ＝１５０ｍｍ）にフィルムを把持し、昇温速度１０℃／ｍｉｎで３０℃から１５０℃まで昇温した時の１８０℃における変形量を寸法安定性とした。測定中の荷重は３６７．５ｋＰａに一定になるようにした。なお、変形量がマイナスの場合、収縮をあらわし、変形量がプラスの場合、伸びを示しているものである。また、ｎ数は３回とし、その平均値を採用した。
(7) Dimensional stability Dimensional stability was evaluated using an EXTAR6000 & TMA / SS6000 manufactured by Seiko Instruments Inc. The sample has a length of 20 mm and a width of 4 mm. In each of the longitudinal direction and the width direction, the film is held between chucks of a constant load elongation tester (distance L = 150 mm), and the temperature rises from 30 ° C. at a rate of temperature increase of 10 ° C./min. The amount of deformation at 180 ° C. when the temperature was raised to 150 ° C. was defined as dimensional stability. The load during measurement was made constant at 367.5 kPa. In addition, when the deformation amount is negative, it indicates contraction, and when the deformation amount is positive, it indicates elongation. The number of n was 3 and the average value was adopted.
（８）、破断伸度、
破断伸度はインストロンタイプの引張試験機（オリエンテック（株）製フィルム強伸度自動測定装置“テンシロンＡＭＦ／ＲＴＡ−１００”）を用いて、２５℃、６５％ＲＨの環境下にてＪＩＳ−Ｋ７１２７（１９９９年）に準拠して測定した。フィルム長手方向およびフィルム幅方向それぞれについて、幅１０ｍｍの試料フィルムを、試長間１００ｍｍ、引張り速度２００ｍｍ／分の条件で引張り、破断伸度を求めた。なお、ｎ数は５回とし、その平均値を採用した。
(8), elongation at break,
The elongation at break was determined by using an Instron type tensile tester (Orientec Co., Ltd. film tensile strength automatic measuring device “Tensilon AMF / RTA-100”) in an environment of 25 ° C. and 65% RH. -Measured according to K7127 (1999). With respect to each of the film longitudinal direction and the film width direction, a sample film having a width of 10 mm was stretched under conditions of 100 mm between test lengths and a pulling speed of 200 mm / min, and the breaking elongation was determined. The number of n was 5 and the average value was adopted.
（９）固有粘度
オルトクロロフェノール中、２５℃で測定した溶液粘度から、算出した。また、溶液粘度はオストワルド粘度計を用いて測定した。単位は［ｄｌ／ｇ］で示した。なお、ｎ数は３回とし、その平均値を採用した。
(9) Intrinsic viscosity Calculated from the solution viscosity measured at 25 ° C in orthochlorophenol. The solution viscosity was measured using an Ostwald viscometer. The unit is [dl / g]. In addition, n number was made into 3 times and the average value was employ | adopted.
（１０）真空成形テスト
真空成形装置ＳＡＮＷＡ ＫＯＧＹＯ ＰＬＡＶＡＣ ＴＹＰＥ ＦＢ−７を用いてテストした。１９３℃に加熱した試料に、深さ１５ｍｍ、直径５０ｍｍの円柱状のカップを押し当て、さらにカップ内の空気を一瞬で抜き取って真空にした。このとき試料がカップの形状に追従して変形するものは、成形性が高いと判断し、○とした。また試料がカップに追従して変形するものの、角部分が十分に成形されないものを△とした。さらに試料がカップに追従せず、ほとんど変形しないものは成形性が低いと判断し、×とした。
(10) Vacuum forming test It tested using the vacuum forming apparatus SANWA KOGYO PLAVAC TYPE FB-7. A columnar cup having a depth of 15 mm and a diameter of 50 mm was pressed against the sample heated to 193 ° C., and the air in the cup was taken out instantaneously to make a vacuum. At this time, the sample that deformed following the shape of the cup was judged to have high moldability, and was evaluated as ◯. Moreover, although the sample was deformed following the cup, the case where the corner portion was not sufficiently formed was indicated as Δ. Further, samples that did not follow the cup and hardly deformed were judged to have low moldability and were evaluated as x.
（実施例１）
熱可塑性樹脂Ａとして、融点Ｔｍ２５５℃、降温結晶化温度Ｔｍｃ１９２℃、固有粘度０．６５のポリエチレンテレフタレート（ＰＥＴ）である東レ社製Ｆ２０Ｓを用いた。この樹脂は、比較例１と同様の延伸条件および熱処理条件でＰＥＴ単体の二軸延伸フィルムとしたとき、動的粘弾性測定におけるα緩和温度が１１８℃に観察されるものである。また熱可塑性樹脂Ｂとして融点Ｔｍ２２３℃、降温結晶化温度Ｔｍｃ１６８℃、固有粘度１．２のポリブチレンテレフタレート（ＰＢＴ）である東レ社製トレコン１２００Ｓを用いた。この樹脂は、実施例１と同様の延伸条件および熱処理条件でＰＢＴ単体の二軸延伸フィルムとしたとき、動的粘弾性測定におけるα緩和温度が４９℃に観察されるものである。ただし本発明で用いたＰＢＴは融点が２２３℃であるため熱処理条件を２３５℃とするとフィルムが融解する問題がある。このためＰＢＴの両表面にＰＥＴの層を積層し、ＰＥＴ／ＰＢＴ／ＰＥＴという３層の構成にして製膜し、α緩和温度を測定した。これらの熱可塑性樹脂は、それぞれ乾燥した後、押出機に供給した。
(Example 1)
As the thermoplastic resin A, F20S manufactured by Toray Industries, Inc., which is polyethylene terephthalate (PET) having a melting point Tm of 255 ° C., a falling crystallization temperature Tmc of 192 ° C., and an intrinsic viscosity of 0.65, was used. When this resin is a biaxially stretched film of PET alone under the same stretching conditions and heat treatment conditions as in Comparative Example 1, the α relaxation temperature in the dynamic viscoelasticity measurement is observed at 118 ° C. As the thermoplastic resin B, Toraycon 1200S manufactured by Toray Industries, Inc., which is polybutylene terephthalate (PBT) having a melting point Tm of 223 ° C., a falling crystallization temperature Tmc of 168 ° C., and an intrinsic viscosity of 1.2 was used. When this resin is a biaxially stretched film of PBT alone under the same stretching conditions and heat treatment conditions as in Example 1, the α relaxation temperature in the dynamic viscoelasticity measurement is observed at 49 ° C. However, since the PBT used in the present invention has a melting point of 223 ° C., there is a problem that the film melts when the heat treatment condition is 235 ° C. For this reason, a PET layer was laminated on both surfaces of the PBT to form a three-layer structure of PET / PBT / PET, and the α relaxation temperature was measured. Each of these thermoplastic resins was dried and then supplied to an extruder.
熱可塑性樹脂ＡおよびＢは、それぞれ、押出機にて２８０℃の溶融状態とし、ギヤポンプおよびフィルタを介した後、１７７層のフィードブロック（圧力損失１ＭＰａ）にて合流させた。合流した熱可塑性樹脂ＡおよびＢは、スタティックミキサーに供給して、スクエア状の流路にて３回分割・結合され、ＰＥＴが７０５層、ＰＢＴが７０４層からなる厚み方向に交互に積層された構造とし、両表層部分がＰＥＴとなった。ここで、積層厚み比（＝重量比）がＡ／Ｂ＝１になるよう、吐出量にて調整した。このようにして得られた計１４０９層からなる積層体をＴダイに供給しシート状に成形した後、静電印加しながら、表面温度２０℃に保たれたキャスティングドラム上で急冷固化した。この時キャスティングフィルムは幅方向の厚みにおいて、フィルムエッジ部分の厚みがフィルム中心部分の厚みの２．３倍となるようにした。
得られたキャストフィルムは、６０℃に設定したロール群で１０秒間予熱し、さらに７０℃に設定したロール群で加熱し、縦方向に３倍延伸した。この一軸延伸フィルムをテンターに導き、７０℃の熱風で予熱後、横方向に３．２倍延伸した。延伸したフィルムは、そのまま、テンター内で２３５℃の熱風にて熱処理を行い、つづいて５％の弛緩処理を施し、室温まで徐冷後、巻き取った。得られたフィルムの厚みは、１２μｍであった。得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表１および表３に示す。
The thermoplastic resins A and B were each melted at 280 ° C. with an extruder, passed through a gear pump and a filter, and then merged in a 177-layer feed block (pressure loss 1 MPa). The joined thermoplastic resins A and B were supplied to a static mixer and divided and combined three times in a square flow path, and were alternately laminated in the thickness direction consisting of 705 layers of PET and 704 layers of PBT. The structure was such that both surface layers were PET. Here, the discharge thickness was adjusted so that the lamination thickness ratio (= weight ratio) was A / B = 1. The thus obtained laminate consisting of a total of 1409 layers was supplied to a T-die and formed into a sheet, and then rapidly cooled and solidified on a casting drum maintained at a surface temperature of 20 ° C. while applying an electrostatic force. At this time, in the thickness of the casting film in the width direction, the thickness of the film edge portion was set to 2.3 times the thickness of the film central portion.
The obtained cast film was preheated with a roll group set at 60 ° C. for 10 seconds, further heated with a roll group set at 70 ° C., and stretched 3 times in the longitudinal direction. The uniaxially stretched film was guided to a tenter, preheated with hot air at 70 ° C., and stretched 3.2 times in the transverse direction. The stretched film was directly heat-treated in a tenter with hot air at 235 ° C., subsequently subjected to a relaxation treatment of 5%, gradually cooled to room temperature, and wound up. The thickness of the obtained film was 12 μm. The obtained film was highly rigid and excellent in dimensional stability at high temperatures, and was also excellent in transparency after heating and moldability in a wide temperature range. The obtained results are shown in Tables 1 and 3.
（実施例２）
スクエアー状流路のスタティックミキサーにて分割・結合される回数が２回であること以外は、実施例１と同様の装置・条件で、計７０５層からなる積層フィルムを得た。積層フィルムの厚みは１２μｍとした。得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表１に示す。
(Example 2)
A laminated film consisting of a total of 705 layers was obtained under the same apparatus and conditions as in Example 1 except that the number of times of division and coupling by the static mixer of the square channel was two. The thickness of the laminated film was 12 μm. The obtained film was highly rigid and excellent in dimensional stability at high temperatures, and was also excellent in transparency after heating and moldability in a wide temperature range. The obtained results are shown in Table 1.
（実施例３）
スクエア状流路のスタティックミキサーにて分割・結合される回数が１回であること以外は実施例１と同様の装置・条件で、計３５３層からなる積層フィルムを得た。積層フィルムの厚みは１２μｍとした。得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表１に示す。
(Example 3)
A laminated film consisting of a total of 353 layers was obtained under the same apparatus and conditions as in Example 1 except that the number of times of division and coupling by the static mixer of the square channel was one. The thickness of the laminated film was 12 μm. The obtained film was highly rigid and excellent in dimensional stability at high temperatures, and was also excellent in transparency after heating and moldability in a wide temperature range. The obtained results are shown in Table 1.
（実施例４）
実施例１と同様の装置・条件で、計１４０９層からなる積層フィルムを得た。但し、製膜速度を調整してフィルム厚みを２５μｍとした。得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表１に示す。
Example 4
A laminated film consisting of a total of 1409 layers was obtained under the same apparatus and conditions as in Example 1. However, the film thickness was adjusted to 25 μm by adjusting the film forming speed. The obtained film was highly rigid and excellent in dimensional stability at high temperatures, and was also excellent in transparency after heating and moldability in a wide temperature range. The obtained results are shown in Table 1.
（実施例５）
実施例１と同様の装置・条件で、計１４０９層からなる積層フィルムを得た。但し、製膜速度を調整してフィルム厚みを４０μｍとした得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表１に示す。
(Example 5)
A laminated film consisting of a total of 1409 layers was obtained under the same apparatus and conditions as in Example 1. However, the resulting film with a film thickness of 40 μm by adjusting the film forming speed is highly rigid and excellent in dimensional stability at high temperature. Furthermore, transparency after heating and moldability in a wide temperature range It was also an excellent film. The obtained results are shown in Table 1.
（実施例６）
実施例１と同様の装置・条件で、計１４０９層からなる積層フィルムを得た。但し、それぞれの熱可塑性樹脂の層厚みがＡ：Ｂ＝３：１になるように調整した。得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表１に示す。
(Example 6)
A laminated film consisting of a total of 1409 layers was obtained under the same apparatus and conditions as in Example 1. However, it adjusted so that the layer thickness of each thermoplastic resin might be set to A: B = 3: 1. The obtained film was highly rigid and excellent in dimensional stability at high temperatures, and was also excellent in transparency after heating and moldability in a wide temperature range. The obtained results are shown in Table 1.
（実施例７）
実施例１と同様の装置・条件で、計１４０９層からなる積層フィルムを得た。但し、それぞれの熱可塑性樹脂の層厚みがＡ：Ｂ＝２：３となるように調整した。得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表２に示す。
(Example 7)
A laminated film consisting of a total of 1409 layers was obtained under the same apparatus and conditions as in Example 1. However, it adjusted so that the layer thickness of each thermoplastic resin might be set to A: B = 2: 3. The obtained film was highly rigid and excellent in dimensional stability at high temperatures, and was also excellent in transparency after heating and moldability in a wide temperature range. The obtained results are shown in Table 2.
（実施例８）
実施例１と同様の装置・条件で、計１４０９層からなる積層フィルムを得た。但し延伸後に行う熱処理温度は２１０℃とした。得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表２に示す。
(Example 8)
A laminated film consisting of a total of 1409 layers was obtained under the same apparatus and conditions as in Example 1. However, the heat treatment temperature performed after stretching was 210 ° C. The obtained film was highly rigid and excellent in dimensional stability at high temperatures, and was also excellent in transparency after heating and moldability in a wide temperature range. The obtained results are shown in Table 2.
（実施例９）
７０５層でかつスリットの加工精度が±５μｍのフィードブロック（圧力損失７ＭＰａ）を用い、またスタティックミキサーは、その流路長Ｌが次の式を満たすものを用い、｝かつ分割・結合される回数が１回であること以外は実施例１と同様の装置・条件で、計１４０９層からなるフィルムを得た。ここでスクエアミキサーは０．７Ｌ＝Ｑ／４０√Ａ （Ｌ：スタティックミキサーの流路長[ｍ]、Ｑ：ポリマー
押出量[ｔ／ｈ]、Ａ：総流路断面積[ｍ２] ） を満たすものである。得られたフィルムは高剛性でかつ高温下での寸法安定性、広い温度範囲での成形加工性に優れ、また加熱後の透明性がさらに優れたフィルムであった。得られた結果を表２に示す。
Example 9
Use a feed block (pressure loss 7MPa) with 705 layers and slit machining accuracy of ± 5μm, and use a static mixer whose flow path length L satisfies the following formula. A film consisting of a total of 1409 layers was obtained under the same apparatus and conditions as in Example 1 except that the number of times was one. Here, the square mixer is 0.7L = Q / 40√A (L: static mixer channel length [m], Q: polymer extrusion amount [t / h], A: total channel cross-sectional area [m2]) To meet. The obtained film was highly rigid, excellent in dimensional stability at high temperatures, excellent in moldability in a wide temperature range, and further excellent in transparency after heating. The obtained results are shown in Table 2.
（実施例１０）
実施例９と同様の装置・条件で計１４０９層からなる積層フィルムを得た。但し延伸後に行う熱処理温度は２１０℃とした。得られたフィルムは高剛性でかつ高温下での寸法安定性、広い温度範囲での成形加工性に優れ、また加熱後の透明性が非常に優れたフィルムであった。得られた結果を表２に示す。
(Example 10)
A laminated film consisting of a total of 1409 layers was obtained using the same apparatus and conditions as in Example 9. However, the heat treatment temperature performed after stretching was 210 ° C. The obtained film was highly rigid, excellent in dimensional stability at high temperatures, excellent in moldability in a wide temperature range, and very excellent in transparency after heating. The obtained results are shown in Table 2.
（実施例１１）
熱可塑性樹脂Ａとして融点Ｔｍ２５５℃、降温結晶化温度Ｔｍｃ１９２℃、固有粘度０．６５のＰＥＴである東レ社製Ｆ２０Ｓを用い、熱可塑性樹脂Ｂとして融点Ｔｍが２２９℃のＤｕＰｏｎｔ社製ポリプロピレンテレフタレート（ＰＰＴ）を用いたこと以外は実施例１と同様の装置・条件で、計１４０９層からなる積層フィルムを得た。なおここで用いたＰＰＴ樹脂は実施例１と同様の延伸条件および熱処理条件でＰＰＴ単体の二軸延伸フィルムとしたとき、動的粘弾性測定におけるα緩和温度が５８℃に観察されるものである。ただし本発明で用いたＰＰＴは融点が１９２℃であるため、熱処理温度を２３５℃とするとフィルムが融解する問題がある。このためＰＰＴの両表面にＰＥＴの層を積層し、ＰＥＴ／ＰＰＴ／ＰＥＴという３層の構成にして製膜し、α緩和温度を測定した。得られたフィルムは高剛性でかつ高温下での寸法安定性に優れ、さらに加熱後の透明性や、広い温度範囲での成型加工性にも優れたフィルムであった。得られた結果を表２に示す。
(Example 11)
As the thermoplastic resin A, F20S manufactured by Toray, which is a PET having a melting point Tm of 255 ° C., a falling crystallization temperature Tmc of 192 ° C., and an intrinsic viscosity of 0.65, is used as the thermoplastic resin B. A laminated film consisting of a total of 1409 layers was obtained using the same apparatus and conditions as in Example 1, except that In addition, when the PPT resin used here is a biaxially stretched film of PPT alone under the same stretching conditions and heat treatment conditions as in Example 1, the α relaxation temperature in dynamic viscoelasticity measurement is observed at 58 ° C. . However, since the PPT used in the present invention has a melting point of 192 ° C., there is a problem that the film melts when the heat treatment temperature is 235 ° C. Therefore, a PET layer was laminated on both surfaces of PPT to form a three-layer structure of PET / PPT / PET, and the α relaxation temperature was measured. The obtained film was highly rigid and excellent in dimensional stability at high temperatures, and was also excellent in transparency after heating and moldability in a wide temperature range. The obtained results are shown in Table 2.
（比較例１）
熱可塑性樹脂Ａとして、融点Ｔｍ２５５℃、降温結晶化温度Ｔｍｃ１９２℃、固有粘度０．６５のＰＥＴである東レ社製Ｆ２０Ｓを用いた。この熱可塑性樹脂Ａを乾燥した後、押出機に供給した。
熱可塑性樹脂Ａは、押出機にて２８０℃の溶融状態とし、ギヤポンプおよびフィルタを介した後、Ｔダイに供給しシート状に成形した後、静電印加しながら、表面温度２０℃に保たれたキャスティングドラム上で急冷固化した。
得られたキャストフィルムは、８５℃に設定したロール群で予熱し、さらに９０℃に設定したロール群で加熱し、縦方向に３．３倍延伸した。この一軸延伸フィルムをテンターに導き、１００℃の熱風で予熱後、横方向に４．０倍延伸した。延伸したフィルムは、そのまま、テンター内で２３５℃の熱風にて熱処理を行い、つづいて５％の弛緩処理を施し、室温まで徐冷後、巻き取った。得られたフィルムの厚みは、１５μｍであった。本フィルムは、高温下での寸法安定性と成形加工性が不適であった。得られた結果を表２に示す。
(Comparative Example 1)
As the thermoplastic resin A, F20S manufactured by Toray Industries, Inc., which is a PET having a melting point Tm of 255 ° C., a falling crystallization temperature Tmc of 192 ° C., and an intrinsic viscosity of 0.65, was used. The thermoplastic resin A was dried and then supplied to an extruder.
The thermoplastic resin A is melted at 280 ° C. with an extruder, passed through a gear pump and a filter, supplied to a T-die and formed into a sheet shape, and kept at a surface temperature of 20 ° C. while applying electrostatic force. It was quickly cooled and solidified on a casting drum.
The obtained cast film was preheated with a roll group set at 85 ° C., further heated with a roll group set at 90 ° C., and stretched 3.3 times in the longitudinal direction. This uniaxially stretched film was guided to a tenter, preheated with hot air at 100 ° C., and then stretched 4.0 times in the transverse direction. The stretched film was directly heat-treated in a tenter with hot air at 235 ° C., subsequently subjected to a relaxation treatment of 5%, gradually cooled to room temperature, and wound up. The thickness of the obtained film was 15 μm. This film was unsuitable for dimensional stability and moldability at high temperatures. The obtained results are shown in Table 2.
（比較例２）
フィードブロック（圧力損失１ＭＰａ）が４１層で、スタティックミキサーを用いないこと以外は実施例１と同様の装置・条件で、計４１層からなる積層フィルムを得た。得られた積層フィルムは、高温下での寸法安定性や加熱後の透明性、さらに成形加工性が不十分であった。得られた結果を表２および表３に示す。
(Comparative Example 2)
A laminated film consisting of a total of 41 layers was obtained under the same apparatus and conditions as in Example 1 except that the feed block (pressure loss 1 MPa) was 41 layers and no static mixer was used. The obtained laminated film was insufficient in dimensional stability at high temperature, transparency after heating, and molding processability. The obtained results are shown in Tables 2 and 3.
本発明は、各種成形体や転写箔、リチウムイオン電池の外装材などに好適に用いられるものであるが、その応用範囲がこれに限られるものではない。 The present invention is suitably used for various molded articles, transfer foils, exterior materials for lithium ion batteries, and the like, but the application range is not limited thereto.
Claims (10)
The lithium ion battery exterior material which comprises the laminated | multilayer film in any one of Claims 1-8.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009172864A (en) * | 2008-01-24 | 2009-08-06 | Teijin Dupont Films Japan Ltd | Multilayered biaxially oriented polyester film for molding |
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| JP2015156403A (en) * | 2015-06-04 | 2015-08-27 | 凸版印刷株式会社 | Exterior material for lithium ion battery |
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| JPWO2016047567A1 (en) * | 2014-09-22 | 2017-07-20 | 株式会社豊田自動織機 | Power storage device |
| WO2017170333A1 (en) * | 2016-03-30 | 2017-10-05 | 東洋紡株式会社 | Laminate for battery packages |
| KR20170139306A (en) * | 2016-06-09 | 2017-12-19 | 주식회사 엘지화학 | Electrode assembly for rechargeable battery |
| JP2020128085A (en) * | 2020-03-30 | 2020-08-27 | 東洋紡株式会社 | Thermoplastic resin sheet, and method for producing molded article obtained by heat molding the same |
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| JP2009172864A (en) * | 2008-01-24 | 2009-08-06 | Teijin Dupont Films Japan Ltd | Multilayered biaxially oriented polyester film for molding |
| JP2010005954A (en) * | 2008-06-27 | 2010-01-14 | Teijin Dupont Films Japan Ltd | Multilayered biaxially oriented polyester film for molding |
| JP2012033394A (en) * | 2010-07-30 | 2012-02-16 | Fujimori Kogyo Co Ltd | Laminate for battery exterior package |
| JP2012033393A (en) * | 2010-07-30 | 2012-02-16 | Fujimori Kogyo Co Ltd | Laminate for battery exterior package |
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| JP2014049307A (en) * | 2012-08-31 | 2014-03-17 | Dainippon Printing Co Ltd | Packaging material for battery |
| JP2014049308A (en) * | 2012-08-31 | 2014-03-17 | Dainippon Printing Co Ltd | Packaging material for battery |
| WO2014050542A1 (en) * | 2012-09-28 | 2014-04-03 | 大日本印刷株式会社 | Packaging material for battery |
| JP2014184562A (en) * | 2013-03-21 | 2014-10-02 | Sumitomo Bakelite Co Ltd | Multilayer film and package |
| JP2014233950A (en) * | 2013-06-05 | 2014-12-15 | 東レ株式会社 | Biaxially-oriented polyester film |
| CN106133942A (en) * | 2014-03-03 | 2016-11-16 | 大日本印刷株式会社 | Battery use packing material |
| JP2014197559A (en) * | 2014-07-15 | 2014-10-16 | 藤森工業株式会社 | Laminate for battery exterior package |
| JPWO2016047567A1 (en) * | 2014-09-22 | 2017-07-20 | 株式会社豊田自動織機 | Power storage device |
| JP2015156403A (en) * | 2015-06-04 | 2015-08-27 | 凸版印刷株式会社 | Exterior material for lithium ion battery |
| JP2015181128A (en) * | 2015-06-04 | 2015-10-15 | 凸版印刷株式会社 | Exterior material for lithium ion battery |
| WO2017170333A1 (en) * | 2016-03-30 | 2017-10-05 | 東洋紡株式会社 | Laminate for battery packages |
| KR20170139306A (en) * | 2016-06-09 | 2017-12-19 | 주식회사 엘지화학 | Electrode assembly for rechargeable battery |
| KR102217441B1 (en) * | 2016-06-09 | 2021-02-22 | 주식회사 엘지화학 | Electrode assembly for rechargeable battery |
| JP2020128085A (en) * | 2020-03-30 | 2020-08-27 | 東洋紡株式会社 | Thermoplastic resin sheet, and method for producing molded article obtained by heat molding the same |
| WO2022131360A1 (en) * | 2020-12-18 | 2022-06-23 | 東洋紡株式会社 | Biaxially stretched polyester film |
| TWI828020B (en) * | 2020-12-18 | 2024-01-01 | 日商東洋紡股份有限公司 | Polyester film, label film, diffusion film for displays and lens film for displays |
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