JP2004142126A - Heat-shrinkabile polyester film - Google Patents
Heat-shrinkabile polyester film Download PDFInfo
- Publication number
- JP2004142126A JP2004142126A JP2002306619A JP2002306619A JP2004142126A JP 2004142126 A JP2004142126 A JP 2004142126A JP 2002306619 A JP2002306619 A JP 2002306619A JP 2002306619 A JP2002306619 A JP 2002306619A JP 2004142126 A JP2004142126 A JP 2004142126A
- Authority
- JP
- Japan
- Prior art keywords
- film
- heat
- longitudinal direction
- polyester film
- shrinkage
- 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
- 229920006267 polyester film Polymers 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 150000002009 diols Chemical class 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229920006257 Heat-shrinkable film Polymers 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-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
- 229920000298 Cellophane Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QZHBYNSSDLTCRG-WUUYCOTASA-N brimonidine tartrate Chemical compound [H+].[H+].[O-]C(=O)[C@@H](O)[C@H](O)C([O-])=O.C1=CC2=NC=CN=C2C(Br)=C1NC1=NCCN1 QZHBYNSSDLTCRG-WUUYCOTASA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- -1 polybutylene terephthalate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 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
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、長手方向に高い収縮率を示す長手方向一軸収縮性フィルムであり、乾電池の外装被覆材などに好適に用いられる熱収縮性ポリエステルフィルムに関する。
【０００２】
【従来の技術およびその課題】
プラスチック熱収縮性フィルムは、容器類のラベルやキャップシール、電子部品等に使用されている。従来、熱収縮フィルム用樹脂にはポリ塩化ビニルからなるものが多くの用途に使用されているが、耐熱性が低い上に焼却時の塩素系ガス発生の問題を抱えており、更にこれを熱収縮ラベルとしてＰＥＴボトルに用いたものは、ＰＥＴボトルの回収時に悪影響を及ぼすという問題もある。
【０００３】
これに対し、ＰＥＴ等のポリエステル系熱収縮フィルムは、耐熱性に優れ、かつ焼却時の問題もないので、ポリ塩化ビニル系熱収縮フィルムに代わるものとして注目されている。
【０００４】
ところが、ＰＥＴのようなホモポリエステルでは、熱収縮開始温度が高すぎる、温度上昇に伴い収縮率が急激に増大する、到達収縮率が低いなどの熱収縮性における問題点のほかに、耐衝撃性が不十分という問題があった。そのため、主として共重合化や共重合ポリエステルの混合等の方法により、結晶性を抑制する方法でフィルム物性の改良が行われてきた。
【０００５】
例えば、特許文献１には、芳香族ジカルボン酸成分としてテレフタル酸、ジオール成分としてエチレングリコールおよび１、４−シクロヘキサンジメタノールからなる共重合ポリエステル系収縮包装用フィルムが開示されるなど、熱収縮性ポリエステルフィルムの熱収縮特性の改良については多くの提案がなされている。
【０００６】
このような熱収縮性ポリエステルフィルムは、用途によって一軸収縮性タイプと二軸収縮性タイプに分けられる。一軸収縮性フィルムは幅方向に一軸収縮性を示すものが主流であり、長手方向に一軸収縮性を示すものはほとんどなかった。
【０００７】
また、特許文献２には長手方向に一軸収縮性を示すポリエステルフィルムが記載されている。しかし、このような熱収縮性ポリエステルフィルムは、通常の幅方向一軸収縮性フィルムと比べて印刷適性や溶剤シール性に劣る上に、縦延伸、横延伸のあと再延伸を行うので工程も煩雑である。
【０００８】
【特許文献１】
特開昭５７−４２７２６号公報
【特許文献２】
特開平８−２４４１４号公報
【０００９】
【本発明が解決しようとする課題】
本発明は、フィルム長手方向に一軸収縮性を示し、長手方向、幅方向の両方向において実用に耐える機械的強度を有し、適度の印刷適性を有する熱収縮性ポリエステルフィルムを提供することにある。
【００１０】
【課題を解決するための手段】
本発明は、フィルム長手方向の屈折率が幅方向の屈折率より大きく、複屈折率が０．０５０〜０．１１０、面配向係数が０．０４０〜０．０９０であるとともに、８０℃の温水中で１０秒収縮させたときの長手方向の収縮率が３０％以上、幅方向の収縮率が１５％以下であることを特徴とする熱収縮性ポリエステルフィルムによって達成される。
【００１１】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明に用いるポリエステルはジカルボン酸成分として、テレフタル酸、アジピン酸、シュウ酸、マロン酸、コハク酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェニルエーテルジカルボン酸、シクロヘキサンジカルボン酸、５−スルホン酸塩イソフタル酸や長鎖脂肪族ジカルボン酸のドデカンジオン酸、エイコ酸、ダイマー酸およびそれらの誘導体等、公知のジカルボン酸成分の一種もしくは二種以上からなり、また、ジオール成分として、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、ヘキサメチレングリコール、１， ４−ブタンジオール、トリメチレングリコール、テトラメチレングリコール、ジエチレングリコール、ポリエチレングリコール、ポリアルキレングリコール、１，４−シクロヘキサンジメタノール、２−アルキル１，３−プロパンジオール、ビスフェノールＡまたはビスフェノールＳのジエトキシ化合物等公知のジオール成分の一種又は二種以上からなるポリエステル又は共重合ポリエステルである。
【００１２】
共重合ポリエステルとしては、ジカルボン酸成分及び／又はグリコール成分の一部を他のジカルボン酸またはグリコール成分に置換することにより得られるものが使用できるが、他の成分、例えば、ｐ−オキシ安息香酸、ｐ−オキシエトキシ安息香酸のごときオキシカルボン酸、安息香酸、メトキシポリアルキレングリコールのごとき一官能性化合物、グリセリン、ペンタエリスリトール、トリメチロールエタン、トリメチロールプロパンのごとき多官能性化合物も、生成物が実質的に線上の高分子を保持できる範囲内で使用することが出来る。
【００１３】
本発明に用いるポリエステルにおいては、ジカルボン酸成分として、テレフタル酸、ジオール成分としてエチレングリコールを主成分とする共重合ポリエステルが好ましく用いられ、該共重合成分としてはジカルボン酸成分としてイソフタル酸、フタル酸、アジピン酸、セバシン酸、ドデカンジオン酸、ダイマー酸、ジオール成分としてジエチレングリコール、ポリエチレングリコール、ポリアルキレングリコール、必要に応じて１， ４シクロヘキサンジメタノールを用いた共重合ポリエステルが、工業的に安価に入手でき、かつ収縮特性も良好で好ましい。
【００１４】
本発明に用いるポリエステルにおいては、ポリエステル樹脂としては、単独のポリエステル樹脂に限らず、２種以上のポリエステル樹脂を混合した混合ポリエステル樹脂として、全ジカルボン酸成分（１００モル％）中のテレフタル酸以外のジカルボン酸成分の割合と全ジオール成分（１００モル％）中のエチレングリコール以外のジオール成分の割合との合計が１０モル％以上である。上記の合計量が１０モル％未満のポリエステルは長手方向の熱収縮率が不足し、十分な溶剤シール性が得られない。
【００１５】
フィルムの易滑性を向上させるために、有機滑剤、無機の滑剤等の微粒子を含有させるもの好ましい。また、必要に応じて安定剤、着色剤、酸化防止剤、消泡剤、帯電防止剤等の添加剤を含有するものであってもよい。滑り性を付与する微粒子としては、カオリン、クレー、炭酸カルシウム、酸化ケイ素、テレフタル酸カルシウム、酸化アルミニウム、酸化チタン、リン酸カルシウム、フッ化リチウム、カーボンブラック等の公知の不活性外部粒子、ポリエステル樹脂の溶融製膜に際して不溶な高融点有機化合物、架橋ポリマ及びポリエステル合成時に使用する金属化合物触媒、例えばアルカリ金属化合物、アルカリ土類金属化合物などによってポリエステル製造時に、ポリマー内部に形成される内部粒子を挙げることができる。フィルム中に含まれる微粒子の含有量は通常、０．００５〜１重量％、該微粒子の平均粒径は、通常、０．００１〜６μｍの範囲である。
【００１６】
本発明に用いるポリエステルは、フェノール／１，１，２，２−テトラクロロエタン（重量比＝１／１）の混合溶媒中で３０℃で測定した固有粘度が０．４〜１．５ｄｌ／ｇであるのが好ましく、０．５〜１．２ｄｌ／ｇであるのがさらに好ましく、０．６〜１．０であるのが特に好ましい。固有粘度が前記範囲未満では、ポリエステルの機械的強度が劣る傾向となり、前記範囲を超えるとフィルム成形が困難となるので好ましくない。
【００１７】
本発明のフィルムにおいて、８０℃の温水中、１０秒収縮させたときのフィルム長手方向における収縮率が３０％以上であることが必要である。本発明においてフィルムの長手方向の収縮率が３０％未満の場合、収縮量が不十分となり、フィルムが被収縮物に十分密着せず好ましくない。
【００１８】
本発明のフィルムにおいて、長手方向と直交する方向、つまり幅方向における８０℃の温水中、１０秒収縮させたときの収縮率が１５％以下であることが必要である。幅方向の収縮率が１５％を越すフィルムでは、一軸収縮性が失われ、さらには収縮時に歪やシワ、端部のカール等が発生するため好ましくない。
【００１９】
本発明の目的とする熱収縮性ポリエステルフィルムを得るためには、ポリマー種、フィルムの収縮率、極限粘度などを特定の範囲内とし、さらにフィルムの３方向の屈折率によって表される複屈折率および面配向係数を特定の範囲内とすることが必要である。
【００２０】
すなわち、フィルム長手方向の屈折率が幅方向の屈折率より大きく、複屈折率が０．０５０〜０．１１０、面配向係数が０．０４０〜０．０９０であることが必要である。複屈折率が０．０５０より小さいとフィルムの一軸収縮性が不足するし、０．１１０より大きいと過度の一軸収縮性となり、いずれも収縮後の仕上がりが不良となる。また、フィルムの面配向係数が０．０４０より小さいとフィルムの機械的強度が不足するし、０．０９０より大きいと溶剤シール性が低下するので好ましくない。
【００２１】
さらに本発明のフィルムには、各種コーティングを施してもよい。また、本発明のフィルムの厚さは特に限定しないが、１〜３００μｍ、好ましくは２０〜７０μｍで有効に使用される。
【００２２】
本発明の組成のポリエステル又は共重合ポリエステルを通常のホッパドライヤー、パドルドライヤー、真空乾燥機等を用いて乾燥した後、２００〜３２０℃の温度で押出しを行う。押出し後、急冷して未延伸フィルムを得る。次いで、この未延伸フィルムをロール延伸法、テンター延伸法、チューブラー延伸法等の公知の延伸方法を適宜選択して、長手方向に２〜６倍、幅方向に１〜２延伸して延伸フィルムを成形する。延伸の順序はいずれでもよい。延伸温度はＴｇ〜（Ｔｇ＋１０）℃とするのがよい。延伸温度がＴｇに満たない場合は延伸時にフィルムが切れやすく、（Ｔｇ＋１０）℃を越えると均一延伸が困難である。
【００２３】
延伸されたフィルムは急冷することなく熱処理工程に送られる。熱処理により、加熱収縮時の急激な収縮を防ぐことができる。熱処理は、ロール、テンター等公知の熱処理機を用いて行う。熱処理条件は、延伸温度〜（延伸温度＋４０℃）で１５〜１２０秒とするのがよい。熱処理温度が延伸温度より低いと十分な熱処理効果が得られないし、（延伸温度＋４０℃）を越えると必要な収縮率が得られない。
【００２４】
また、熱処理時間が５秒未満の場合は、熱処理にむらが生じ、収縮むらや皺の原因となる。一方、熱処理温度が１２０秒を越える場合は、収縮率の低下が大きく、生産性も低下する。前記延伸工程中、延伸前、又は延伸後にフィルムの片面又は両面にコロナ放電処理を施し、フィルムの印刷層等に対する密着性を向上させることも可能である。さらに、上記延伸工程中、延伸前、又は延伸後にフィルムの片面又は両面に塗布を行い、フィルムの密着性、帯電防止性、易滑性、遮光性等を向上させることも可能である。
【００２５】
【実施例】
以下、本発明を実施例によりさらに具体的に説明するが、本発明は実施例の内容に限定されるものではない。実施例中の物性は以下に示す方法によった。
【００２６】
（１）屈折率、複屈折率、面配向係数
アタゴ社製「アッベ屈折率計」を用い、ナトリウムランプを光源として、フィルムの長手方向の屈折率（ｎγ）、幅方向の屈折率（ｎβ）および厚さ方向の屈折率（ｎα）を測定し、下記の式により複屈折率（Δｎ）、面配向係数（ΔＰ）を求めた。
Δｎ＝ｎγ−ｎβ
ΔＰ＝（ｎγ＋ｎβ）／２−ｎα
【００２７】
（２）収縮率
フィルムの長手方向および幅方向の収縮率の測定は下記の方法により行った。フィルムの測定方向に７０ｍｍ、測定方向と直角方向に１０ｍｍの大きさに切り取ってサンプルを作製し、測定方向に５０ｍｍ間隔の標線を付して、８０℃の温水バスに１０秒間浸漬し、下記の式により収縮率を用いた。
収縮率＝｛（５０−Ｌ）／５０｝×１００（％）
Ｌ（単位ｍｍ）は収縮後の標線間隔
【００２８】
（３）収縮仕上がり
一般的に乾電池被覆包装に使われるフィルム構成は、該フィルムにおける乾電池本体の軸方向の両端部を加熱させることにより折り曲げ、全面が接着剤を介して乾電池本体に接着されるが、ここでは、簡易的に以下の方法で収縮仕上がりを評価した。所定のフィルムから縦方向（長手方向）５１ｍｍ×横方向（巾方向）５３ｍｍに切り出して、縦方向の端部を５ｍｍの巾で重ね合わせてＴＨＦで溶剤シールし、折り径２３ｍｍの筒状サンプルを作製した。先サンプルを上下に各２．５ｍｍのはみ出し部を形成するよう単３型乾電池に装着させ、１５０℃の熱風シュリンカーにて１０秒間加熱を行った。評価は下記にて行った。
・収縮ムラが無い…… ○
・収縮に若干ムラがあるが、実用上問題ない…… △
・収縮ムラが大きく、シワや破れが発生する…… ×
【００２９】
（４）印刷適性
日商グラビア社製「ＧＲＡＶＯ−ＰＲＯＯＦ ＣＭミニ校正機」を用い、大日精化社製「ＶＹＳ ＰＥＴ用ＨＣ白色インキ」（ザーンカップ♯３にて１３秒に調製）にて速度４０ｍ／ｍｉｎで印刷した。３０秒放置後、ニチバン製セロテープを貼り付けて指で押さえ、セロテープを剥がすことでインキ密着性（印刷適性）の評価を行った。
・剥離しない…… ○
・僅かに剥離する…… △
・剥離する…… ×
【００３０】
［実施例１〜実施例４、比較例１，２］
ジカルボン酸成分としてテレフタル酸９０モル％、イソフタル酸１０モル％、ジオール成分としてエチレングリコール７９モル％、シクロヘキサンジメタノール２１モル％からなり、平均粒径２．４μｍの無定形シリカ（富士シリシア社製サイリシア３２０）を０．３重量％加えた共重合ポリエステルとポリブチレンテレフタレート（三菱エンジニアリンウグプラスチック社製ノバデュール５００８）とを８５：１５の重量比で混合し、２７０℃で溶融押出後冷却固化してＩＶ０．７５の未延伸シートを得た。
ロール式縦延伸機にヘレウス製中波長ヒーターを取り付けた縦延伸機で未延伸シートが表１に示すシート温度▲１▼になるようロール温度及びヒーター出力を調整し表に示した縦延伸倍率▲２▼の倍率で長手方向に延伸した。その後横延伸機内にて表に示す予熱温度▲３▼／延伸温度８５℃／横延伸倍率▲４▼にて横延伸を行い、フィルムの厚さがいずれも５０μｍである延伸フィルムを得た。
【表１】
以上、得られたフィルムの評価結果を表２に示す。
【００３２】
比較例１のフィルムは面配向係数が高すぎるため、印刷適性が不十分である。比較例２のフィルムは一軸収縮性が不足するため収縮仕上がりがよくない。
【００３４】
【発明の効果】
本発明のフィルムは、フィルム長手方向に一軸収縮性を示し、長手方向、幅方向の両方向において実用に耐える機械的強度を有し、適度の溶剤シール性を有するので、電池の内装又は外装被覆材などの熱収縮性フィルムとして好適に用いられる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a heat-shrinkable polyester film which is a longitudinally uniaxially shrinkable film exhibiting a high shrinkage rate in a longitudinal direction, and which is suitably used for an outer covering material of a dry battery.
[0002]
[Prior art and its problems]
Plastic heat-shrinkable films are used for labels and cap seals of containers, electronic components, and the like. Conventionally, polyvinyl chloride resin has been used for many applications for heat-shrinkable films, but it has low heat resistance and has the problem of chlorine-based gas generation during incineration. What is used for a PET bottle as a shrinkable label also has a problem that it has an adverse effect when the PET bottle is collected.
[0003]
On the other hand, polyester-based heat-shrinkable films such as PET are attracting attention as an alternative to polyvinyl chloride-based heat-shrinkable films because they have excellent heat resistance and do not cause problems during incineration.
[0004]
However, in the case of homopolyesters such as PET, the heat shrinkage start temperature is too high, the shrinkage rate increases sharply with increasing temperature, and the ultimate shrinkage rate is low. Was insufficient. For this reason, film properties have been improved mainly by a method such as copolymerization or mixing of a copolyester to suppress crystallinity.
[0005]
For example, Patent Document 1 discloses a heat-shrinkable polyester such as a copolymerized polyester-based shrinkable packaging film composed of terephthalic acid as an aromatic dicarboxylic acid component, ethylene glycol and 1,4-cyclohexanedimethanol as diol components. Many proposals have been made for improving the heat shrinkage properties of films.
[0006]
Such a heat-shrinkable polyester film is classified into a uniaxial shrinkable type and a biaxial shrinkable type depending on the application. Most uniaxially contractible films exhibit uniaxial contractility in the width direction, and few films exhibit uniaxial contractility in the longitudinal direction.
[0007]
Patent Document 2 describes a polyester film exhibiting uniaxial shrinkage in the longitudinal direction. However, such a heat-shrinkable polyester film is inferior in printability and solvent sealability as compared with a normal width-direction uniaxially shrinkable film, and is also subjected to longitudinal stretching and transverse stretching followed by re-stretching, so that the process is complicated. is there.
[0008]
[Patent Document 1]
JP-A-57-42726 [Patent Document 2]
Japanese Patent Application Laid-Open No. Hei 8-24414
[Problems to be solved by the present invention]
An object of the present invention is to provide a heat-shrinkable polyester film which exhibits uniaxial shrinkage in the longitudinal direction of the film, has practically sufficient mechanical strength in both the longitudinal direction and the width direction, and has appropriate printability.
[0010]
[Means for Solving the Problems]
In the present invention, the refractive index in the longitudinal direction of the film is larger than the refractive index in the width direction, the birefringence is 0.050 to 0.110, the plane orientation coefficient is 0.040 to 0.090, and the temperature is 80 ° C. This is achieved by a heat-shrinkable polyester film having a shrinkage ratio in the longitudinal direction of 30% or more and a shrinkage ratio in the width direction of 15% or less when shrunk in the medium for 10 seconds.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
Polyester used in the present invention, as a dicarboxylic acid component, terephthalic acid, adipic acid, oxalic acid, malonic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenylether dicarboxylic acid, cyclohexanedicarboxylic acid, 5-sulfonic acid salt isophthalic acid or long-chain aliphatic dicarboxylic acid dodecanedioic acid, eicoic acid, dimer acid and their derivatives, such as one or more known dicarboxylic acid components, and as a diol component, Ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol, 1,4-butanediol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polyalkylene glycol It is a polyester or copolymerized polyester comprising one or more known diol components such as recol, 1,4-cyclohexanedimethanol, 2-alkyl-1,3-propanediol, a diethoxy compound of bisphenol A or bisphenol S.
[0012]
As the copolyester, those obtained by substituting a part of a dicarboxylic acid component and / or a glycol component with another dicarboxylic acid or a glycol component can be used. Other components, for example, p-oxybenzoic acid, Oxycarboxylic acids such as p-oxyethoxybenzoic acid, benzoic acid, monofunctional compounds such as methoxypolyalkylene glycol, and polyfunctional compounds such as glycerin, pentaerythritol, trimethylolethane, and trimethylolpropane also have substantially the same products. It can be used as long as the polymer on the line can be retained.
[0013]
In the polyester used in the present invention, terephthalic acid as a dicarboxylic acid component, a copolymerized polyester containing ethylene glycol as a main component as a diol component are preferably used, and as the copolymerization component, isophthalic acid, phthalic acid, Copolymerized polyesters using adipic acid, sebacic acid, dodecanedioic acid, dimer acid, diethylene glycol, polyethylene glycol, polyalkylene glycol as a diol component, and 1,4-cyclohexanedimethanol as required can be obtained industrially at low cost. In addition, the shrinkage characteristics are good and preferable.
[0014]
In the polyester used in the present invention, the polyester resin is not limited to a single polyester resin, and may be a mixed polyester resin obtained by mixing two or more polyester resins, other than terephthalic acid in all dicarboxylic acid components (100 mol%). The sum of the ratio of the dicarboxylic acid component and the ratio of the diol components other than ethylene glycol in all the diol components (100 mol%) is 10 mol% or more. If the total amount of the polyester is less than 10 mol%, the heat shrinkage in the longitudinal direction is insufficient, and sufficient solvent sealing properties cannot be obtained.
[0015]
In order to improve the lubricity of the film, those containing fine particles such as an organic lubricant and an inorganic lubricant are preferable. Further, if necessary, additives such as a stabilizer, a coloring agent, an antioxidant, an antifoaming agent, and an antistatic agent may be contained. Known fine particles for imparting lubricating properties include known inert external particles such as kaolin, clay, calcium carbonate, silicon oxide, calcium terephthalate, aluminum oxide, titanium oxide, calcium phosphate, lithium fluoride, and carbon black, and the melting of polyester resin. Insoluble high-melting point compounds during film formation, cross-linked polymers and metal compound catalysts used during polyester synthesis, such as alkali metal compounds, alkaline earth metal compounds, etc., during polyester production, include internal particles formed inside the polymer. it can. The content of the fine particles contained in the film is usually 0.005 to 1% by weight, and the average particle size of the fine particles is usually in the range of 0.001 to 6 μm.
[0016]
The polyester used in the present invention has an intrinsic viscosity of 0.4 to 1.5 dl / g measured at 30 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (weight ratio = 1/1). Preferably, it is 0.5 to 1.2 dl / g, more preferably 0.6 to 1.0. If the intrinsic viscosity is less than the above range, the mechanical strength of the polyester tends to be inferior, and if it exceeds the above range, film forming becomes difficult, which is not preferable.
[0017]
In the film of the present invention, it is necessary that the shrinkage in the longitudinal direction of the film when shrinking in warm water at 80 ° C. for 10 seconds is 30% or more. In the present invention, when the shrinkage in the longitudinal direction of the film is less than 30%, the amount of shrinkage becomes insufficient, and the film does not adhere sufficiently to the object to be shrunk, which is not preferable.
[0018]
In the film of the present invention, it is necessary that the shrinkage rate when shrinking in hot water at 80 ° C. for 10 seconds in the direction orthogonal to the longitudinal direction, that is, the width direction is 15% or less. A film having a shrinkage ratio in the width direction of more than 15% is not preferable because the uniaxial shrinkage is lost, and furthermore, distortion, wrinkles, curl at the end and the like are generated during shrinkage.
[0019]
In order to obtain the heat-shrinkable polyester film intended for the present invention, the polymer type, the shrinkage of the film, the intrinsic viscosity and the like are within a specific range, and the birefringence represented by the refractive index in three directions of the film. In addition, the plane orientation coefficient needs to be within a specific range.
[0020]
That is, it is necessary that the refractive index in the longitudinal direction of the film is larger than the refractive index in the width direction, the birefringence is 0.050 to 0.110, and the plane orientation coefficient is 0.040 to 0.090. When the birefringence is less than 0.050, the uniaxial shrinkage of the film becomes insufficient, and when it is more than 0.110, the film becomes excessively uniaxially shrinkable, and in any case, the finish after shrinkage becomes poor. On the other hand, if the plane orientation coefficient of the film is smaller than 0.040, the mechanical strength of the film becomes insufficient, and if it is larger than 0.090, the solvent sealing property is undesirably reduced.
[0021]
Further, the film of the present invention may be provided with various coatings. Although the thickness of the film of the present invention is not particularly limited, it is effectively used at 1 to 300 μm, preferably 20 to 70 μm.
[0022]
The polyester or copolyester of the composition of the present invention is dried using a usual hopper dryer, paddle dryer, vacuum dryer or the like, and then extruded at a temperature of 200 to 320 ° C. After extrusion, it is quenched to obtain an unstretched film. Next, this unstretched film is appropriately selected from known stretching methods such as a roll stretching method, a tenter stretching method, and a tubular stretching method, and is stretched 2 to 6 times in the longitudinal direction and 1 to 2 in the width direction. Is molded. The order of stretching may be any. The stretching temperature is preferably from Tg to (Tg + 10) ° C. When the stretching temperature is lower than Tg, the film tends to break during stretching, and when the temperature exceeds (Tg + 10) ° C., uniform stretching is difficult.
[0023]
The stretched film is sent to a heat treatment step without quenching. The heat treatment can prevent rapid shrinkage during heat shrinkage. The heat treatment is performed using a known heat treatment machine such as a roll and a tenter. The heat treatment is preferably performed at a stretching temperature to (stretching temperature + 40 ° C) for 15 to 120 seconds. If the heat treatment temperature is lower than the stretching temperature, a sufficient heat treatment effect cannot be obtained, and if it exceeds (stretching temperature + 40 ° C), the required shrinkage cannot be obtained.
[0024]
If the heat treatment time is less than 5 seconds, the heat treatment becomes uneven, causing uneven shrinkage and wrinkles. On the other hand, when the heat treatment temperature exceeds 120 seconds, the shrinkage rate is greatly reduced, and the productivity is also reduced. During the stretching step, before or after the stretching, one or both sides of the film may be subjected to a corona discharge treatment to improve the adhesion of the film to a printed layer or the like. Furthermore, it is also possible to improve the adhesion, antistatic properties, slipperiness, light-shielding properties, etc. of the film by applying the film to one or both sides of the film during, before or after the stretching step.
[0025]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples. The physical properties in the examples were determined by the following methods.
[0026]
(1) Refractive index, birefringence index, plane orientation coefficient Using an Abbe refractometer manufactured by Atago, using a sodium lamp as a light source, a refractive index in the longitudinal direction of the film (nγ) and a refractive index in the width direction (nβ). And the refractive index (nα) in the thickness direction were measured, and the birefringence (Δn) and the plane orientation coefficient (ΔP) were determined by the following equations.
Δn = nγ−nβ
ΔP = (nγ + nβ) / 2−nα
[0027]
(2) Shrinkage Ratio The measurement of the shrinkage ratio in the longitudinal direction and the width direction of the film was performed by the following method. The sample was cut out to a size of 70 mm in the measurement direction of the film and 10 mm in a direction perpendicular to the measurement direction, and a sample was prepared, marked with 50 mm intervals in the measurement direction, and immersed in a hot water bath at 80 ° C. for 10 seconds. The contraction rate was used according to the following equation.
Shrinkage = {(50−L) / 50} × 100 (%)
L (unit: mm) is the distance between marked lines after contraction.
(3) Shrink finish A film structure generally used for dry battery covering packaging is bent by heating both ends of the film in the axial direction of the dry battery main body, and the entire surface is adhered to the dry battery main body via an adhesive. Here, the shrink finish was simply evaluated by the following method. A 51 mm vertical (longitudinal) × 53 mm (horizontal) transverse direction is cut out from a predetermined film, the longitudinal ends are overlapped with a width of 5 mm, solvent-sealed with THF, and a cylindrical sample having a folded diameter of 23 mm is obtained. Produced. The sample was mounted on an AA battery so as to form a 2.5 mm protruding part at the top and bottom, and heated with a hot air shrinker at 150 ° C. for 10 seconds. The evaluation was performed as follows.
・ There is no shrinkage unevenness …… ○
-Although there is slight unevenness in shrinkage, there is no problem in practical use .... △
-Large uneven shrinkage causes wrinkles and tears .... ×
[0029]
(4) Printability Using Nissho Gravure's "GRAVO-PROOF CM mini-proofing machine", speed using Dainichi Seika's "HC white ink for VYS PET" (prepared in Zahn cup # 3 for 13 seconds). Printing was performed at 40 m / min. After standing for 30 seconds, Nichiban cellophane tape was attached and pressed with a finger, and the cellophane tape was peeled off to evaluate ink adhesion (printability).
・ Does not peel off ...
・ Slightly peels off …… △
・ Peel off ... ×
[0030]
[Examples 1 to 4, Comparative Examples 1 and 2]
Amorphous silica having a mean particle size of 2.4 μm (Fyricia, Inc., composed of 90 mol% of terephthalic acid, 10 mol% of isophthalic acid, 79 mol% of ethylene glycol and 21 mol% of cyclohexane dimethanol as a diol component) 320) and polybutylene terephthalate (Novadur® 5008, manufactured by Mitsubishi Engineering Ug Plastics Co., Ltd.) in a weight ratio of 85:15 mixed with 0.3% by weight of 0.3), melt-extruded at 270 ° C., and cooled and solidified. An unstretched sheet having an IV of 0.75 was obtained.
Adjust the roll temperature and heater output so that the unstretched sheet becomes the sheet temperature (1) shown in Table 1 with a longitudinal stretching machine equipped with a Heraeus medium-wavelength heater on a roll-type longitudinal stretching machine, and the longitudinal stretching ratio shown in the table. The film was stretched in the longitudinal direction at a magnification of 2 ▼. Thereafter, the film was horizontally stretched in a transverse stretching machine at a preheating temperature (3) / a stretching temperature of 85 ° C./a transverse stretching ratio (4) shown in the table to obtain a stretched film having a film thickness of 50 μm.
[Table 1]
Table 2 shows the evaluation results of the obtained films.
[0032]
The film of Comparative Example 1 has insufficient printability because the plane orientation coefficient is too high. The film of Comparative Example 2 is insufficient in uniaxial shrinkage and thus has poor shrink finish.
[0034]
【The invention's effect】
The film of the present invention exhibits uniaxial shrinkage in the longitudinal direction of the film, has mechanical strength sufficient for practical use in both the longitudinal direction and the width direction, and has an appropriate solvent sealing property. It is suitably used as a heat-shrinkable film.
Claims (3)
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| JP2002306619A JP5004398B2 (en) | 2002-10-22 | 2002-10-22 | Heat shrinkable polyester film |
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