JP2004051959A - Aliphatic polyester film and laminated product - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は脂肪族ポリエステルフィルムに関する。特に詳しくは、透明性を損なうことなく耐熱性および低温での耐屈曲性に優れ、包装用フィルムとして有用な脂肪族ポリエステルフィルムおよびそれを用いた積層体に関する。
【０００２】
【従来の技術】
従来、ポリ乳酸を始めとする脂肪族ポリエステルフィルムは自然環境に廃棄された際に分解すること、例えば土壌中で自然に加水分解した後に微生物によって無害な分解物となることを特徴として開発された。しかしながら脂肪族ポリエステルフィルムは柔軟性が不足し、耐屈曲性に劣ることから、包装用途や農業資材用途に展開しようとすると問題が生じ留ことが多い。このような脂肪族ポリエステルのの柔軟化の方法として、生分解性樹脂に比較的分子量が低い柔軟剤（可塑剤）を添加して柔軟性を改良する方法が広く知られている（例えば特許文献１および２参照）が、時間が経つと、柔軟剤が析出し柔軟化効果が著しく低下したり、柔軟剤を加えたフィルムの透明性が低下したりする問題があった。また、このようなフィルムを高温下で使用すると、著しい透明性の低下や可塑剤の飛散・滲出、フィルムの硬化等の問題があり、実質的に製品化出来るものは無い現状である。
【０００３】
【特許文献１】特開平１０−３１６８４６号公報
【０００４】
【特許文献２】特開２０００−７２９６１号公報
【０００５】
【発明が解決しようとする課題】
本発明は、かかる課題を解決するために、耐熱性と透明性、耐屈曲性を両立した脂肪族ポリエステルフィルムおよびそれを用いた積層体に関するものである。
【０００６】
【課題を解決するための手段】
上記課題を達成するするため、本発明の脂肪族ポリエステルフィルムは次の構成を有する。すなわち、脂肪族ポリエステルを５０〜９５重量％、融点が１５０〜２２０℃、ガラス転移点が０℃以下、好ましくは−３０℃以下のポリエステルエラストマーを５〜５０重量％含有し、１３５〜１４５℃の範囲に結晶融解ピークが存在することを特徴とする脂肪族ポリエステルフィルムである。
【０００７】
また、本発明の積層体は、上記脂肪族ポリエステルフィルムと、融点が１８０℃以下の実質的に無配向な熱可塑性樹脂からなるフィルムを積層してなる積層体である。
【０００８】
【発明の実施の形態】
本発明における脂肪族ポリエステルとは、一般式−Ｏ−ＣＨＲ−ＣＯ−（Ｒは水素または炭素数１〜３のアルキル基）を主たる繰り返し単位とする。このような脂肪族ポリエステルとしては、例えばポリ乳酸、ポリグリコール酸、ポリ（２−オキシ酪酸）等を挙げることができるが、これらに限定されるものではない。また、これらの脂肪族ポリエステルは単独で用いても良いが、２種類以上の混合物、共重合体を使用してもかまわない。ポリマー中に不斉炭素を有する物は、Ｌ−体、ＤＬ−体、Ｄ−体といった光学異性体が存在するが、それらのいずれでも良く、また、それら異性体の混合物でも良い。これらフィルムの素材となる上述したポリマーは、対応するα−オキシ酸の脱水環状エステル化合物を開環重合する等公知の方法で製造される。
【０００９】
上記脂肪族ポリエステルの中では、ポリ乳酸系ポリエステルが最も好ましい。ここで言うポリ乳酸系ポリエステルとは、ポリ乳酸または乳酸と他のヒドロキシカルボン酸との共重合体、もしくはこれらの混合物であり、本発明の目的を阻害しない範囲であれば、取扱性、加工性、物性を調整する目的で、可塑剤、滑剤、熱安定剤、着色防止剤、紫外線吸収剤、光安定剤、酸化防止剤等の添加剤を含有させてもよい。乳酸としては、Ｌ−乳酸、Ｄ−乳酸が挙げられ、他のヒドロキシカルボン酸としては、グリコール酸、３−ヒドロキシ酪酸、４−ヒドロキシ酪酸、４−ヒドロキシ吉草酸、５−ヒドロキシ吉草酸、６−ヒドロキシカプロン酸が挙げられる。
【００１０】
本発明の脂肪族ポリエステルフィルムに用いるポリエステルエラストマーは、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸から選ばれる芳香族ジカルボン酸と、炭素数２〜４の直鎖アルキレングリコールの重合物であるハードセグメントと、長鎖アルキル鎖を有するソフトセグメントからなる共重合ポリエステルであることが好ましい。ソフトセグメントとしては、直鎖アルキレングリコールとセバチン酸、ダイマー酸などの長鎖を有するジカルボン酸からなるポリエステル単位や、芳香族ジカルボン酸とポリオキシアルキレングリコールからなるポリエステル単位などを用いることが出来るが、特に芳香族ジカルボン酸と、炭素数２〜４の直鎖アルキレングリコールおよびポリオキシアルキレングリコールの共重合ポリエステルをポリエステルエラストマーとして用いることが好ましい。ここで、ポリオキシアルキレングリコールとしてはポリエチレングリコール、ポリトリメチレングリコール、ポリテトラメチレングリコール、ポリペンタメチレングリコール、ポリヘキサメチレングリコール、ポリヘプタメチレングリコール、ポリオクタメチレングリコール、ポリデカメチレングリコール、ポリ１−メチルジメチレングリコール、ポリ２−メチルトリメチレングリコールなどが挙げられる。この中でも、ポリジメチレングリコール、ポリトリメチレングリコール、ポリテトラメチレングリコールが好ましい。耐ピンホール性の観点からはポリテトラメチレングリコールが特に好ましい。さらに、ポリオキシメチレングリコールのポリエステル中の分散性、フィルムのヘイズを低く抑えるという観点から、ポリオキシメチレングリコールの分子量が５００〜４０００であることが好ましい。ポリエステルとの重合を考慮すると６００〜２５００であるとより好ましく、分子量が８００〜１５００であると特に好ましい。このようなポリエステルエラストマーは、ソフトセグメントとハードセグメントの繰り返し単位が交互に結合しているようなランダム共重合体であっても良いが、ソフトセグメントがある程度以上の長さを有するブロック共重合体であった方が、ポリエステルエラストマーのガラス転移点が０℃以下となりやすいため好ましい。
【００１１】
また、本発明の脂肪族ポリエステルフィルムに用いるポリエステルエラストマーとしては、脂肪族ジオールと芳香族ジカルボン酸および脂肪族ジカルボン酸を主たる構成単位とする融点が９０〜１４０℃の共重合ポリエステルを用いることができる。特に、芳香族ポリエステル単位としてエチレンテレフタレート、ブチレンテレフタレート、ヘキサメチレンテレフタレート、エチレン−２，６−ナフタレート、ブチレン−２，６−ナフタレートから選ばれる少なくとも１種の芳香族ポリエステル単位と、脂肪族カルボン酸を主たる構成単位とする柔軟成分の共重合ポリエステル樹脂を用いることが好ましく、中でも得られるフィルムの柔軟性を高めるためには、特に、ブチレンテレフタレートと脂肪族カルボン酸を主たる構成単位とする、融点が９０〜１２０℃である共重合ポリエステルが好ましい。とりわけ、脂肪族カルボン酸としてアジピン酸を用い、ブチレンテレフタレート共重合比率を３０モル％以下とした場合、生分解性を有するポリエステルエラストマーとすることができるので特に好ましい。
【００１２】
本発明の脂肪族ポリエステルフィルムは上記の脂肪族ポリエステルを５０〜９５重量％、好ましくは７０〜９０重量％、融点が１５０〜２２０℃、ガラス転移点が０℃以下のポリエステルエラストマーを５〜５０重量％、好ましくは１０〜３０重量％含有する。脂肪族ポリエステルの含有量が９５重量％より大きいか、ポリエステルエラストマーの含有量が５重量％より小さい場合は、耐屈曲性の悪いフィルムとなってしまう。また、脂肪族ポリエステルの含有量を５０重量％より少なくしたり、ポリエステルエラストマーの含有量を５０重量％より多くすると溶融時の粘度が小さくなるため製膜性が悪化してしまうか、製膜できた場合でも耐熱性、透明性に劣ったフィルムとなってしまう。
【００１３】
また、本発明の脂肪族ポリエステルフィルムには取り扱い性、加工性を向上させるために、滑剤として平均粒子径０．０１〜１０μｍの公知の無機粒子および／または有機粒子を０．０１〜３重量％含有することが好ましい。また、耐電防止剤や紫外線吸収剤等を本発明の目的を阻害しない範囲で５重量％以下の範囲で添加しても良い。
【００１４】
上記のような配合の脂肪族ポリエステルは単体の脂肪族ポリエステルと比較して柔軟になるが、優れた耐屈曲性と耐熱性を両立させるためには脂肪族ポリエステルフィルムに熱処理を行い１３５〜１４５℃の範囲に結晶融解ピークを有することが必要となる。結晶融解ピークが存在しないか、もしくは１３５℃より低い場合は後加工や実使用時の熱により強度が著しく低下したり、収縮率が大きなフィルムとなってしまう。結晶融解ピークが１４５℃より高い場合は、耐屈曲性が低下してしまう。
【００１５】
本発明の脂肪族ポリエステルフィルムは耐熱性を確保するためには二軸延伸することが好ましく、フィルム長手方向の屈折率とフィルム幅方向の屈折率の平均値として求められる面内平均屈折率が１．４６０以上、好ましくは１．４６５以上であることが好ましく、フィルムの面配向係数が０．０１４以上、好ましくは０．０１５以上であることが好ましい。面内平均屈折率がかかる好ましい範囲であると、耐熱性の良好なフィルムとすることができる。面内平均屈折率および面配向係数の上限は特に設けないが、フィルム破れによる生産性低下が起こらない範囲では一般に面内平均屈折率は１．４７５以下、面配向係数は０．０１６以上とすることは困難である。
【００１６】
本発明の脂肪族ポリエステルフィルムを包装袋用として使用する場合には、ヒートシール性を付与するためにポリエチレンやポリプロピレン、エチレン−酢酸ビニル共重合体、芳香族共重合ポリエステルや脂肪族ポリエステルの無延伸フィルムを熱接着層として積層して積層体として用いられる。ラミネート方法としては、ポリウレタン系の接着剤などを用いたドライラミネート法、押出ラミネート法などの方法が用いられる。
【００１７】
本発明の脂肪族ポリエステルフィルムは、インフレーション法、同時二軸延伸法、逐次二軸延伸法などの既存の延伸フィルムの製造法により得ることが出来るが、製膜速度を高速に出来ることから逐次二軸延伸法が好ましい。逐次二軸延伸法での本発明の白色脂肪族ポリエステルフィルムの製造においては、まず真空下で乾燥した脂肪族ポリエステルチップとポリエステルエラストマーのチップをブレンドして押出機に供給し、公知の方法でスリット状の口金よりシート状に溶融押し出し、キャスティングドラムに密着させて冷却固化せしめて未延伸フィルムを得る。フィルムの表層に無機粒子を少なく含有した層を設ける場合は、２台以上の押出機を用いて、口金内または口金の上流で溶融ポリマーを合流させ積層未延伸フィルムを得る複合押出が最も好ましい。かかる方法で得た未延伸フィルムを連続して少なくとも一方向に延伸し、更に直交方向に延伸し、熱処理することで、薄膜層の基材との密着性や薄膜層の強靱性を高めることが好ましい。フィルム長手方向の延伸には加熱ロールの周速差を利用したロール延伸が、フィルム幅方向の延伸や二軸延伸後の熱処理には連続クリップを有するテンターを用いることが好ましい。
【００１８】
本発明の白色脂肪族ポリエステルフィルムは、インクや他素材と貼り合わせるための接着剤との密着性や帯電防止性などを付与する目的でコーティングによる機能層を設けても良い。
【００１９】
本発明の脂肪族ポリエステルフィルムは、耐熱性と耐屈曲性、透明性を要求される保護フィルムや包装用袋などに広く用いることができるが、特に包装用袋に好ましく用いることができる。
【００２０】
【実施例】
以下、実施例により本発明をさらに説明する。特に代表的な脂肪族ポリエステルであるポリ乳酸を例にとって説明するが、これに限定されない。
［特性の測定方法］
（１）ガラス転移点、融点、結晶融解熱
・ポリエステルエラストマーのガラス転移点、融点
セイコーインスツルメント社製のＤＳＣ（示差走査熱量計）ＲＤＣ２２０を用いて測定した。試料５ｍｇをＤＳＣ装置にセットし、−１００℃から２０℃／分で２５０℃まで昇温し、ガラス転移点および融点を測定した。
・脂肪族ポリエステルフィルムの結晶融解温度
セイコーインスツルメント社製のＤＳＣ（示差走査熱量計）ＲＤＣ２２０を用いて測定した。試料５ｍｇをＤＳＣ装置にセットし、２５℃から２０℃／分で２５０℃まで昇温し、融点以下に結晶融解によるサブピークの有無を確認し、ピーク温度を測定した。
（２）面内平均屈折率、面配向係数
偏光子を備えた（株）アタゴ製アッベ屈折率計４Ｔ型を用いて、フィルム長手方向の屈折率（ｎｘ）、幅方向の屈折率（ｎｙ）、厚さ方向の屈折率（ｎｚ）を求め、下式より面内平均屈折率および面配向係数を求めた。なお、屈折率１．７４の補助プリズム、浸液としてヨウ化メチレンを用いた。
【００２１】
面内平均屈折率＝（ｎｘ＋ｎｙ）／２
面配向係数＝｛（ｎｘ＋ｎｙ）／２｝−ｎｚ
（３）耐熱性（熱収縮率）
フィルム長手方向の１２０℃における収縮率より求めた。フィルム長手方向に幅１０ｍｍ、長さ３０ｃｍに切り取り、１００ｍｍの間隔でマーキングした。サンプルの一方に５ｇのクリップを吊り下げて１２０℃のオーブンで３０分処理を行い、処理前後の長さ（Ｌ１、Ｌ２）を万能投影機を用いて求め、下式より熱収縮率を求めた。
熱収縮率（％）＝（Ｌ１−Ｌ２）／Ｌ１×１００
収縮率が４％以上か、逆に１％以上膨張する場合は耐熱性不良とした。
（４）耐屈曲性
ＡＳＴＭ Ｆ−３９２に従って、２９７×２１０ｍｍの大きさに切り出したフィルムをゲルボテスターを使用し、炭酸ガスを使用して５℃の温度雰囲気にて、５００回の繰り返し屈曲試験を実施した。試験を５回行い、ピンホール個数の平均値を算出した。フィルム単体、積層体いずれの場合も１０個以上のピンホールが発生すると不良と判定した。
（５）ヘイズ
ＪＩＳ Ｋ ６７１４−５８に従って、ＳＥＰ−Ｈ−２系濁度計（日本精密光学社製）を用いてヘイズを測定した。ヘイズ１０％以上を不良と判定した。
【００２２】
（脂肪族ポリエステル樹脂およびポリエステルエラストマーの準備）
［脂肪族ポリエステル樹脂Ａ］：重量平均分子量約２０万のＬ−ポリ乳酸（融点１７０℃）を用いた。
【００２３】
［脂肪族ポリエステル樹脂Ｂ］：脂肪族ポリエステル樹脂Ａに対し、公知の二軸押出機を用いて２００℃でシリカ粒子（富士シリシア化学（株）製サイリシア）を添加量が２．５重量％となるように混練し、マスターペレットとした。
【００２４】
［ポリエステルエラストマーＡ］：１，４−ブタンジオール４０重量部および数平均分子量約１０００のポリテトラメチレングリコール６０重量部、テレフタル酸８３．７重量部の混合物に、テレフタル酸に対してチタンテトラブトキシド０．０４７重量％を添加し、１９０〜２２５℃でエステル化反応を行なった。次いで酸化防止剤を０．２重量％添加し、減圧下で常法により重縮合反応を行いポリエステルエラストマーを得た。得られたポリエステルエラストマーのガラス転移温度は−６０℃、融点は１７０℃であった。
【００２５】
［ポリエステルエラストマーＢ］：１，４−ブタンジオール７０重量部および数平均分子量約１０００のポリテトラメチレングリコール３０重量部、テレフタル酸６７．６重量部の混合物に、テレフタル酸に対してチタンテトラブトキシド０．０４７重量％を添加し、１９０〜２２５℃でエステル化反応を行なった。次いで酸化防止剤を０．２重量％添加し、減圧下で常法により重縮合反応を行いポリエステルエラストマーを得た。得られたポリエステルエラストマーのガラス転移温度は−２０℃、融点は２０８℃であった。
【００２６】
［ポリエステルエラストマーＣ］：１，４−ブタンジオール７７重量部および数平均分子量約１０００のポリテトラメチレングリコール２３重量部、テレフタル酸５９．４重量部の混合物に、テレフタル酸に対してチタンテトラブトキシド０．０４７重量％を添加し、１９０〜２２５℃でエステル化反応を行なった。次いで酸化防止剤を０．２重量％添加し、減圧下で常法により重縮合反応を行いポリエステルエラストマーを得た。得られたポリエステルエラストマーのガラス転移温度は１２℃、融点は２１９℃であった。
【００２７】
［ポリエステルエラストマーＤ］：ジメチルテレフタレート３４１ｇ、１，４−ブタンジオール６４５ｇ、ピロメリット酸ジアンヒドリド０．６５ｇ、テトラブチルオルトチタネートを窒素雰囲気下でゆっくり撹拌しながら１８０℃で処理し、反応で生成したメタノールを除去した。これにアジピン酸３１２ｇを添加した後、混合物を撹拌しながら２時間にわたり２３０℃まで加熱し、反応で生成した水を除去した。さらに１時間後に５０重量％亜リン酸水溶液０．４ｇを添加し、１時間かけて圧力を２ミリバール以下とし、２４０℃で１時間加熱した。その間過剰の１，４ブタンジオールを除去した。融点は１１０℃であった。
なお、脂肪族ポリエステル樹脂チップはそれぞれ真空、１２０℃の条件下で５時間乾燥し、ポリエステルエラストマーは８０℃の真空オーブンで１２時間乾燥して用いた。
【００２８】
実施例１
脂肪族ポリエステル樹脂Ａを７８重量％、脂肪族ポリエステル樹脂Ｂを２重量％、ポリエステルエラストマーＡを２０重量％混合して用いた。混合した原料チップを押出機に供給し、Ｔダイ口金温度２００℃でフィルム状に押し出し、２５℃に冷却したドラム上にキャストして未延伸フィルムを作製した。連続して７０℃の加熱ロール間で長手方向に３倍延伸た後、一軸延伸フィルムをクリップで把持してテンター内に導き、８０℃の温度で加熱しつつ横方向に３．６倍延伸し、幅方向に固定した状態で１４０℃、１０秒間の熱処理を行い、厚さ１２μｍの脂肪族ポリエステルフィルムを得た。結果を表１に示す。
【００２９】
【表１】
実施例２
脂肪族ポリエステル樹脂Ａを６３重量％、脂肪族ポリエステル樹脂Ｂを２重量％、ポリエステルエラストマーＢを３５重量％混合して用いた以外は実施例１と同様にして脂肪族ポリエステルフィルムを得た。結果を表１に併せて示す。
【００３１】
実施例３
脂肪族ポリエステル樹脂Ａを６８重量％、脂肪族ポリエステル樹脂Ｂを２重量％、ポリエステルエラストマーＡを３０重量％混合して用い、横方向の延伸倍率を３．０倍とした以外は実施例１と同様にして脂肪族ポリエステルフィルムを得た。結果を表１に併せて示す。
【００３２】
比較例１
脂肪族ポリエステル樹脂Ａを９８重量％、脂肪族ポリエステル樹脂Ｂを２重量％混合して用いた以外は実施例１と同様にして脂肪族ポリエステルフィルムを得た。結果を表１に併せて示す。耐屈曲性に劣るフィルムであった。
【００３３】
比較例２
脂肪族ポリエステル樹脂Ａを９４重量％、脂肪族ポリエステル樹脂Ｂを２重量％、ポリエステルエラストマーＡを４重量％混合して用いた以外は実施例１と同様にして脂肪族ポリエステルフィルムを得た。結果を表１に併せて示す。耐熱性、耐屈曲性とも劣るフィルムであった。
【００３４】
比較例３
横方向への延伸後の熱処理温度を１２７℃とした以外は実施例１と同様にして脂肪族ポリエステルフィルムを得た。結果を表１に併せて示す。収縮率が大きなフィルムであった。
【００３５】
比較例４
脂肪族ポリエステル樹脂Ａを７８重量％、脂肪族ポリエステル樹脂Ｂを２重量％、ポリエステルエラストマーＣを２０重量％混合して用いた以外は実施例１と同様にして脂肪族ポリエステルフィルムを得た。結果を表１に併せて示す。耐屈曲性に劣るフィルムであった。
【００３６】
比較例５
脂肪族ポリエステル樹脂Ａを４３重量％、脂肪族ポリエステル樹脂Ｂを２重量％、ポリエステルエラストマーＣを５５重量％混合して用いた以外は実施例１と同様にして脂肪族ポリエステルフィルムを得た。結果を表１に併せて示す。耐熱性、透明性に劣ったフィルムであった。
【００３７】
実施例４、比較例６
実施例１および比較例２の脂肪族ポリエステルフィルムに三井武田ケミカル（株）製タケラックＡ−６１０と同社製タケネートＡ−５０を重量比で９：１に混合した接着剤を用いて、厚さ６０μｍの東レ合成（株）製無延伸ポリプロピレンシートと貼り合わせ、４０℃で４８時間エージング処理を行い、実施例４および比較例６の積層体を得た。それぞれの積層体について耐屈曲性の評価を行った結果、実施例４の積層体ではピンホール個数が１．０個と良好であったが、比較例７の積層体では６５個と劣ったものであった。
【００３８】
実施例５ 脂肪族ポリエステル樹脂Ａを７８重量％、脂肪族ポリエステル樹脂Ｂを２重量％、ポリエステルエラストマーＤを２０重量％混合して用いた以外は実施例１と同様にして脂肪族ポリエステルフィルムを得た。結果を表１に併せて示す。
【００３９】
【発明の効果】
耐熱性、耐屈曲性、透明性が良好で、包装用袋として有用な脂肪族ポリエステルフィルムおよびそれを用いた積層体を得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an aliphatic polyester film. More specifically, the present invention relates to an aliphatic polyester film having excellent heat resistance and low-temperature bending resistance without impairing transparency and useful as a packaging film, and a laminate using the same.
[0002]
[Prior art]
Conventionally, aliphatic polyester films such as polylactic acid have been developed to be degraded when disposed of in the natural environment, for example, after being naturally hydrolyzed in soil, become harmless degradation products by microorganisms. . However, the aliphatic polyester film is insufficient in flexibility and inferior in bending resistance. Therefore, when it is applied to packaging applications and agricultural material applications, there are many problems and problems arise. As a method for softening such an aliphatic polyester, a method for improving flexibility by adding a softener (plasticizer) having a relatively low molecular weight to a biodegradable resin is widely known (for example, Patent Document 1). However, over time, there was a problem that the softening agent was deposited and the softening effect was significantly reduced, and the transparency of the film to which the softening agent was added was lowered. In addition, when such a film is used at a high temperature, there are problems such as remarkable decrease in transparency, scattering and leaching of a plasticizer, curing of the film, and the like.
[0003]
[Patent Document 1] Japanese Patent Application Laid-Open No. 10-316846
[Patent Document 2] Japanese Patent Application Laid-Open No. 2000-72961
[Problems to be solved by the invention]
The present invention relates to an aliphatic polyester film having both heat resistance, transparency and bending resistance, and a laminate using the same, in order to solve such problems.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the aliphatic polyester film of the present invention has the following configuration. That is, it contains 50 to 95% by weight of an aliphatic polyester, 5 to 50% by weight of a polyester elastomer having a melting point of 150 to 220C and a glass transition point of 0C or less, preferably -30C or less. An aliphatic polyester film having a crystal melting peak in a range.
[0007]
The laminate of the present invention is a laminate obtained by laminating the aliphatic polyester film and a film made of a substantially non-oriented thermoplastic resin having a melting point of 180 ° C. or less.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
The aliphatic polyester in the present invention has a general repeating unit of the general formula -O-CHR-CO- (R is hydrogen or an alkyl group having 1 to 3 carbon atoms). Examples of such an aliphatic polyester include, but are not limited to, polylactic acid, polyglycolic acid, and poly (2-oxybutyric acid). In addition, these aliphatic polyesters may be used alone, or a mixture or copolymer of two or more kinds may be used. Compounds having an asymmetric carbon in the polymer include optical isomers such as L-form, DL-form and D-form, and any of them may be used, or a mixture of these isomers may be used. The above-mentioned polymers used as materials for these films are produced by a known method such as ring-opening polymerization of a corresponding dehydrated cyclic ester compound of α-oxyacid.
[0009]
Among the above aliphatic polyesters, a polylactic acid-based polyester is most preferred. The polylactic acid-based polyester referred to here is polylactic acid or a copolymer of lactic acid and another hydroxycarboxylic acid, or a mixture thereof, and as long as the object of the present invention is not impaired, handleability, processability For the purpose of adjusting the physical properties, additives such as a plasticizer, a lubricant, a heat stabilizer, a coloring inhibitor, an ultraviolet absorber, a light stabilizer, and an antioxidant may be contained. Lactic acid includes L-lactic acid and D-lactic acid, and other hydroxycarboxylic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, and 6-hydroxyvaleric acid. Hydroxycaproic acid;
[0010]
Polyester elastomer used in the aliphatic polyester film of the present invention, terephthalic acid, isophthalic acid, an aromatic dicarboxylic acid selected from naphthalenedicarboxylic acid, and a hard segment which is a polymer of a linear alkylene glycol having 2 to 4 carbon atoms, It is preferably a copolymerized polyester comprising a soft segment having a long alkyl chain. As the soft segment, a linear alkylene glycol and sebacic acid, a polyester unit composed of a dicarboxylic acid having a long chain such as dimer acid, or a polyester unit composed of an aromatic dicarboxylic acid and a polyoxyalkylene glycol can be used. In particular, it is preferable to use a copolymer polyester of an aromatic dicarboxylic acid, a linear alkylene glycol having 2 to 4 carbon atoms and a polyoxyalkylene glycol as the polyester elastomer. Here, as polyoxyalkylene glycol, polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, polypentamethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polyoctamethylene glycol, polydecamethylene glycol, poly1- Methyl dimethylene glycol, poly 2-methyl trimethylene glycol and the like can be mentioned. Among them, polydimethylene glycol, polytrimethylene glycol and polytetramethylene glycol are preferred. Polytetramethylene glycol is particularly preferred from the viewpoint of pinhole resistance. Further, the molecular weight of the polyoxymethylene glycol is preferably from 500 to 4,000 from the viewpoint of the dispersibility of the polyoxymethylene glycol in the polyester and the haze of the film is kept low. In consideration of polymerization with the polyester, it is more preferably from 600 to 2500, and particularly preferably from 800 to 1500. Such a polyester elastomer may be a random copolymer in which repeating units of a soft segment and a hard segment are alternately bonded, but a block copolymer in which a soft segment has a certain length or more. It is preferable because the glass transition point of the polyester elastomer tends to be 0 ° C. or lower.
[0011]
In addition, as the polyester elastomer used for the aliphatic polyester film of the present invention, a copolymerized polyester having an aliphatic diol, an aromatic dicarboxylic acid, and an aliphatic dicarboxylic acid as main components and a melting point of 90 to 140 ° C can be used. . In particular, at least one aromatic polyester unit selected from ethylene terephthalate, butylene terephthalate, hexamethylene terephthalate, ethylene-2,6-naphthalate, butylene-2,6-naphthalate as an aromatic polyester unit, and an aliphatic carboxylic acid It is preferable to use a copolymerized polyester resin of a flexible component as a main constituent unit. Among them, in order to enhance the flexibility of the obtained film, in particular, butylene terephthalate and an aliphatic carboxylic acid as a main constituent unit have a melting point of 90%. Copolymerized polyesters having a temperature of from -120 ° C are preferred. In particular, when adipic acid is used as the aliphatic carboxylic acid and the butylene terephthalate copolymerization ratio is 30 mol% or less, it is particularly preferable because a polyester elastomer having biodegradability can be obtained.
[0012]
The aliphatic polyester film of the present invention contains 50 to 95% by weight of the above aliphatic polyester, preferably 70 to 90% by weight, a melting point of 150 to 220 ° C, and a glass transition point of 5 to 50% by weight of a polyester elastomer. %, Preferably 10 to 30% by weight. When the content of the aliphatic polyester is greater than 95% by weight or the content of the polyester elastomer is less than 5% by weight, the resulting film has poor bending resistance. Further, when the content of the aliphatic polyester is less than 50% by weight or the content of the polyester elastomer is more than 50% by weight, the viscosity at the time of melting becomes low, so that the film-forming property is deteriorated, In this case, the resulting film is inferior in heat resistance and transparency.
[0013]
In order to improve the handleability and processability of the aliphatic polyester film of the present invention, known inorganic particles and / or organic particles having an average particle diameter of 0.01 to 10 μm are used as a lubricant in an amount of 0.01 to 3% by weight. It is preferred to contain. Further, an antistatic agent, an ultraviolet absorber and the like may be added in a range of 5% by weight or less as long as the object of the present invention is not impaired.
[0014]
The aliphatic polyester having the above composition is softer than a single aliphatic polyester. However, in order to achieve both excellent bending resistance and heat resistance, the aliphatic polyester film is heat-treated at 135 to 145 ° C. It is necessary to have a crystal melting peak in the range. If the crystal melting peak does not exist or is lower than 135 ° C., the strength is remarkably reduced due to heat during post-processing or actual use, and a film having a large shrinkage ratio is obtained. When the crystal melting peak is higher than 145 ° C., the bending resistance is reduced.
[0015]
The aliphatic polyester film of the present invention is preferably biaxially stretched in order to secure heat resistance, and has an in-plane average refractive index of 1 as an average value of the refractive index in the film longitudinal direction and the refractive index in the film width direction. It is preferably at least 4.460, more preferably at least 1.465, and the plane orientation coefficient of the film is at least 0.014, preferably at least 0.015. When the in-plane average refractive index is in such a preferable range, a film having good heat resistance can be obtained. The upper limit of the in-plane average refractive index and the upper limit of the plane orientation coefficient are not particularly set. It is difficult.
[0016]
When using the aliphatic polyester film of the present invention for packaging bags, non-stretching of polyethylene or polypropylene, ethylene-vinyl acetate copolymer, aromatic copolymer polyester or aliphatic polyester to impart heat sealability The film is laminated as a heat bonding layer and used as a laminate. As a lamination method, a method such as a dry lamination method using a polyurethane adhesive or the like, an extrusion lamination method, or the like is used.
[0017]
The aliphatic polyester film of the present invention can be obtained by an existing stretched film production method such as an inflation method, a simultaneous biaxial stretching method, and a sequential biaxial stretching method. Axial stretching is preferred. In the production of the white aliphatic polyester film of the present invention by the sequential biaxial stretching method, first, the aliphatic polyester chips and polyester elastomer chips dried under vacuum are blended and supplied to an extruder, and slitting is performed by a known method. It is melt-extruded into a sheet form from a cylindrical die, brought into close contact with a casting drum, and cooled and solidified to obtain an unstretched film. In the case where a layer containing a small amount of inorganic particles is provided on the surface layer of the film, composite extrusion is most preferable to obtain a laminated unstretched film by combining two or more extruders with a molten polymer in a die or upstream of a die. The unstretched film obtained by such a method is continuously stretched in at least one direction, further stretched in the orthogonal direction, and subjected to heat treatment, thereby increasing the adhesion of the thin film layer to the substrate and the toughness of the thin film layer. preferable. Roll stretching using a peripheral speed difference of a heating roll is preferably used for stretching in the film longitudinal direction, and a tenter having a continuous clip is preferably used for stretching in the film width direction or heat treatment after biaxial stretching.
[0018]
The white aliphatic polyester film of the present invention may be provided with a functional layer by coating for the purpose of imparting adhesion to an adhesive for bonding to an ink or another material, antistatic properties, and the like.
[0019]
The aliphatic polyester film of the present invention can be widely used for a protective film or a packaging bag which is required to have heat resistance, bending resistance and transparency, but is particularly preferably used for a packaging bag.
[0020]
【Example】
Hereinafter, the present invention will be further described with reference to examples. In particular, a description will be given of polylactic acid which is a typical aliphatic polyester as an example, but the present invention is not limited thereto.
[Method of measuring characteristics]
(1) Glass transition point, melting point, heat of crystal fusion, glass transition point of polyester elastomer, melting point Measured using a DSC (differential scanning calorimeter) RDC220 manufactured by Seiko Instruments Inc. A sample (5 mg) was set in a DSC device, and the temperature was raised from −100 ° C. to 250 ° C. at a rate of 20 ° C./min, and the glass transition point and melting point were measured.
Crystal melting temperature of aliphatic polyester film Measured using a DSC (differential scanning calorimeter) RDC220 manufactured by Seiko Instruments Inc. A sample (5 mg) was set in a DSC apparatus, and the temperature was raised from 25 ° C. to 250 ° C. at a rate of 20 ° C./min.
(2) Using an Atago Co., Ltd. Abbe refractometer 4T type equipped with an in-plane average refractive index and a plane orientation coefficient polarizer, a refractive index in the longitudinal direction of the film (nx) and a refractive index in the width direction (ny). , The refractive index (nz) in the thickness direction was determined, and the in-plane average refractive index and the plane orientation coefficient were determined from the following equations. Note that an auxiliary prism having a refractive index of 1.74 and methylene iodide as an immersion liquid were used.
[0021]
In-plane average refractive index = (nx + ny) / 2
Plane orientation coefficient = {(nx + ny) / 2} -nz
(3) Heat resistance (heat shrinkage)
It was determined from the shrinkage at 120 ° C. in the longitudinal direction of the film. The film was cut into a width of 10 mm and a length of 30 cm in the longitudinal direction of the film, and marked at intervals of 100 mm. A sample of 5 g is hung on one side of the sample, and the sample is processed in an oven at 120 ° C. for 30 minutes. The length (L 1 , L 2 ) before and after the process is obtained using a universal projector, and the heat shrinkage is calculated from the following equation. I asked.
Heat shrinkage (%) = (L 1 −L 2 ) / L 1 × 100
When the shrinkage ratio was 4% or more, or conversely, the expansion was 1% or more, it was regarded as poor heat resistance.
(4) Flex resistance According to ASTM F-392, a film cut out to a size of 297 × 210 mm was subjected to a repetitive flex test 500 times in a 5 ° C. temperature atmosphere using carbon dioxide gas using a gel botester. did. The test was performed five times, and the average value of the number of pinholes was calculated. In each case of the film alone or the laminate, when 10 or more pinholes were generated, it was determined to be defective.
(5) Haze Haze was measured using a SEP-H-2 turbidimeter (manufactured by Nippon Seimitsu Optical Co., Ltd.) in accordance with JIS K 6714-58. A haze of 10% or more was determined to be defective.
[0022]
(Preparation of aliphatic polyester resin and polyester elastomer)
[Aliphatic polyester resin A]: L-polylactic acid having a weight average molecular weight of about 200,000 (melting point: 170 ° C.) was used.
[0023]
[Aliphatic polyester resin B]: The amount of silica particles (Fuji Silysia Chemical Ltd., Sylysia) added to aliphatic polyester resin A by 2.5% by weight at 200 ° C. using a known twin-screw extruder. And kneaded so as to obtain a master pellet.
[0024]
[Polyester Elastomer A]: A mixture of 40 parts by weight of 1,4-butanediol, 60 parts by weight of polytetramethylene glycol having a number average molecular weight of about 1000, and 83.7 parts by weight of terephthalic acid was added to titanium tetrabutoxide with respect to terephthalic acid. 0.047% by weight was added, and an esterification reaction was performed at 190 to 225 ° C. Next, 0.2% by weight of an antioxidant was added, and a polycondensation reaction was carried out under reduced pressure by a conventional method to obtain a polyester elastomer. The glass transition temperature of the obtained polyester elastomer was −60 ° C., and the melting point was 170 ° C.
[0025]
[Polyester Elastomer B]: A mixture of 70 parts by weight of 1,4-butanediol, 30 parts by weight of polytetramethylene glycol having a number average molecular weight of about 1000, and 67.6 parts by weight of terephthalic acid was added with titanium tetrabutoxide to terephthalic acid. 0.047% by weight was added, and an esterification reaction was performed at 190 to 225 ° C. Next, 0.2% by weight of an antioxidant was added, and a polycondensation reaction was carried out under reduced pressure by a conventional method to obtain a polyester elastomer. The obtained polyester elastomer had a glass transition temperature of −20 ° C. and a melting point of 208 ° C.
[0026]
[Polyester Elastomer C]: A mixture of 77 parts by weight of 1,4-butanediol, 23 parts by weight of polytetramethylene glycol having a number average molecular weight of about 1000, and 59.4 parts by weight of terephthalic acid was added with titanium tetrabutoxide to terephthalic acid. 0.047% by weight was added, and an esterification reaction was performed at 190 to 225 ° C. Next, 0.2% by weight of an antioxidant was added, and a polycondensation reaction was carried out under reduced pressure by a conventional method to obtain a polyester elastomer. The glass transition temperature of the obtained polyester elastomer was 12 ° C, and the melting point was 219 ° C.
[0027]
[Polyester Elastomer D]: 341 g of dimethyl terephthalate, 645 g of 1,4-butanediol, 0.65 g of pyromellitic acid dianhydride, and tetrabutyl orthotitanate were treated at 180 ° C. while being slowly stirred under a nitrogen atmosphere to form a reaction. The methanol was removed. After adding 312 g of adipic acid thereto, the mixture was heated to 230 ° C. for 2 hours while stirring to remove water generated by the reaction. One hour later, 0.4 g of a 50% by weight aqueous phosphorous acid solution was added, the pressure was reduced to 2 mbar or less over 1 hour, and the mixture was heated at 240 ° C. for 1 hour. During that time, excess 1,4 butanediol was removed. The melting point was 110 ° C.
The aliphatic polyester resin chips were each dried under vacuum and 120 ° C. for 5 hours, and the polyester elastomer was dried in a vacuum oven at 80 ° C. for 12 hours.
[0028]
Example 1
78% by weight of aliphatic polyester resin A, 2% by weight of aliphatic polyester resin B, and 20% by weight of polyester elastomer A were used. The mixed raw material chips were supplied to an extruder, extruded into a film at a T die die temperature of 200 ° C., and cast on a drum cooled to 25 ° C. to produce an unstretched film. After continuously stretching three times in the longitudinal direction between heating rolls at 70 ° C., the uniaxially stretched film is gripped with a clip and guided into a tenter, and stretched 3.6 times in the transverse direction while heating at a temperature of 80 ° C. Then, heat treatment was performed at 140 ° C. for 10 seconds while being fixed in the width direction to obtain an aliphatic polyester film having a thickness of 12 μm. Table 1 shows the results.
[0029]
[Table 1]
Example 2
An aliphatic polyester film was obtained in the same manner as in Example 1 except that 63% by weight of the aliphatic polyester resin A, 2% by weight of the aliphatic polyester resin B, and 35% by weight of the polyester elastomer B were used. The results are shown in Table 1.
[0031]
Example 3
Example 1 was repeated except that 68% by weight of the aliphatic polyester resin A, 2% by weight of the aliphatic polyester resin B, and 30% by weight of the polyester elastomer A were used and the stretching ratio in the horizontal direction was 3.0 times. Similarly, an aliphatic polyester film was obtained. The results are shown in Table 1.
[0032]
Comparative Example 1
An aliphatic polyester film was obtained in the same manner as in Example 1, except that the aliphatic polyester resin A was mixed at 98% by weight and the aliphatic polyester resin B was mixed at 2% by weight. The results are shown in Table 1. The film was inferior in bending resistance.
[0033]
Comparative Example 2
An aliphatic polyester film was obtained in the same manner as in Example 1 except that 94% by weight of the aliphatic polyester resin A, 2% by weight of the aliphatic polyester resin B, and 4% by weight of the polyester elastomer A were used. The results are shown in Table 1. The film had poor heat resistance and bending resistance.
[0034]
Comparative Example 3
An aliphatic polyester film was obtained in the same manner as in Example 1 except that the heat treatment temperature after stretching in the transverse direction was set to 127 ° C. The results are shown in Table 1. The film had a large shrinkage.
[0035]
Comparative Example 4
An aliphatic polyester film was obtained in the same manner as in Example 1, except that 78% by weight of the aliphatic polyester resin A, 2% by weight of the aliphatic polyester resin B, and 20% by weight of the polyester elastomer C were used. The results are shown in Table 1. The film was inferior in bending resistance.
[0036]
Comparative Example 5
An aliphatic polyester film was obtained in the same manner as in Example 1, except that 43% by weight of the aliphatic polyester resin A, 2% by weight of the aliphatic polyester resin B, and 55% by weight of the polyester elastomer C were used. The results are shown in Table 1. The film was inferior in heat resistance and transparency.
[0037]
Example 4, Comparative Example 6
The aliphatic polyester films of Example 1 and Comparative Example 2 were mixed with Takei Mitsui Chemicals Co., Ltd. Takelac A-610 and Takenate A-50 manufactured by the company at a weight ratio of 9: 1, using an adhesive mixed at a weight ratio of 60 μm. And an aging treatment at 40 ° C. for 48 hours to obtain laminates of Example 4 and Comparative Example 6. As a result of evaluating the bending resistance of each laminate, the laminate of Example 4 had a good number of pinholes of 1.0, but the laminate of Comparative Example 7 was inferior to 65. Met.
[0038]
Example 5 An aliphatic polyester film was obtained in the same manner as in Example 1, except that 78% by weight of the aliphatic polyester resin A, 2% by weight of the aliphatic polyester resin B, and 20% by weight of the polyester elastomer D were used. Was. The results are shown in Table 1.
[0039]
【The invention's effect】
An aliphatic polyester film having good heat resistance, bending resistance, and transparency and useful as a packaging bag, and a laminate using the same can be obtained.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003143107A JP2004051959A (en) | 2002-05-30 | 2003-05-21 | Aliphatic polyester film and laminated product |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002157377 | 2002-05-30 | ||
| JP2003143107A JP2004051959A (en) | 2002-05-30 | 2003-05-21 | Aliphatic polyester film and laminated product |
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| Publication Number | Publication Date |
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| JP2004051959A true JP2004051959A (en) | 2004-02-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003143107A Pending JP2004051959A (en) | 2002-05-30 | 2003-05-21 | Aliphatic polyester film and laminated product |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005329658A (en) * | 2004-05-21 | 2005-12-02 | Mitsubishi Polyester Film Copp | Biaxially oriented aliphatic polyester film |
| JP2006124662A (en) * | 2004-09-29 | 2006-05-18 | Toray Ind Inc | Biaxially oriented polylactic acid film, molding composed of the same and substrate |
| JP2006160981A (en) * | 2004-12-10 | 2006-06-22 | Toray Ind Inc | Polyester film |
| WO2008012946A1 (en) * | 2006-07-27 | 2008-01-31 | Techno Polymer Co., Ltd. | Thermoplastic polymer composition and molded article |
| JP2008265117A (en) * | 2007-04-19 | 2008-11-06 | Dainippon Printing Co Ltd | Multilayered laminated film |
| JP2008265118A (en) * | 2007-04-19 | 2008-11-06 | Dainippon Printing Co Ltd | Multilayered laminated film |
| JP2009293044A (en) * | 2009-09-18 | 2009-12-17 | Kureha Corp | Polyglygolic acid-based resin composition and molded article of the same |
| JP2010532286A (en) * | 2007-07-03 | 2010-10-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Multilayer film structure containing biological material |
| CN104105744A (en) * | 2012-02-10 | 2014-10-15 | 日东电工株式会社 | Separator |
| JP7528464B2 (en) | 2019-03-11 | 2024-08-06 | 三菱ケミカル株式会社 | Polyalkylene glycol copolymer polyester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005329658A (en) * | 2004-05-21 | 2005-12-02 | Mitsubishi Polyester Film Copp | Biaxially oriented aliphatic polyester film |
| JP2006124662A (en) * | 2004-09-29 | 2006-05-18 | Toray Ind Inc | Biaxially oriented polylactic acid film, molding composed of the same and substrate |
| JP2006160981A (en) * | 2004-12-10 | 2006-06-22 | Toray Ind Inc | Polyester film |
| WO2008012946A1 (en) * | 2006-07-27 | 2008-01-31 | Techno Polymer Co., Ltd. | Thermoplastic polymer composition and molded article |
| US8084538B2 (en) | 2006-07-27 | 2011-12-27 | Techno Polymer Co., Ltd. | Thermoplastic polymer composition and molded product |
| US8252868B2 (en) | 2006-07-27 | 2012-08-28 | Techno Polymer Co., Ltd. | Thermoplastic polymer composition and molded product |
| JP2008265117A (en) * | 2007-04-19 | 2008-11-06 | Dainippon Printing Co Ltd | Multilayered laminated film |
| JP2008265118A (en) * | 2007-04-19 | 2008-11-06 | Dainippon Printing Co Ltd | Multilayered laminated film |
| JP2010532286A (en) * | 2007-07-03 | 2010-10-07 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Multilayer film structure containing biological material |
| JP2009293044A (en) * | 2009-09-18 | 2009-12-17 | Kureha Corp | Polyglygolic acid-based resin composition and molded article of the same |
| CN104105744A (en) * | 2012-02-10 | 2014-10-15 | 日东电工株式会社 | Separator |
| JP7528464B2 (en) | 2019-03-11 | 2024-08-06 | 三菱ケミカル株式会社 | Polyalkylene glycol copolymer polyester |
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