JP4233899B2 - Biaxially stretched laminated film and use thereof - Google Patents
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- 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
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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共重合体とポリ乳酸との組成物を基材層とし、脂肪族ポリエステル共重合体を被覆層とする二軸延伸積層フィルムに関し、該フィルムは、生分解性を備え、且つ熱融着性、透明性に優れ、包装用フィルムに好適である。
【０００２】
【従来の技術】
生分解可能なプラスチックとして、汎用性の高い脂肪族ポリエステルが注目されており、ポリ乳酸（ＰＬＡ）、ポリブチレンサクシネート（ＰＢＳ）、ポリエチレンサクシネート（ＰＥＳ）、ポリカプロラクトン（ＰＣＬ）などが上市されている。
これら生分解性脂肪族ポリエステルの用途の一つとして包装用、農業用、食品用などのフィルム分野があり、用途に応じた高強度、耐熱性および生分解性が、基本性能として要求されている。
【０００３】
上記脂肪族ポリエステルの中で、ＰＬＡは、高いものでは１７０℃付近に融点を持ち高耐熱性であるが、脆いために成形品の伸度は低く、また土中で分解しにくいためコンポスト化設備が必要である。ＰＢＳおよびＰＥＳは融点が１００℃付近で十分な耐熱性を有するが、生分解速度が小さく、実用的には不充分であり、また機械的性質では柔軟性に欠ける。ＰＣＬは柔軟性に優れるものの、融点６０℃と耐熱性が低いために用途が限定されているが、生分解速度は非常に速い。
【０００４】
一方、特許２９９７７５６号公報記載のポリブチレンサクシネート−ポリカプロラクトン共重合体（ＰＢＳＣ）のように、脂肪族ポリエステル共重合体中にカプロラクトンユニットを導入することにより、実用的な柔軟性と適度な生分解性を実現することができ、また、カプロラクトンユニットの含有量を制御することにより、融点を８０℃以上として十分な耐熱性を保持することと、生分解性を制御することが可能であることが見出されている。（特許文献１）
【０００５】
又、ＷＯ ０２−４４２４９号公報には、脂肪族ジオール、脂肪族ジカルボン酸及び脂肪族ヒドロキシカルボン酸またはその無水環状化合物（ラクトン類）の３成分からなる混合物の重縮合反応により合成した重量平均分子量４０，０００以上の高分子量脂肪族ポリエステル共重合体と他の生分解性樹脂を使用することにより、フィルム等の成形時の分子量安定性が良く、成形が良好であることが開示されている。（特許文献２）
【０００６】
しかし、上記技術の脂肪族ポリエステル共重合体から得られる二軸延伸フィルムは、熱融着性がないので包装用フィルムに使用するには制限があった。
【０００７】
【特許文献１】
特許２９９７７５６号（請求項１〜３、実施例１〜５）
【特許文献２】
ＷＯ ０２−４４２４９号公報（請求項、発明の開示の項の最終段落、表VII−１）
【０００８】
【発明が解決しようとする課題】
本発明は、特定の生分解性脂肪族ポリエステルを使用して、透明性、柔軟性および熱融着性を有する二軸延伸フィルムを開発することを目的とした。
【０００９】
【課題を解決するための手段】
本発明者らは、基材層（Ｉ）に脂肪族ジオール、脂肪族ジカルボン酸、及びラクトンからなる３成分系脂肪族ポリエステル共重合体とポリ乳酸との特定比率の組成物を使用し、被覆層（II）に上記３成分系脂肪族ポリエステル共重合体を使用することにより、かかる問題点を解決し得ることを見い出し、本発明を完成するに至った。
【００１０】
すなわち本発明の第１は、分子鎖が、下記一般式（１）〜（３）で示される繰返し単位：
−ＣＯ−Ｒ1−ＣＯ− （１）
（式中、Ｒ1は炭素数１〜１２の二価脂肪族基を表す。）
−Ｏ−Ｒ2−Ｏ− （２）
（式中、Ｒ2は炭素数２〜１２の二価脂肪族基を表す。）
下記一般式（３）で示される繰返し単位：
−ＣＯ−Ｒ3−Ｏ− （３）
（式中、Ｒ3は炭素数１〜１０の二価脂肪族基を表す。）
からなり、
一般式（３）で示される繰返し単位が１〜３０モル％
（一般式（１）〜（３）で、繰返し単位（１）と（２）の量は実質的に等しく、（１）、（２）及び（３）の量の合計は１００モル％である。）
である脂肪族ポリエステル共重合体（Ａ）９７〜６０重量％とポリ乳酸（Ｂ）３〜４０重量％との脂肪族ポリエステル組成物（Ｃ）からなる二軸延伸フィルム基材層（Ｉ）の少なくとも片面に、上記脂肪族ポリエステル共重合体（Ａ）からなる被覆層（II）を有してなることを特徴とする二軸延伸積層フィルムを提供する。
本発明の第２は、脂肪族ポリエステル共重合体（Ａ）の融点が、８５〜１２０℃の範囲にある本発明の第１記載の二軸延伸積層フィルムを提供する。
本発明の第３は、脂肪族ポリエステル共重合体（Ａ）が、該脂肪族ポリエステル共重合体（Ａ）の重合中間体である重量平均分子量５，０００以上の低分子量脂肪族ポリエステル共重合体（Ａ’）１００重量部に対し、０．１〜５重量部のジイソシアネート化合物を反応させて高分子量化されたものである本発明の第１又は２に記載の二軸延伸積層フィルムを提供する。
本発明の第４は、一般式（１）が、コハク酸残基及び／又はアジピン酸残基である本発明の第１〜３の何れか１項に記載の二軸延伸積層フィルムを提供する。
本発明の第５は、一般式（２）が、エチレングリコール残基及び／又は１，４−ブタンジオール残基である本発明の第１〜４の何れか１項に記載の二軸延伸積層フィルムを提供する。
本発明の第６は、一般式（３）が、ε−カプロラクトンの開環した基である本発明の第１〜５の何れか１項に記載の二軸延伸積層フィルムを提供する。
本発明の第７は、二軸延伸積層フィルムが、脂肪族ポリエステル共重合体（Ａ）と脂肪族ポリエステル組成物（Ｃ）とを共押出し成形して得られる積層シートを二軸延伸してなる本発明の第１〜６の何れかに記載の二軸延伸積層フィルムを提供する。
本発明の第８は、同時二軸延伸方法により得られる本発明の第１〜７の何れか１項に記載の二軸延伸積層フィルムを提供する。
本発明の第９は、基材層（Ｉ）の両面に被覆層（II）を有する本発明の第１〜８の何れか１項に記載の二軸延伸積層フィルムを提供する。
本発明の第１０は、本発明の第９に記載の二軸延伸積層フィルムからなるオーバーラップ包装用フィルムを提供する。
本発明の第１１は、本発明の第１〜９の何れか１項に記載の二軸延伸積層フィルムからなる収縮包装用フィルムを提供する。
【００１１】
【発明の実施の形態】
本発明の二軸延伸積層フィルムは、脂肪族ポリエステル共重合体（Ａ）およびポリ乳酸（Ｂ）からなる脂肪族ポリエステル組成物（Ｃ）の基材層（Ｉ）と、脂肪族ポリエステル共重合体（Ａ）からなる被覆層（II）とからなる。
【００１２】
基材層（Ｉ）
本発明に係る基材層（Ｉ）は、脂肪族ポリエステル共重合体（Ａ）およびポリ乳酸（Ｂ）からなる。
【００１３】
脂肪族ポリエステル共重合体（Ａ）
本発明に係る上記脂肪族ポリエステル共重合体（Ａ）は、分子鎖が、下記一般式（１）〜（３）で示される繰返し単位：
−ＣＯ−Ｒ1−ＣＯ− （１）
（式中、Ｒ1は炭素数１〜１２の二価脂肪族基を表す。）
−Ｏ−Ｒ2−Ｏ− （２）
（式中、Ｒ2は炭素数２〜１２の二価脂肪族基を表す。）
下記一般式（３）で示される繰返し単位：
−ＣＯ−Ｒ3−Ｏ− （３）
（式中、Ｒ3は炭素数１〜１０の二価脂肪族基を表す。）
からなる。
基材層（Ｉ）では、二種以上の脂肪族ポリエステル共重合体（Ａ）を混合使用してもよい。
【００１４】
脂肪族ポリエステル共重合体（Ａ）の組成及び基礎物性は下記の通りである。
一般式（３）で示される繰返し単位の含有率は、１〜３０モル％、好ましくは１〜２０モル％、更に好ましくは１〜１５モル％の範囲にある（一般式（１）〜（３）で、繰返し単位（１）と（２）の量は実質的に等しく、（１）、（２）及び（３）の量の合計は１００モル％である。）。
上記脂肪族ポリエステル共重合体（Ａ）は、フィルム形成能がある限り、分子量は特に限定はされないが、通常、重量平均分子量が４０，０００以上、好ましくは、７０，０００〜３００，０００、より好ましくは１２０，０００〜２５０，０００の範囲にある。
又、好ましくは重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）で表される分子量分布が通常２〜５、好ましくは２〜３の範囲である。
共重合体（Ａ）の融点は、通常８５℃以上、好ましくは８５〜１２０℃、より好ましくは９０〜１１０℃の範囲にある。
【００１５】
脂肪族ポリエステル共重合体（Ａ）は、一般式（３）で示される繰返し単位が１モル％未満では、得られる二軸延伸積層フィルムは透明性、柔軟性、延伸性が失われる傾向にあり、３０モル％を超えると、得られるポリマーの融点が低く、結晶性が極端に低下するため、得られる二軸延伸積層フィルムは耐熱性が劣る傾向にある。
【００１６】
一般式（１）で表される繰り返し単位である脂肪族ジカルボン酸残基を与える化合物としては、脂肪族ジカルボン酸、その無水物、又はそのモノまたはジエステル体が挙げられ、下記一般式（４）で表される化合物を挙げることができる。
Ｒ4ＯＣＯ−Ｒ1−ＣＯＯＲ5 （４）
（式中、Ｒ1は炭素数１〜１２の二価脂肪族基、Ｒ4及びＲ5は水素原子、又は炭素数１〜６の脂肪族基もしくは芳香族基を示す。Ｒ4およびＲ5は同一でも異なっていてもよい。）
前記Ｒ1で示される二価脂肪族基は、好ましくは炭素数２〜８の鎖状又は環状のアルキレン基であり、−(ＣＨ2)2−、−(ＣＨ2)4−、−(ＣＨ2)6−等の炭素数２〜６の直鎖状低級アルキレン基が挙げられる。Ｒ4及びＲ5が水素原子であるときには脂肪族ジカルボン酸を表わしている。脂肪族ジカルボン酸の具体例としては、例えば、コハク酸、アジピン酸、ピメリン酸、アゼライン酸、セバシン酸、ジグリコール酸などである。
【００１７】
上記一般式（２）で表される繰り返し単位である脂肪族ジオール残基を与える化合物としては、脂肪族ジオールが挙げられ、下記一般式（５）で表される化合物を挙げることができる。
ＨＯ−Ｒ2−ＯＨ （５）
（式中、Ｒ2は炭素数２〜１２の二価脂肪族基を示す。）
二価の脂肪族基としては、炭素数２〜１２、好ましくは２〜８の鎖状又は環状のアルキレン基が挙げられる。好ましいアルキレン基は、−(ＣＨ2)2−、−(ＣＨ2)4−等の炭素数２〜６の直鎖状低級アルキレン基である。
脂肪族ジオールとしては、例えば、エチレングリコール、１，３‐プロパンジオール、１，３−ブタンジオール、２−メチル−プロパンジオール、１，４−ブタンジオール、ネオペンチルグリコール、ペンタメチレングリコール、へキサメチレングリコール、オクタメチレングリコール、デカメチレングリコール、ドデカメチレングリコール、１，４−シクロヘキサンジメタノール等を用いることができる。これらのものは単独で用いてよいし、２種以上組合せて用いてもよい。
【００１８】
上記一般式（３）で表される繰り返し単位である脂肪族ヒドロキシカルボン酸残基を与える化合物としては、下記一般式（６）で表されるヒドロキシカルボン酸もしくはヒドロキシカルボン酸エステル、又は下記一般式（７）で表されるラクトン類が挙げられる。これらは２種以上を混合して使用してもよい。
ＨＯ−Ｒ3−ＣＯＯＲ6 （６）
（式中、Ｒ3は炭素数１〜１０の二価脂肪族基、Ｒ6は水素原子または炭素数１〜６の脂肪族基又は芳香族基を表す。）
【００１９】
【化１】
（式中、Ｒ3は炭素数４〜１０の二価脂肪族基を表す。）
【００２１】
上記式（６）において、二価脂肪族基Ｒ3としては、炭素数１〜１０、好ましくは２〜８の鎖状又は環状のアルキレン基が挙げられる。
Ｒ6は水素、脂肪族基又は芳香族基である。脂肪族基としては、炭素数１〜６、好ましくは１〜４の直鎖状又は分岐鎖状の低級アルキル基や、シクロヘキシル基等の炭素数５〜１２のシクロアルキル基、芳香族基としては、フェニル基、ベンジル基等が挙げられる。
上記ヒドロキシカルボン酸としては、グリコール酸、Ｌ−乳酸、Ｄ−乳酸、Ｄ，Ｌ−乳酸、２−メチル乳酸、３−ヒドロキシ酪酸、４−ヒドロキシ酪酸、２−ヒドロキシ−ｎ−酪酸、２−ヒドロキシ−３，３−ジメチル酪酸、２−ヒドロキシ−２−メチル酪酸、２−ヒドロキシ−３−メチル酪酸、ヒドロキシピバリン酸、ヒドロキシイソカプロン酸及びヒドロキシカプロン酸等が挙げられる。上記ヒドロキシカルボン酸エステルとしては、上記ヒドロキシカルボン酸のメチル、エチル、プロピル、ブチル、シクロヘキシル、フェニルエステル等が挙げられる。
【００２２】
前記一般式（７）において、二価脂肪族基Ｒ3としては、炭素数４〜１０、好ましくは４〜８の直鎖状又は分岐鎖状のアルキレン基が挙げられる。
ラクトンの具体例としては、例えば、γ−バレロラクトン、δ−バレロラクトン、ε−カプロラクトン、１，３−ジオキソラン−４−オン、１，４−ジオキサン−３−オン、１，５−ジオキセパン−２−オン等を挙げることができる。
また、前記ヒドロキシカルボン酸の２分子が結合した環状二量体エステル（ラクチド）であってもよく、グリコール酸から得られるグリコリドや、乳酸から得られるラクチド等が挙げられる。
【００２３】
脂肪族ポリエステル共重合体（Ａ）の製造方法
本発明に係わる脂肪族ポリエステル共重合体（Ａ）は種々公知の方法、例えば、前記一般式（１）で表される繰り返し単位を有する脂肪族ジカルボン酸又は脂肪族ジカルボン酸ジエステル、前記一般式（２）で表される繰り返し単位を有する脂肪族ジオール、及び前記一般式（３）で表される繰り返し単位を有するオキシカルボン酸又はオキシカルボン酸エステル若しくはラクトン類を触媒の存在下に重縮合反応させることにより得られる。
【００２４】
本発明に係る脂肪族ポリエステル共重合体（Ａ）は、一旦重量平均分子量５，０００以上の低分子量の脂肪族ポリエステル共重合体（Ａ’）を得た後、溶融状態の低分子量脂肪族ポリエステル共重合体（Ａ’）にジイソシアネート化合物を加えて重量平均分子量を４０，０００以上に高めるようにしてもよい。
またウレタン結合を含む脂肪族ポリエステル共重合体は、重量平均分子量が前記共重合体（Ａ）の範囲と同じであるが、４０，０００以上、通常７０，０００〜３００，０００、好ましくは１２０，０００〜２５０，０００の範囲のものである。
本発明に係る脂肪族ポリエステル共重合体（Ａ）は、詳しくは、例えば、特許第２９９７７５６号公報及びＷＯ ０２−４４２４９号公報に記載の製造方法により得られる。
【００２５】
ポリ乳酸（Ｂ）
ポリ乳酸（Ｂ）は、乳酸の構造単位がＬ−乳酸であるポリ（Ｌ−乳酸）、構造単位がＤ−乳酸であるポリ（Ｄ−乳酸）、更にはＬ−乳酸とＤ−乳酸の任意混合物であるポリ（ＤＬ−乳酸）、等量混合物から得られたラセミ体のポリ（ＤＬ−乳酸）等の乳酸重合体、及び乳酸を主成分とし、乳酸以外の共重合可能なコモノマーを、例えば５０重量％未満、好ましくは３０重量％以下、より好ましくは１０重量％以下の割合で共重合したコポリマー、あるいはこれらの混合物等の乳酸を主成分とする重合体である。乳酸と共重合可能なコモノマーとしては、例えば３−ヒドロキシブチレート、カプロラクトン、グリコール酸などを挙げることができる。
かかるポリ乳酸の重合法としては、縮重合法、開環重合法など公知のいずれの方法を採用することができる。例えば、縮重合法ではＬ−乳酸またはＤ−乳酸あるいはこれらの混合物を直接脱水縮重合して任意の組成を持ったポリ乳酸を得ることができる。
脂肪族ポリエステル共重合体（Ａ）に、かかるポリ乳酸（Ｂ）を添加することにより、得られる二軸延伸積層フィルムの基材層（Ｉ）がシールバーの熱と圧力によって、薄くならず、又シールバーへの融着が防げるという、利点がある。
これらポリ乳酸の中でも、Ｄ−乳酸を０〜３０重量％、好ましくは０〜２５重量％含むＬ−乳酸の単独重合体若しくはＤ−乳酸とＬ−乳酸の共重合体が、基材層を構成する前記脂肪族ポリエステル（Ａ）に添加して得られる二軸延伸積層フィルムの透明性、光線透過率が良好である。なお、ポリ乳酸共重合体におけるＤ−乳酸含有量は、クロムバック社製ガスクロマトグラフCP ＣＹＣＬＯＤＥＸ B ２３６Ｍを用いて測定した値である。
上記ポリ乳酸（Ｂ）としては、ＭＦＲ（ＡＳＴＭ Ｄ−１２３８による。荷重２１６０ｇ、温度１９０℃）が０．１〜１００ｇ／１０分、好ましくは１〜５０ｇ／１０分、特に好ましくは２〜１０ｇ／１０分のものが使用される。
【００２６】
脂肪族ポリエステル組成物（Ｃ）
本発明に係る脂肪族ポリエステル組成物（Ｃ）は、前記脂肪族ポリエステル共重合体（Ａ）９７〜６０重量％、好ましくは９５〜７０重量％、更に好ましくは８５〜７５重量％と、前記ポリ乳酸（Ｂ）３〜４０重量％、好ましくは５〜３０重量％、更に好ましくは１５〜２５重量％との組成物である。
脂肪族ポリエステル組成物（Ｃ）中のポリ乳酸（Ｂ）の量が３重量％未満では、基材層としての二軸延伸積層フィルムの充分な熱融着性が得られないおそれがあり、一方、４０重量％を超えると二軸延伸積層フィルムの柔軟性が劣るおそれがある。
【００２７】
本発明に係る脂肪族ポリエステル組成物（Ｃ）は、脂肪族ポリエステル共重合体（Ａ）及びポリ乳酸（Ｂ）を夫々上記範囲でヘンシェルミキサー、Ｖ−ブレンダー、リボンブレンダー、タンブラーミキサー等で混合する方法、混合後更に単軸押出機、多軸押出機、バンバリーミキサー等で溶融混練する方法等により得られる。
【００２８】
本発明に係る脂肪族ポリエステル組成物（Ｃ）には、脂肪族ポリエステル共重合体（Ａ）及びポリ乳酸（Ｂ）を夫々別個に、あるいは組成物（Ｃ）を製造する際に、本発明の目的を損なわない範囲で、通常用いられる酸化防止剤、耐候安定剤、帯電防止剤、防曇剤、アンチブロッキング剤、スリップ剤、耐光安定剤、紫外線吸収剤、蛍光増白剤、抗菌剤、核剤、無機あるいは有機化合物充填材等の添加剤を必要に応じて配合することができる。
【００２９】
被覆層（II）
本発明に係る被覆層（II）は、前記脂肪族ポリエステル共重合体（Ａ）からなる。脂肪族ポリエステル共重合体（Ａ）は二種以上の混合物であってもよい。
被覆層（II）に用いる脂肪族ポリエステル共重合体（Ａ）は、基材層（Ｉ）に用いる脂肪族ポリエステル共重合体（Ａ）と同じであっても、異なっていてもよい。
【００３０】
被覆層（II）に使用される脂肪族ポリエステル共重合体（Ａ）には、必要に応じて基材層（Ｉ）で用いられる添加剤を添加することができる。
【００３１】
二軸延伸積層フィルム
本発明の二軸延伸積層フィルムは、前記脂肪族ポリエステル組成物（Ｃ）からなる二軸延伸フィルム基材層（Ｉ）の片面若しくは両面に脂肪族ポリエステル共重合体（Ａ）からなる被覆層（II）を有してなる二軸延伸積層フィルムである。本発明の二軸延伸積層フィルムは、二軸延伸フィルム基材層（Ｉ）として、脂肪族ポリエステル組成物（Ｃ）を用いてなるので、得られる二軸延伸積層フィルムは柔軟性、透明性に優れ、且つ表面には、脂肪族ポリエステル共重合体（Ａ）から得られる被覆層（II）を有することにより熱融着性を有する。
【００３２】
本発明の二軸延伸積層フィルムの厚さは用途に応じて種々決め得るが、通常、基材層（Ｉ）となる二軸延伸フィルムの厚さは５〜５００μｍ、好ましくは１０〜２００μｍ、被覆層（II）の厚さは０．１〜５μｍ、好ましくは０．３〜２μｍの範囲にあり、二軸延伸積層フィルムの厚さは約５〜５００μｍ、好ましくは１０〜２００μｍの範囲にある。
【００３３】
本発明の二軸延伸積層フィルムは、二軸延伸フィルム（基材層（Ｉ））として脂肪族ポリエステル組成物（Ｃ）を、被覆層（II）として脂肪族ポリエステル共重合体（Ａ）を用いて共押出し成形して得た積層シートを、公知の同時二軸延伸法あるいは逐次二軸延伸法等の二軸延伸フィルム製造方法により得られる。
二軸延伸の条件は、脂肪族ポリエステル組成物（Ｃ）を延伸し得る条件、例えば、同時二軸延伸法では、延伸温度を６０〜１２０℃、延伸倍率を３〜６倍（面倍率で９〜３６倍）の範囲にすればよい。
二軸延伸後は二軸延伸積層フィルムの用途に応じて種々条件でヒートセット（熱処理）を行うことにより、得られる二軸延伸積層フィルムの熱収縮率を任意の範囲、例えば８０℃、１５分の条件下における縦方向の熱収縮率を１〜５％、横方向の熱収縮率を０〜１０％の範囲、また１００℃、１５分の条件下における縦方向の熱収縮率を５〜１５％、横方向の熱収縮率を１０〜２０％の範囲にすることができる。
ヒートセットの温度は、通常、脂肪族ポリエステル組成物（Ｃ）の結晶化温度以上の温度範囲である１００〜１３０℃である。
熱収縮フィルムを得るためにはヒートセットを行わないか、あるいは延伸温度近辺またはそれ以下の温度に置くことで、例えば、８０℃、１５分の条件下における縦方向の熱収縮率を５〜１０％、横方向の熱収縮率を１０〜１５％、また１００℃、１５分の条件下における縦方向の熱収縮率を２０〜７０％、横方向の熱収縮率を２０〜７０％の範囲にすることができる。
【００３４】
二軸延伸積層フィルムを製造する方法としては前記共押出し積層シートを延伸せずに、予め前記方法で脂肪族ポリエステル組成物（Ｃ）を用いて二軸延伸フィルムを製造した後、かかる二軸延伸フィルム基材層（Ｉ）の片面あるいは両面に脂肪族ポリエステル共重合体（Ａ）を押出し被覆する方法、あるいは予め脂肪族ポリエステル共重合体（Ａ）からなるフィルムを得た後、二軸延伸フィルム基材と貼り合せる方法をとり得るが、共押出し積層シートを延伸する方法が、脂肪族ポリエステル組成物（Ｃ）からなる二軸延伸フィルムと脂肪族ポリエステル共重合体（Ａ）からなる被覆層との層間密着性に優れるので好ましい。
又、二軸延伸積層フィルムを得た後、熱処理を行わないか、あるいは熱処理の条件を種々選択することにより、熱収縮性を備えた二軸延伸積層フィルムあるいは熱収縮性を抑えた二軸延伸積層フィルムを得ることができる。
【００３５】
オーバーラップ包装用フィルム
本発明のオーバーラップ包装用フィルムは、上記基材層（Ｉ）の両面に上記被覆層（II）を有する二軸延伸積層フィルムからなる。
本発明のオーバーラップ包装用フィルムは、二軸延伸フィルム基材層（Ｉ）として、脂肪族ポリエステル共重合体（Ａ）とポリ乳酸（Ｂ）からなる組成物を用いてなるので、得られるオーバーラップ包装用フィルムは柔軟性、透明性に優れ、且つ両表面に、低温でのヒートシール性を有するポリエステル組成物（Ｃ）から得られる被覆層（II）を有しているので、オーバーラップ適性に優れている。
【００３６】
本発明のオーバーラップ包装用フィルムは、柔軟性、透明性に優れ、熱融着性を備えており、又、運搬に耐え得る耐衝撃性も有しているので、従来ポリオレフィンフィルムからなるオーバーラップ包装用フィルムが使用されているあらゆる用途、例えば、チョコレート、ガム、キャンデー等の菓子類、たばこ、化粧品等の嗜好品、カセットテープ、ビデオテープ、ＣＤ、ＣＤＲ、ＤＶＤ、ゲームソフト等の記録材料、およびそれらの集積包装材料等の、箱物包装の包装用フィルムとして好適に使用できる。
【００３７】
収縮包装用フィルム
本発明の収縮包装用フィルムは、上記基材層（Ｉ）の片面又は両面に被覆層（II）を有する二軸延伸積層フィルムからなる。収縮包装用フィルムは、通常、縦方向の熱収縮率が２０〜７０％、好ましくは３０〜６０％の範囲、横方向の熱収縮率が２０〜７０％、好ましくは３０〜６０％の範囲にある。
本発明の収縮包装用フィルムは、柔軟性、透明性に優れ、且つ（両）表面に、ポリエステル組成物（Ｃ）から得られる被覆層（II）を有しているので熱融着性、熱収縮性を備えており、又、運搬に耐え得る耐衝撃性も有しているので、従来ポリオレフィンフィルムからなる熱収縮フィルムが使用されているあらゆる用途、例えば、ラーメン、うどん、そば、焼きそば等の即席カップ麺食品、ヨーグルト、プリン、ゼリー等の乳酸菌飲料のような飲料デザート類カップ食品の個別あるいは複数個等の熱収縮包装用フィルムに限らず、エアゾール製品、インテリア製品、ＣＤ類、磁気テープ製品の一般シュリンク包装、缶・瓶詰飲料、調味料などの集積シュリンクパックや、プラスチック容器、ガラス瓶などの胴張りシュリンクラベル、ワイン、ウイスキー等の瓶のキャップシール等、種々の収縮包装用フィルム等に用い得る。
【００３８】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
【００３９】
実施例及び比較例で使用した原料は次の通りである。
（Ａ）脂肪族ポリエステル共重合体
PCBS-1'：ダイセル化学工業社製、コハク酸−１，４−ブタンジオール−ε−カプロラクトン三元共重合体、カプロラクトン含有量４モル％、ＭＦＲ（温度１９０℃、荷重２１６０ｇ）０．９ｇ／１０分、Ｍｗ２２０，０００、Ｔｍ１０４℃、生分解性良好。
（Ｂ）ポリ乳酸
PLA-1：ポリ乳酸、Ｄ−乳酸含有量１．９重量％、比重：１．３、Ｔｍ：１６８℃、Ｔｇ：５９．８℃、ＭＦＲ（温度１９０℃、荷重２１６０ｇ）：６．７ｇ／１０分。
PLA-2：ポリ乳酸、Ｄ−乳酸含有量：１２．６重量％、比重：１．３、Ｔｍ：なし、Ｔｇ：５６．９℃、ＭＦＲ（温度１９０℃、荷重２１６０ｇ）：２．６ｇ／１０分。
PLA-3：ポリ乳酸、Ｄ−乳酸含有量：１．６重量％、比重：１．３、Ｔｍ：１６７℃、Ｔｇ：５７．８℃、ＭＦＲ（温度１９０℃、荷重２１６０ｇ）：２．６ｇ／１０分。
【００４０】
本発明における各種測定方法は以下の通りである。
（１）重量平均分子量等の分子量：ＧＰＣにより測定し、標準ポリスチレンにて換算して求めた。
（２）光学特性（ヘーズ（ＨＺ）及び平行光線透過率（ＰＬＴ））：二軸延伸三層フィルムの両表面を木綿布で拭い取り、日本電色工業社製ヘーズメーター３００Ａを用いて、ヘイズ（ＨＺ：％）及び平行光線透過率（ＰＴ：％）を測定した。測定値は５回の平均値である。
（３）ヒートシール強度：二軸延伸積層フィルムを重ね合わせた後に、厚さ１２μｍの二軸延伸ポリエチレンテレフタレートフィルム（東レ社製 商品名 ルミラー）で挟み、テスター産業株式会社製ＴＰ−７０１−Ｂ HEAT SEAL TESTERを用いて、各温度で、シール面圧１kg／cm2、時間１秒の条件下で熱融着した。尚、加熱は上側のみとした。次いで、熱融着した二軸延伸積層フィルムをオリエンテック社製テンシロン万能試験機 ＲＴＣ−２２５を用いて幅１５ｍｍの熱融着したサンプルを３００mm／分の引張り速度で剥離し、その最大強度をヒートシール強度（熱融着強度）とした。
（４）ヤング率：試験片として、フィルムからＭＤ方向又はＴＤ方向の短冊状フィルム片（長さ１５０ｍｍ、巾１５ｍｍ）を採取して、チャック間距離１００ｍｍで、引張試験を行い、ヤング率（ＭPa）を求めた。
なお、測定条件は以下の通りである。
使用機器：オリエンテック社製テンシロン万能試験機RTC-1225
クロスヘッドスピード：５ｍｍ／分
測定値は５回の平均値である。
【００４１】
［実施例１〜５及び比較例１］
＜基材層用組成物（Ｃ）の製造＞
脂肪族ポリエステル組成物（Ｃ）として表１に示す比率で原料樹脂を計量し、４０ｍｍφの１軸押出機を用いて１８０℃で溶融混練して基材層用組成物を得た。
＜無延伸シートの製造＞
先端にＴ−ダイを具備した４０ｍｍφの三種三層１軸押出機を用い、ＰＣＢＳ（被覆層）／組成物（Ｃ）（基材層）／ＰＣＢＳ（被覆層）を１０／８０／１０の厚み比率で、成形温度２２０℃で押出し、厚さ３００μｍの無延伸三層シートを得た。
＜二軸延伸フィルムの製造＞
得られた無延伸三層シートの表面を木綿布で拭いた後、パンタグラフ式バッチ２軸延伸装置（東洋精機製作所 ヘビー型）を用いて８５℃×５〜３０秒のホットエアーにより予熱した後、５ｍ／分の速度に縦横方向に３．０倍延伸（同時二軸延伸）した。予熱時間は各試料の状態を見て最適な時間を選定した。また延伸後８５℃雰囲気中で１分間ヒートセットした後、直ちに試料を扇風機で冷却し、厚さ３０μの二軸延伸三層フィルムを得た。測定結果を表１に示す。
【００４２】
【表１】
表１から明らかなように、脂肪族ポリエステル共重合体（Ａ）としてコハク酸−１，４−ブタンジオール−ε−カプロラクトン三元共重合体を用いた単体の二軸延伸フィルム（比較例１）は、熱融着に至る前にフィルムが溶融して切れてしまい、全く熱融着性ができないのに対し、二軸延伸フィルム基材に用いる上記脂肪族ポリエステル共重合体に、ポリ乳酸（ＰＬＡ−１〜３）を添加した積層二軸延伸フィルム（実施例１〜５）は、熱融着できることが分る。またポリ乳酸の添加量を増すことのより、熱融着強度が強くなり、又、ポリ乳酸として、結晶性で且つ分子量が高い重合体（実施例５）を用いるとその改良効果が大きいことが判る。ヤング率が高くなり剛性が増したフィルムとなることが判る。
【００４４】
【発明の効果】
本発明の積層二軸延伸フィルムは柔軟性、透明性に優れ、熱融着性を有するので、従来のポリオレフィンフィルムからなる包装用フィルムと同様に包装用フィルムとして好適に使用し得る。それに加え、本発明の積層二軸延伸フィルムは、脂肪族ポリエステル共重合体（Ａ）本来の生分解性も有するので、使用済みの包装材料は、食品等の分解される被包装物が付着していてもコンポストとして、ごみの回収、処理が容易になる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a biaxially stretched laminated film having a composition of an aliphatic polyester copolymer and polylactic acid as a base layer and an aliphatic polyester copolymer as a coating layer, the film having biodegradability. In addition, it has excellent heat-fusibility and transparency, and is suitable for packaging films.
[0002]
[Prior art]
As biodegradable plastics, highly versatile aliphatic polyesters are attracting attention, and polylactic acid (PLA), polybutylene succinate (PBS), polyethylene succinate (PES), polycaprolactone (PCL), etc. are marketed. ing.
One of the uses of these biodegradable aliphatic polyesters is the film field for packaging, agriculture, food, etc., and high strength, heat resistance and biodegradability according to the use are required as basic performance. .
[0003]
Among the above aliphatic polyesters, PLA has a melting point near 170 ° C. and high heat resistance, but it is brittle, so the elongation of the molded product is low and it is difficult to decompose in the soil. is required. PBS and PES have sufficient heat resistance at a melting point of around 100 ° C., but have a low biodegradation rate, are insufficient in practical use, and lack flexibility in mechanical properties. Although PCL is excellent in flexibility, its application is limited due to its low melting point of 60 ° C. and heat resistance, but its biodegradation rate is very fast.
[0004]
On the other hand, by introducing a caprolactone unit into an aliphatic polyester copolymer, such as a polybutylene succinate-polycaprolactone copolymer (PBSC) described in Japanese Patent No. 2997756, practical flexibility and moderate life can be achieved. Degradability can be realized, and by controlling the caprolactone unit content, it is possible to maintain a sufficient heat resistance with a melting point of 80 ° C. or higher and to control biodegradability. Has been found. (Patent Document 1)
[0005]
WO 02-44249 discloses a weight average molecular weight synthesized by a polycondensation reaction of a mixture of three components of an aliphatic diol, an aliphatic dicarboxylic acid and an aliphatic hydroxycarboxylic acid or an anhydrous cyclic compound (lactone) thereof. It is disclosed that by using a high molecular weight aliphatic polyester copolymer of 40,000 or more and other biodegradable resins, the molecular weight stability during molding of a film or the like is good and the molding is good. (Patent Document 2)
[0006]
However, since the biaxially stretched film obtained from the aliphatic polyester copolymer of the above technique has no heat-fusibility, there is a limit to use it for a packaging film.
[0007]
[Patent Document 1]
Patent No. 2997756 (Claims 1 to 3, Examples 1 to 5)
[Patent Document 2]
WO 02-44249 (claim, final paragraph of invention disclosure section, Table VII-1)
[0008]
[Problems to be solved by the invention]
An object of the present invention is to develop a biaxially stretched film having transparency, flexibility and heat-sealability using a specific biodegradable aliphatic polyester.
[0009]
[Means for Solving the Problems]
The present inventors used a base layer (I) with a composition in a specific ratio of a ternary aliphatic polyester copolymer comprising an aliphatic diol, an aliphatic dicarboxylic acid, and a lactone and polylactic acid, It has been found that such a problem can be solved by using the above three-component aliphatic polyester copolymer in the layer (II), and the present invention has been completed.
[0010]
That is, the first of the present invention is a repeating unit in which the molecular chain is represented by the following general formulas (1) to (3):
-CO-R 1 -CO- (1)
(Wherein R 1 Represents a C1-C12 divalent aliphatic group. )
-O-R 2 -O- (2)
(Wherein R 2 Represents a divalent aliphatic group having 2 to 12 carbon atoms. )
A repeating unit represented by the following general formula (3):
-CO-R Three -O- (3)
(Wherein R Three Represents a C1-C10 divalent aliphatic group. )
Consists of
1 to 30 mol% of the repeating unit represented by the general formula (3)
(In the general formulas (1) to (3), the amounts of the repeating units (1) and (2) are substantially equal, and the sum of the amounts of (1), (2) and (3) is 100 mol%. .)
Of the biaxially stretched film substrate layer (I) comprising the aliphatic polyester composition (C) of the aliphatic polyester copolymer (A) 97 to 60% by weight and the polylactic acid (B) 3 to 40% by weight Provided is a biaxially stretched laminated film characterized by having a coating layer (II) composed of the aliphatic polyester copolymer (A) on at least one surface.
A second aspect of the present invention provides the biaxially stretched laminated film according to the first aspect of the present invention, wherein the aliphatic polyester copolymer (A) has a melting point in the range of 85 to 120 ° C.
A third aspect of the present invention is a low molecular weight aliphatic polyester copolymer having a weight average molecular weight of 5,000 or more, wherein the aliphatic polyester copolymer (A) is a polymerization intermediate of the aliphatic polyester copolymer (A). (A ′) The biaxially stretched laminated film according to the first or second aspect of the present invention, which is obtained by reacting 0.1 to 5 parts by weight of a diisocyanate compound with respect to 100 parts by weight. .
4th of this invention provides the biaxially stretched laminated film of any one of 1st-3rd of this invention whose general formula (1) is a succinic acid residue and / or an adipic acid residue. .
A fifth aspect of the present invention is the biaxially stretched laminate according to any one of the first to fourth aspects of the present invention, wherein the general formula (2) is an ethylene glycol residue and / or a 1,4-butanediol residue. Provide film.
A sixth aspect of the present invention provides the biaxially stretched laminated film according to any one of the first to fifth aspects of the present invention, wherein the general formula (3) is a ring-opened group of ε-caprolactone.
In the seventh aspect of the present invention, the biaxially stretched laminated film is obtained by biaxially stretching a laminated sheet obtained by coextrusion molding of the aliphatic polyester copolymer (A) and the aliphatic polyester composition (C). The biaxially stretched laminated film according to any one of the first to sixth aspects of the present invention is provided.
8th of this invention provides the biaxially stretched laminated film of any one of 1st-7th of this invention obtained by the simultaneous biaxial stretching method.
9th of this invention provides the biaxially stretched laminated film of any one of 1st-8 of this invention which has coating layer (II) on both surfaces of base material layer (I).
The tenth aspect of the present invention provides an overlap wrapping film comprising the biaxially stretched laminated film according to the ninth aspect of the present invention.
The eleventh aspect of the present invention provides a shrink-wrapping film comprising the biaxially stretched laminated film according to any one of the first to ninth aspects of the present invention.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The biaxially stretched laminated film of the present invention comprises a base layer (I) of an aliphatic polyester composition (C) comprising an aliphatic polyester copolymer (A) and a polylactic acid (B), and an aliphatic polyester copolymer. It consists of coating layer (II) which consists of (A).
[0012]
Base material layer (I)
The base material layer (I) according to the present invention comprises an aliphatic polyester copolymer (A) and polylactic acid (B).
[0013]
Aliphatic polyester copolymer (A)
The aliphatic polyester copolymer (A) according to the present invention has a repeating unit in which a molecular chain is represented by the following general formulas (1) to (3):
-CO-R 1 -CO- (1)
(Wherein R 1 Represents a C1-C12 divalent aliphatic group. )
-O-R 2 -O- (2)
(Wherein R 2 Represents a divalent aliphatic group having 2 to 12 carbon atoms. )
A repeating unit represented by the following general formula (3):
-CO-R Three -O- (3)
(Wherein R Three Represents a C1-C10 divalent aliphatic group. )
Consists of.
In the base material layer (I), two or more kinds of aliphatic polyester copolymers (A) may be mixed and used.
[0014]
The composition and basic physical properties of the aliphatic polyester copolymer (A) are as follows.
The content of the repeating unit represented by the general formula (3) is in the range of 1 to 30 mol%, preferably 1 to 20 mol%, more preferably 1 to 15 mol% (general formulas (1) to (3 ), The amounts of repeating units (1) and (2) are substantially equal, and the sum of the amounts of (1), (2) and (3) is 100 mol%.
The aliphatic polyester copolymer (A) is not particularly limited in molecular weight as long as it has a film-forming ability, but usually has a weight average molecular weight of 40,000 or more, preferably 70,000 to 300,000. Preferably it exists in the range of 120,000-250,000.
The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 2 to 5, preferably 2 to 3.
The melting point of the copolymer (A) is usually 85 ° C. or higher, preferably 85 to 120 ° C., more preferably 90 to 110 ° C.
[0015]
In the aliphatic polyester copolymer (A), when the repeating unit represented by the general formula (3) is less than 1 mol%, the obtained biaxially stretched laminated film tends to lose transparency, flexibility, and stretchability. If it exceeds 30 mol%, the melting point of the resulting polymer is low and the crystallinity is extremely lowered, so that the obtained biaxially stretched laminated film tends to have poor heat resistance.
[0016]
Examples of the compound that gives an aliphatic dicarboxylic acid residue that is a repeating unit represented by the general formula (1) include an aliphatic dicarboxylic acid, an anhydride thereof, or a mono- or diester thereof, and the following general formula (4) The compound represented by these can be mentioned.
R Four OCO-R 1 -COOR Five (4)
(Wherein R 1 Is a divalent aliphatic group having 1 to 12 carbon atoms, R Four And R Five Represents a hydrogen atom or an aliphatic or aromatic group having 1 to 6 carbon atoms. R Four And R Five May be the same or different. )
R 1 The divalent aliphatic group represented by is preferably a linear or cyclic alkylene group having 2 to 8 carbon atoms, and — (CH 2 ) 2 -,-(CH 2 ) Four -,-(CH 2 ) 6 C2-C6 linear lower alkylene groups, such as-. R Four And R Five When is a hydrogen atom, it represents an aliphatic dicarboxylic acid. Specific examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, and diglycolic acid.
[0017]
Examples of the compound that gives an aliphatic diol residue that is a repeating unit represented by the general formula (2) include aliphatic diols, and examples thereof include compounds represented by the following general formula (5).
HO-R 2 -OH (5)
(Wherein R 2 Represents a divalent aliphatic group having 2 to 12 carbon atoms. )
Examples of the divalent aliphatic group include chain or cyclic alkylene groups having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms. Preferred alkylene groups are — (CH 2 ) 2 -,-(CH 2 ) Four A linear lower alkylene group having 2 to 6 carbon atoms such as-.
Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,3-butanediol, 2-methyl-propanediol, 1,4-butanediol, neopentyl glycol, pentamethylene glycol, and hexamethylene. Glycol, octamethylene glycol, decamethylene glycol, dodecamethylene glycol, 1,4-cyclohexanedimethanol and the like can be used. These may be used alone or in combination of two or more.
[0018]
As a compound which gives the aliphatic hydroxycarboxylic acid residue which is a repeating unit represented by the general formula (3), a hydroxycarboxylic acid or a hydroxycarboxylic acid ester represented by the following general formula (6), or the following general formula And lactones represented by (7). You may use these in mixture of 2 or more types.
HO-R Three -COOR 6 (6)
(Wherein R Three Is a divalent aliphatic group having 1 to 10 carbon atoms, R 6 Represents a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms or an aromatic group. )
[0019]
[Chemical 1]
(Wherein R Three Represents a divalent aliphatic group having 4 to 10 carbon atoms. )
[0021]
In the above formula (6), the divalent aliphatic group R Three As the above, a linear or cyclic alkylene group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms may be mentioned.
R 6 Is hydrogen, an aliphatic group or an aromatic group. Examples of the aliphatic group include a linear or branched lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms such as a cyclohexyl group, and an aromatic group. , Phenyl group, benzyl group and the like.
Examples of the hydroxycarboxylic acid include glycolic acid, L-lactic acid, D-lactic acid, D, L-lactic acid, 2-methyl lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-n-butyric acid, and 2-hydroxy. Examples include −3,3-dimethylbutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxy-3-methylbutyric acid, hydroxypivalic acid, hydroxyisocaproic acid, and hydroxycaproic acid. Examples of the hydroxycarboxylic acid ester include methyl, ethyl, propyl, butyl, cyclohexyl, and phenyl esters of the hydroxycarboxylic acid.
[0022]
In the general formula (7), a divalent aliphatic group R Three As, a C4-C10, Preferably a C4-C8 linear or branched alkylene group is mentioned.
Specific examples of lactones include, for example, γ-valerolactone, δ-valerolactone, ε-caprolactone, 1,3-dioxolan-4-one, 1,4-dioxane-3-one, 1,5-dioxepane-2. -ON etc. can be mentioned.
Further, it may be a cyclic dimer ester (lactide) in which two molecules of the hydroxycarboxylic acid are bonded, and examples thereof include glycolide obtained from glycolic acid, lactide obtained from lactic acid, and the like.
[0023]
Process for producing aliphatic polyester copolymer (A)
The aliphatic polyester copolymer (A) according to the present invention can be obtained by various known methods, for example, an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid diester having a repeating unit represented by the general formula (1), 2) A polycondensation reaction of an aliphatic diol having a repeating unit represented by 2) and an oxycarboxylic acid or oxycarboxylic acid ester or lactone having a repeating unit represented by the general formula (3) in the presence of a catalyst. Can be obtained.
[0024]
The aliphatic polyester copolymer (A) according to the present invention is obtained by once obtaining a low molecular weight aliphatic polyester copolymer (A ′) having a weight average molecular weight of 5,000 or more, and then in a molten state low molecular weight aliphatic polyester. A diisocyanate compound may be added to the copolymer (A ′) to increase the weight average molecular weight to 40,000 or more.
The aliphatic polyester copolymer containing a urethane bond has the same weight average molecular weight as that of the copolymer (A), but is 40,000 or more, usually 70,000 to 300,000, preferably 120,000. The range is from 000 to 250,000.
The aliphatic polyester copolymer (A) according to the present invention is specifically obtained by the production methods described in, for example, Japanese Patent No. 2997756 and WO 02-44249.
[0025]
Polylactic acid (B)
Polylactic acid (B) is poly (L-lactic acid) in which the structural unit of lactic acid is L-lactic acid, poly (D-lactic acid) in which the structural unit is D-lactic acid, and any of L-lactic acid and D-lactic acid. Poly (DL-lactic acid) that is a mixture, a lactic acid polymer such as racemic poly (DL-lactic acid) obtained from an equal amount mixture, and a comonomer that is copolymerizable with lactic acid as a main component and other than lactic acid, for example, A copolymer having a main component of lactic acid, such as a copolymer copolymerized at a ratio of less than 50% by weight, preferably 30% by weight or less, more preferably 10% by weight or less, or a mixture thereof. Examples of the comonomer copolymerizable with lactic acid include 3-hydroxybutyrate, caprolactone, glycolic acid and the like.
As a method for polymerizing such polylactic acid, any known method such as a condensation polymerization method or a ring-opening polymerization method can be employed. For example, in the condensation polymerization method, polylactic acid having an arbitrary composition can be obtained by directly dehydrating condensation polymerization of L-lactic acid, D-lactic acid or a mixture thereof.
By adding such polylactic acid (B) to the aliphatic polyester copolymer (A), the base layer (I) of the resulting biaxially stretched laminated film is not thinned by the heat and pressure of the seal bar, There is also an advantage that fusion to the seal bar can be prevented.
Among these polylactic acids, a homopolymer of L-lactic acid or a copolymer of D-lactic acid and L-lactic acid containing 0 to 30% by weight, preferably 0 to 25% by weight of D-lactic acid, constitutes the base material layer. The biaxially stretched laminated film obtained by adding to the aliphatic polyester (A) has good transparency and light transmittance. The D-lactic acid content in the polylactic acid copolymer is a value measured using a gas chromatograph CP CYCLODEX B 236M manufactured by Chromeback.
As said polylactic acid (B), MFR (according to ASTM D-1238. Load 2160 g, temperature 190 ° C.) is 0.1 to 100 g / 10 min, preferably 1 to 50 g / 10 min, particularly preferably 2 to 10 g / A 10-minute version is used.
[0026]
Aliphatic polyester composition (C)
The aliphatic polyester composition (C) according to the present invention comprises 97 to 60% by weight, preferably 95 to 70% by weight, more preferably 85 to 75% by weight of the aliphatic polyester copolymer (A). The composition of lactic acid (B) is 3 to 40% by weight, preferably 5 to 30% by weight, and more preferably 15 to 25% by weight.
When the amount of the polylactic acid (B) in the aliphatic polyester composition (C) is less than 3% by weight, there is a possibility that sufficient heat-sealing property of the biaxially stretched laminated film as the base material layer may not be obtained. If it exceeds 40% by weight, the flexibility of the biaxially stretched laminated film may be inferior.
[0027]
In the aliphatic polyester composition (C) according to the present invention, the aliphatic polyester copolymer (A) and the polylactic acid (B) are mixed in the above ranges by a Henschel mixer, a V-blender, a ribbon blender, a tumbler mixer, or the like. It is obtained by a method, a method of melt-kneading with a single screw extruder, a multi-screw extruder, a Banbury mixer or the like after mixing.
[0028]
In the aliphatic polyester composition (C) according to the present invention, the aliphatic polyester copolymer (A) and the polylactic acid (B) are prepared separately or when the composition (C) is produced. Antioxidants, weathering stabilizers, antistatic agents, anti-fogging agents, anti-blocking agents, slip agents, light-resistant stabilizers, UV absorbers, fluorescent whitening agents, antibacterial agents, cores Additives such as additives and inorganic or organic compound fillers can be blended as required.
[0029]
Coating layer (II)
The coating layer (II) according to the present invention is composed of the aliphatic polyester copolymer (A). The aliphatic polyester copolymer (A) may be a mixture of two or more.
The aliphatic polyester copolymer (A) used for the coating layer (II) may be the same as or different from the aliphatic polyester copolymer (A) used for the base layer (I).
[0030]
Additives used in the base material layer (I) can be added to the aliphatic polyester copolymer (A) used in the coating layer (II), if necessary.
[0031]
Biaxially stretched laminated film
The biaxially stretched laminated film of the present invention comprises a coating layer comprising an aliphatic polyester copolymer (A) on one or both sides of a biaxially stretched film substrate layer (I) comprising the aliphatic polyester composition (C) ( II) is a biaxially stretched laminated film. Since the biaxially stretched laminated film of the present invention uses the aliphatic polyester composition (C) as the biaxially stretched film substrate layer (I), the obtained biaxially stretched laminated film is flexible and transparent. Excellent and aliphatic polyester on the surface Copolymer (A) By having a coating layer (II) obtained from
[0032]
Although the thickness of the biaxially stretched laminated film of the present invention can be variously determined according to the use, the thickness of the biaxially stretched film to be the base material layer (I) is usually 5 to 500 μm, preferably 10 to 200 μm, coating The thickness of the layer (II) is in the range of 0.1 to 5 μm, preferably 0.3 to 2 μm, and the thickness of the biaxially stretched laminated film is in the range of about 5 to 500 μm, preferably 10 to 200 μm.
[0033]
The biaxially stretched laminated film of the present invention uses an aliphatic polyester composition (C) as a biaxially stretched film (base material layer (I)) and an aliphatic polyester copolymer (A) as a coating layer (II). The laminated sheet obtained by coextrusion molding is obtained by a biaxially stretched film manufacturing method such as a known simultaneous biaxial stretching method or sequential biaxial stretching method.
The biaxial stretching conditions are the conditions under which the aliphatic polyester composition (C) can be stretched, for example, in the simultaneous biaxial stretching method, the stretching temperature is 60 to 120 ° C., the stretching ratio is 3 to 6 times (the surface ratio is 9). (36 times)).
After biaxial stretching, the heat shrinkage rate of the obtained biaxially stretched laminated film can be set within an arbitrary range, for example, 80 ° C. for 15 minutes by performing heat setting (heat treatment) under various conditions depending on the use of the biaxially stretched laminated film. The thermal contraction rate in the vertical direction under the conditions of 1 to 5%, the thermal contraction rate in the horizontal direction within the range of 0 to 10%, and the thermal contraction rate in the vertical direction under the conditions of 100 ° C. and 15 minutes is 5 to 15%. %, The heat shrinkage rate in the transverse direction can be in the range of 10 to 20%.
The temperature of heat setting is 100-130 degreeC which is the temperature range more than the crystallization temperature of an aliphatic polyester composition (C) normally.
In order to obtain a heat-shrinkable film, heat set is not performed, or it is placed at a temperature near or below the stretching temperature. %, The horizontal heat shrinkage rate is in the range of 10 to 15%, the heat shrinkage rate in the vertical direction under the condition of 100 ° C. for 15 minutes is 20 to 70%, and the horizontal heat shrinkage rate is in the range of 20 to 70%. can do.
[0034]
As a method for producing a biaxially stretched laminated film, a biaxially stretched film is produced in advance using the aliphatic polyester composition (C) by the above-mentioned method without stretching the co-extruded laminated sheet, and then the biaxially stretched film. A method of extruding and coating the aliphatic polyester copolymer (A) on one side or both sides of the film base layer (I), or after obtaining a film made of the aliphatic polyester copolymer (A) in advance, and then biaxially stretched film Although the method of sticking with a base material can be taken, the method of extending | stretching a coextrusion laminated sheet is a biaxially stretched film which consists of an aliphatic polyester composition (C), and the coating layer which consists of an aliphatic polyester copolymer (A) It is preferable because of excellent interlayer adhesion.
Also, after obtaining a biaxially stretched laminated film, heat treatment is not performed, or by selecting various conditions for heat treatment, biaxially stretched laminated film with heat shrinkability or biaxial stretching with reduced heat shrinkability A laminated film can be obtained.
[0035]
Overwrap packaging film
The overlap packaging film of the present invention comprises a biaxially stretched laminated film having the coating layer (II) on both sides of the base material layer (I).
Since the film for overlap wrapping of the present invention uses a composition comprising an aliphatic polyester copolymer (A) and a polylactic acid (B) as the biaxially stretched film substrate layer (I), the obtained over film The film for wrap packaging is excellent in flexibility and transparency, and has a coating layer (II) obtained from the polyester composition (C) having heat-sealability at low temperature on both surfaces. Is excellent.
[0036]
The overlap wrapping film of the present invention is excellent in flexibility and transparency, has heat fusion properties, and has impact resistance that can withstand transportation. All uses for which packaging films are used, for example, chocolate, gum, candy and other confectionery, tobacco, cosmetics and other favorite items, cassette tapes, video tapes, CDs, CDRs, DVDs, game software recording materials, It can also be suitably used as a packaging film for box packaging, such as their integrated packaging materials.
[0037]
Shrink wrapping film
The film for shrink wrapping of the present invention comprises a biaxially stretched laminated film having a coating layer (II) on one side or both sides of the base material layer (I). The shrink-wrapping film usually has a longitudinal heat shrinkage of 20 to 70%, preferably 30 to 60%, and a transverse heat shrinkage of 20 to 70%, preferably 30 to 60%. is there.
The film for shrink wrapping of the present invention is excellent in flexibility and transparency, and has a coating layer (II) obtained from the polyester composition (C) on the surfaces of both, so that it has heat fusion properties, heat Because it has shrinkability and also has impact resistance that can withstand transportation, it can be used in all applications where heat-shrinkable film made of polyolefin film is used, such as ramen, udon, buckwheat, and yakisoba. Instant cup noodle foods, yogurt, pudding, jelly beverages such as lactic acid bacteria beverages such as jelly, etc. Not limited to individual or multiple heat shrink wrapping films, aerosol products, interior products, CDs, magnetic tape products General shrink packaging, canned and bottled beverages, seasoning and other integrated shrink packs, plastic containers, glass bottles and other shell shrink labels, wine, Cap seal such as a bottle or the like Isuki may be used in a variety of shrink wrapping film.
[0038]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[0039]
The raw materials used in Examples and Comparative Examples are as follows.
(A) Aliphatic polyester copolymer
PCBS-1 ′: Daicel Chemical Industries, Ltd., succinic acid-1,4-butanediol-ε-caprolactone terpolymer, caprolactone content 4 mol%, MFR (temperature 190 ° C., load 2160 g) 0.9 g / 10 minutes, Mw 220,000, Tm 104 ° C., good biodegradability.
(B) Polylactic acid
PLA-1: polylactic acid, D-lactic acid content 1.9% by weight, specific gravity: 1.3, Tm: 168 ° C., Tg: 59.8 ° C., MFR (temperature 190 ° C., load 2160 g): 6.7 g / 10 minutes.
PLA-2: polylactic acid, D-lactic acid content: 12.6% by weight, specific gravity: 1.3, Tm: none, Tg: 56.9 ° C., MFR (temperature 190 ° C., load 2160 g): 2.6 g / 10 minutes.
PLA-3: Polylactic acid, D-lactic acid content: 1.6% by weight, specific gravity: 1.3, Tm: 167 ° C., Tg: 57.8 ° C., MFR (temperature 190 ° C., load 2160 g): 2.6 g / 10 minutes.
[0040]
Various measurement methods in the present invention are as follows.
(1) Molecular weight such as weight average molecular weight: measured by GPC and calculated by standard polystyrene.
(2) Optical properties (haze (HZ) and parallel light transmittance (PLT)): Both surfaces of a biaxially stretched three-layer film are wiped with a cotton cloth, and a haze is used using a Nippon Denshoku Industries Co., Ltd. haze meter 300A. (HZ:%) and parallel light transmittance (PT:%) were measured. The measured value is an average value of 5 times.
(3) Heat-sealing strength: after superposing biaxially stretched laminated films, sandwiched between 12 μm thick biaxially stretched polyethylene terephthalate films (trade name Lumirror, manufactured by Toray Industries, Inc.), TP-701-B HEAT manufactured by Tester Sangyo Co., Ltd. Using SEAL TESTER, seal surface pressure 1kg / cm at each temperature 2 And heat-sealing under conditions of 1 second. The heating was performed only on the upper side. Next, the heat-fused biaxially stretched laminated film was peeled off at 15 mm wide with a tensile rate of 300 mm / min using a Tensilon universal testing machine RTC-225 manufactured by Orientec, and the maximum strength was heated. The sealing strength (heat fusion strength) was used.
(4) Young's modulus: As a test piece, a strip-like film piece (length 150 mm, width 15 mm) in the MD direction or TD direction is taken from the film, and a tensile test is performed at a distance between chucks of 100 mm. )
Measurement conditions are as follows.
Equipment Used: Orientec Tensilon Universal Testing Machine RTC-1225
Crosshead speed: 5mm / min
The measured value is an average value of 5 times.
[0041]
[Examples 1 to 5 and Comparative Example 1]
<Manufacture of composition for substrate layer (C)>
The raw material resin was weighed in the ratio shown in Table 1 as the aliphatic polyester composition (C), and melt-kneaded at 180 ° C. using a 40 mmφ single-screw extruder to obtain a composition for a base layer.
<Manufacture of non-stretched sheet>
Using a 40 mmφ three-type three-layer single-screw extruder equipped with a T-die at the tip, the thickness of PCBS (coating layer) / composition (C) (base material layer) / PCBS (coating layer) was 10/80/10. By the ratio, extrusion was performed at a molding temperature of 220 ° C. to obtain an unstretched three-layer sheet having a thickness of 300 μm.
<Manufacture of biaxially stretched film>
After wiping the surface of the obtained non-stretched three-layer sheet with a cotton cloth, after preheating with hot air at 85 ° C. × 5 to 30 seconds using a pantograph batch biaxial stretching device (Toyo Seiki Seisakusho Heavy type), The film was stretched 3.0 times (simultaneous biaxial stretching) in the longitudinal and transverse directions at a speed of 5 m / min. The optimal preheating time was selected by looking at the state of each sample. Moreover, after extending | stretching for 1 minute in 85 degreeC atmosphere after extending | stretching, the sample was immediately cooled with the electric fan and the biaxially-stretched three-layer film with a thickness of 30 micrometers was obtained. The measurement results are shown in Table 1.
[0042]
[Table 1]
As is apparent from Table 1, a single biaxially stretched film using succinic acid-1,4-butanediol-ε-caprolactone terpolymer as the aliphatic polyester copolymer (A) (Comparative Example 1) In contrast to the fact that the film melts and breaks before reaching thermal fusion and cannot be fused at all, polylactic acid (PLA) is added to the aliphatic polyester copolymer used for the biaxially stretched film substrate. It can be seen that the laminated biaxially stretched films (Examples 1 to 5) added with -1 to 3) can be heat-sealed. Further, the heat fusion strength is increased by increasing the amount of polylactic acid added, and the improvement effect is large when a crystalline polymer having high molecular weight (Example 5) is used as polylactic acid. I understand. It can be seen that the film has a higher Young's modulus and increased rigidity.
[0044]
【The invention's effect】
Since the laminated biaxially stretched film of the present invention is excellent in flexibility and transparency and has heat fusion properties, it can be suitably used as a packaging film in the same manner as a packaging film made of a conventional polyolefin film. In addition, since the laminated biaxially stretched film of the present invention has the inherent biodegradability of the aliphatic polyester copolymer (A), the packaging material to be decomposed such as food adheres to the used packaging material. However, it is easy to collect and dispose of waste as compost.
Claims (11)
−ＣＯ−Ｒ1−ＣＯ− （１）
（式中、Ｒ1は炭素数１〜１２の二価脂肪族基を表す。）
−Ｏ−Ｒ2−Ｏ− （２）
（式中、Ｒ2は炭素数２〜１２の二価脂肪族基を表す。）
下記一般式（３）で示される繰返し単位：
−ＣＯ−Ｒ3−Ｏ− （３）
（式中、Ｒ3は炭素数１〜１０の二価脂肪族基を表す。）
からなり、
一般式（３）で示される繰返し単位が１〜３０モル％
（一般式（１）〜（３）で、繰返し単位（１）と（２）の量は実質的に等しく、（１）、（２）及び（３）の量の合計は１００モル％である。）
である脂肪族ポリエステル共重合体（Ａ）９７〜６０重量％とポリ乳酸（Ｂ）３〜４０重量％との脂肪族ポリエステル組成物（Ｃ）からなる二軸延伸フィルム基材層（Ｉ）の少なくとも片面に、上記脂肪族ポリエステル共重合体（Ａ）からなる熱融着層である被覆層（II）を有してなることを特徴とする二軸延伸積層フィルム。A repeating unit in which the molecular chain is represented by the following general formulas (1) to (3):
—CO—R 1 —CO— (1)
(In the formula, R 1 represents a C 1-12 divalent aliphatic group.)
—O—R 2 —O— (2)
(In the formula, R 2 represents a divalent aliphatic group having 2 to 12 carbon atoms.)
A repeating unit represented by the following general formula (3):
—CO—R 3 —O— (3)
(In the formula, R 3 represents a divalent aliphatic group having 1 to 10 carbon atoms.)
Consists of
1 to 30 mol% of the repeating unit represented by the general formula (3)
(In the general formulas (1) to (3), the amounts of the repeating units (1) and (2) are substantially equal, and the sum of the amounts of (1), (2) and (3) is 100 mol%. .)
Of the biaxially stretched film substrate layer (I) comprising the aliphatic polyester composition (C) of the aliphatic polyester copolymer (A) 97 to 60% by weight and the polylactic acid (B) 3 to 40% by weight A biaxially stretched laminated film comprising a coating layer (II), which is a heat- sealing layer made of the aliphatic polyester copolymer (A), on at least one surface.
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| JP2003074624A JP4233899B2 (en) | 2003-03-18 | 2003-03-18 | Biaxially stretched laminated film and use thereof |
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| JP2003074624A JP4233899B2 (en) | 2003-03-18 | 2003-03-18 | Biaxially stretched laminated film and use thereof |
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| JP4233899B2 true JP4233899B2 (en) | 2009-03-04 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0716456D0 (en) * | 2007-08-23 | 2007-10-03 | Innovia Films Ltd | Packaging article |
| JP2006137074A (en) * | 2004-11-11 | 2006-06-01 | Tohcello Co Ltd | Multilayered biaxially stretched film |
| JP2006137156A (en) * | 2004-11-15 | 2006-06-01 | Tohcello Co Ltd | Multilayered biaxially stretched film and its use |
| JP4660168B2 (en) * | 2004-11-18 | 2011-03-30 | 三井化学東セロ株式会社 | Aliphatic polyester copolymer film. |
| DE102005053343B3 (en) * | 2005-11-03 | 2007-06-28 | Treofan Germany Gmbh & Co.Kg | Cigarette package with inner wrapping of polymer film |
| JP4753247B2 (en) * | 2005-12-21 | 2011-08-24 | タカタ株式会社 | Airbag device |
| JP4753246B2 (en) * | 2005-12-19 | 2011-08-24 | タカタ株式会社 | Airbag device |
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