JP2005008771A - POLYESTER RESIN COMPOSITION FOR CALENDAR MOLDING, AND FILM OR SHEET COMPRISING THE RESIN COMPOSITION - Google Patents

Abstract

An object of the present invention is to peel off from a metal roll, take-up with a cooling roll, and good rotation of a bank. To provide a polyester-based resin composition capable of obtaining a small film or sheet having excellent transparency, rigidity, gas barrier property, and wettability.
An organically modified layered silicate, a fatty acid having 18 or more carbon atoms, and a fatty acid metal salt or an organic phosphate ester are blended in a thermoplastic polyester resin with controlled crystallinity.
[Selection figure] None

Description

（但し、式中Ｒ１〜Ｒ４は、水素、炭素数１〜３０のアルキル基、ベンジル基、炭素数１〜３０のヒドロキシアルキル基、ヒドロキシベンジル基、−（ＣＨ_２−ＣＨ_２−Ｏ）_ｎ−Ｈ基、−（ＣＨ_２−ＣＨ（ＣＨ_３）−Ｏ）_ｍ−Ｈ基から選ばれる（但し、ｎ、ｍは１〜３０の整数である。）。）、
および、アニリン、ｐ−フェニレンジアミン、α−ナフチルアミン、ｐ−アミノジメチルアニリン、ベンジジン、ピリジン、ピペリジン、４−アミノドデカン酸、６−アミノカプロン酸−１２−アミノドデカン酸−１８−アミノオクタデカン酸などから誘導される化合物および、ベンセトニウムイオンなどを挙げることができる。
【００３８】
なお、上記一般式で示されるアンモニウムイオン化合物の具体例として、ステアリルアンモニウムイオン、ドデシルアンモニウムイオン、ベンジルアンモニウムイオン、ヘキシルアンモニウムイオン、オクチルアンモニウムイオン、２−エチルヘキシルアンモニウムイオン、ラウリルアンモニウムイオン、メチルステアリルアンモニウムイオン、ジステアリルアンモニウムイオン、メチルジステアリルアンモニウムイオン、トリオクチルアンモニウムイオン、ジメチルステアリルベンジルアンモニウムイオン、メチルジステアリルベンジルアンモニウムイオン、ジステアリルジベンジルアンモニウムイオン、ベンザルコニウムイオン、トリメチルステアリルアンモニウムイオン、ジメチルジステアリルアンモニウムイオン、ジメチル２エチルヘキシルステアリルアンモニウムイオン、メチルトリステアリルアンモニウムイオン、ジ牛脂アルキルジメチルアンモニウムイオン、ジヤシ油アルキルジメチルアンモミウムイオン、ジメチルジヒドロキシエチルアンモニウムイオン、ジメチルベンジル水添牛脂アンモニウムイオン、ジメチルジ水添牛脂アンモニウムイオン、メチル牛脂アルキルビス２ヒドロキシエチルアンモニウムイオン、メチルステアリルビス２ヒドロキシエチルアンモニウムイオン、ジメチル水添牛脂ベンジルアンモニウムイオン、ジメチル２エチルヘキシル水添牛脂アンモニウムイオン、メチルジ水添牛脂アンモニウムイオン、下式で示される化合物（但し、ｍ、ｎは１〜３０の整数である。）
【化２】

【化３】

、などを挙げることができる。
層状珪酸塩にイオン交換により導入されるこれらのアンモニウムイオンは単独であっても、複数の混合物であってもかまわない。
【００３９】
これらのアンモニウムイオンの中でも、炭素数が６〜３０のアルキル基、ベンジル基、ヒドロキシアルキル基などの置換基を有する有機アンモニウムイオンであることが好ましく、中でも、トリメチルステアリルアンモニウムイオン、ジメチルジステアリルアンモニウムイオン、ジメチルステアリルベンジルアンモニウムイオン、メチルジステアリルベンジルアンモニウムイオン、ベンザルコニウムイオン、ジメチルベンジル水添牛脂アンモニウムイオン、ジメチルジ水添牛脂アンモニウムイオン、メチル牛脂アルキルビス２ヒドロキシエチルアンモニウムイオン、メチルステアリルビス２ヒドロキシエチルアンモニウムイオンが特に好ましい。
【００４０】
有機化層状珪酸塩に占める有機オニウムイオンの量は、用いる層状珪酸塩の陽イオン交換量や有機オニウムイオンの種類に左右されるが、通常１５〜８０重量％の範囲にある。
【００４１】
有機化層状珪酸塩（Ｂ）の配合量は、非結晶性若しくは低結晶性ポリエステル系樹脂（Ａ）１００重量部に対し、０．５〜２０重量部の範囲であり、好ましくは１．０〜１５．０重量部、さらに好ましくは２．０〜１３．０重量部である。有機化層状珪酸塩（Ｂ）の配合量が０．５重量部未満では、カレンダー成形における成形性の改善効果に乏しいことに加え、製造されたフィルムやシートの強度や剛性、ならびにガスバリア性、収縮性などの性能が不十分になる恐れがある。また、有機化層状珪酸塩（Ｂ）の配合量が２０重量部を超えると、フィルムやシートが脆くなる恐れがある。
【００４２】
一方、本発明に用いられる炭素数１８以上の脂肪酸（Ｃ）は、カレンダー成形時のカレンダーロールからの剥離性ならびに、有機化層状珪酸塩（Ｂ）の分散性を向上させるために配合される成分であり、例えば、ステアリン酸、ベヘン酸、テトラコサン酸、ヘキサコサン酸、ヘプタコサン酸、モンタン酸、トリアコンタン酸、ドトリアコンタン酸などが挙げられる。
これらの脂肪酸は、純度の高いものが試薬として入手できるが、多くの場合高価であり、樹脂組成物の添加剤としては一般には用いられていない。しかし、炭素数が１８以上である脂肪酸（Ｃ）の中には、ステアリン酸やベヘン酸、モンタン酸のように樹脂用の添加剤として安価に提供されているものがあり、本発明においてもこのような樹脂添加剤用の脂肪酸が好適に用いられる。
【００４３】
これらの脂肪酸の中でも、熱可塑性ポリエステル樹脂を成形加工する温度で劣化や蒸発などをしにくいことから、炭素数が２０以上の脂肪酸で樹脂用の添加剤として安価に提供されているベヘン酸若しくはモンタン酸が好ましく、さらには炭素数が２５以上の脂肪酸で樹脂用の添加剤として安価に提供されているモンタン酸が本発明に好適に用いられる。
【００４４】
ポリエステル系樹脂（Ａ）１００重量部に配合される炭素数が１８以上の脂肪酸（Ｃ）の配合量は０．１〜１０．０重量部の範囲であり、好ましくは０．３〜７．５重量部、さらに好ましくは０．５〜５．０重量部である。炭素数が１８以上の脂肪酸（Ｃ）の配合量が０．１重量部より少ないと、カレンダーロールからの剥離性が不十分となることに加え、有機化層状珪酸塩（Ｂ）の分散が不十分となり、透明性の優れたフィルムやシートが得られなくなる。炭素数１８以上の脂肪酸（Ｃ）の配合量が１０．０重量部を越えるとシートやフィルムの透明性が低下してしまうばかりでなく、滑性過多となりカレンダー成形によりフィルムやシートを製造することができなくなる可能性がある。
【００４５】
本発明に係る樹脂組成物は、非結晶性若しくは低結晶性ポリエステル系樹脂（Ａ）１００重量部に対して配合する有機化層状珪酸塩（Ｂ）中の珪酸塩の重量部（ｂ’）と、同ポリエステル系樹脂（Ａ）１００重量部に対して配合する炭素数１８以上の脂肪酸（Ｃ）の重量部（ｃ’）の比（ｃ’／ｂ’）を、０．１以上とすることが好ましく、さらに好ましくは０．１５以上、最も好ましくは０．２以上とすることにより、より高い効果が得られる。
【００４６】
ここで言う有機化層状珪酸塩（Ｂ）中の珪酸塩の重量部（ｂ’）とは、有機化層状珪酸塩（Ｂ）を１０００℃の電気炉中で３０分間加熱して、水分や有機化層状珪酸塩の層間に含まれる有機オニウムイオンを蒸発や燃焼させた後に、残った灰分重量から求まる有機化層状珪酸塩中の灰分の重量％（Ａｓｈ（％））および、非結晶性若しくは低結晶性ポリエステル系樹脂（Ａ）１００重量部に対して配合した有機化層状珪酸塩（Ｂ）の重量部（ｂ”）とから、以下の式により求められる数値である。
ｂ’＝ｂ”×Ａｓｈ（％）−１００
ポリエステル系樹脂（Ａ）１００重量部に対して配合する有機化層状珪酸塩中の珪酸塩の重量部（ｂ’）と、同ポリエステル系樹脂（Ａ）１００重量部に対して配合する炭素数１８以上の脂肪酸の重量部（ｃ’）の比（ｃ’／ｂ’）が０．１未満では、ポリエステル系樹脂中での有機化層状珪酸塩の分散が不十分となり、本発明の目的を達することが困難になることがある。
【００４７】
更に、本発明に用いる脂肪酸金属塩（Ｄ）若しくは有機リン酸エステル類（Ｅ）は、カレンダー成形において、カレンダーロール間に形成される溶融樹脂だまり（通常、バンクと称される。）にエアーが巻き込まれ、それが縦筋となってシートやフィルムの表面に現れること防止するために配合される成分である。
【００４８】
脂肪酸金属塩（Ｄ）を配合する場合、脂肪酸部分の炭素数については、特に限定されない。使用が可能な脂肪酸金属塩としては、例えば、ステアリン酸リチウム、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸カリウム、ステアリン酸アルミニウム、ステアリン酸ストロンチウム、ステアリン酸バリウム、ステアリン酸カドミウム、ステアリン酸亜鉛、ステアリン酸鉛、ラウリル酸カルシウム、ラウリル酸バリウム、ラウリル酸カドミウム、ラウリル酸亜鉛、ミリスチン酸リチウム、オレイン酸亜鉛、ベヘン酸カルシウム、ベヘン酸亜鉛、ベヘン酸マグネシウム、ベヘン酸リチウム、モンタン酸カルシウム、モンタン酸マグネシウム、モンタン酸ナトリウム、２ーエチルヘキソイン酸カドミウム、２ーエチルヘキソイン酸亜鉛、などを挙げることができる。これらの脂肪酸金属塩は、樹脂用添加剤として市販されているものがあり、コストの面でこれらが好適に用いられる。
【００４９】
また、本発明に用いられる有機リン酸エステル類（Ｅ）は、有機リン酸エステルおよび有機リン酸エステルの部分ケン化物のことを指し、これらの１種または２種類以上の混合物が使用できる。
【００５０】
有機リン酸エステル（Ｅ）の種類は特に限定されず、例えば、モノステアリルリン酸エステル、ジステアリルリン酸エステル、トリステアリルリン酸エステル、モノラウリルリン酸エステル、ジラウリルリン酸エステル、トリラウリルリン酸エステル、モノノニルフェニルポリオキシエチレンリン酸エステル、ジノニルフェニルポリオキシエチレンリン酸エステル、トリノニルフェニルポリオキシエチレンリン酸エステル、モノラウリルポリオキシエチレンリン酸エステル、ジラウリルポリオキシエチレンリン酸エステル、トリラウリルポリオキシエチレンリン酸エステル、モノデシルポリオキシエチレンリン酸エステル、ジデシルポリオキシエチレンリン酸エステル、トリデシルポリオキシエチレンリン酸エステル、モノドデシルポリオキシエチレンリン酸エステル、ジドデシルポリオキシエチレンリン酸エステル、トリドデシルポリオキシエチレンリン酸エステル、モノオクチルフェニルポリオキシエチレンリン酸エステル、ジオクチルフェニルポリオキシエチレンリン酸エステル、トリオクチルフェニルポリオキシエチレンリン酸エステル、モノドデシルフェニルポリオキシエチレンリン酸エステル、ジドデシルフェニルポリオキシエチレンリン酸エステル、トリドデシルフェニルポリオキシエチレンリン酸エステル、モノステアリルジラウリルリン酸エステル、モノラウリルジステアリルリン酸エステル、モノステアリルジノニルフェニルポリオキシエチレンリン酸エステル、モノノニルフェニルポリオキシエチレンジステアリルリン酸エステル、モノラウリルジノニルフェニルポリオキシエチレンリン酸エステル、モノノニルフェニルポリオキシエチレンジラウリルリン酸エステル、モノステアリルジラウリルポリオキシエチレンリン酸エステル、モノラウリルポリオキシエチレンジステアリルリン酸エステル、モノラウリルジラウリルポリオキシエチレンリン酸エステル、モノラウリルポリオキシエチレンジラウリルリン酸エステルなどが挙げられ、これらの１種または２種類以上の混合物が使用できる。これらの有機リン酸エステルは、樹脂用添加剤として市販されているものがあり、コストの面でこれらが好適に用いられる。
【００５１】
また、有機リン酸エステルの部分ケン化物についても、その種類は特に限定されものではなく、上記のモノおよびジリン酸エステルに対して、残りの酸基部分でケン化した物質などが挙げられる。具体的には、上記有機リン酸エステルのカルシウムケン化物、マグネシウムケン化物、亜鉛ケン化物、例えば、モノステアリルリン酸エステルのカルシウムケン化物、モノステアリルリン酸エステルのマグネシウムケン化物、モノステアリルリン酸エステルの亜鉛ケン化物、モノラウリルリン酸エステルのカルシウムケン化物、モノラウリルリン酸エステルのマグネシウムケン化物、モノラウリルリン酸エステルの亜鉛ケン化物、モノノニルフェニルポリオキシエチレンリン酸エステルのカルシウムケン化物、モノノニルフェニルポリオキシエチレンリン酸エステルのマグネシウムケン化物、モノノニルフェニルポリオキシエチレンリン酸エステルの亜鉛ケン化物、モノラウリルポリオキシエチレンリン酸エステルのカルシウムケン化物、モノラウリルポリオキシエチレンリン酸エステルのマグネシウムケン化物、モノラウリルポリオキシエチレンリン酸エステルの亜鉛ケン化物などが挙げられ、これらの１種または２種類以上の混合物が使用できる。これらの有機リン酸エステルの部分ケン化物についても、樹脂用添加剤として市販されているものがあり、コストの面でこれらが好適に用いられる。
【００５２】
ここで、本発明のポリエステル系樹脂組成物に用いられる脂肪酸金属塩（Ｄ）若しくは有機リン酸エステル類（Ｅ）の配合量は、ポリエステル系樹脂（Ａ）１００重量部に対して０．０１〜５重量部の範囲、好ましくは０．０２〜４重量部、さらに好ましくは０．０３〜３重量部の範囲である。脂肪酸金属塩（Ｄ）若しくは有機リン酸エステル類（Ｅ）の配合量が０．０１重量部より少ないと所望の効果が得られず、配合量が５重量部を超えると、成形されたシートやフィルムの透明性が低下してしまう。
【００５３】
また、本発明に係るポリエステル系樹脂組成物には、金属ロール（カレンダーリロール）からの剥離性の向上を補うことを目的として、脂肪酸エステルまたは酸化型ポリエチレンワックスを併用して配合することが有効である。但し、脂肪酸エステルまたは酸化型ポリエチレンワックスは、剥離性を向上させる効果が大きいために、成形されたシートやフィルムの透明性の低下やプレートアウトの発生を招きやすい。従って、配合する場合には少量に抑えることが肝要である。具体的には、ポリエステル系樹脂（Ａ）１００重量部に対して０．５重量部以下とすることが好ましい。
【００５４】
ここで使用する脂肪酸エステルについて、その脂肪酸部分の炭素数は特に限定されない。但し、得られたエステルの揮発性を考慮すると、その炭素数が１２〜２８の脂肪族飽和カルボン酸と炭素数が２〜３０の脂肪族飽和アルコールとのエステルからなる合成ワックスまたは天然ワックスが好ましい。合成ワックスを構成する炭素数が１２〜２８の脂肪族飽和カルボン酸には、例えば、ラウリン酸、ミスチリン酸、ステアリン酸、ベヘン酸、リグノセリン酸、セロチン酸、モンタン酸などが挙げられ、炭素数が２〜３０の脂肪族飽和アルコールには、例えば、エチルアルコール、オクチルアルコール、ラウリルアルコール、ステアリルアルコール、ベヘニルアルコール、ペンタコシルアルコール、セリルアルコール、オクタコシルアルコール、メリシルアルコールなどの１価アルコール、およびエチレングリコール−１，２−ブタンジオール−１，３−ブタンジオール−１，４−ブタンジオール、２，３−ブタンジオールなどの２価アルコール、そしてグリセリンなどの３価アルコールなどの多価アルコールなどが挙げられる。
【００５５】
更に上記の合成ワックスとしては、例えば、ラウリン酸ステアリル、ミスチリン酸ステアリル、ステアリン酸ステアリル、ベヘン酸オクチル、ベヘン酸ラウリル、ベヘン酸ミリスチル、ベヘン酸ステアリル、ベヘン酸ベヘニル、ベヘン酸ペンタコシル、リグノセリン酸セリル、リグノセリン酸オクタコシル、リグノセリン酸メリシル、セロチン酸ステアリル、セロチン酸ベヘニル、セロチン酸セリル、セロチン酸メリシル、モンタン酸エチル、モンタン酸セリル、モンタン酸グリコールエステルなどが挙げられる。また、天然ワックスとしては、モンタンワックス、カルナバワックス、ビーズワックス、カンデリラワックス、ヌカロウ、イボタロウなどが挙げられる。これらの中で、揮発性や金属ロールに対する剥離性を踏まえて、モンタン酸グリコールエステル、モンタン酸グリセリド、モンタンワックスなどが好ましく、これらの物質は樹脂用添加剤として市販されており、コストの面でこれらが好適に用いられる。
【００５６】
また、酸化型ポリエチレンワックスについては、その種類は特に限定されず、低密度または高密度のいずれのものでも構わない。ただし、金属ロールからの剥離性を考慮すると、酸価が１〜４０ｍｇＫＯＨ／ｇで、分子量が重量平均分子量で１００００以下である部分酸化型のポリエチレンワックスが好ましい。これらの物質についても、樹脂用添加剤として市販されているものがあり、コストの面でこれらが好適に用いられる。
【００５７】
本発明に係るフィルムまたはシートは、上述したカレンダー成形用熱可塑性ポリエステル系樹脂組成物用いてカレンダー成形法により成形されるものである。また、フィルムまたはシートを、上述したカレンダー成形用熱可塑性ポリエステル系樹脂組成物用いてカレンダー成形法により成形する場合、その厚さを０．２ｍｍ以下とし、且つ成形体のガラス転移温度より１０℃高い温度で６０分間熱処理したときの成形体の収縮率が１０％未満であり、成形体のガラス転移温度より２０℃高い温度で６０分間熱処理したときの成形体の収縮率が１５％未満であり、成形体のガラス転移温度より４０℃高い温度で６０分間熱処理したときの成形体の収縮率が２０％未満とする。
【００５８】
ここで言うガラス転移温度とは、引張型動的粘弾性測定装置を用いて、フィルムまたはシートのガラス転移温度より少なくとも５０℃以上低い温度から、昇温しながら測定した時に現れる複素弾性率Ｅ”のピーク温度として求められるものであり、測定は、昇温速度は２〜１０℃／ｍｉｎ、周波数は５〜２０Ｈｚの範囲で行われる。
【００５９】
本発明に係るカレンダー成形用熱可塑性ポリエステル系樹脂組成物を用いて上記のような特性を有するフィルムやシートを得る方法としては、カレンダーロールの温度を本発明の組成物のガラス転移温度より８０℃以上で１５０℃未満、好ましくは９０℃以上で１４０℃未満、さらに好ましくは１００℃以上で１３０℃未満の温度に設定したカレンダー成形装置でもって、１３０％以上で５００％未満、好ましくは１４０％以上で４００％未満、更に好ましくは１５０％以上で３５０％未満の延伸比で冷却ロールにより引き取ることによって製造することができる。
【００６０】
ここで言う延伸比とはカレンダー成形機で圧延された溶融樹脂を冷却ロールで引き取る際の溶融樹脂を供給する側のカレンダーロールの面速度に対する冷却ロールの面速度の比を指す。
【００６１】
カレンダーロールの温度が本発明に係る熱可塑性ポリエステル系樹脂組成物のガラス転移温度より８０℃未満では、カレンダーロール間に形成される溶融樹脂だまり（通常、バンクと称される。）の回転が不規則になるため、透明なフィルムやシートが得難くなる。また、カレンダーロールの温度が本発明に係る熱可塑性ポリエステル系樹脂組成物のガラス転移温度より１５０℃以上では、溶融樹脂がカレンダーロールに粘着してしまい、カレンダー成形法によりフィルムやシートを製造することができなくなる恐れがある。
【００６２】
また、引き取りロールでの延伸比が１３０％未満でフィルムやシートを製造した場合には、厚みが０．２ｍｍ以下のフィルムやシートをカレンダー成形法により安定して生産できない恐れがある。何故ならば、延伸比を１３０％未満にして厚みが０．２ｍｍ以下のフィルムやシートを製造しようとした場合、カレンダーロールの間隙を狭くして製造する必要があるため、たとえカレンダーロールの温度を低く設定しても樹脂組成物の溶融体が発熱して高温になり、カレンダーロールに粘着する恐れがあるためである。加えて、カレンダーロールの間隙を狭くすることよるカレンダー成形装置の駆動電力の増大、さらには延伸比が小さいため生産スピードに劣るという、工業上のデメリットも生じる。
他方、引き取りロールでの延伸比が５００％以上でフィルムやシートを製造した場合には、本発明に係る熱可塑性ポリエステル系樹脂組成物を用いても収縮率が大きくなるという問題が生じる。
【００６３】
本発明に係る熱可塑性ポリエステル系樹脂組成物は、ペレットまたは粉体状のポリエステル系樹脂（Ａ）に、有機化層状珪酸塩（Ｂ）と、炭素数が１８以上の脂肪酸（Ｃ）、および脂肪酸金属塩（Ｄ）若しくは有機リン酸エステル類（Ｅ）を、また必要に応じて脂肪酸エステルや酸化型ポリエチレンワックスを単純に混ぜ合わせることにより、または予め混練機で溶融混練することによって作製することができる。
ここで使用される混練機としては公知の装置が使用できるが、取り扱いが容易で均一な分散が可能であるロール−１軸または２軸押出機、ニーダー、コニーダー、プラネタリーミキサー、バンバリーミキサー、などが好ましく用いられる。
【００６４】
また、本発明におけるポリエステル系樹脂組成物は、ポリエステル系樹脂（Ａ）に有機化層状珪酸塩（Ｂ）と、脂肪酸（Ｃ）および脂肪酸金属塩（Ｄ）または有機リン酸エステル類（Ｅ）、さらには脂肪酸エステルや酸化型ポリエチレンワックスを高濃度で配合した材料（通常、マスターバッチと称されるもの。）を前もって調製しておき、これらをポリエステル系樹脂（Ａ）と溶融混練することによって作製することもできる。マスターバッチの作製に関しても、上記に例示した混練機が好適に用いられる。
【００６５】
他方、本発明におけるポリエステル系樹脂組成物には、カレンダー成形における加工性を損なわない範囲内において、ヒンダードフェノール系、チオエーテル系、アミン系、リン酸系などの従来公知の酸化防止剤や、ベンゾフェノン系、ベンゾエート系、ベンゾトリアゾール系、シアノアクリレート系、ヒンダードアミン系などの従来公知の紫外線吸収剤、或いはアニオン系、カチオン系、非イオン系の低分子または高分子型の帯電防止剤、エポキシ化合物やイソシアネート化合物などの増粘剤、染料や顔料などの着色剤、酸化チタンやカーボンブラックなどの紫外線遮断剤、ガラス繊維やカーボンファイバーなどの強化材、シリカ、クレー、炭酸カルシウム、硫酸バリウム、ガラスビーズ、タルクなどの充填剤、難燃剤、可塑剤、発泡剤、抗菌剤、防カビ剤、蛍光剤、界面活性剤、架橋剤、などを適宜配合することができる。
【００６６】
更に、本発明におけるポリエステル系樹脂組成物には、カレンダー成形における成形加工性を損なわない範囲内で、ポリオレフィン系、ポリ塩化ビニル系、ポリスチレン系、ポリエーテル系、ポリエステル系、ポリアミド系、ポリイミド系などの他の熱可塑性樹脂を配合しても構わない。
【００６７】
本発明におけるポリエステル系樹脂組成物は、ミキサーや１軸または２軸押出機を用いて溶融混練した後に、カレンダー成形機によってフィルムやシートを作製するのに適した樹脂組成物である。フィルムやシートの作製時において、溶融樹脂のカレンダーロールからの剥離性および冷却ロールの引き取り性は良好で、且つ透明性も良好である。さらに、カレンダーロールへのプレートアウトも発生せずに、得られたフィルムやシートにエアーの巻き込みによる縦筋も発生しない。従って、当該ポリエステル系樹脂組成物をカレンダー成形することによって、外観の優れたフィルムやシートを高い生産性で成形することが可能となる。
【００６８】
本発明に係るポリエステル系樹脂組成物を用いてカレンダー成形することによって得られたフィルムやシートは、透明性、剛性、ガスバリア性、濡れ性に優れ、且つ収縮が小さいことから、化粧フィルムやシート用の透明または着色のフィルムまたはシート、カード用のフィルムまたはシート、各種包装容器用のフィルムまたはシート、印刷用や粘着加工に供されるフィルムまたはシート、金属の蒸着やスパッターリングなどによる表面加工を施されるフィルムまたはシート、窓など比較的高い温度になる部位に貼られるガラスの飛散防止や遮熱用に使用されるフィルムまたはシート、広告用に使用されるフィルムおよびシート、等に好適に用いられる。
【００６９】
【実施例】
次に、具体的な実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
【００７０】
まず、実施例または比較例に使用した材料について以下に説明する。
＜ポリエステル系樹脂（Ａ）＞
Ａ−１：ジカルボン酸成分がテレフタル酸１００モル％であって他のジカルボン酸は含まず、グリコール成分がエチレングリコール６０〜７５モル％と１，４−シクロヘキサンジメタノール４０〜２５モル％あってそれ以外のグリコール成分を含まず、これらジカルボン酸成分とグリコール成分との繰り返し単位からなる数平均分子量が２５０００のペレット状のポリエステル系樹脂（商品名；Ｔｓｕｎａｍｉ Ｃｏｐｏｌｙｅｓｔｅｒ ＧＳ２、Ｅａｓｔｍａｎ Ｃｈｅｍｉｃａｌ Ｐｒｏｄｕｃｔｓ，Ｉｎｃ．社製）。Ｆ−１：ポリエチレンテレフタレート（商品名；ＴＲ８５８０ＨＰ、帝人社製）
なお、パーキンエルマー社製のＤＳＣを使って２０℃／分の昇温速度でポリエステル系樹脂Ａ−１およびＦ−１を測定した結果、表１の通りであった。
【００７１】
【表１】

【００７２】
＜有機化層状珪酸塩（Ｂ）＞
Ｂ−１：参考例１に従い調整した有機化層状珪酸塩
Ｂ−２：参考例２に従い調整した有機化層状珪酸塩
Ｂ−３：参考例３に従い調整した有機化層状珪酸塩
Ｂ−４：陽イオン交換量が１２５ｍｅｑ／１００ｇのモンモリロナイトの層間に、イオン交換によってジメチルベンジル水添牛脂アンモニウムイオンを３９重量％挿入された有機化層状珪酸塩（商品名；ｃｌｏｉｓｉｔｅ１０Ａ、Ｓｏｕｔｈｅｒｎ Ｃｌａｙ Ｐｒｏｄｕｃｔｓ社製）。
Ｂ−５：陽イオン交換量が１２５ｍｅｑ／１００ｇのモンモリロナイトの層間にイオン交換によってジメチルジ水添牛脂アンモニウムイオンを４３重量％挿入された有機化層状珪酸塩（商品名；ｃｌｏｉｓｉｔｅ１５Ａ、Ｓｏｕｔｈｅｒｎ Ｃｌａｙ Ｐｒｏｄｕｃｔｓ社製）。
Ｂ−６：陽イオン交換量が９０ｍｅｑ／１００ｇのモンモリロナイトの層間にイオン交換によってメチルジ牛脂アルキルビス２ヒドロキシエチルアンモニウムイオンを３０重量％挿入された有機化層状珪酸塩（商品名；ｃｌｏｉｓｉｔｅ３０Ｂ、Ｓｏｕｔｈｅｒｎ Ｃｌａｙ Ｐｒｏｄｕｃｔｓ社製）。
＜層状珪酸塩＞
Ｇ−１：製高純度モンモリロナイト（商品名；ベンゲルＡ、ホージュン社製）
【００７３】
［参考例１］
天然Ｎａモンモリロナイト（商品名；クニピアＦ、クニミネ工業社製；陽イオン交換量１２０ｍｅｑ／１００ｇ）３ｋｇを１００Ｌの温水に撹拌分散し、これに陽イオン交換量の１．０倍量のジメチルステアリルベンジルアンモニウム塩を添加して１時間撹拌した後、生じた沈殿物をろ過し、温水で洗浄した。更に、洗浄とろ過を３回繰り返した後、得られた固体を乾燥して、有機化層状珪酸塩Ｂ−１を得た。
【００７４】
［参考例２］
天然Ｎａモンモリロナイト（商品名；クニピアＦ、クニミネ工業社製；陽イオン交換量１２０ｍｅｑ／１００ｇ）３ｋｇを１００Ｌの温水に撹拌分散し、これに陽イオン交換量の１．０倍量のベンザルコニウム塩を添加して１時間撹拌した後、生じた沈殿物をろ過し、温水で洗浄した。更に、洗浄とろ過を３回繰り返した後、得られた固体を乾燥して、有機化層状珪酸塩Ｂ−２を得た。
【００７５】
［参考例３］
天然Ｎａ型モンモリロナイト（商品名；ベンゲルＡ、ホージュン社製；陽イオン交換量９４ｍｅｑ／１００ｇ）３ｋｇを１００Ｌの温水に撹拌分散し、これに陽イオン交換量の１．０倍量のジメチルジステアリルアンモニウム塩を添加して１時間撹拌した後、生じた沈殿物をろ過し、温水で洗浄した。更に、洗浄とろ過を３回繰り返した後、得られた固体を乾燥して、有機化層状珪酸塩Ｂ−３を得た。
なお、有機化層状珪酸塩Ｂ−１〜Ｂ−５および、層状珪酸塩Ｇ−１を、それぞれ１０ｇ量り取り、１０００℃の電気炉中で３０分間加熱した後に残った灰分重量から求めた灰分の重量％（Ａｓｈ（％））は表２の通りであった。
【００７６】
【表２】

【００７７】
＜炭素数が１８以上の脂肪酸（Ｃ）＞
Ｃ−１：モンタン酸（商品名；Ｌｉｃｏｗａｘ Ｓ、クラリアントジャパン社製）
＜脂肪酸の金属塩（Ｄ）＞
Ｄ−１：モンタン酸カルシウム（商品名；Ｌｉｃｏｍｏｎｔ ＣａＶ１０２、クラリアントジャパン社製）
＜有機リン酸エステル類（Ｅ）＞
Ｅ−１：モノステアリルリン酸エステルおよびジステアリルリン酸エステルが重量比で６：４となる混合物（商品名；ＡＸ−５１８、大協化成工業社製）
【００７８】
＜その他の添加剤＞
脂肪酸エステル：モンタン酸と１，４−ブタンジオールとのエステル（商品名；Ｌｉｃｏｗａｘ Ｅ、クラリアントジャパン社製）
酸化型ポリエチレンワックス：酸価が１５〜１９ｍｇＫＯＨ／ｇのもの（商品名；Ｌｉｃｏｗａｘ ＰＥＤ１９１、クラリアントジャパン社製）
酸化防止剤：テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン（商品名；アデカスタブＡＯー６０、旭電化社製）
【００７９】
次に、表３および表４に記載した数値等について説明する。
「樹脂１００重量部当たりの珪酸塩量」および、「配合剤Ｃ−１／珪酸塩」については、次のようにして求めた。
「樹脂１００重量部当たりの珪酸塩量（ｂ’）」
有機化層状珪酸塩（Ｂ）および、層状珪酸塩には水分やイオン交換により挿入された有機オニウムイオンなど珪酸塩以外の成分が含まれることから、ポリエステル系樹脂（Ａ）１００重量部に対して配合した有機化層状珪酸塩（Ｂ）若しくは、層状珪酸塩の重量部（ｂ”）および、表２に示した有機化層状珪酸塩（Ｂ）または、層状珪酸塩の灰分の重量％（Ａｓｈ（％））より以下の式を用いて「ポリエステル系樹脂（Ａ）１００重量部当たりの珪酸塩量（ｂ’）」を、重量部として求めた。
ｂ’＝ｂ”×Ａｓｈ（％）／１００
「配合剤Ｃ−１／珪酸塩」
「配合剤Ｃ−１／珪酸塩」は、上に示した式を使って求めた「樹脂１００重量部当たりの珪酸塩量（ｂ’）」（重量部）に対する「樹脂１００重量部に対して配合した配合剤Ｃ−１の量（ｃ’）」（重量部）であり、次のようにして求めた。
配合剤Ｃ−１／珪酸塩（重量部／重量部）＝ｃ’／ｂ’
ここに示した以外の数値や評価方法に関しては、実施例若しくは、比較例中で説明する。
【００８０】
＜実施例１〜８＞
配合剤を表３に示した重量部で配合し、東洋精機製作所製ラボプラストミルミキサー（Ｒ−６０）を用い１８０℃で１０分間溶融混練して組成物を得た。この組成物を１８０℃で１ｍｍ厚みにプレス成形して得たシートのガラス転移温度を、東洋精機製作所製のレオログラフを用いて、昇温速度２℃／ｍｉｎ、周波数１０Ｈｚで測定された複素弾性率Ｅ”のピーク温度として求めた結果、いずれのシートも８０℃であった。
次に、配合剤を表３に示した重量部で配合し、ヘンシェルミキサーで均一に混合した後、バンバリーミキサーで樹脂温度が１６０〜１７５℃の範囲になるまで混練して、ポリエステル系樹脂組成物を調製した。これを、組成物のガラス転移温度より１１０℃高い温度である１９０℃に調整された逆Ｌ型形の４本ロールのカレンダー成形機を用いて圧延し、−１５０％若しくは２５０の延伸倍率で引き取り、冷却工程を経て、幅１０００ｍｍ、厚さ１００μｍのシートを作製した。
カレンダー成形により得られたシートのガラス転移温度を、東洋精機製作所製のレオログラフを用いて、昇温速度２℃／ｍｉｎ、周波数１０Ｈｚで測定された複素弾性率Ｅ”のピーク温度として求めた結果、いずれのシートも組成物と同じ８０℃であった。
【００８１】
なお、表３に示した評価は次のような方法で実施した。
［有機化層状珪酸塩の分散性の評価および金属からの剥離性の評価］
カレンダー成形機で成形する前に、東洋精機製作所製ラボプラストミルミキサー（Ｒ−６０）を用い１８０℃で１０分間溶融混練した際、混練直後の溶融体を観察して、溶融状態での有機化層状珪酸塩（Ｂ）の分散状態を判定した。また、溶融混練したコンパウンドを１８０℃で圧縮成形して厚さ１ｍｍの成形体を作製した際、成形体の目視評価により成形体中での有機化層状珪酸塩（Ｂ）の分散状態を判定した。有機化層状珪酸塩（Ｂ）の分散状態は、溶融体若しくは成形体中に有機化層状珪酸塩（Ｂ）の粒が観察されない場合は「○」とし、粒が観察される場合は「×」とした。
更に、東洋精機製作所製ラボプラストミルミキサー（Ｒ−６０）を用い１８０℃で１０分間予備混練した後、ミキサーからの溶融体の剥離性を評価することによって、金属からの剥離性を判定した。混練後の溶融体がミキサーから容易に剥離できた場合を「○」とし、溶融体が粘着してミキサーから剥離ができなかった場合を「×」とした。
【００８２】
［ロール加工性・シートの表面状態・シートの柔軟性の評価］
更に、カレンダー成形機で成形する前に、東洋精機製作所製ラボプラストミルミキサー（Ｒ−６０）を用い１８０℃で１０分間予備混練して得たコンパウンドを１９０℃に加熱した１０インチの２本ロールで、シート厚みが１５０μｍとなるように調製して混練し、ロールへの粘着性およびバンクの状態を評価した。
なお、ロールへの粘着性は、溶融体がロール面に粘着せず加工が可能であった場合は「○」とし、ロール面に粘着した場合は「×」とした。バンクの状態評価は、バンクが紡錘形になり、バンクにエアーを巻き込まず、バンク表面が滑らかで、回転がスムーズな状態を「○」とし、バンクが紡錘形にならないか、バンクにエアーを巻き込むか、表面が毛羽立った状態であるか、回転がスムーズでない場合を「×」とした。
シート引き取り性は、ロール混練時にシートを取り出し、シートが引き取れた場合は「○」とし、シートが伸びて引き取れなかった場合は「×」とした。
シートの表面状態は、シートを離型紙にラミネートしてサンプリングし、採取したシートの表面状態を目視観察し、エアーの巻き込みによる縦筋の発生がなく表面が平滑で透明なシートが得られた場合は「○」とし、エアーの巻き込みによる縦筋がある場合や不透明であった場合は「×」とした。
シートの柔軟性は、離型紙にラミネートしてサンプリングしたシートから１０ｃｍ角のシートを切り出し、このシートを９０度の角度で折り曲げ、シートが割れなかった場合には「○」とし、シートが割れた場合には「×」とした。
【００８３】
［溶融張力の測定］
カレンダー成形機で成形する前に、カレンダー成形の際の冷却ロールでの引き取り性を評価するために溶融張力の測定を行なった。測定は、東洋精機製作所製ラボプラストミルミキサー（Ｒ−６０）を用い１８０℃で１０分間溶融混練して得たコンパウンドを、Ｌ／Ｄ＝２０／１ｍｍのキャピラリーを装着した東洋精機製作所製キャピログラフを用いて、温度１９０℃、クロスヘッド速度５ｍｍ／分、巻き取り速度２０ｍ／分の条件で実施した。
【００８４】
［溶融粘度の測定］
また、カレンダー成形機で成形する前に、カレンダー成形の際のカレンダー装置の駆動に要する電力の大小を評価するために溶融粘度の測定を行なった。測定は、東洋精機製作所製ラボプラストミルミキサー（Ｒ−６０）を用い１８０℃で１０分間溶融混練して得たコンパウンドを、Ｌ／Ｄ＝２０／１ｍｍのキャピラリーを装着した東洋精機製作所製キャピログラフを用いて、温度１９０℃、剪断速度２５０／秒の条件で実施した。
【００８５】
［収縮率の測定］
カレンダー成形により得られたシートから１５ｃｍ角のシートを切り出し、このシートを所定温度（表３、表４に記載）に設定したオーブン中で６０分間熱処理した後取り出して、その熱処理前後でのシートの長さの変化からシートの延伸方向の収縮率を求めた。
【００８６】
［引張り試験］
カレンダー成形により得られたシートから延伸方向が長辺となるようにして、長さ２００ｍｍ、幅１９ｍｍの短冊状試験片を打ち抜き、ＪＩＳ Ｋー７１２７に従って引張り試験を行なった。
【００８７】
［酸素透過係数の測定］
カレンダー成形により得られたシートを用いて、東洋精機製作所製の差圧式ガス透過試験機により測定した。
【００８８】
［濡れ張力の測定］
カレンダー成形により得られたシートを用いて、濡れ試薬によりシート表面の濡れ張力を測定した。
評価結果をまとめて、表３に示す。
【００８９】
＜比較例１＞
東洋精機製作所製ラボプラストミルミキサー（Ｒ−６０）を用い１８０℃で１０分間溶融混練して組成物を得た。この組成物を１８０℃で１ｍｍの厚みにプレス成形して得たシートのガラス転移温度を、東洋精機製作所製のレオログラフを用いて、昇温速度２℃／ｍｉｎ、周波数１０Ｈｚで測定された複素弾性率Ｅ”のピーク温度として求めた結果、８０℃であった。
次に、配合剤を表４に示した重量部で配合し、ヘンシェルミキサーで均一に混合した後、バンバリーミキサーで樹脂温度が１６０〜１７５℃の範囲になるまで混練して、ポリエステル樹脂組成物を調製した。これを、組成物のガラス転移温度より１１０℃高い温度である１９０℃に調整された逆Ｌ型形の４本ロールのカレンダー成形機を用いて圧延し、１５０％および２５０％の延伸倍率で引き取りを行おうとしたがシートが伸びて冷却ロールで引き取ることができなかったため、３５０％の延伸倍率で引き取り、冷却工程を経て幅１０００ｍｍ、厚さ１００μｍのシートを作製した。なお、本組成物をカレンダー成形した際に成形機の駆動に要した電力は、実施例１、２および５〜７に比べて５割、実施例３に比べて２割、実施例４に比べて７割、実施例８に比べて３割高かった。
得られたシートのガラス転移温度を、東洋精機製作所製のレオログラフを用いて、昇温速度２℃／ｍｉｎ、周波数１０Ｈｚで測定された複素弾性率Ｅ”のピーク温度として求めた結果、組成物と同じ８０℃であった。
カレンダー成形機で成形する前に行なった評価結果および、カレンダー成形機で製造したシートの評価結果を表４に示す。
なお、表４に示した評価は、実施例と同様の方法および基準で評価したものである。
この比較例から、有機化層状珪酸塩（Ｂ）を配合しない場合は、実施例に比べ溶融張力が低く、ロール加工性の評価においてもシートの引き取り性に劣ることが分かる。カレンダー成形時にも延伸倍率を高くしないと引き取りが行えず、実施例に比べシートの引き取り性は劣っていた。
また、実施例に比べ溶融粘度が高く、カレンダー成形を行なった際の成形機の駆動に要する電力も、実施例に比べ高くなった。さらに、カレンダー成形機で得られたシートは、表３の実施例に示したシートに比べ、収縮性、引張物性、酸素バリア性、濡れ性に劣ることが分かる。
【００９０】
＜比較例２＞
配合剤を表４に示した重量部で配合した組成物を、実施例と同様の方法で有機化層状珪酸塩（Ｂ）の分散性の評価、金属からの剥離性の評価、溶融張力の評価、溶融粘度の評価、およびロール加工性、シートの表面状態、シートの柔軟性の評価をそれぞれ行なった。
この評価において、脂肪酸の金属塩若しくはリン酸エステル類を含まない比較例２の組成物は、バンクに大量のエアーが巻き込まれ、それがシートに縦筋となって転写され、シートの表面状態に劣り、しかも厚みが不均一となったことから、カレンダー成形を含め、他の評価は実施しなかった。
評価結果を表４に示す。なお、表４に示した評価結果は、実施例と同様の方法および基準で評価したものである。
この比較例から、脂肪酸の金属塩若しくはリン酸エステル類を含まない場合は、バンクにエアーが巻き込まれるため、表面状態や厚み均一性に優れるシートが得られないことが分かる。
【００９１】
＜比較例３＞
配合剤を表４に示した重量部で配合した組成物を、実施例と同様の方法で有機化層状珪酸塩（Ｂ）の分散性の評価、金属からの剥離性の評価、およびロール加工性の評価、シートの表面状態、シートの柔軟性の評価を行なった。
この評価において、ポリエステル系樹脂（Ａ）１００重量部に対して、２０重量部を超えた量で有機化層状珪酸塩（Ｂ）が配合されている比較例３の組成物は、シートの柔軟性の評価においてシートが割れたため、カレンダー成形を含め、他の評価は行なわなかった。
評価結果を表４に示す。なお、表４に示した評価結果は、実施例と同様の方法および基準で評価したものである。
この比較例から、ポリエステル系樹脂（Ａ）１００重量部に対して、２０重量部を超えた量で有機化層状珪酸塩（Ｂ）が配合されている場合は、シートが脆くなることが分かる。
【００９２】
＜比較例４＞
配合剤を表４に示した重量部で配合した組成物を、実施例と同様の方法で有機化層状珪酸塩（Ｂ）の分散性の評価、金属からの剥離性の評価、およびロール加工性の評価をそれぞれ行なった。
この評価において、ポリエステル系樹脂（Ａ）１００重量部に対して、１０重量部を超えた量で炭素数１８以上の脂肪酸（Ｃ）が配合されている比較例３の組成物は、冷えると白濁したことから、成形体中での有機化層状珪酸塩の分散状態の評価は行なわなかった。ロール加工性の評価において、ロール表面で溶融樹脂が滑り、シート化できず、バンクも紡錘形にならなかった。そのため、シートの表面状態・シートの柔軟性の評価は行なわなかった。また、カレンダー成形を含め、他の評価も行なわなかった。
評価結果を表４に示す。なお、表４に示した評価結果は、実施例と同様の方法および基準で評価したものである。
この比較例から、ポリエステル系樹脂（Ａ）１００重量部に対して、１０重量部を超えた量で炭素数１８以上の脂肪酸（Ｃ）が配合されている場合は、透明性に劣るシートしか得られないばかりか、滑性過多となりロール加工自体が不可能であることが分かる。
【００９３】
＜比較例５、６＞
配合剤を表４に示した重量部で配合した組成物を、実施例と同様の方法で有機化層状珪酸塩（Ｂ）の分散性の評価および金属からの剥離性の評価を行なった。
その結果、これらの組成物は、溶融体を金属から剥離することができず、また冷えると白濁したことから、成形体中での有機化層状珪酸塩の分散状態の評価ならびに、カレンダー成形を含め、他の評価は行なわなかった。
評価結果を表４に示す。なお、表４に示した評価結果は、実施例と同様の方法および基準で評価したものである。
これらの評価結果から、ポリエステル系樹脂（Ａ）１００重量部に対して、５重量部を超えた量で脂肪酸金属塩（Ｄ）もしくは有機リン酸エステル類（Ｅ）が配合されている場合は、透明性に劣るシートしか得られないばかりか、溶融体を金属から剥離することができないことが分かる。
【００９４】
＜比較例７〜１０＞
配合剤を表４に示した重量部で配合した組成物を、実施例と同様の方法で有機化層状珪酸塩の分散性の評価および金属からの剥離性の評価を行なった。
その結果、これらの組成物は溶融体および成形体中に有機化層状珪酸塩の粒が多数見られ、プレス成形で得たシートも不透明なものとなったため、カレンダー成形を含め、他の評価は行なわなかった。
評価結果を表４に示す。なお、表４に示した評価結果は、実施例と同様の方法および基準で評価したものである。
これらの評価結果から、比較例７、８のように炭素数１８以上の脂肪酸（Ｃ）を含まない場合、並びに、比較例９のようにポリエステル系樹脂（Ａ）１００重量部に対して配合する有機化層状珪酸塩中の珪酸塩の重量部（ｂ’）とポリエステル系樹脂（Ａ）樹脂１００重量部に対して配合する炭素数１８以上の脂肪酸の重量部（ｃ’）の比（ｃ’／ｂ’）が０．１未満である場合には、有機化層状珪酸塩（Ｂ）の分散が不十分となり、透明性に劣るシートしか得られないことが分かる。また、比較例１０のように有機化されていない層状珪酸塩を用いた場合にも、層状珪酸塩の分散が不十分であり、透明性に劣るシートしか得られない。
【００９５】
＜比較例１１、１２＞
配合剤を表４に示した重量部で配合し、東洋精機製作所製ラボプラストミルミキサー（Ｒ−６０）を用い１８０℃で１０分間溶融混練したが、ポリエステル系樹脂（Ｆ−１）が溶融しなかった。そのため、混練温度を２７０℃にして１０分間混練した後、混練直後の溶融体を観察して、溶融状態での有機化層状珪酸塩の分散状態を評価した結果、溶融体中に有機化層状珪酸塩の粒が多数見られた。また、組成物の溶融体を金属から剥離することもできなかった。
なお、ポリエステル系樹脂Ｆ−１を含む組成物の溶融体は、冷えると白濁したことから、成形体中での有機化層状珪酸塩の分散状態の評価は実施しなかった。また、カレンダー成形を含め、他の評価も実施しなかった。
評価結果を表４に示す。表４に示した評価結果は、実施例と同様の基準で行なったものである。
これらの比較例から、ＤＳＣで測定した場合に結晶融解ピークが２００℃を超え、結晶融解熱量が５０Ｊ／ｇを超えた結晶性ポリエステル系樹脂を用いた場合には、有機化層状珪酸塩の分散が不十分となり、また溶融体を金属から剥離することもできないことが分かる。
【００９６】
【表３】

【００９７】
【表４】

【００９８】
【発明の効果】
表３および表４に示した評価結果から明らかなように、本発明に係るカレンダー成形用ポリエステル系樹脂組成物は、金属からの剥離性、バンクの回転性、シートの引き取り性、カレンダー成形時の装置の駆動に要する電力が低減できるなど、カレンダー成形を行う上での適正に優れ、透明な成形体が得られ、また、カレンダー成形により得られたシートやフィルムは表面状態が良好で、収縮が小さく、機械物性、ガスバリア性、濡れ性に優れたものとなる。[0001]
BACKGROUND OF THE INVENTION
The present invention particularly relates to a polyester-based resin composition molded by a calendar molding method, and a film or sheet obtained by calendar molding of the resin composition.
[0002]
[Prior art]
Thermoplastic polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) are excellent in mechanical properties, heat resistance and gas barrier properties. Therefore, packaging materials for foods and pharmaceuticals, lid materials for containers-blister packaging Widely used as materials for containers, as well as films and sheets for laminating for construction, home appliances, and automobiles.
[0003]
When a film or sheet is formed using a thermoplastic polyester resin, it is generally produced by an extrusion method. In the extrusion molding method, after adjusting the die so that the sheet has a specific thickness, the molten resin is discharged from the die by using the pushing force of the screw, and the molten resin is rapidly cooled to a temperature lower than its softening temperature. It is a molding process method to take off while. For this reason, it is easy to take out the melt with a cooling roll, but even if the die is adjusted, parts with different thickness are likely to occur, and the thickness accuracy as a sheet is poor, so printing, laminating, coating Such as post-processing is likely to be hindered, and a hole may be formed in the sheet during secondary forming such as vacuum / pressure forming. In addition, the sheet forming by the extrusion method has a low forming speed and is difficult to say that the productivity is good.
[0004]
For these reasons, in general, when a sheet or film is produced, not the extrusion molding method but the calender molding method is often applied. The calendar molding method is a molding method in which a molten resin is rolled with a plurality of heated metal rolls (calendar rolls) and then taken with a cooled roll to produce a sheet or film having a desired thickness. There is no trouble in the vicinity of the dies in the die, and it is possible to produce a sheet and film with a good thickness accuracy and excellent quality, as well as a high molding speed and excellent productivity. Suitable for mass production.
[0005]
However, in the case of a thermoplastic polyester resin such as PET or PBT, it has been impossible to produce a film or sheet by a calendar molding method. This is because, in the case of the calendar molding method, unlike the extrusion method, unlike the processing method in which the molten resin discharged from the die is drawn with a cooling roll using the extrusion force of the screw, it is heated. This is a processing method in which a molten resin rolled by a plurality of calender rolls is formed into a film or sheet by pulling it with a cooling roll while pulling it away from the calender roll using the tension of the molten resin. This is because take-up resistance is required.
That is, generally, a thermoplastic polyester-based resin such as PET or PBT needs to be molded at a temperature of 250 ° C. or higher, but this type of thermoplastic polyester-based resin has a melt viscosity at a temperature of 250 ° C. or higher. Since the melt tension is remarkably low, there is no large take-up resistance, and therefore the calendering method cannot be applied.
[0006]
In contrast, among the thermoplastic polyester resins, for example, in the case of PET resins, the terephthalic acid and ethylene glycol, which are monomer components, are partially replaced with other components to form a random copolymer. Attempts have been made to increase the take-up resistance by applying a calendering control at a temperature of about 200 ° C. so that it can be applied to calendar molding. However, since the PET resin has a large polarity, the adhesion to the calender roll is remarkable, and even if the take-up resistance increases, the resin alone cannot be used for calender molding.
[0007]
Therefore, as a method for facilitating peeling from the calender roll, for example, JP-A-11-343353, JP-A 2000-186191, JP-A 2000-302951, JP-A 2000-327891, JP 2001-64496 A proposes blending various additives.
[0008]
As an additive for achieving easy peelability from a metal roll (calendar roll), in general, those having low affinity with the resin are effective, but when such an additive is blended, The transparency of the formed sheet or film may be reduced, or it may lead to plate-out to a metal roll. Therefore, even if the polyester resin is modified so that it can be applied to calendar molding by controlling the crystallinity of the resin, and the polyester additive resin is calendered by the disclosed additive compounding technique, It has been very difficult to facilitate peeling from the metal roll while maintaining transparency without causing plate-out to the metal roll.
[0009]
Furthermore, even if an additive for facilitating peelability is blended so that calendering is possible, the resin melts when molding is performed at a temperature at which a take-off resistance capable of calendering is obtained. Since the viscosity is high, the driving power of the calender molding apparatus increases. As a result, the power cost for manufacturing increases, and at the same time, there is a problem that the molding apparatus with a small driving motor power hinders the manufacturing.
[0010]
On the other hand, in the calendering method, it is a common practice to efficiently produce a thin product by melting and stretching the take-up speed of the cooling roll faster than the rotation speed of the calendar roll. This is because if the gap between the calender rolls is too narrow, the calender rolls may come into contact with each other, and even if the gap between the calender rolls is set to be narrow, the resin melt after rolling expands. There is a limit to the production of thin films and sheets by adjusting only the gap between rolls, and by narrowing the gap between the calender rolls, the heat generated from the molten resin increases and sticking to the calender rolls tends to occur. Because. Furthermore, it is because the production speed is increased by making the drawing speed of the cooling roll faster than the rotation speed of the calendar roll and performing melt drawing.
[0011]
However, the film or sheet manufactured by the calendering method through such a melt stretching process is coated with printing ink or pressure sensitive adhesive and dried, and the film or sheet is reheated in the melt stretching direction. In some cases, the shrinkage is large. In addition, the product may shrink and become a problem even in the case of a film for preventing scattering of glass or a film and sheet used for heat shielding and advertisement, which are applied to a relatively high temperature part such as a window. Such shrinkage is particularly remarkable in the case of a thermoplastic polyester resin.
[0012]
On the other hand, when improving the dimensional stability, mechanical properties, heat resistance, gas barrier properties, etc. of thermoplastic polyester resins such as PET and PBT, conventionally, a method of blending fillers such as glass fiber, calcium carbonate, talc, etc. However, these conventional methods have drawbacks such as an increase in specific gravity as a film or sheet, deterioration of the surface appearance, and inability to obtain a transparent product.
[0013]
A smectite clay typified by montmorillonite is a method that can improve these disadvantages and can improve the dimensional stability, mechanical properties, heat resistance, gas barrier properties, etc. of films and sheets made of thermoplastic polyester resins. There are known techniques relating to composite materials and compositions in which an organically modified layered silicate obtained by ion exchange of mineral ions and interlayer ions such as fluorinated mica with organic onium ions is finely dispersed in a thermoplastic polyester resin.
[0014]
For example, JP-A-3-62846 discloses a layered clay mineral containing a thermoplastic aromatic polyester, a layered clay mineral bonded with organic onium ions, and a compatibilizer, and bonded with organic onium ions. Disclosed is a polyester composite material having a structure in which it is uniformly dispersed in a thermoplastic aromatic polyester by the affinity action of the agent and has been crosslinked by molecular chains of the thermoplastic aromatic polyester, and a production method thereof.
JP-A-7-166036 discloses an intercalation compound having a cation exchange amount of 30 meq / 100 g or more as a host and a quaternary ammonium ion as a guest, and an inorganic ash content of 0.5 to An aromatic polyester resin containing 10 parts by weight, and Japanese Patent Application Laid-Open No. 2000-53847, melt knead a thermoplastic polyester and a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions. A polyester resin composition in which the amount of carboxyl terminal groups of the thermoplastic polyester is 10 to 80 eq / t is further disclosed in Japanese Patent Application Laid-Open No. 2000-212424 in 100 parts by weight of the thermoplastic polyester. In contrast, a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions. 40 parts by weight, the polyester resin composition obtained by blending 0.001 parts by weight of at least one of montanic acid and a low molecular weight polyolefin is disclosed.
[0015]
However, even if the techniques disclosed regarding the composite materials and compositions of these thermoplastic polyester resins are used, thermoplastic polyester resins having excellent dimensional stability, mechanical properties, heat resistance, gas barrier properties, etc. It was even more difficult to perform the molding process by a calendar molding method that required take-up resistance. In addition, these conventional technical documents do not disclose any method for reducing shrinkage, which is particularly problematic when a film or sheet of a thermoplastic polyester resin is produced by a calender molding method.
[0016]
[Disclosure of prior art documents]
[Patent Document 1]
Japanese Patent Laid-Open No. 3-62846
[Patent Document 2]
Japanese Patent Laid-Open No. 7-166036
[Patent Document 3]
JP 2000-53847 A
[Patent Document 4]
JP 2000-212424 A
[0017]
[Problems to be solved by the invention]
The present invention has been made in view of such a current situation, and the problem to be solved is excellent in easy moldability by a calendar molding method, transparency as a resin molded product, rigidity, gas barrier property and wettability, In addition, it is an object to provide a thermoplastic polyester resin composition for calendering that provides a film or sheet with reduced shrinkage due to molding, and a film or sheet obtained by a calendering method using the resin composition. .
[0018]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, and as a result, by using a resin composition in which a specific additive is added to a specific thermoplastic polyester-based resin, the calendar moldability is improved. The inventors have found that it is possible to produce a film or sheet that is excellent, has reduced shrinkage due to molding, and has excellent transparency, rigidity, gas barrier properties, and wettability, and has completed the present invention.
[0019]
That is, the calender-molding polyester resin composition according to claim 1 of the present invention does not show a crystal melting peak or has a crystal melting peak of 200 ° C. or less when measured by DSC (Differential Scanning Calorimeter). 0.5 to 20 parts by weight of organic layered silicate (B) and 18 or more carbon atoms with respect to 100 parts by weight of non-crystalline or low-crystalline polyester resin (A) having a heat of fusion of 50 J / g or less The fatty acid (C) is 0.1 to 10 parts by weight and the fatty acid metal salt (D) is 0.01 to 5 parts by weight.
[0020]
Incidentally, DSC in the present invention is an abbreviation for differential scanning calorimeter or measuring method (Differential Scanning Calorimeter), and refers to an apparatus or measuring method used for measuring the melting point and heat of fusion of a resin. JIS K-7121 , K-7122 and the like. In addition, the measurement of the crystal melting peak and the heat of crystal melting is performed in accordance with JIS K-7121 and K-7122.
[0021]
Moreover, the polyester resin composition for calender molding which concerns on Claim 2 is organically modified layered silicate (B) with respect to 100 weight part of non-crystalline or low crystalline polyester-type resin (A) of Claim 1. 0.5 to 20 parts by weight, 0.1 to 10 parts by weight of a fatty acid (C) having 18 or more carbon atoms, and 0.01 to 5 parts by weight of an organic phosphate ester (E) It is characterized by.
As the non-crystalline or low-crystalline polyester resin (A), at least 80 mol of one or a mixture of two or more selected from terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and isophthalic acid is used. % Or more of a dicarboxylic acid component that is at least 80 mol% or more of a mixture of one or more selected from ethylene glycol, neopentyl glycol, diethylene glycol, and 1,4-cyclohexanedimethanol It is most preferable to use a polyester-based resin.
Further, as the organically modified layered silicate (B), it is preferable to use one having an organic onium ion inserted between the layers (Claim 4).
Under the present circumstances, the weight part (b ') of the silicate in the organic layered silicate mix | blended with respect to 100 weight part of non-crystalline or low crystalline polyester-type resin (A), and the polyester-type resin (A) resin It is desirable that the ratio (c ′ / b ′) of parts by weight (c ′) of fatty acids having 18 or more carbon atoms to be blended with respect to 100 parts by weight is 0.1 or more (Claim 5).
Moreover, the film or sheet | seat (Claim 6) shape | molded by the calender molding method using the thermoplastic polyester-type resin composition for calendar | calender shaping | molding of any one of the said Claims 1-5 has the thickness. It is a film or sheet of 0.2 mm or less, and the shrinkage ratio of the molded body when heat-treated for 60 minutes at a temperature 10 ° C. higher than the glass transition temperature of the molded body is less than 10%, and is 20 from the glass transition temperature of the molded body. The shrinkage ratio of the molded product when heat-treated at a high temperature of 60 ° C. for 60 minutes is less than 15%, and the shrinkage rate of the molded product when heat-treated for 60 minutes at a temperature 40 ° C. higher than the glass transition temperature of the molded product is less than 20%. It is characterized in that (Claim 7).
[0022]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described.
As the polyester resin (A) used in the polyester resin composition for calender molding of the present invention, a crystal melting peak is not observed when measured by DSC, or the crystal melting peak is 200 ° C. or less and crystal melting. An amorphous or low crystalline polyester resin having a heat quantity of 50 J / g or less is used.
[0023]
A polyester resin having a crystal melting peak exceeding 200 ° C melts only at a temperature exceeding 200 ° C. For this reason, if the molding process is performed in such a temperature range, the melt viscosity and melt tension of the polyester-based resin are remarkably lowered, so that it becomes difficult to form a film or a sheet by a calendar molding method.
The amount of heat of crystal fusion of the polyester-based resin is 50 J / g or less because it can reduce the occurrence of problems caused by the unmelted resin remaining as a gel in the form of a film or sheet, particularly when used for calender molding. Although it is necessary, the heat of crystal fusion is preferably 30 J / g or less, and more preferably 10 J / g or less. Among such polyester resins, an amorphous polyester resin that does not substantially exhibit a crystal melting peak is most preferably used because it can be melted at a low temperature.
[0024]
In addition to the polyester resin having a single composition that satisfies the above requirements, the polyester resin (A) includes a mixture of a plurality of polyester resins, 50% by weight or more of a polyester resin, and a polyolefin resin. Mixtures with resins other than polyester resins, such as polyamide resins or vinyl chloride resins, can also be used. However, as the polyester resin (A) used in the present invention, it is necessary to have excellent calendar moldability and excellent transparency of the obtained film or sheet. Resin is suitable.
[0025]
The polyester resin (A) used in the present invention can be obtained by copolymerizing one or more carboxylic acid components and / or one or more glycol components.
Carboxylic acid components include terephthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, azelaic acid, dodecanedioic acid, fumaric acid, maleic acid Acid, itaconic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,6-naphthalenedidimethylenecarboxylic acid, dicarboxylic acid such as paraphenylenedicarboxylic acid, trivalent carboxylic acid such as trimellitic acid, pyromellitic acid, etc. The tetravalent carboxylic acid can be mentioned.
[0026]
The glycol component includes ethylene glycol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, propylene glycol, 1,3-propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol. 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol 1,4-butanediol, neopentyl glycol, 1,5-pentadiol, 1,6-hexanediol, 1,8-octanediol, 2,2,4-trimethyl-1,6-hexanediol, thiodiethanol -1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethano Le, can be mentioned dihydric alcohols such as 2,2,4,4 over tetramethyl-1,3 chromatography cyclobutanediol, trihydric alcohols such as trimethylolpropane, tetravalent alcohols such as pentaerythritol.
[0027]
Among these carboxylic components and glycol components, the polyester resin used in the present invention is one selected from terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and isophthalic acid as the carboxylic acid component. Or the mixture of 2 or more types is at least 80 mol% or more, and 1 type, or 2 or more types of mixtures chosen from ethylene glycol, neopentyl glycol, diethylene glycol, and 1, 4- cyclohexane dimethanol as a glycol component are at least 80. It is preferably at least mol%.
Among these, the dicarboxylic acid component in which terephthalic acid is at least 90 mol%, including 10-95 mol% of 1,4-cyclohexanedimethanol and ethylene glycol of 90-5 mol%, including being easily available as a raw material. It is preferable to use a polyester resin having a glycol component as a repeating unit, and among them, an amorphous polyester resin comprising this component is most preferably used.
This is because non-crystalline polyester resins can be melted at low temperatures, which is advantageous for calender molding that requires particularly high melt tension, and at the same time, the surface of sheets and films obtained by calender molding. This is because smoothness and transparency are good.
[0028]
The non-crystallinity of the polyester-based resin varies depending on the composition ratio of the monomer components, but in order to achieve the non-crystallinity and at the same time to improve the moldability in calender molding, 100 mol% of terephthalic acid and 30 of ethylene glycol are used. -90 mol%, 1,4-cyclohexanedimethanol is preferably 10-70 mol%, terephthalic acid is 100 mol%, ethylene glycol is 60-75 mol%, 1,4- It is preferable that cyclohexanedimethanol is 40-25 mol%.
[0029]
The polyester resin preferably used in the present invention is a polycondensation in the presence of a specific catalyst after reacting a dicarboxylic acid component containing terephthalic acid with a glycol component containing 1,4-cyclohexanedimethanol and ethylene glycol. Is obtained. That is, a dicarboxylic acid component containing at least 90 mol% terephthalic acid and a glycol component containing 10 to 95 mol% 1,4-cyclohexanedimethanol and 90 to 5 mol% ethylene glycol component are esterified or transesterified. The reaction product obtained is then reacted at a temperature sufficient to allow the reaction to occur, and the resulting reaction product is then subjected to an absolute pressure below 1.333 KPa for less than 2 hours for 0 to 75 ppm Mn, based on the weight of the copolyester, It is obtained as a colorless and transparent copolyester by polycondensation in the presence of a catalyst and inhibitor system consisting of 50 to 150 ppm Zn, 5 to 20 ppm Ti, 5 to 200 ppm Ge and 10 to 80 ppm P.
[0030]
In order to increase the melt tension of the polyester resin thus obtained and at the same time improve the calendar moldability, the polyester resin may be crosslinked within a range that does not adversely affect the transparency when molded into a film or sheet. This cross-linking is performed by a process of polycondensation of the polyester resin or by reacting with a compound having cross-linkability after the polycondensation.
[0031]
Incidentally, some polyester resins that can be used in the present invention are already on the market. For example, an amorphous polyester resin comprising 100 mol% terephthalic acid, 60 to 75 mol% ethylene glycol, and 40 to 25 mol% 1,4-cyclohexanedimethanol is available from Eastman Chemical Products, Inc. Kodder PETG Copolyester (trade name) and Tsunami Copolyester (trade name) are commercially available from the company. In the present invention, such a polyester resin can be suitably used.
[0032]
Further, the molecular weight of the non-crystalline or low-crystalline polyester resin (A) used in the present invention is not particularly limited, but if the number average molecular weight is less than 10,000, the melt tension of the molten resin is small, In addition, the temperature range in which the molding process can be performed in calendar molding becomes narrow and molding may become difficult. If the number average molecular weight exceeds 200,000, the surface smoothness of the obtained sheet or film may be inferior. There is. Therefore, the number average molecular weight is preferably in the range of 10,000 to 200,000 in consideration of the moldability by calendering and the good surface smoothness of the obtained sheet or film.
[0033]
Organized layered silicate (B) used in the present invention improves the moldability in calendar molding, and improves the performance of the film or sheet obtained by the calendar molding method, such as rigidity, gas barrier properties, wettability, Furthermore, a compound that is blended to reduce shrinkage of the molded film or sheet, and a compound obtained by substituting an exchangeable cation existing between layers of layered silicic acid with an organic onium ion is preferably used.
[0034]
A layered silicate having an exchangeable cation between layers has a structure in which plates having a thickness of 0.5 to 2 nm and a width of 0.02 to 2 μm are laminated, and an alkali metal such as Li +, Na +, K + between the layers. Or, an exchangeable cation of an alkaline earth metal such as Ca 2+ or Mg 2+ exists in a state where water molecules are hydrated. The cation exchange amount is preferably 30 to 300 meq / 100 g, more preferably 50 to 150 meq / 100 g.
When the amount of cation exchange is less than 30 meq / 100 g, organic onium ions are not sufficiently exchanged, and the layers of the layered silicate are aggregated in the resin without peeling off, so that the formed film or sheet is opaque. At the same time, the effect of the present invention may not be obtained. When the cation exchange amount exceeds 300 meq / 100 g, the bonding strength between layers of the layered silicate becomes strong, and thus the agglomerates in the resin. As a result, the molded film or sheet becomes opaque and the effects of the present invention may not be obtained.
[0035]
Specific examples of layered silicates having exchangeable cations between layers include montmorillonite, saponite, hectorite, fluorine hectorite, beidellite, stevensite, etc., smectite clay minerals, Li type fluorine teniolite, Na type fluorine teniolite Synthetic mica such as Na type tetrasilicon fluorine mica and Li type tetrasilicon fluorine mica, vermiculite, fluorine vermiculite, halosite, kanemite, kenyanite, zirconium phosphate, titanium phosphate, etc., natural products Or a synthetic product.
Among these, montmorillonite, saponite, hectorite, fluorine hectorite, beidellite, stevensite, and other smectite clay minerals, Li-type fluorine teniolite, Na-type fluorine teniolite, Na Synthetic mica such as type 4 tetrasilicon fluorine mica and Li type tetrasilicon fluorine mica is preferred.
[0036]
Examples of organic onium ions that can be exchanged for exchangeable cations in layered silicates include ammonium ions, phosphonium ions, and sulfonium ions. Among them, ammonium ions and phosphonium ions are industrially readily available. Are preferred, and ammonium ions are particularly preferred.
[0037]
Specific ammonium ions include compounds represented by the following general formula
[Chemical 1]

(In the formula, R1 to R4 are hydrogen, an alkyl group having 1 to 30 carbon atoms, a benzyl group, a hydroxyalkyl group having 1 to 30 carbon atoms, a hydroxybenzyl group,-(CH ₂ -CH ₂ -O) _n -H group,-(CH ₂ -CH (CH ₃ -O) _m It is selected from —H groups (where n and m are integers of 1 to 30). ),
And derived from aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 4-aminododecanoic acid, 6-aminocaproic acid-12-aminododecanoic acid-18-aminooctadecanoic acid, etc. And benzethonium ions.
[0038]
Specific examples of the ammonium ion compound represented by the above general formula include stearyl ammonium ion, dodecyl ammonium ion, benzyl ammonium ion, hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, lauryl ammonium ion, methyl stearyl ammonium ion. , Distearyl ammonium ion, methyl distearyl ammonium ion, trioctyl ammonium ion, dimethyl stearyl benzyl ammonium ion, methyl distearyl benzyl ammonium ion, distearyl dibenzyl ammonium ion, benzalkonium ion, trimethyl stearyl ammonium ion, dimethyl distearyl Ammonium ion, dimethyl 2-ethyl Xylstearylammonium ion, methyltristearylammonium ion, di-tallow alkyldimethylammonium ion, coconut oil alkyldimethylammonium ion, dimethyldihydroxyethylammonium ion, dimethylbenzyl hydrogenated tallow ammonium ion, dimethyldihydrogenated tallow ammonium ion, methyl tallow alkyl Bis-2-hydroxyethylammonium ion, methylstearylbis-2-hydroxyethylammonium ion, dimethyl hydrogenated tallow benzylammonium ion, dimethyl-2-ethylhexyl hydrogenated tallow ammonium ion, methyldihydrogenated tallow ammonium ion, a compound represented by the following formula (m , N is an integer from 1 to 30.)
[Chemical 2]

[Chemical 3]

, Etc.
These ammonium ions introduced into the layered silicate by ion exchange may be single or plural mixtures.
[0039]
Among these ammonium ions, an organic ammonium ion having a substituent such as an alkyl group having 6 to 30 carbon atoms, a benzyl group, or a hydroxyalkyl group is preferable. Among them, a trimethyl stearyl ammonium ion, a dimethyl distearyl ammonium ion are preferable. Dimethylstearylbenzylammonium ion, methyldistearylbenzylammonium ion, benzalkonium ion, dimethylbenzyl hydrogenated beef tallow ammonium ion, dimethyldihydrogenated beef tallow ammonium ion, methyl beef tallow alkyl bis 2-hydroxyethyl ammonium ion, methyl stearyl bis 2-hydroxyethyl Ammonium ions are particularly preferred.
[0040]
The amount of organic onium ions in the organic layered silicate depends on the cation exchange amount of the layered silicate used and the type of organic onium ion, but is usually in the range of 15 to 80% by weight.
[0041]
The amount of the organically modified layered silicate (B) is in the range of 0.5 to 20 parts by weight, preferably 1.0 to 100 parts by weight of the non-crystalline or low crystalline polyester resin (A). The amount is 15.0 parts by weight, more preferably 2.0 to 13.0 parts by weight. If the amount of the organic layered silicate (B) is less than 0.5 parts by weight, the effect of improving the moldability in calender molding is poor, and the strength and rigidity of the produced film and sheet, as well as gas barrier properties and shrinkage. There is a risk that performance such as performance will be insufficient. Moreover, when the compounding quantity of organic-ized layered silicate (B) exceeds 20 weight part, there exists a possibility that a film and a sheet | seat may become weak.
[0042]
On the other hand, the fatty acid (C) having 18 or more carbon atoms used in the present invention is a component blended to improve the releasability from the calender roll during calendering and the dispersibility of the organically modified layered silicate (B). Examples thereof include stearic acid, behenic acid, tetracosanoic acid, hexacosanoic acid, heptacosanoic acid, montanic acid, triacontanoic acid, and dotriacontanoic acid.
These fatty acids are available in high purity as reagents, but are often expensive and are not generally used as additives for resin compositions. However, some of the fatty acids (C) having 18 or more carbon atoms are provided at low cost as additives for resins, such as stearic acid, behenic acid, and montanic acid. Such fatty acids for resin additives are preferably used.
[0043]
Among these fatty acids, behenic acid or montan, which is a fatty acid having a carbon number of 20 or more and is inexpensively provided as an additive for resins, because it is difficult to deteriorate or evaporate at the temperature at which a thermoplastic polyester resin is molded. Acids are preferred, and montanic acid, which is a fatty acid having 25 or more carbon atoms and is inexpensively provided as an additive for resins, is preferably used in the present invention.
[0044]
The blending amount of the fatty acid (C) having 18 or more carbon atoms blended with 100 parts by weight of the polyester resin (A) is in the range of 0.1 to 10.0 parts by weight, preferably 0.3 to 7.5. Parts by weight, more preferably 0.5 to 5.0 parts by weight. When the blending amount of the fatty acid (C) having 18 or more carbon atoms is less than 0.1 parts by weight, the peelability from the calender roll becomes insufficient and the dispersion of the organically modified layered silicate (B) is not good. It becomes sufficient, and a film or sheet having excellent transparency cannot be obtained. When the blending amount of the fatty acid (C) having 18 or more carbon atoms exceeds 10.0 parts by weight, not only the transparency of the sheet or film is deteriorated but also the slipperiness becomes excessive, and the film or sheet is produced by calendar molding. May not be possible.
[0045]
The resin composition according to the present invention includes a weight part (b ′) of silicate in the organically modified layered silicate (B) to be blended with respect to 100 parts by weight of the non-crystalline or low crystalline polyester resin (A). The ratio (c ′ / b ′) of the weight part (c ′) of the fatty acid (C) having 18 or more carbon atoms to be blended with respect to 100 parts by weight of the polyester resin (A) is 0.1 or more. More preferably, by setting it to 0.15 or more, most preferably 0.2 or more, a higher effect can be obtained.
[0046]
The weight part (b ′) of the silicate in the organically modified layered silicate (B) mentioned here means that the organically modified layered silicate (B) is heated in an electric furnace at 1000 ° C. for 30 minutes, and moisture or organic The weight% (Ash (%)) of the ash content in the organic layered silicate obtained from the weight of the remaining ash after evaporating or burning the organic onium ions contained between the layers of the layered layer silicate, and non-crystalline or low It is a numerical value obtained by the following formula from the weight part (b ″) of the organically modified layered silicate (B) blended with respect to 100 parts by weight of the crystalline polyester resin (A).
b ′ = b ″ × Ash (%) − 100
18 parts by weight of carbon added to 100 parts by weight of the polyester resin (A) and 100 parts by weight of the polyester resin (A). When the ratio (c ′ / b ′) of the above-mentioned fatty acid parts by weight (c ′) is less than 0.1, the organic layered silicate is not sufficiently dispersed in the polyester resin, and the object of the present invention is achieved. Can be difficult.
[0047]
Furthermore, in the fatty acid metal salt (D) or the organic phosphate ester (E) used in the present invention, air is fed to a molten resin pool (usually referred to as a bank) formed between calender rolls in calender molding. It is a component blended in order to prevent it from being caught up and appearing on the surface of the sheet or film as a vertical line.
[0048]
When mix | blending fatty-acid metal salt (D), it does not specifically limit about carbon number of a fatty-acid part. Examples of fatty acid metal salts that can be used include lithium stearate, magnesium stearate, calcium stearate, potassium stearate, aluminum stearate, strontium stearate, barium stearate, cadmium stearate, zinc stearate, lead stearate. , Calcium laurate, barium laurate, cadmium laurate, zinc laurate, lithium myristate, zinc oleate, calcium behenate, zinc behenate, magnesium behenate, lithium behenate, calcium montanate, magnesium montanate, montan Examples thereof include sodium acid, cadmium 2-ethylhexoate, zinc 2-ethylhexoate, and the like. Some of these fatty acid metal salts are commercially available as additives for resins, and these are preferably used in terms of cost.
[0049]
Moreover, the organic phosphate ester (E) used in the present invention refers to a partial saponified product of an organic phosphate ester and an organic phosphate ester, and one or a mixture of two or more of these can be used.
[0050]
The type of the organic phosphate ester (E) is not particularly limited. For example, monostearyl phosphate ester, distearyl phosphate ester, tristearyl phosphate ester, monolauryl phosphate ester, dilauryl phosphate ester, trilauryl phosphate ester , Monononylphenyl polyoxyethylene phosphate, dinonylphenyl polyoxyethylene phosphate, trinonylphenyl polyoxyethylene phosphate, monolauryl polyoxyethylene phosphate, dilauryl polyoxyethylene phosphate, Lauryl polyoxyethylene phosphate, monodecyl polyoxyethylene phosphate, didecyl polyoxyethylene phosphate, tridecyl polyoxyethylene phosphate, monododecyl polyoxy Ethylene phosphate, didodecyl polyoxyethylene phosphate, tridodecyl polyoxyethylene phosphate, monooctylphenyl polyoxyethylene phosphate, dioctylphenyl polyoxyethylene phosphate, trioctylphenyl polyoxyethylene phosphate Ester, monododecylphenyl polyoxyethylene phosphate, didodecylphenyl polyoxyethylene phosphate, tridodecylphenyl polyoxyethylene phosphate, monostearyl dilauryl phosphate, monolauryl distearyl phosphate, monostearyl Dinonylphenyl polyoxyethylene phosphate, monononylphenyl polyoxyethylene distearyl phosphate, monolauryl dinonyl ester Nyl polyoxyethylene phosphate, monononylphenyl polyoxyethylene dilauryl phosphate, monostearyl dilauryl polyoxyethylene phosphate, monolauryl polyoxyethylene distearyl phosphate, monolauryl dilauryl polyoxyethylene phosphorus Examples thereof include acid esters and monolauryl polyoxyethylene dilauryl phosphate, and one or a mixture of two or more of these can be used. Some of these organophosphates are commercially available as additives for resins, and these are preferably used in terms of cost.
[0051]
Further, the type of the partially saponified product of the organic phosphate ester is not particularly limited, and examples thereof include substances obtained by saponifying the above mono and diphosphate esters with the remaining acid group portion. Specifically, calcium saponified products, magnesium saponified products, and zinc saponified products of the above organic phosphate esters, such as calcium saponified products of monostearyl phosphate esters, magnesium saponified products of monostearyl phosphate esters, and monostearyl phosphate esters. Zinc saponified product, calcium saponified product of monolauryl phosphate, magnesium saponified product of monolauryl phosphate, zinc saponified product of monolauryl phosphate, calcium saponified product of monononylphenyl polyoxyethylene phosphate, mono Magnesium saponified nonylphenyl polyoxyethylene phosphate, zinc saponified monononylphenyl polyoxyethylene phosphate, calcium saponified monolauryl polyoxyethylene phosphate, Magnesium saponified lauryl polyoxyethylene phosphoric acid ester, are mentioned and zinc saponified monolauryl polyoxyethylene phosphoric acid ester, one or a mixture of two or more thereof can be used. Some of these organic phosphate esters are commercially available as additives for resins, and these are preferably used in terms of cost.
[0052]
Here, the compounding amount of the fatty acid metal salt (D) or the organic phosphate ester (E) used in the polyester resin composition of the present invention is 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyester resin (A). The range is 5 parts by weight, preferably 0.02 to 4 parts by weight, and more preferably 0.03 to 3 parts by weight. If the blending amount of the fatty acid metal salt (D) or the organophosphate ester (E) is less than 0.01 parts by weight, the desired effect cannot be obtained, and if the blending amount exceeds 5 parts by weight, The transparency of the film is reduced.
[0053]
In addition, it is effective to use a fatty acid ester or an oxidized polyethylene wax in combination with the polyester resin composition according to the present invention in order to supplement the improvement in peelability from a metal roll (calendar roll). is there. However, since fatty acid ester or oxidized polyethylene wax has a large effect of improving the peelability, it tends to cause a decrease in transparency of the molded sheet or film and occurrence of plate-out. Therefore, it is important to keep the amount small when blending. Specifically, it is preferably 0.5 parts by weight or less with respect to 100 parts by weight of the polyester resin (A).
[0054]
About the fatty acid ester used here, the carbon number of the fatty acid part is not particularly limited. However, in consideration of the volatility of the obtained ester, a synthetic wax or natural wax comprising an ester of an aliphatic saturated carboxylic acid having 12 to 28 carbon atoms and an aliphatic saturated alcohol having 2 to 30 carbon atoms is preferable. . Examples of the aliphatic saturated carboxylic acid having 12 to 28 carbon atoms constituting the synthetic wax include lauric acid, myristylic acid, stearic acid, behenic acid, lignoceric acid, serotic acid, and montanic acid. 2-30 aliphatic saturated alcohols include, for example, monohydric alcohols such as ethyl alcohol, octyl alcohol, lauryl alcohol, stearyl alcohol, behenyl alcohol, pentacosyl alcohol, seryl alcohol, octacosyl alcohol, melyl alcohol, and the like Polyhydric alcohols such as ethylene glycol-1,2-butanediol-1,3-butanediol-1,4-butanediol, dihydric alcohols such as 2,3-butanediol, and trihydric alcohols such as glycerin, etc. Can be mentioned.
[0055]
Further, as the synthetic wax, for example, stearyl laurate, stearyl myristate, stearyl stearate, octyl behenate, lauryl behenate, myristyl behenate, stearyl behenate, behenyl behenate, pentacosyl behenate, seryl lignocerate, Examples include octacosyl lignocerate, merisyl lignocerate, stearyl cellotate, behenyl serotic acid, ceryl serotic acid, melyl cellocate, ethyl montanate, seryl montanate, and montanic acid glycol ester. Examples of natural waxes include montan wax, carnauba wax, bead wax, candelilla wax, nuka wax, ibotarou, and the like. Among these, based on volatility and releasability to metal rolls, preferred are montanic acid glycol ester, montanic acid glyceride, montan wax, etc., and these substances are commercially available as additives for resins, and in terms of cost. These are preferably used.
[0056]
In addition, the type of oxidized polyethylene wax is not particularly limited, and any of low density and high density may be used. However, in consideration of peelability from the metal roll, a partially oxidized polyethylene wax having an acid value of 1 to 40 mgKOH / g and a molecular weight of 10,000 or less in terms of a weight average molecular weight is preferable. Some of these substances are commercially available as additives for resins, and these are preferably used in terms of cost.
[0057]
The film or sheet according to the present invention is formed by a calender molding method using the above-described calender molding thermoplastic polyester resin composition. Further, when the film or sheet is molded by the calender molding method using the above-mentioned calender molding thermoplastic polyester resin composition, the thickness is 0.2 mm or less and 10 ° C. higher than the glass transition temperature of the molded body. The shrinkage ratio of the molded body when heat-treated at a temperature for 60 minutes is less than 10%, and the shrinkage ratio of the molded body when heat-treated for 60 minutes at a temperature 20 ° C. higher than the glass transition temperature of the molded body is less than 15%, The shrinkage rate of the molded body when heat-treated for 60 minutes at a temperature 40 ° C. higher than the glass transition temperature of the molded body is less than 20%.
[0058]
The glass transition temperature mentioned here is a complex elastic modulus E "that appears when measured while raising the temperature from at least 50 ° C. lower than the glass transition temperature of the film or sheet using a tensile dynamic viscoelasticity measuring device. The measurement is carried out in the range of a temperature rising rate of 2 to 10 ° C./min and a frequency of 5 to 20 Hz.
[0059]
As a method for obtaining a film or sheet having the above-described characteristics using the thermoplastic polyester resin composition for calendering according to the present invention, the temperature of the calender roll is set to 80 ° C. from the glass transition temperature of the composition of the present invention. In a calender molding apparatus set to a temperature of 150 ° C. or lower, preferably 90 ° C. or higher and lower than 140 ° C., more preferably 100 ° C. or higher and lower than 130 ° C., 130% or higher and lower than 500%, preferably 140% or higher. Can be produced by drawing with a cooling roll at a draw ratio of less than 400%, more preferably 150% or more and less than 350%.
[0060]
The drawing ratio here refers to the ratio of the surface speed of the cooling roll to the surface speed of the calendar roll on the side of supplying the molten resin when the molten resin rolled by the calendering machine is taken up by the cooling roll.
[0061]
When the temperature of the calender roll is less than 80 ° C. from the glass transition temperature of the thermoplastic polyester resin composition according to the present invention, the rotation of the molten resin pool (usually referred to as a bank) formed between the calender rolls is not possible. Since it becomes a rule, it becomes difficult to obtain a transparent film or sheet. In addition, when the temperature of the calender roll is 150 ° C. or higher than the glass transition temperature of the thermoplastic polyester resin composition according to the present invention, the molten resin sticks to the calender roll, and a film or sheet is produced by the calender molding method. There is a risk that it will not be possible.
[0062]
In addition, when a film or sheet is produced with a draw ratio of less than 130% on the take-up roll, a film or sheet having a thickness of 0.2 mm or less may not be stably produced by the calendering method. This is because when it is intended to produce a film or sheet having a thickness of less than 130% and a thickness of 0.2 mm or less, it is necessary to produce the film with a narrow gap between the calender rolls. This is because even if the temperature is set low, the melt of the resin composition generates heat and becomes high temperature, and may adhere to the calendar roll. In addition, an increase in driving power of the calendering device by narrowing the gap between the calender rolls and an industrial demerit that the production speed is inferior due to the small stretch ratio.
On the other hand, when a film or sheet is produced with a draw ratio of 500% or more on the take-up roll, there arises a problem that the shrinkage ratio is increased even when the thermoplastic polyester resin composition according to the present invention is used.
[0063]
The thermoplastic polyester resin composition according to the present invention includes a pellet or powdery polyester resin (A), an organically modified layered silicate (B), a fatty acid (C) having 18 or more carbon atoms, and a fatty acid. The metal salt (D) or the organic phosphate ester (E) can be prepared by simply mixing a fatty acid ester or an oxidized polyethylene wax, if necessary, or by melt-kneading in advance with a kneader. it can.
As a kneading machine used here, a known apparatus can be used, but a roll-single or twin-screw extruder, a kneader, a kneader, a planetary mixer, a banbury mixer, etc. that are easy to handle and can be uniformly dispersed. Is preferably used.
[0064]
Moreover, the polyester-type resin composition in this invention is the polyester-type resin (A). Organized layered silicate (B), a fatty acid (C), a fatty-acid metal salt (D), or organophosphate (E), Furthermore, a material (usually referred to as a masterbatch) containing a high concentration of fatty acid ester or oxidized polyethylene wax is prepared in advance, and prepared by melt-kneading these with a polyester resin (A). You can also Regarding the production of the master batch, the kneader exemplified above is preferably used.
[0065]
On the other hand, the polyester resin composition according to the present invention includes conventionally known antioxidants such as hindered phenols, thioethers, amines, and phosphates, and benzophenone as long as the processability in calender molding is not impaired. -Based, benzoate-based, benzotriazole-based, cyanoacrylate-based, hindered amine-based and other known UV absorbers, or anionic, cationic, and nonionic low-molecular or high-molecular antistatic agents, epoxy compounds and isocyanates Thickeners such as compounds, colorants such as dyes and pigments, UV blockers such as titanium oxide and carbon black, reinforcing materials such as glass fibers and carbon fibers, silica, clay, calcium carbonate, barium sulfate, glass beads, talc Such as filler, flame retardant, plasticizer, foaming agent, Bacteriostat, fungicide, fluorescent agents, surfactants, crosslinking agents, and the like may be appropriately blended.
[0066]
Furthermore, the polyester-based resin composition in the present invention has a polyolefin-based, polyvinyl chloride-based, polystyrene-based, polyether-based, polyester-based, polyamide-based, polyimide-based, etc. within a range that does not impair the moldability in calender molding. Other thermoplastic resins may be blended.
[0067]
The polyester-based resin composition in the present invention is a resin composition suitable for producing a film or sheet by a calender molding machine after melt-kneading using a mixer or a single-screw or twin-screw extruder. When the film or sheet is produced, the peelability of the molten resin from the calendar roll and the take-up property of the cooling roll are good, and the transparency is also good. Further, no plate-out to the calendar roll occurs, and no vertical streak due to air entrainment occurs in the obtained film or sheet. Therefore, by calendering the polyester resin composition, a film or sheet having an excellent appearance can be formed with high productivity.
[0068]
Films and sheets obtained by calendering using the polyester-based resin composition according to the present invention are excellent in transparency, rigidity, gas barrier properties, wettability and small shrinkage. Transparent or colored film or sheet, film or sheet for cards, film or sheet for various packaging containers, film or sheet for printing or adhesive processing, surface treatment by metal deposition or sputtering, etc. Films or sheets used for prevention of scattering and heat insulation of glass affixed to a relatively high temperature part such as a window or film, a film or sheet used for advertising, etc. .
[0069]
【Example】
Next, the present invention will be described in more detail with specific examples, but the present invention is not limited to these examples.
[0070]
First, materials used in Examples or Comparative Examples will be described below.
<Polyester resin (A)>
A-1: The dicarboxylic acid component is 100 mol% of terephthalic acid and does not contain other dicarboxylic acids, and the glycol components are 60 to 75 mol% of ethylene glycol and 40 to 25 mol% of 1,4-cyclohexanedimethanol. A pellet-shaped polyester resin having a number average molecular weight of 25000 consisting of repeating units of the dicarboxylic acid component and the glycol component (trade name; Tsunami Copolymerester GS2, Eastman Chemical Products, Inc.) . F-1: Polyethylene terephthalate (trade name: TR8580HP, manufactured by Teijin Limited)
In addition, it was as Table 1 as a result of measuring polyester-type resin A-1 and F-1 with the temperature increase rate of 20 degree-C / min using DSC made from Perkin Elmer.
[0071]
[Table 1]

[0072]
<Organized layered silicate (B)>
B-1: Organized layered silicate prepared according to Reference Example 1
B-2: Organic layered silicate prepared according to Reference Example 2
B-3: Organized layered silicate prepared according to Reference Example 3
B-4: Organized layered silicate in which 39% by weight of dimethylbenzyl hydrogenated tallow ammonium ion was inserted by ion exchange between layers of montmorillonite having a cation exchange amount of 125 meq / 100 g (trade name: Cloisite 10A, Southern Clay Products, Inc.) Made).
B-5: Organized layered silicate in which 43% by weight of dimethyl dihydrogenated tallow ammonium ion was inserted by ion exchange between layers of montmorillonite having a cation exchange amount of 125 meq / 100 g (trade name: cloite 15A, manufactured by Southern Clay Products) .
B-6: An organic layered silicate in which 30% by weight of methyldi-tallow alkylbis2-hydroxyethylammonium ion was inserted by ion exchange between layers of montmorillonite having a cation exchange amount of 90 meq / 100 g (trade name: cloiteite 30B, Southern Clay Products) Company-made).
<Layered silicate>
G-1: High purity montmorillonite (trade name; Bengel A, manufactured by Hojun Co.)
[0073]
[Reference Example 1]
3 kg of natural Na montmorillonite (trade name; Kunipia F, manufactured by Kunimine Kogyo; cation exchange amount 120 meq / 100 g) is stirred and dispersed in 100 L of warm water, and 1.0 times the amount of cation exchange dimethylstearylbenzylammonium After adding salt and stirring for 1 hour, the resulting precipitate was filtered and washed with warm water. Further, after washing and filtration were repeated three times, the obtained solid was dried to obtain an organically modified layered silicate B-1.
[0074]
[Reference Example 2]
3 kg of natural Na montmorillonite (trade name; Kunipia F, manufactured by Kunimine Kogyo Co., Ltd .; cation exchange amount 120 meq / 100 g) is stirred and dispersed in 100 L of warm water, and 1.0 times the amount of cation exchange benzalkonium salt After stirring for 1 hour, the resulting precipitate was filtered and washed with warm water. Further, washing and filtration were repeated three times, and then the obtained solid was dried to obtain an organically modified layered silicate B-2.
[0075]
[Reference Example 3]
3 kg of natural Na-type montmorillonite (trade name; Bengel A, manufactured by Hojung; cation exchange amount 94 meq / 100 g) is stirred and dispersed in 100 L of warm water, and 1.0 times the amount of cation exchange dimethyl distearyl ammonium After adding salt and stirring for 1 hour, the resulting precipitate was filtered and washed with warm water. Further, washing and filtration were repeated three times, and then the obtained solid was dried to obtain an organically modified layered silicate B-3.
It should be noted that 10 g of each of the layered silicates B-1 to B-5 and the layered silicate G-1 were weighed and ash content determined from the ash weight remaining after heating in an electric furnace at 1000 ° C. for 30 minutes. The weight% (Ash (%)) was as shown in Table 2.
[0076]
[Table 2]

[0077]
<C18 or more fatty acid (C)>
C-1: Montanic acid (trade name; Licowax S, manufactured by Clariant Japan)
<Fatty acid metal salt (D)>
D-1: Calcium montanate (trade name; Licomont CaV102, manufactured by Clariant Japan)
<Organic phosphate esters (E)>
E-1: Mixture of monostearyl phosphate and distearyl phosphate in a weight ratio of 6: 4 (trade name; AX-518, manufactured by Daikyo Kasei Kogyo Co., Ltd.)
[0078]
<Other additives>
Fatty acid ester: ester of montanic acid and 1,4-butanediol (trade name; Licowax E, manufactured by Clariant Japan)
Oxidized polyethylene wax: having an acid value of 15 to 19 mg KOH / g (trade name; Licowax PED191, manufactured by Clariant Japan)
Antioxidant: Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane (trade name; ADK STAB AO-60, manufactured by Asahi Denka Co., Ltd.)
[0079]
Next, numerical values described in Tables 3 and 4 will be described.
About "the amount of silicate per 100 weight part of resin" and "compounding agent C-1 / silicate", it calculated | required as follows.
“Silicate content per 100 parts by weight of resin (b ′)”
Since the organic layered silicate (B) and the layered silicate contain components other than the silicate such as moisture and organic onium ions inserted by ion exchange, 100 parts by weight of the polyester resin (A) The weight ratio (b ″) of the organically modified layered silicate (B) or layered silicate and the weight percent (Ash () of the ash content of the organized layered silicate (B) or layered silicate shown in Table 2 %)) Using the following formula, “amount of silicate per 100 parts by weight of polyester resin (A) (b ′)” was determined as parts by weight.
b ′ = b ″ × Ash (%) / 100
"Compounding agent C-1 / silicate"
“Compounding agent C-1 / silicate” is obtained by using the formula shown above, with respect to “100 parts by weight of resin” based on “amount of silicate per 100 parts by weight of resin (b ′)” (parts by weight). It is the amount (c ′) ”(part by weight) of the compounded compounding agent C-1, and was determined as follows.
Formulation C-1 / silicate (parts by weight / parts by weight) = c ′ / b ′
Numerical values and evaluation methods other than those shown here will be described in Examples or Comparative Examples.
[0080]
<Examples 1-8>
The compounding agents were blended in the parts by weight shown in Table 3 and melt-kneaded at 180 ° C. for 10 minutes using a Toyo Seiki Seisakusho Lab Plast Mill mixer (R-60) to obtain a composition. The complex elastic modulus of a glass transition temperature of a sheet obtained by press-molding this composition at 180 ° C. to a thickness of 1 mm was measured at a heating rate of 2 ° C./min and a frequency of 10 Hz using a rheograph manufactured by Toyo Seiki Seisakusho. As a result of obtaining the peak temperature of E ″, all the sheets were 80 ° C.
Next, the compounding agent was blended in the parts by weight shown in Table 3, mixed uniformly with a Henschel mixer, then kneaded with a Banbury mixer until the resin temperature was in the range of 160 to 175 ° C., and the polyester resin composition Was prepared. This was rolled using a reverse L-shaped four-roll calender molding machine adjusted to 190 ° C., which is 110 ° C. higher than the glass transition temperature of the composition, and taken up at a draw ratio of −150% or 250 Through a cooling process, a sheet having a width of 1000 mm and a thickness of 100 μm was produced.
As a result of determining the glass transition temperature of the sheet obtained by calendering as the peak temperature of the complex elastic modulus E ″ measured at a heating rate of 2 ° C./min and a frequency of 10 Hz using a rheograph manufactured by Toyo Seiki Seisakusho, All sheets were at 80 ° C., the same as the composition.
[0081]
The evaluation shown in Table 3 was performed by the following method.
[Evaluation of dispersibility of organic layered silicate and evaluation of peelability from metal]
Before molding with a calendering machine, when melt-kneading at 180 ° C for 10 minutes using a lab plast mill mixer (R-60) manufactured by Toyo Seiki Seisakusho, the melt immediately after kneading is observed and organicized in the molten state The dispersion state of the layered silicate (B) was determined. In addition, when a melt-kneaded compound was compression-molded at 180 ° C. to produce a molded body having a thickness of 1 mm, the dispersion state of the organically modified layered silicate (B) in the molded body was determined by visual evaluation of the molded body. . The dispersion state of the organic layered silicate (B) is “◯” when the particles of the organic layered silicate (B) are not observed in the melt or molded body, and “×” when the particles are observed. It was.
Furthermore, after pre-kneading for 10 minutes at 180 ° C. using a lab plast mill mixer (R-60) manufactured by Toyo Seiki Seisakusho, the peelability from the metal was determined by evaluating the peelability of the melt from the mixer. The case where the melt after kneading could be easily peeled off from the mixer was indicated as “◯”, and the case where the melt adhered and could not be peeled off from the mixer was indicated as “x”.
[0082]
[Evaluation of roll processability, sheet surface condition, and sheet flexibility]
Furthermore, before molding with a calendar molding machine, a 10-inch two-roll roll in which a compound obtained by pre-kneading for 10 minutes at 180 ° C. using a lab plast mill mixer (R-60) manufactured by Toyo Seiki Seisakusho was heated to 190 ° C. Then, the sheet thickness was adjusted to 150 μm and kneaded, and the adhesiveness to the roll and the state of the bank were evaluated.
The adhesiveness to the roll was “◯” when the melt was not sticking to the roll surface and could be processed, and “X” when sticking to the roll surface. The state evaluation of the bank is that the bank is spindle shaped, air is not caught in the bank, the bank surface is smooth, the rotation is smooth, `` ○ '', the bank does not become spindle shaped, air is rolled into the bank, The case where the surface was fuzzy or the rotation was not smooth was marked with “x”.
The sheet take-out property was “◯” when the sheet was taken out during roll kneading and the sheet was pulled, and “X” when the sheet was stretched and could not be pulled.
The surface condition of the sheet is sampled by laminating the sheet on the release paper, the surface condition of the collected sheet is visually observed, and there is no generation of vertical streaks due to air entrainment and the surface is smooth and transparent. Was marked with “◯”, and when there were vertical streaks due to air entrainment or when it was opaque, it was marked “x”.
The flexibility of the sheet was determined by cutting out a 10 cm square sheet from a sample sampled by laminating on a release paper, bending the sheet at an angle of 90 degrees, and when the sheet was not broken, it was “◯”, and the sheet was broken. In this case, “x” was used.
[0083]
[Measurement of melt tension]
Prior to molding with a calendar molding machine, melt tension was measured in order to evaluate the take-up performance with a cooling roll during calendar molding. For the measurement, a compound obtained by melting and kneading for 10 minutes at 180 ° C. using a lab plast mill mixer (R-60) manufactured by Toyo Seiki Seisakusho was measured using a Capillograph manufactured by Toyo Seiki Seisakusho equipped with a capillary of L / D = 20/1 mm. It was carried out under conditions of a temperature of 190 ° C., a crosshead speed of 5 mm / min, and a winding speed of 20 m / min.
[0084]
[Measurement of melt viscosity]
Prior to molding with a calendar molding machine, the melt viscosity was measured in order to evaluate the magnitude of the electric power required to drive the calendar device during calendar molding. For the measurement, a compound obtained by melting and kneading for 10 minutes at 180 ° C. using a lab plast mill mixer (R-60) manufactured by Toyo Seiki Seisakusho was measured using a Capillograph manufactured by Toyo Seiki Seisakusho equipped with a capillary of L / D = 20/1 mm. And carried out under conditions of a temperature of 190 ° C. and a shear rate of 250 / sec.
[0085]
[Measurement of shrinkage]
A 15 cm square sheet was cut out from the sheet obtained by calendering, and this sheet was heat treated in an oven set at a predetermined temperature (described in Tables 3 and 4) for 60 minutes and then taken out. The shrinkage ratio in the stretching direction of the sheet was determined from the change in length.
[0086]
[Tensile test]
A strip-shaped test piece having a length of 200 mm and a width of 19 mm was punched out from the sheet obtained by calendering so that the stretching direction was a long side, and a tensile test was performed according to JIS K-7127.
[0087]
[Measurement of oxygen permeability coefficient]
Using a sheet obtained by calendering, measurement was performed with a differential pressure type gas permeation tester manufactured by Toyo Seiki Seisakusho.
[0088]
[Measurement of wetting tension]
Using the sheet obtained by calendering, the wetting tension of the sheet surface was measured with a wetting reagent.
The evaluation results are summarized in Table 3.
[0089]
<Comparative Example 1>
A composition was obtained by melt-kneading at 180 ° C. for 10 minutes using a lab plast mill mixer (R-60) manufactured by Toyo Seiki Seisakusho. Complex elasticity measured at a heating rate of 2 ° C./min and a frequency of 10 Hz using a rheograph manufactured by Toyo Seiki Seisakusho, the glass transition temperature of a sheet obtained by press molding this composition to a thickness of 1 mm at 180 ° C. As a result of obtaining the peak temperature of the rate E ″, it was 80 ° C.
Next, the compounding agent was blended in the parts by weight shown in Table 4, mixed uniformly with a Henschel mixer, and then kneaded with a Banbury mixer until the resin temperature was in the range of 160 to 175 ° C. to obtain a polyester resin composition. Prepared. This was rolled using an inverted L-shaped four-roll calender molding machine adjusted to 190 ° C., which is 110 ° C. higher than the glass transition temperature of the composition, and taken up at draw ratios of 150% and 250%. However, since the sheet was stretched and could not be taken up by the cooling roll, it was taken up at a draw ratio of 350%, and a sheet having a width of 1000 mm and a thickness of 100 μm was produced through a cooling step. The power required for driving the molding machine when calendering this composition was 50% compared to Examples 1, 2, and 5-7, 20% compared to Example 3, and compared to Example 4. 70%, 30% higher than Example 8.
The glass transition temperature of the obtained sheet was determined as the peak temperature of the complex elastic modulus E ″ measured at a heating rate of 2 ° C./min and a frequency of 10 Hz using a rheograph manufactured by Toyo Seiki Seisakusho. It was the same 80 degreeC.
Table 4 shows the evaluation results performed before molding with the calendar molding machine and the evaluation results of the sheets manufactured with the calendar molding machine.
The evaluations shown in Table 4 were evaluated by the same methods and standards as in the examples.
From this comparative example, it can be seen that when the organic layered silicate (B) is not blended, the melt tension is lower than in the examples, and the sheet take-up property is inferior in the evaluation of roll processability. Even when the calendar was formed, the sheet could not be taken up unless the draw ratio was increased, and the sheet take-up property was inferior to that of the example.
In addition, the melt viscosity was higher than that of the example, and the electric power required to drive the molding machine when performing calendar molding was also higher than that of the example. Furthermore, it can be seen that the sheet obtained by the calendering machine is inferior in shrinkage, tensile properties, oxygen barrier properties, and wettability compared to the sheets shown in the examples of Table 3.
[0090]
<Comparative example 2>
Compositions containing the compounding agents in parts by weight shown in Table 4 were evaluated for dispersibility of the organically modified layered silicate (B), evaluation of peelability from metal, and evaluation of melt tension in the same manner as in the examples. Evaluation of melt viscosity, roll processability, sheet surface condition, and sheet flexibility were performed.
In this evaluation, in the composition of Comparative Example 2 that does not contain a fatty acid metal salt or phosphate ester, a large amount of air is entrained in the bank, which is transferred to the sheet as vertical stripes, and the surface state of the sheet is obtained. Since it was inferior and the thickness became nonuniform, other evaluation including calendar molding was not implemented.
The evaluation results are shown in Table 4. The evaluation results shown in Table 4 were evaluated by the same methods and standards as in the examples.
From this comparative example, it can be seen that when a fatty acid metal salt or phosphate ester is not included, air is caught in the bank, and a sheet having excellent surface condition and thickness uniformity cannot be obtained.
[0091]
<Comparative Example 3>
Compositions containing the compounding agents in parts by weight shown in Table 4 were evaluated for dispersibility of the organically modified layered silicate (B), evaluation of peelability from metal, and roll processability in the same manner as in Examples. Of the sheet, the surface condition of the sheet, and the flexibility of the sheet.
In this evaluation, the composition of Comparative Example 3 in which the organic layered silicate (B) is blended in an amount exceeding 20 parts by weight with respect to 100 parts by weight of the polyester resin (A) is the flexibility of the sheet. Since the sheet was cracked in the evaluation, no other evaluation including calendar molding was performed.
The evaluation results are shown in Table 4. The evaluation results shown in Table 4 were evaluated by the same methods and standards as in the examples.
From this comparative example, it can be seen that when the organic layered silicate (B) is blended in an amount exceeding 20 parts by weight with respect to 100 parts by weight of the polyester resin (A), the sheet becomes brittle.
[0092]
<Comparative example 4>
Compositions containing the compounding agents in parts by weight shown in Table 4 were evaluated for dispersibility of the organically modified layered silicate (B), evaluation of peelability from metal, and roll processability in the same manner as in Examples. Each of the evaluations was performed.
In this evaluation, the composition of Comparative Example 3 in which the fatty acid (C) having 18 or more carbon atoms was blended in an amount exceeding 10 parts by weight with respect to 100 parts by weight of the polyester resin (A) was clouded when cooled. Therefore, the dispersion state of the organically modified layered silicate in the molded body was not evaluated. In the evaluation of roll processability, the molten resin slipped on the roll surface and could not be formed into a sheet, and the bank did not have a spindle shape. Therefore, the evaluation of the sheet surface state and sheet flexibility was not performed. Also, other evaluations including calendar molding were not performed.
The evaluation results are shown in Table 4. The evaluation results shown in Table 4 were evaluated by the same methods and standards as in the examples.
From this comparative example, when the fatty acid (C) having 18 or more carbon atoms is blended in an amount exceeding 10 parts by weight with respect to 100 parts by weight of the polyester resin (A), only a sheet having poor transparency is obtained. It can be seen that not only is it difficult to roll, but it is too slippery.
[0093]
<Comparative Examples 5 and 6>
The composition containing the compounding agent in parts by weight shown in Table 4 was evaluated for dispersibility of the organically modified layered silicate (B) and peelability from the metal in the same manner as in the examples.
As a result, these compositions cannot peel the melt from the metal and become cloudy when cooled, and therefore include evaluation of the dispersion state of the organically modified layered silicate in the molded body and calendar molding. No other evaluation was performed.
The evaluation results are shown in Table 4. The evaluation results shown in Table 4 were evaluated by the same methods and standards as in the examples.
From these evaluation results, when the fatty acid metal salt (D) or the organic phosphate ester (E) is blended in an amount exceeding 5 parts by weight with respect to 100 parts by weight of the polyester resin (A), It turns out that not only the sheet | seat inferior to transparency is obtained but a melt cannot be peeled from a metal.
[0094]
<Comparative Examples 7 to 10>
The composition containing the compounding agent in parts by weight shown in Table 4 was evaluated for the dispersibility of the organically modified layered silicate and the peelability from the metal in the same manner as in the examples.
As a result, these compositions had many organic layered silicate grains in the melt and molded body, and the sheet obtained by press molding became opaque. Not done.
The evaluation results are shown in Table 4. The evaluation results shown in Table 4 were evaluated by the same methods and standards as in the examples.
From these evaluation results, when not containing a fatty acid (C) having 18 or more carbon atoms as in Comparative Examples 7 and 8, and blending with respect to 100 parts by weight of the polyester-based resin (A) as in Comparative Example 9. Ratio (c ′) of weight part (c ′) of fatty acid having 18 or more carbon atoms to be blended with respect to 100 parts by weight of polyester resin (A) resin and weight part (b ′) of silicate in organic layered silicate When / b ′) is less than 0.1, it is understood that the dispersion of the organically modified layered silicate (B) becomes insufficient, and only a sheet having poor transparency can be obtained. Moreover, also when using the layered silicate which is not made organic like the comparative example 10, dispersion | distribution of a layered silicate is inadequate and only a sheet | seat inferior to transparency is obtained.
[0095]
<Comparative Examples 11 and 12>
The compounding agent was blended in the parts by weight shown in Table 4, and melt-kneaded for 10 minutes at 180 ° C. using a lab plast mill mixer (R-60) manufactured by Toyo Seiki Seisakusho, but the polyester resin (F-1) was melted. There wasn't. Therefore, after kneading for 10 minutes at a kneading temperature of 270 ° C., the melt immediately after kneading was observed, and the dispersion state of the organically modified layered silicate in the molten state was evaluated. Many grains of salt were seen. Moreover, the melt of the composition could not be peeled from the metal.
In addition, since the melt of the composition containing polyester-type resin F-1 became cloudy when it cooled, evaluation of the dispersion state of the organically modified layered silicate in a molded object was not implemented. Also, other evaluations including calendar molding were not performed.
The evaluation results are shown in Table 4. The evaluation results shown in Table 4 are based on the same criteria as in the examples.
From these comparative examples, when a crystalline polyester resin having a crystal melting peak exceeding 200 ° C. and a crystal melting heat amount exceeding 50 J / g when measured by DSC is used, the dispersion of the organically modified layered silicate It becomes clear that the melt cannot be peeled off from the metal.
[0096]
[Table 3]

[0097]
[Table 4]

[0098]
【The invention's effect】
As is clear from the evaluation results shown in Table 3 and Table 4, the polyester resin composition for calender molding according to the present invention has a peelability from metal, a bank rotation property, a sheet take-up property, and a calendar molding time. The power required for driving the device can be reduced, so that it is excellent in calender molding and a transparent molded body is obtained. Also, the sheet and film obtained by calender molding have a good surface condition and shrinkage. It is small and has excellent mechanical properties, gas barrier properties, and wettability.

Claims (7)

Non-crystalline or low-crystalline polyester resin in which no crystal melting peak is observed when measured by DSC (Differential Scanning Calorimeter) or the crystal melting peak is 200 ° C. or less and the heat of crystal melting is 50 J / g or less (A) 0.5 to 20 parts by weight of organic layered silicate (B), 0.1 to 10 parts by weight of fatty acid (C) having 18 or more carbon atoms, and metal salt of fatty acid with respect to 100 parts by weight (D) A polyester-based resin composition for calendering, characterized by comprising 0.01 to 5 parts by weight. Fatty acid having an organic layered silicate (B) of 0.5 to 20 parts by weight and a carbon number of 18 or more with respect to 100 parts by weight of the noncrystalline or low crystalline polyester resin (A) according to claim 1 (C) A polyester resin composition for calendar molding, comprising 0.1 to 10 parts by weight and 0.01 to 5 parts by weight of an organophosphate (E). A dicarboxylic acid component in which the polyester-based resin (A) is at least 80 mol% of one or a mixture of two or more selected from terephthalic acid, naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and isophthalic acid; It is a polyester-based resin comprising a repeating unit of a glycol component in which one or a mixture of two or more selected from ethylene glycol, neopentyl glycol, diethylene glycol, and 1,4-cyclohexanedimethanol is at least 80 mol% or more. The polyester-based resin composition for calendering according to claim 1 or 2. The polyester resin composition for calender molding according to any one of claims 1 to 3, wherein the organic layered silicate (B) has an organic onium ion inserted between layers. To 100 parts by weight of the polyester resin (A) and 100 parts by weight of the polyester resin (A). 5. The ratio (c ′ / b ′) of parts by weight (c ′) of fatty acids having 18 or more carbon atoms to be blended is 0.1 or more, 5. A polyester resin composition for calendar molding. The film or sheet | seat shape | molded by the calendering method using the thermoplastic polyester-type resin composition for calendering of any one of Claims 1-5. A film or sheet having a thickness of 0.2 mm or less molded by the calender molding method using the thermoplastic polyester resin composition for calender molding according to any one of claims 1 to 5, The shrinkage ratio of the molded product when heat-treated for 60 minutes at a temperature 10 ° C. higher than the glass transition temperature is less than 10%. A film or sheet having a rate of less than 15% and a shrinkage of the molded product of less than 20% when heat-treated for 60 minutes at a temperature 40 ° C. higher than the glass transition temperature of the molded product.