JP2019218542A - 熱成形可能な透明二軸延伸ポリエステルフィルム、その製造方法ならびにその使用 - Google Patents
熱成形可能な透明二軸延伸ポリエステルフィルム、その製造方法ならびにその使用 Download PDFInfo
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- JP2019218542A JP2019218542A JP2019112432A JP2019112432A JP2019218542A JP 2019218542 A JP2019218542 A JP 2019218542A JP 2019112432 A JP2019112432 A JP 2019112432A JP 2019112432 A JP2019112432 A JP 2019112432A JP 2019218542 A JP2019218542 A JP 2019218542A
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Images
Classifications
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
Description
熱成形用途に使用されるフィルムは公知である。
特許文献1は、メタルラミネート用、食品包装材用、例えば包装材から予め食品を取り出さないでオーブン内で調理するため(パッケージ内で調理)のアンチモンを含まない、熱成形可能で温度安定性の二軸延伸ポリエステルフィルムが記載されている。特許文献1のフィルムでこの目的に好適なのは、アンチモンフリーポリエステル及びラジカル捕捉剤から製造されるポリエステルフィルムを有するからである。二軸延伸ポリエステルフィルムは、1つ以上の層から成り、この層は95モル%未満のホモポリマーと300ppmのラジカル捕捉剤とをこの層に含有し、フィルムは、蓋、フィルムパウチ、フィルムホース又は金属ラミネートフィルムの製造に使用される。
b)フィルム中に存在させる粒子の濃度は0〜0.1重量%(1000ppm)である。フィルム中の粒子濃度は、好ましくは1.0×10−5〜0.075重量%、更に好ましくは1.1×10−5〜0.05重量%である。
原料およびフィルムの特性付けのために、以下の測定方法を用いた。
弾性率は、100mm×15mmのフィルム片で、DIN EN ISO 572−1及び−3(タイプ2の試料)に従って決定された。面弾性率は、以下の式より計算される。
σ5値は、100mm×15mmのフィルム片で、DIN EN ISO 572−1及び−3(タイプ2の試料)に従って決定された。
フィルムの密度はASTM−D 1505−68,Method Cに従って決定した。
ポリエステルフィルムのこの測定は、Hazegard XL−211 Hazemeter(BYK−Gardner GmbH社製(ドイツ))を使用して行われる。ヘーズはASTM−D 1003−61,Method Aによって決定された。透明度は、装置の「clarity port」を使用し、ASTM−D1003に従って測定される。測定はフィルムの製造後に直接行われた。
グロスはDIN 67530に従って決定する。反射率を測定し、これをフィルム表面の光学的特性値とする。ASTM D523−78規格およびISO 2813規格を基にした方法を使用し、入射角を20°にセットする。光線はセットした入射角度から平面の試料表面を照射し、表面から反射および/または散乱する。光電子検出器に当たる光線が比例電気変数が映し出される。測定値は無次元であり、入射角とともに報告されるべきである。
希薄溶液中の標準粘度(SV)は、ジクロロ酢酸(DCA)を溶媒とし、ウベロ−デ型粘度計を用い、25±0.05℃で、DIN 53728 Part 3に記載の方法に従って測定した。ポリマ−濃度は、ポリマ−1g/100ml純溶媒である。溶解には60℃で1時間を必要とする。この後、サンプルがなお完全に溶解していない場合は、80℃で40分間を2回繰り返し、溶液を4100分−1の回転速度の遠心分離で1時間処理する。
平均ポリマー粒径d50は、Malvern Mastersizer 2000の測定器により決定した。この測定に関し、使用する粒子を水中に分散させ、測定器で分析されるセル中に入れ、粒径はレーザー回折の手段により測定される。一般論として、検出器は回折されたレーザー光の強度曲線を記録し、数学的な相間関数が、回折されたレーザー光の角度依存光強度から粒径分布を決定するのに使用される。粒径分布は、メジアン値d50(=中央値の位置を示す)と、SPAN98として知られる散乱度(=粒径の散乱を示す)との2つのパラメータによって特性付けされる。測定は自動的に行われ、d50値の数学的計算も含まれる。
耐穿刺性(突刺し試験)は、EN 14477(欧州規格)に従い測定される。包装材の項目において、固い物への曝露、刺し方および角度は重要な変数である。フィルムが食品の包装材または鋭利な刃の部分に使用される場合、耐穿刺性を知ることは有利である。EN 14477突刺し試験は0.8mm径のチップに関しての挙動を測定する。試験はParkerペン試験/Parkerボールペン試験としても知られている。
フィルムの熱成形性の評価のため、フィルムは、Multivac装置(例えば、R245/SN:166619)を用い、(加熱時間:2〜3秒、爆発成形/圧縮空気リザーバー:2bar、成形圧力:2barで試験、成形:2秒)の成形条件で熱成形された。作られた殻部のための型は図1より明らかである。本発明のフィルムの熱成形性を特徴付ける2つの性質は以下の通りである。
・熱成形深さ比率Ashell/Afilm(Ashell=熱成形された殻の表面積、Afilm=使用された本発明のフィルムの表面積)
ISO 15106−3に従い、種々のフィルム厚さにおいて、23℃で相対湿度85%の水蒸気透過率(WVTR)が測定された。酸素バリア性(OTR)は、OXTRAN(登録商標)100(Mocon Modern Controls社製、米国)を使用し、ISO 15105−2、Annex Aに従い、23.0℃/相対湿度50%で測定された。OTRは、種々のフィルム厚さにおいて再度測定された。
本発明の製造方法が、エチレンテレフタレート−エチレンイソフタレート共重合体から成る二軸延伸フィルムの製造に使用された。フィルムの厚さは96μmであった。フィルムの製造のために、押出機に共重合体のチップを供給した。以下の表に示す製造条件に従って、共重合体は溶融され、押出機内で均一化された。
エチレンイソフタレート単位:89モル%
エチレンイソフタレート単位:11モル%
実施例1において、フィルムの製造方法を変更した。熱固定における収縮を1.75%とした(実施例1では0%であった)。それ以外は同じであり、フィルムの耐穿刺性がわずかに向上した。
実施例1において、押出し機に供給する原料混合物の組成のみ変更した。原料混合物は、更に、ポリエチレンテレフタレートを基準とするマスターバッチの形状で計って1500ppmのラジカル捕捉剤(Irganox 1010)を含む。新たな原料混合物は以下の表より明らかである。原料混合物は更に、10.18モル%のエチレンイソフタレート単位を含む。
実施例1において、フィルム中のイソフタレート単位の量を5.0モル%に低減した以外は実施例1と同様に操作を行った。表3にフィルムの特性を示す。
欧州特許第1697129号明細書の実施例1を追試した。表3にフィルムの特性を示す。ラミネートは上記の用途には適していたものの、熱成形性、耐穿刺性および特に光学的特性(ヘーズ)に関して改良の必要がある。
欧州特許第1945512号明細書の実施例1を追試した。このプロセスは上記の用途には適していた。欧州特許第1945512号明細書に詳細が記載されているフィルムは、しかしながら、熱成形性、耐穿刺性および特に光学的特性(ヘーズ)に関して改良の必要がある。
欧州特許出願第2810776号明細書の実施例3を追試した。表3にフィルムの特性を示す。フィルムは上記の用途、例えば、低い熱成形性比率の熱成形性フィルムパウチに適している。延伸装置が選択される製造条件によりフィルムは、更にクックイン法(パッケージ内調理法)にも適している。しかしながら、熱成形性および耐穿刺性に関して改良の必要がある。それに増して、欧州特許出願第2810776号明細書の実施例3のフィルムは光学的特性(ヘーズ)の改良の必要がある。
Claims (7)
- ジカルボン酸成分が85〜94モル%のテレフタル酸系単位と6〜15モル%のイソフタル酸系単位から成る共重合ポリエステル85重量%以上から成る熱成形可能な透明二軸延伸ポリエステルフィルムであって、フィルムは、a)面弾性率が4500〜6400N/mm2であり、b)長手方向と横方向の合計のσ5応力が170〜220MPaであり、c)密度が1390kg/m3未満であり、d)ヘーズが2.0%未満、透明度が85%以上、グロスが120以上であり、e)厚さが50〜300μmであることを特徴とする透明二軸延伸ポリエステルフィルム。
- ジカルボン酸成分が85〜94モル%のテレフタル酸系単位と6〜15モル%のイソフタル酸系単位から成る共重合ポリエステル85重量%以上から成る熱成形可能な透明二軸延伸ポリエステルフィルムであって、フィルムは、a)面弾性率が4500〜6300N/mm2であり、b)長手方向と横方向の合計のσ5応力が170〜220MPaであり、c)密度が1390kg/m3未満であり、d)ヘーズが2.0%未満、透明度が85%以上、グロスが120以上であり、e)厚さが50〜300μmであることを特徴とする透明二軸延伸ポリエステルフィルム。
- ポリエステルフィルムが1つ以上のラジカル捕捉剤を含有する請求項1又は2に記載の透明ポリエステルフィルム。
- ラジカル捕捉剤/捕捉剤が酸化防止剤であり、好ましくはフェノール系酸化防止剤であり、更に好ましくはペンタエリスリトールテトラキス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]及び1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)ベンゼンの群より選択される酸化防止剤である請求項3に記載の透明ポリエステルフィルム。
- ポリエステルフィルムがアンチモンを含まない請求項1〜4の何れかに記載の透明ポリエステルフィルム。
- 各層のポリマー溶融体を押出す工程と、温度70〜100℃、延伸比2.2:1〜3.8:1で長手方向延伸を行ない、温度90〜140℃で延伸比2.2:1〜3.8:1で横方向延伸を行なう二軸延伸工程と、175〜220℃で5〜25秒間熱固定を行なう工程と、延伸フィルムを巻取る工程とから成る請求項1〜5の何れかに記載のフィルムの製造方法。
- 請求項1〜5の何れかに記載のフィルムのインモールド装飾フィルム、食品包装材、リスター、外側の固いケース、家具ラミネート又は金属ラミネート(缶ライナー)への使用。
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- 2019-06-13 PL PL19179987T patent/PL3584275T3/pl unknown
- 2019-06-13 EP EP19179987.3A patent/EP3584275B1/de active Active
- 2019-06-18 KR KR1020190071965A patent/KR20190143394A/ko not_active Application Discontinuation
- 2019-06-18 JP JP2019112432A patent/JP2019218542A/ja active Pending
- 2019-06-19 US US16/445,829 patent/US11041056B2/en active Active
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Also Published As
Publication number | Publication date |
---|---|
KR20190143394A (ko) | 2019-12-30 |
US11041056B2 (en) | 2021-06-22 |
EP3584275A1 (de) | 2019-12-25 |
PL3584275T3 (pl) | 2021-10-25 |
US20190390002A1 (en) | 2019-12-26 |
EP3584275B1 (de) | 2021-03-31 |
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