JP4082780B2 - Manufacturing method of resin composition - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、エチレン−酢酸ビニル共重合体ケン化物（以下、ＥＶＯＨと略記する）の樹脂組成物の製造法に関し、更に詳しくは多層積層体としたときの溶融成形性に優れたＥＶＯＨの樹脂組成物の製造法に関する。
【０００２】
【従来の技術】
一般に、ＥＶＯＨはその透明性、ガスバリヤー性、保香性、耐溶剤性、耐油性などに優れており、かかる特性を生かして、食品包装材料、医薬品包装材料、工業薬品包装材料、農薬包装材料等のフィルムやシート、或いはボトル等の容器等に成形されて利用されている。
かかる成形にあたっては、通常溶融成形が行われ、かかる成形により、フィルム状、シート状、ボトル状、カップ状、チューブ状、パイプ状等の形状に加工されて実用に供されており、その加工性（成形性）は大変重要であり、かかる成形性を向上させるために、ＥＶＯＨにリン酸化合物を配合すること（特開昭５２−９５４号公報、特開平２−２３５９５２号公報等）が試みられており、本出願人も熱安定性や溶融成形性（フィッシュアイやゲルの抑制等）の改善のために、ＥＶＯＨをリン酸化合物で処理する方法（特開昭６２−１４３９５４号公報）を提案した。
【０００３】
【発明が解決しようとする課題】
しかしながら、昨今の新たなる成形物への要求性能の高まりに対応すべく、上記の技術について、詳細に検討を重ねた結果、直径が０．１ｍｍ以上のフィッシュアイやゲル等の改善は認められるものの、０．１ｍｍ未満の小さなものについては、上記の技術では必ずしも解決できるものではなく、特に多層積層体製造時については十分な考慮がなされておらず、多層積層体としたときの成形条件等により０．１ｍｍ未満のフィッシュアイ等が発生する恐れがあり、新たなる改良が望まれることが判明した。
【０００４】
【課題を解決するための手段】
そこで、本発明者等は、かかる現況に鑑みて鋭意研究を重ねた結果、ＥＶＯＨ（Ａ）１００重量部に対してリン酸化合物（Ｂ）を０．０００５〜０．１重量部（リン酸根換算）含有する樹脂組成物を製造するにあたり、０．１〜１０μｍ径の細孔が均一に分布した多孔性析出物である含水率２０〜８０重量％のＥＶＯＨ（Ａ）をリン酸化合物（Ｂ）水溶液と接触させ、かつリン酸化合物（Ｂ）水溶液中のリン酸化合物（Ｂ）の含有量をＥＶＯＨ（Ａ）に含有される水とリン酸化合物（Ｂ）水溶液に含有される水の合計量１００重量部に対して０．０００１〜０．５重量部とすることにより、溶融成形性に優れ、特に多層積層体製造時において直径が０．１ｍｍ未満のフィッシュアイ等の発生を抑制することのでき、かつロングラン成形性も良好であるＥＶＯＨの樹脂組成物が得られ、更にはＥＶＯＨ（Ａ）とリン酸化合物（Ｂ）を接触させた後、流動乾燥を行い、かつ該流動乾燥の前または後に静置乾燥を行うことにより、本発明の作用効果を顕著に得ることができることを見出し、本発明を完成するに至った。
【０００５】
【発明の実施の形態】
以下に、本発明を詳細に述べる。
本発明に用いられるＥＶＯＨ（Ａ）としては、特に限定されないが、エチレン含有量が２０〜６０モル％（更には２５〜５５モル％）、ケン化度が９０モル％以上（更には９５モル％以上）のものが用いられ、該エチレン含有量が２０モル％未満では高湿時のガスバリヤー性、溶融成形性が低下し、逆に６０モル％を越えると充分なガスバリヤー性が得られず、更にケン化度が９０モル％未満ではガスバリヤー性、熱安定性、耐湿性等が低下して、好ましくない。
また、ＥＶＯＨ（Ａ）は、メルトインデックス（ＭＩ）（２１０℃、荷重２１６０ｇ）が０．１〜１００ｇ／１０分（更には０．５〜５０ｇ／１０分）のものが好ましく、該メルトインデックスが該範囲よりも小さい場合には、成形時に押出機内が高トルク状態となって押出加工が困難となり、また該範囲よりも大きい場合には、溶融成形性や成形物の機械的強度が低下して好ましくない。
【０００６】
該ＥＶＯＨ（Ａ）は、エチレン−酢酸ビニル共重合体のケン化によって得られ、該エチレン−酢酸ビニル共重合体は、公知の任意の重合法、例えば懸濁重合、エマルジョン重合、溶液重合などにより製造され、エチレン−酢酸ビニル共重合体のケン化も公知の方法で行い得る。
該ＥＶＯＨは、少量であればα−オレフィン、不飽和カルボン酸系化合物、不飽和スルホン酸系化合物、（メタ）アクリロニトリル、（メタ）アクリルアミド、ビニルエーテル、ビニルシラン化合物、塩化ビニル、スチレンなどの他のコモノマーで「共重合変性」されても差し支えない。又、本発明の趣旨を損なわない範囲で、ウレタン化、アセタール化、シアノエチル化など「後変性」されても差し支えない。
【０００７】
また、本発明で用いられるリン酸化合物（Ｂ）としては、リン酸二水素ナトリウム、リン酸水素二ナトリウム、リン酸二水素カリウム、リン酸水素二カリウム、リン酸三カリウム、リン酸一水素カルシウム、リン酸二水素カルシウム、リン酸三カルシウム、リン酸マグネシウム、リン酸水素マグネシウム、リン酸二水素マグネシウム、リン酸水素亜鉛、リン酸水素バリウム、リン酸水素マンガン等を挙げることができ、好適にはリン酸二水素ナトリウム、リン酸二水素カリウム、リン酸二水素カルシウム、リン酸二水素マグネシウムが用いられる。
【０００８】
本発明においては、上記の如き（Ａ）及び（Ｂ）を用いて、ＥＶＯＨ（Ａ）１００重量部に対してリン酸化合物（Ｂ）を０．０００５〜０．１（リン酸根換算）含有する樹脂組成物を製造するにあたり、０．１〜１０μｍ径の細孔が均一に分布した多孔性析出物である含水率２０〜８０重量％のＥＶＯＨ（Ａ）をリン酸化合物（Ｂ）水溶液と接触させ、かつリン酸化合物（Ｂ）水溶液中のリン酸化合物（Ｂ）の含有量をＥＶＯＨ（Ａ）に含有される水とリン酸化合物（Ｂ）水溶液に含有される水の合計量１００重量部に対して０．０００１〜０．５重量部とすることを特徴とするもので、かかる方法について具体的に説明する。
【０００９】
含水率２０〜８０重量％（更には３０〜７０重量％、特に３５〜６５重量％）のＥＶＯＨ（Ａ）を調製するにあたっては、特に限定されず、（ペレット状や紛体状の）ＥＶＯＨと水を混合撹拌して該ＥＶＯＨに吸水させても良いし、蒸気を吹き込む方法も採用される。又、ＥＶＯＨの製造時に若干のメタノール、イソプロピルアルコール等のアルコールと共に含水させることも可能であり、この際、少量のエチレングリコール、プロピレングリコール、グリセリンなどの可塑剤を含んでいても差し支えない。該含水率が、２０重量％未満では、得られる樹脂組成物を溶融成形した場合に微小フィッシュアイが多発し、逆に８０重量％を越えると、後の乾燥工程においてペレット状や粉体状のＥＶＯＨが融着を起こして本発明の目的を達成できない。
【００１０】
本発明では、かかるＥＶＯＨが、多孔性析出物であり、かかる多孔性析出物とは、径が０．１〜１０μｍの細孔が均一に分布したミクロポーラスな内部構造をもつもので、ＥＶＯＨの溶液（水／アルコール混合溶媒等）を凝固浴中に押し出すにあたって、ＥＶＯＨ溶液の濃度（２０〜８０重量％）、温度（４５〜７０℃）、溶媒の種類（水／アルコール混合重量比＝８０／２０〜５／９５）、凝固浴の温度（１〜２０℃）、滞留時間（０．２５〜３０時間）、凝固液中でのＥＶＯＨ量（０．０２〜２重量％）等を任意に調節することにより得ることができる。また、リン酸化合物（Ｂ）水溶液中のリン酸化合物（Ｂ）の含有量をＥＶＯＨ（Ａ）に含有される水とリン酸化合物（Ｂ）水溶液に含有される水の合計量１００重量部に対して０．０００１〜０．５重量部（更には０．０００５〜０．３重量部、特に０．００１〜０．１重量部）とするには、ＥＶＯＨ（Ａ）中の水（含水率）を考慮して、リン酸化合物（Ｂ）水溶液を調製すればよく、かかる水溶液濃度が０．０００１重量部未満では、ＥＶＯＨ（Ａ）にリン酸化合物（Ｂ）を所定量含有させることが困難となり、逆に０．５重量部を越えると樹脂組成物の成形品に微小フィッシュアイが多発して本発明の目的を達成できない。このとき０．００１〜０．１重量％程度のメタノール、エタノール、プロパノール、酢酸メチル、酢酸エチル等を含有していても差し支えない。
【００１１】
かくして得られたＥＶＯＨ（Ａ）とリン酸化合物（Ｂ）水溶液と接触せしめて、目的とする樹脂組成物を得るのであるが、リン酸化合物（Ｂ）水溶液にＥＶＯＨ（Ａ）を接触させて、最終的にＥＶＯＨ（Ａ）にリン酸化合物（Ｂ）を含有（付着）させればよく、かかる方法としては、ＥＶＯＨ（Ａ）の水／アルコール混合溶液の多孔性析出物をリン酸化合物（Ｂ）水溶液中に浸漬させて含有させる方法が、リン酸化合物（Ｂ）をより均一に効率良く含有させるという点で好適に用いられる。
【００１２】
かくして本発明の方法により目的とする樹脂組成物が得られるのであるが、通常は、上記の接触処理後に乾燥工程を経て、樹脂組成物が得られるのである。
本発明においては、かかる乾燥方法として、種々の乾燥方法を採用することが可能であるが、本発明では、流動乾燥を行い、かつ該流動乾燥の前または後に静置乾燥を行う乾燥方法、即ち、流動乾燥処理後に静置乾燥処理を行う方法又は静置乾燥処理後に流動乾燥処理を行う方法が特に好ましく、かかる乾燥方法について説明する。
ここで言う流動乾燥とは、実質的にペレット状または粉体状等の樹脂組成物が機械的にもしくは熱風により撹拌分散されながら行われる乾燥を意味し、該乾燥を行うための乾燥器としては、円筒・溝型撹拌乾燥器、円筒乾燥器、回転乾燥器、流動層乾燥器、振動流動層乾燥器、円錐回転型乾燥器等が挙げられ、また、静置乾燥とは、実質的に樹脂組成物が撹拌、分散などの動的な作用を与えられずに行われる乾燥を意味し、該乾燥を行うための乾燥器として、材料静置型としては回分式箱型乾燥器が、材料移送型としてはバンド乾燥器、トンネル乾燥器、竪型サイロ乾燥器等を挙げることができるが、これらに限定されるものではない。
まず、流動乾燥処理後に静置乾燥処理を行う方法について説明する。
【００１３】
該流動乾燥処理時に用いられる加熱ガスとしては空気または不活性ガス（窒素ガス、ヘリウムガス、アルゴンガス等）が用いられ、該加熱ガスの温度としては、９５℃以下が好ましく、更には４０〜９０℃が好ましく、該温度が９５℃を越えるとペレット状や粉体状のＥＶＯＨが融着を起こして好ましくない。
更に、乾燥器内の加熱ガスの速度は、０．７〜１０ｍ／ｓｅｃとすることが好ましく、更には０．７〜５．０ｍ／ｓｅｃで、特に１．０〜３．０ｍ／ｓｅｃが好ましく、かかる速度が０．７ｍ／ｓｅｃ未満ではペレット状や紛体状のＥＶＯＨの融着が起こりやすく、逆に１０ｍ／ｓｅｃを越えるとペレットの欠けや微紛の発生が起こりやすくなって好ましくない。
また、流動乾燥の時間としては、樹脂組成物の処理量にもよるが、通常は５分〜３６時間が好ましく、更には１０分〜２４時間が好ましい。
【００１４】
上記の条件で樹脂組成物が流動乾燥処理されるのであるが、該処理後の樹脂組成物の含水率は５．０〜６０重量％（更には１０〜５５重量％）とすることが好ましく、かかる含水率が５．０重量％未満では、静置乾燥処理後の最終製品を溶融成形した場合に吐出変動が起こり易く、逆に６０重量％を越えると後の静置乾燥処理時にペレット状や紛体状の樹脂組成物の融着が起こりやすく、また、得られる樹脂組成物を溶融成形した場合に微小フィッシュアイが多発する傾向にあり好ましくない。
また、かかる流動乾燥処理において、該処理前より５．０重量％以上（更には１０〜４５重量％）含水率を低くすることが好ましく、該含水率の低下が５．０重量％未満の場合にも、得られる樹脂組成物を溶融成形した場合に微小フィッシュアイが多発する傾向にあり好ましくない。
【００１５】
上記の如く流動乾燥処理された樹脂組成物は、次いで静置乾燥処理に供されるのであるが、かかる静置乾燥処理に用いられる加熱ガスも同様に不活性ガス（窒素ガス、ヘリウムガス、アルゴンガス等）が用いられるが、該加熱ガスの温度は７５℃以上が好ましく、更には８５〜１５０℃で、該温度が７５℃未満では、乾燥時間を極端に長くする必要があり、経済的に不利となって好ましくない。
更に乾燥器内のガスの速度は１．０ｍ／ｓｅｃ未満とすることが好ましく、更には０．０１〜０．５ｍ／ｓｅｃが好ましく、かかる速度が１ｍ／ｓｅｃを越えると樹脂組成物を静置状態に保つことが困難となり好ましくない。
また、静置乾燥処理の時間も樹脂組成物の処理量により一概に言えないが、通常は１０分〜７２時間が好ましく、更には１．０〜４８時間が好ましい。
上記の条件で樹脂組成物が静置乾燥処理されて最終的に目的とする樹脂組成物が得られるのであるが、該処理後（最終）の樹脂組成物の含水率は０．００１〜２．０重量％（更には０．０１〜１．０重量％）になるようにするのが好ましく、該含水率が０．００１重量％未満では、樹脂組成物のロングラン成形性が低下する傾向にあり、逆に２．０重量％を越えると成形品に水の発泡が発生しやすくなり好ましくない。
【００１６】
次に、静置乾燥処理後に流動乾燥処理を行う方法について説明する。
このときの静置乾燥処理時の条件は、上記の静置乾燥処理時の条件と基本的には同じであるが、加熱ガスの温度を１００℃以下とすることが好ましく、更には４０〜９５℃が好ましく、該温度が１００℃を越えるとペレット状や粉体状のＥＶＯＨが融着が起こりやすくなって好ましくない。
また、静置乾燥処理の時間としては、樹脂組成物の処理量にもよるが、通常は１０分〜４８時間が好ましく、更には３０分〜３６時間が好ましい。
該処理後の樹脂組成物の含水率は１０〜７０重量％（更には１５〜６０重量％）とすることが好ましく、かかる含水率が１０重量％未満では、流動乾燥処理後の最終製品を溶融成形した場合に微小フィッシュアイが多発する傾向にあり、逆に７０重量％を越えても、最終製品を溶融成形した場合に吐出変動が起こり易いため好ましくない。
また、かかる静置乾燥処理において、該処理前より３．０重量％以上（更には５．０〜３０重量％）含水率を低くすることが好ましく、該含水率の低下が３．０重量％未満の場合は、最終製品に微粉やペレットの欠けが発生しやすくなり好ましくない。
【００１７】
上記の如く静置乾燥処理された樹脂組成物は、次いで流動乾燥処理に供されるのであるが、かかる流動乾燥処理の条件も上記の流動乾燥処理時の条件と基本的には同じではあるが、加熱ガスの温度を８０℃以上とすることが好ましく、更には９５〜１５０℃が好ましく、該温度が８０℃未満では、乾燥時間を極端に長くする必要があり、経済的に不利となって好ましくない。
また、流動乾燥処理の時間も樹脂組成物の処理量にもよるが、通常は１０分〜４８時間が好ましく、更には３０分〜２４時間が好ましい。
かかる流動乾燥条処理を経て、上記と同様、最終的に目的とする含水率０．００１〜２．０重量％の樹脂組成物が得られるのである。
【００１８】
尚、本発明においては、得られる樹脂組成物のＥＶＯＨ（Ａ）１００重量部に対するリン酸化合物（Ｂ）の含有量をリン酸根換算で（Ａ）１００重量部に対して０．０００５〜０．１重量部（更には０．００１〜０．０５重量部、特には０．００２〜０．０３重量部）にすることが必要で、かかるリン酸化合物（Ｂ）の量がリン酸根換算で０．０００５重量部未満では目的とする樹脂組成物の成形性が悪くなり、逆に０．１重量部を越えると成形物の外観が低下する。
上記のリン酸化合物（Ｂ）の含有量を調整するには、前述の接触処理時において、リン酸化合物（Ｂ）水溶液の濃度やＥＶＯＨ（Ａ）の含水率、接触時間、温度、撹拌速度等をコントロールすればよく、特に限定はされない。
【００１９】
上記の如き本発明方法により、熱安定性やロングラン成形性等に優れた樹脂組成物が得られるわけであるが、かかる樹脂組成物には、更に、必要に応じて、可塑剤、熱安定剤、紫外線吸収剤、酸化防止剤、着色剤、抗菌剤、フィラー、他樹脂などの添加剤を使用することも可能である。特にゲル発生防止剤として、ハイドロタルサイト系化合物、ヒンダードフェノール系、ヒンダードアミン系熱安定剤、高級脂肪族カルボン酸の金属塩を添加することもできる。
また、ＥＶＯＨ（Ａ）として、異なる２種以上のＥＶＯＨを用いることも可能で、このときは、エチレン含有量が５モル％以上異なり、及び／又はケン化度が１モル％以上異なるＥＶＯＨのブレンド物を用いることにより、ガスバリヤー性を保持したまま、更に高延伸時の延伸性、真空圧空成形や深絞り成形などの２次加工性が向上するので有用である。
【００２０】
かくして得られた樹脂組成物は、成形物の用途に多用され、溶融成形等によりペレット、フィルム、シート、容器、繊維、棒、管、各種成形品等に成形され、又、これらの粉砕品（回収品を再使用する時など）やペレットを用いて再び溶融成形に供することもでき、かかる溶融成形方法としては、押出成形法（Ｔ−ダイ押出、インフレーション押出、ブロー成形、溶融紡糸、異型押出等）、射出成形法が主として採用される。溶融成形温度は、１５０〜３００℃の範囲から選ぶことが多い。
また、本発明で得られた樹脂組成物は、単層として用いることができるが、前述のように、特に積層体用途に供した時に本発明の作用効果を十分に発揮することができ、具体的には該樹脂組成物からなる層の少なくとも片面に熱可塑性樹脂層等を積層して多層積層体として用いることが有用である。
【００２１】
該積層体を製造するに当たっては、該樹脂組成物の層の片面又は両面に他の基材を積層するのであるが、積層方法としては、例えば該樹脂組成物のフィルムやシートに熱可塑性樹脂を溶融押出する方法、逆に熱可塑性樹脂等の基材に該樹脂組成物を溶融押出する方法、該樹脂組成物と他の熱可塑性樹脂とを共押出する方法、更には本発明で得られた樹脂組成物のフィルムやシートと他の基材のフィルム、シートとを有機チタン化合物、イソシアネート化合物、ポリエステル系化合物、ポリウレタン化合物等の公知の接着剤を用いてドライラミネートする方法等が挙げられる。
【００２２】
共押出の場合の相手側樹脂としては直鎖状低密度ポリエチレン、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、エチレン−酢酸ビニル共重合体、アイオノマー、エチレン−プロピレン共重合体、エチレン−アクリル酸エステル共重合体、ポリプロピレン、プロピレン−α−オレフィン（炭素数４〜２０のα−オレフィン）共重合体、ポリブテン、ポリペンテン等のオレフィンの単独又は共重合体、或いはこれらのオレフィンの単独又は共重合体を不飽和カルボン酸又はそのエステルでグラフト変性したものなどの広義のポリオレフィン系樹脂、ポリエステル、ポリアミド、共重合ポリアミド、ポリ塩化ビニル、ポリ塩化ビニリデン、アクリル系樹脂、ポリスチレン、ビニルエステル系樹脂、ポリエステルエラストマー、ポリウレタンエラストマー、塩素化ポリエチレン、塩素化ポリプロピレン等が挙げられる。ＥＶＯＨも共押出可能である。上記のなかでも、共押出製膜の容易さ、フィルム物性（特に強度）の実用性の点から、ポリプロピレン、ポリアミド、ポリエチレン、エチレン−酢酸ビニル共重合体、ポリスチレン、ＰＥＴが好ましく用いられる。
【００２３】
更に、本発明で得られる樹脂組成物から一旦フィルムやシート等の成形物を得、これに他の基材を押出コートしたり、他の基材のフィルム、シート等を接着剤を用いてラミネートする場合、前記の熱可塑性樹脂以外に任意の基材（紙、金属箔、一軸又は二軸延伸プラスチックフィルム又はシート、織布、不織布、金属綿状、木質等）が使用可能である。
【００２４】
積層体の層構成は、本発明で得られた樹脂組成物の層をａ（ａ1、ａ2、・・・）、他の基材、例えば熱可塑性樹脂層をｂ（ｂ1、ｂ2、・・・）とするとき、フィルム、シート、ボトル状であれば、ａ／ｂの二層構造のみならず、ｂ／ａ／ｂ、ａ／ｂ／ａ、ａ1／ａ2／ｂ、ａ／ｂ1／ｂ2、ｂ2／ｂ1／ａ／ｂ1／ｂ2等任意の組み合わせが可能であり、フィラメント状ではａ、ｂがバイメタル型、芯（ａ）−鞘（ｂ）型、芯（ｂ）−鞘（ａ）型、或いは偏心芯鞘型等任意の組み合わせが可能である。
【００２５】
該積層体は、そのまま各種形状のものに使用されるが、更に該積層体の物性を改善するためには延伸処理を施すことも好ましく、かかる延伸については、一軸延伸、二軸延伸のいずれであってもよく、できるだけ高倍率の延伸を行ったほうが物性的に良好で、延伸時にピンホールやクラック、延伸ムラ、デラミ等の生じない延伸フィルムや延伸シート等が得られる。
【００２６】
延伸方法としては、ロール延伸法、テンター延伸法、チューブラー延伸法、延伸ブロー法等の他、深絞成形、真空成形等のうち延伸倍率の高いものも採用できる。二軸延伸の場合は同時二軸延伸方式、逐次二軸延伸方式のいずれの方式も採用できる。延伸温度は８０〜１７０℃、好ましくは１００〜１６０℃程度の範囲から選ばれる。
【００２７】
延伸が終了した後、次いで熱固定を行う。熱固定は周知の手段で実施可能であり、上記延伸フィルムを緊張状態を保ちながら８０〜１７０℃、好ましくは１００〜１６０℃で２〜６００秒間程度熱処理を行う。
また、生肉、加工肉、チーズ等の熱収縮包装用途に用いる場合には、延伸後の熱固定は行わずに製品フィルムとし、上記の生肉、加工肉、チーズ等を該フィルムに収納した後、５０〜１３０℃、好ましくは７０〜１２０℃で、２〜３００秒程度の熱処理を行って、該フィルムを熱収縮させて密着包装をする。
【００２８】
かくして得られた積層体の形状としては任意のものであってよく、フィルム、シート、テープ、ボトル、パイプ、フィラメント、異型断面押出物等が例示される。又、得られる積層体は必要に応じ、熱処理、冷却処理、圧延処理、印刷処理、ドライラミネート処理、溶液又は溶融コート処理、製袋加工、深絞り加工、箱加工、チューブ加工、スプリット加工等を行うことができる。
上記の如く得られたフィルム、シート或いは容器等は食品、医薬品、工業薬品、農薬等各種の包装材料として有用である。
【００２９】
【実施例】
以下、実施例を挙げて本発明を具体的に説明する。
尚、実施例中「部」、「％」とあるのは特に断りのない限り重量基準を示す。
実施例１
ＥＶＯＨ［エチレン含有量３５モル％、ケン化度９９．５モル％、ＭＩ１２ｇ／１０分（２１０℃、荷重２１６０ｇ）］（Ａ）の水／メタノール（水／メタノール＝４０／６０混合重量比）溶液（６０℃、ＥＶＯＨ濃度４５％）を５℃に維持された水槽にストランド状に押し出して凝固させた後、カッターで切断してペレット状（直径４ｍｍ、長さ４ｍｍ）のＥＶＯＨを得て、更に該ＥＶＯＨを３０℃の温水に投入して、約４時間撹拌を行って含水率５０％の多孔性析出物（平均４μｍ径のミクロポーラスが均一に存在）を得た。
次いで、得られた多孔性析出物１００部を０．０６％のリン酸二水素マグネシウム（Ｂ）水溶液２００部に投入し（全水分１００部に対してリン酸二水素マグネシウム（Ｂ）が０．０４８部）、３０℃で５時間撹拌して、ＥＶＯＨ（Ａ）及びリン酸化合物（Ｂ）からなる樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０１２重量部含有］を得た。
得られた樹脂組成物を下記の方法により乾燥処理を行った。
【００３０】
＜流動乾燥工程＞
上記で得られた樹脂組成物を回分式流動層乾燥器（塔型）を用いて、７５℃の窒素ガスを流動させながら、約３時間乾燥を行って含水率２０％の樹脂組成物を得た。
尚、流動乾燥前の樹脂組成物の含水率は、５０％で、流動乾燥前後の樹脂組成物の含水率差は３０％であった。
＜静置乾燥工程＞
次いで、流動乾燥処理後の樹脂組成物を回分式箱型乾燥器（通気式）を用いて、１２５℃の窒素ガスで、約１８時間乾燥を行って含水率０．３％の目的とする樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０１２重量部含有］を得た。
【００３１】
次いで、得られた樹脂組成物をフィードブロック５層Ｔダイを備えた多層押出装置に供給して、ポリエチレン層（三菱化学社製『ノバテックＬＤ ＬＦ５２５Ｈ』）／接着樹脂層（三菱化学社製『モディックＡＰ２４０Ｈ』）／樹脂組成物層／接着樹脂層（同左）／ポリエチレン層（同左）の３種５層の多層積層体（厚みが５０／１０／２０／１０／５０（μｍ））を得て、下記の要領で直径が０．１ｍｍ未満の微細なフィッシュアイの発生およびロングラン成形性の評価を行った。
（フィッシュアイ）
上記の成形直後のフィルム（１０ｃｍ×１０ｃｍ）について、直径が０．０１〜０．１ｍｍ未満のフィッシュアイの発生状況を目視観察して、以下のとおり評価とした。
◎ −−− ０〜 ３個
○ −−− ４〜１０個
△ −−− １１〜５０個
× −−− ５１個以上
（ロングラン成形性）
また、上記の成形を１０日間連続に行って、その時の成形フィルムについて、同様にフィッシュアイの増加状況を目視観察して、以下のとおり評価した。
○ −−− 増加は認められなかった
△ −−− 若干の増加が認められた
× −−− 著しい増加が認められた
【００３２】
実施例２
ＥＶＯＨ［エチレン含有量４０モル％、ケン化度９９．０モル％、ＭＩ６ｇ／１０分（２１０℃、荷重２１６０ｇ）］（Ａ）の水／メタノール（水／メタノール＝２０／８０混合重量比）溶液（６０℃）を５℃に維持された水槽にストランド状に押し出して凝固させた後、カッターで切断してペレット状（直径４ｍｍ、長さ４ｍｍ）のＥＶＯＨを得て、更に該ＥＶＯＨを３０℃の温水で洗浄後、酢酸水溶液中に投入して、約２時間撹拌を行って含水率５５％の多孔性析出物（平均５μｍ径のミクロポーラスが均一に存在）を得た。
次いで、得られた多孔性析出物１００部を０．００７％のリン酸二水素カルシウム（Ｂ）水溶液３００部に投入し（全水分１００部に対してリン酸二水素カルシウム（Ｂ）が０．００６部）、３０℃で５時間撹拌して、ＥＶＯＨ（Ａ）及びリン酸化合物（Ｂ）からなる樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．００２重量部含有］を得た。
得られた樹脂組成物を下記の方法により乾燥処理を行った。
【００３３】
＜流動乾燥工程＞
上記で得られた樹脂組成物を流動層乾燥器（連続横型多室式）を用いて、７５℃の窒素ガスを流動させながら、約３時間乾燥を行って含水率２０％の樹脂組成物を得た。
尚、流動乾燥前の樹脂組成物の含水率は、５５％で、流動乾燥前後の樹脂組成物の含水率差は３５％であった。
＜静置乾燥工程＞
次いで、流動乾燥処理後の樹脂組成物を回分式箱型乾燥器（通気式）を用いて、１２０℃の窒素ガスで、約２４時間乾燥を行って含水率０．２％の目的とする樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．００２重量部含有］を得た。
得られた樹脂組成物について、実施例１と同様に評価を行った。
【００３４】
実施例３
実施例１において、乾燥処理方法を以下の如く変えて乾燥処理を行った以外は同様に行って、目的とする樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０１１重量部含有］を得て同様に評価を行った。
＜静置乾燥工程＞
得られた樹脂組成物を回分式箱型乾燥器（通気式）を用いて、７０℃の窒素ガスで、約５時間乾燥を行って含水率３０％の樹脂組成物を得た。
尚、静置乾燥前の樹脂組成物の含水率は、５０％で、静置乾燥前後の樹脂組成物の含水率差は２０％であった。
＜流動乾燥工程＞
次いで、静置乾燥処理後の樹脂組成物を、回分式箱型乾燥器（通気式）を用いて、１２０℃の窒素ガスを流動させながら、約１８時間乾燥を行って含水率０．２％の目的とする樹脂組成物を得た。
【００３５】
実施例４
実施例１において、リン酸二水素マグネシウム（Ｂ）に代えて、リン酸二水素ナトリウム０．０３部を用いて、ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．００９重量部含有する乾燥前の樹脂組成物を得て、かつ乾燥処理方法を以下の如く変えて乾燥処理を行った以外は同様に行って、目的とする樹脂組成物を得て同様に評価を行った。
＜静置乾燥工程＞
得られた樹脂組成物を回分式箱型乾燥器（通気式）を用いて、７０℃の窒素ガスで、約５時間乾燥を行って含水率３０％の樹脂組成物を得た。
尚、静置乾燥前の樹脂組成物の含水率は、５０％で、静置乾燥前後の樹脂組成物の含水率差は２０％であった。
＜流動乾燥工程＞
次いで、静置乾燥処理後の樹脂組成物を、回分式箱型乾燥器（通気式）を用いて、１２０℃の窒素ガスを流動させながら、約１８時間乾燥を行って含水率０．２％の目的とする樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．００９重量部含有］を得た。
【００３６】
実施例５
ＥＶＯＨ［エチレン含有量３０モル％、ケン化度９９．６モル％、ＭＩ１２ｇ／１０分（２１０℃、荷重２１６０ｇ）］（Ａ）の水／メタノール（水／メタノール＝５０／５０混合重量比）溶液（６０℃）を５℃に維持された水槽にストランド状に押し出して凝固させた後、カッターで切断してペレット状（直径４ｍｍ、長さ５ｍｍ）のＥＶＯＨを得て、更に該ＥＶＯＨを３０℃の温水で洗浄後、酢酸水溶液中に投入して、約２時間撹拌を行って含水率５０％の多孔性析出物（平均４μｍ径のミクロポーラスが均一に存在）を得た。
次いで、得られた多孔性析出物１００部を０．０６％のリン酸二水素マグネシウム（Ｂ）水溶液２５０部に投入し、３０℃で約４時間撹拌して、ＥＶＯＨ（Ａ）及びリン酸二水素マグネシウム（Ｂ）からなる樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０１０重量部含有］を得た。
得られた樹脂組成物を下記の方法により乾燥処理を行った。
【００３７】
＜静置乾燥工程＞
得られた樹脂組成物を回分式通気流箱型乾燥器を用いて、７０℃の窒素ガスで、約８時間乾燥を行って含水率２５％の樹脂組成物を得た。
尚、静置乾燥前の樹脂組成物の含水率は、５０％で、静置乾燥前後の樹脂組成物の含水率差は２５％であった。
＜流動乾燥工程＞
次いで、静置乾燥処理後の樹脂組成物を、回分式塔型流動層乾燥器を用いて、１２５℃の窒素ガスを流動させながら、約１８時間乾燥を行って含水率０．３％の目的とする樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０１０重量部含有］を得た。
得られた樹脂組成物について、実施例１と同様に評価を行った。
【００３８】
比較例１
実施例１において、ＥＶＯＨ（Ａ）の多孔性析出物の含水率を１０％に調整した以外は同様に行って、樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０２４重量部含有］を得た後、同様の条件で乾燥処理を行って、同様に評価を行った。
但し、流動乾燥処理後の樹脂組成物の含水率は、６％で、静置乾燥処理後の樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０２４重量部含有］の最終含水率は０．１％であった。
【００３９】
比較例２
実施例１において、ＥＶＯＨ（Ａ）のケン化後の水／メタノール溶液の多孔性析出物の含水率を９０％に調整した以外は同様に行って、樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．００２重量部含有］を得た後、同様の条件で乾燥処理を行って、同様に評価を行った。但し、流動乾燥処理後の樹脂組成物の含水率は、３０％で、静置乾燥処理後の樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．００２重量部含有］の最終含水率は０．３％であった。
【００４０】
比較例３
実施例１において、全水分１００部に対するリン酸化合物（Ｂ）を０．００００５に調整した以外は同様に行って、樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０００１重量部以下含有］を得た後、同様の条件で乾燥処理を行って、同様に評価を行った。
但し、流動乾燥処理後の樹脂組成物の含水率は、２０％で、静置乾燥処理後の樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．０００１重量部以下含有］の最終含水率は０．３％であった。
【００４１】
比較例４
実施例１において、全水分１００部に対するリン酸化合物（Ｂ）を２部に調整した以外は同様に行って、樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．２５重量部含有］を得た後、同様の条件で乾燥処理を行って、同様に評価を行った。
但し、流動乾燥処理後の樹脂組成物の含水率は、２０％で、静置乾燥処理後の樹脂組成物［ＥＶＯＨ（Ａ）１００重量部に対して、リン酸化合物（Ｂ）をリン酸根換算で０．２５重量部含有］の最終含水率は０．３％であった。
実施例、比較例のそれぞれの評価結果を表１にまとめて示す。
【００４２】
【表１】
【発明の効果】
本発明の方法で得られた樹脂組成物は、多層積層体としたとき直径が０．１ｍｍ未満の微細なフィッシュアイの発生がなく、かつロングラン成形性にも優れ、各種の積層体とすることができ、食品や医薬品、農薬品、工業薬品包装用のフィルム、シート、チューブ、袋、容器等の用途に非常に有用で、延伸を伴う二次加工製品等にも好適に用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a resin composition of a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH), and more specifically, a resin composition of EVOH having excellent melt moldability when formed into a multilayer laminate. The present invention relates to a manufacturing method of goods.
[0002]
[Prior art]
In general, EVOH is excellent in transparency, gas barrier properties, fragrance retention, solvent resistance, oil resistance, etc., and taking advantage of these properties, food packaging materials, pharmaceutical packaging materials, industrial chemical packaging materials, agricultural chemical packaging materials It is used after being formed into a film or sheet such as a container or a container such as a bottle.
In such molding, melt molding is usually performed, and by such molding, it is processed into a film shape, a sheet shape, a bottle shape, a cup shape, a tube shape, a pipe shape, etc. and is practically used. (Moldability) is very important. In order to improve the moldability, it is attempted to add a phosphoric acid compound to EVOH (Japanese Patent Laid-Open No. 52-954, Japanese Patent Laid-Open No. Hei 2-235952, etc.). The present applicant also proposed a method of treating EVOH with a phosphoric acid compound (Japanese Patent Laid-Open No. Sho 62-143954) in order to improve thermal stability and melt moldability (such as suppression of fish eyes and gels). did.
[0003]
[Problems to be solved by the invention]
However, in order to respond to the recent increase in performance required for new molded products, as a result of detailed examination of the above technology, improvement of fish eyes and gels having a diameter of 0.1 mm or more is recognized. In the case of a small one of less than 0.1 mm, the above-mentioned technique cannot always solve the problem. In particular, the multilayer laminate is not sufficiently considered, and depending on the molding conditions when the multilayer laminate is formed. It has been found that fish eyes of less than 0.1 mm may occur, and a new improvement is desired.
[0004]
[Means for Solving the Problems]
Therefore, as a result of intensive research in view of the present situation, the present inventors, as a result, 0.0005 to 0.1 parts by weight (in terms of phosphate group) of phosphoric acid compound (B) with respect to 100 parts by weight of EVOH (A). ) In producing the resin composition to contain, It is a porous precipitate in which pores having a diameter of 0.1 to 10 μm are uniformly distributed EVOH (A) having a water content of 20 to 80% by weight is brought into contact with the phosphoric acid compound (B) aqueous solution, and the content of the phosphoric acid compound (B) in the phosphoric acid compound (B) aqueous solution is contained in EVOH (A). By making 0.0001 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of water contained in the water and the phosphoric acid compound (B) aqueous solution, it is excellent in melt moldability, particularly for producing a multilayer laminate. An EVOH resin composition capable of suppressing the occurrence of fish eyes with a diameter of less than 0.1 mm and having good long-run moldability is obtained. Furthermore, EVOH (A) and a phosphoric acid compound (B ) Is contacted, followed by fluidized drying, and static drying before or after fluidized drying, the effect of the present invention can be remarkably obtained, and the present invention has been completed. It was.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
EVOH (A) used in the present invention is not particularly limited, but the ethylene content is 20 to 60 mol% (more preferably 25 to 55 mol%), and the saponification degree is 90 mol% or more (further 95 mol%). When the ethylene content is less than 20 mol%, the gas barrier property and melt moldability at high humidity are reduced. On the other hand, when the ethylene content exceeds 60 mol%, sufficient gas barrier property cannot be obtained. Further, if the degree of saponification is less than 90 mol%, gas barrier properties, thermal stability, moisture resistance and the like are lowered, which is not preferable.
EVOH (A) preferably has a melt index (MI) (210 ° C., load 2160 g) of 0.1 to 100 g / 10 minutes (more preferably 0.5 to 50 g / 10 minutes). If it is smaller than this range, the inside of the extruder will be in a high torque state at the time of molding, making extrusion difficult, and if it is larger than this range, the melt moldability and the mechanical strength of the molded product will decrease. It is not preferable.
[0006]
The EVOH (A) is obtained by saponification of an ethylene-vinyl acetate copolymer, and the ethylene-vinyl acetate copolymer is obtained by any known polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization and the like. The ethylene-vinyl acetate copolymer produced can be saponified by a known method.
If the EVOH is a small amount, other comonomer such as α-olefin, unsaturated carboxylic acid compound, unsaturated sulfonic acid compound, (meth) acrylonitrile, (meth) acrylamide, vinyl ether, vinyl silane compound, vinyl chloride, styrene, etc. However, it may be “copolymerized”. Further, it may be “post-modified” such as urethanization, acetalization, cyanoethylation and the like within a range not impairing the gist of the present invention.
[0007]
The phosphoric acid compound (B) used in the present invention includes sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, calcium monohydrogen phosphate. , Calcium dihydrogen phosphate, tricalcium phosphate, magnesium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, zinc hydrogen phosphate, barium hydrogen phosphate, manganese hydrogen phosphate, etc. Sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, and magnesium dihydrogen phosphate are used.
[0008]
In the present invention, using (A) and (B) as described above, the phosphoric acid compound (B) is contained in an amount of 0.0005 to 0.1 (in terms of phosphate radical) with respect to 100 parts by weight of EVOH (A). In producing the resin composition, It is a porous precipitate in which pores having a diameter of 0.1 to 10 μm are uniformly distributed EVOH (A) having a water content of 20 to 80% by weight is brought into contact with the phosphoric acid compound (B) aqueous solution, and the content of the phosphoric acid compound (B) in the phosphoric acid compound (B) aqueous solution is contained in EVOH (A). The water and the phosphoric acid compound (B) aqueous solution are 0.0001 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of water contained in the aqueous solution of the phosphoric acid compound (B). explain.
[0009]
In preparing EVOH (A) having a water content of 20 to 80% by weight (further 30 to 70% by weight, particularly 35 to 65% by weight), there is no particular limitation. EVOH (in pellet form or powder form) and water The EVOH may be mixed and stirred to absorb water, or a method of blowing steam may be employed. Further, it is possible to contain water together with some alcohol such as methanol and isopropyl alcohol during the production of EVOH. At this time, a small amount of plasticizer such as ethylene glycol, propylene glycol and glycerin may be included. If the water content is less than 20% by weight, fine fish eyes frequently occur when the resulting resin composition is melt-molded. Conversely, if the water content exceeds 80% by weight, pellets and powders are formed in the subsequent drying step. EVOH causes fusion and cannot achieve the object of the present invention.
[0010]
In the present invention, such EVOH is a porous precipitate. R Such a porous precipitate has a microporous internal structure in which pores having a diameter of 0.1 to 10 μm are uniformly distributed, and an EVOH solution (water / alcohol mixed solvent or the like) is placed in a coagulation bath. In extruding, the concentration of EVOH solution (20 to 80% by weight), temperature (45 to 70 ° C.), type of solvent (water / alcohol mixing weight ratio = 80/20 to 5/95), coagulation bath temperature (1 to 20 ° C.), residence time (0.25 to 30 hours), EVOH amount (0.02 to 2% by weight) in the coagulation liquid, and the like can be arbitrarily adjusted. Further, the content of the phosphoric acid compound (B) in the aqueous solution of the phosphoric acid compound (B) is 100 parts by weight of the total amount of water contained in the EVOH (A) and the water contained in the aqueous solution of the phosphoric acid compound (B). On the other hand, in order to obtain 0.0001 to 0.5 parts by weight (further 0.0005 to 0.3 parts by weight, particularly 0.001 to 0.1 parts by weight), water (water content) in EVOH (A) ), The phosphoric acid compound (B) aqueous solution may be prepared. When the concentration of the aqueous solution is less than 0.0001 parts by weight, it is difficult to contain a predetermined amount of the phosphoric acid compound (B) in EVOH (A). On the other hand, if the amount exceeds 0.5 parts by weight, fine fish eyes frequently occur in the molded product of the resin composition, and the object of the present invention cannot be achieved. At this time, about 0.001 to 0.1% by weight of methanol, ethanol, propanol, methyl acetate, ethyl acetate or the like may be contained.
[0011]
The EVOH (A) thus obtained and the phosphoric acid compound (B) aqueous solution are brought into contact with each other to obtain the target resin composition. The phosphoric acid compound (B) aqueous solution is brought into contact with EVOH (A), Finally, the phosphoric acid compound (B) may be contained (attached) to EVOH (A). , E A method in which a porous precipitate of a water / alcohol mixed solution of VOH (A) is immersed in a phosphoric acid compound (B) aqueous solution. Law The point of containing the phosphoric acid compound (B) more uniformly and efficiently Good Appropriately used.
[0012]
Thus, the target resin composition can be obtained by the method of the present invention. Usually, the resin composition is obtained through the drying process after the contact treatment.
In the present invention, various drying methods can be adopted as such a drying method. In the present invention, a drying method in which fluidized drying is performed and static drying is performed before or after the fluidized drying, that is, A method of performing a stationary drying process after the fluidized drying process or a method of performing a fluidized drying process after the stationary drying process is particularly preferable, and this drying method will be described.
As used herein, fluidized drying means drying performed while the resin composition substantially in the form of pellets or powder is stirred or dispersed mechanically or with hot air. As a dryer for performing the drying, , Cylindrical / groove type agitating dryer, cylindrical dryer, rotary dryer, fluidized bed dryer, vibrating fluidized bed dryer, conical rotary dryer, etc. Still standing drying is substantially a resin It means drying performed without giving a dynamic action such as stirring and dispersion to the composition. As a dryer for performing the drying, a batch type box dryer is used as a stationary material type, and a material transfer type is used. Examples thereof include, but are not limited to, a band dryer, a tunnel dryer, and a vertical silo dryer.
First, a method for performing a stationary drying process after the fluidized drying process will be described.
[0013]
Air or an inert gas (nitrogen gas, helium gas, argon gas, etc.) is used as the heating gas used in the fluidized drying treatment, and the temperature of the heating gas is preferably 95 ° C. or less, and more preferably 40 to 90. ° C is preferred, and when the temperature exceeds 95 ° C, pellet-like or powder-like EVOH causes fusion, which is not preferred.
Furthermore, the speed of the heated gas in the dryer is preferably 0.7 to 10 m / sec, more preferably 0.7 to 5.0 m / sec, and particularly preferably 1.0 to 3.0 m / sec. If the speed is less than 0.7 m / sec, fusion of pellet-form or powder-form EVOH tends to occur, and conversely if it exceeds 10 m / sec, chipping of the pellet or generation of fine powder tends to occur.
The fluid drying time is usually preferably 5 minutes to 36 hours, more preferably 10 minutes to 24 hours, although it depends on the processing amount of the resin composition.
[0014]
The resin composition is fluidized and dried under the above conditions. The water content of the resin composition after the treatment is preferably 5.0 to 60% by weight (more preferably 10 to 55% by weight), When the moisture content is less than 5.0% by weight, discharge fluctuation is likely to occur when the final product after the stationary drying treatment is melt-molded. Conversely, when the moisture content exceeds 60% by weight, It is not preferable because the powdery resin composition is likely to be fused, and when the resulting resin composition is melt-molded, fine fish eyes tend to occur frequently.
Further, in such fluid drying treatment, it is preferable to lower the moisture content by 5.0% by weight or more (more preferably 10 to 45% by weight) before the treatment, and the decrease in the moisture content is less than 5.0% by weight. In addition, when the resulting resin composition is melt-molded, fine fish eyes tend to occur frequently, which is not preferable.
[0015]
The resin composition that has been fluidized and dried as described above is then subjected to a stationary drying process. The heating gas used in the stationary drying process is also an inert gas (nitrogen gas, helium gas, argon). Gas, etc.) is used, but the temperature of the heated gas is preferably 75 ° C. or higher, more preferably 85 to 150 ° C. If the temperature is lower than 75 ° C., the drying time needs to be extremely long, and economically It is disadvantageous and not preferable.
Further, the gas speed in the dryer is preferably less than 1.0 m / sec, more preferably 0.01 to 0.5 m / sec. When this speed exceeds 1 m / sec, the resin composition is allowed to stand still. It is difficult to maintain the state, which is not preferable.
Moreover, although the time of a stationary drying process cannot be generally said with the processing amount of a resin composition, Usually, 10 minutes-72 hours are preferable, Furthermore, 1.0-48 hours are preferable.
The resin composition is subjected to a stationary drying treatment under the above conditions to finally obtain a target resin composition. The water content of the resin composition after the treatment (final) is 0.001 to 2. It is preferable to make it 0% by weight (further 0.01 to 1.0% by weight). If the water content is less than 0.001% by weight, the long run moldability of the resin composition tends to be lowered. On the other hand, if it exceeds 2.0% by weight, foaming of water tends to occur in the molded product, which is not preferable.
[0016]
Next, a method for performing fluidized drying after stationary drying will be described.
The conditions during the stationary drying treatment at this time are basically the same as the conditions during the stationary drying treatment described above, but the temperature of the heated gas is preferably 100 ° C. or lower, and more preferably 40 to 95. When the temperature exceeds 100 ° C., the pellet-like or powder-like EVOH is liable to be fused, which is not preferable.
Further, the time for the stationary drying treatment is preferably 10 minutes to 48 hours, more preferably 30 minutes to 36 hours, although it depends on the amount of treatment of the resin composition.
The water content of the resin composition after the treatment is preferably 10 to 70% by weight (more preferably 15 to 60% by weight). When the water content is less than 10% by weight, the final product after the fluidized drying treatment is melted. When molded, fine fish eyes tend to occur frequently. Conversely, even if it exceeds 70% by weight, it is not preferable because the discharge fluctuation is likely to occur when the final product is melt-molded.
In this stationary drying treatment, it is preferable to lower the water content by 3.0% by weight or more (more preferably from 5.0 to 30% by weight) before the treatment, and the decrease in the water content is 3.0% by weight. If it is less than 1, it is not preferable because chipping of fine powder or pellets is likely to occur in the final product.
[0017]
The resin composition that has been subjected to the stationary drying treatment as described above is then subjected to a fluidized drying treatment. The conditions of the fluidized drying treatment are basically the same as the conditions during the fluidized drying treatment. The temperature of the heated gas is preferably 80 ° C. or higher, more preferably 95 to 150 ° C. If the temperature is lower than 80 ° C., the drying time needs to be extremely long, which is economically disadvantageous. It is not preferable.
Moreover, although it depends on the processing amount of the resin composition, the time for fluid drying treatment is preferably 10 minutes to 48 hours, more preferably 30 minutes to 24 hours.
Through this fluidized drying treatment, the final resin composition having a moisture content of 0.001 to 2.0% by weight is obtained in the same manner as described above.
[0018]
In the present invention, the content of the phosphoric acid compound (B) with respect to 100 parts by weight of EVOH (A) in the obtained resin composition is 0.0005 to 0.005 with respect to 100 parts by weight of (A) in terms of phosphate radical. 1 part by weight (further 0.001 to 0.05 part by weight, especially 0.002 to 0.03 part by weight) is required, and the amount of the phosphoric acid compound (B) is 0 in terms of phosphate radical. If it is less than .0005 parts by weight, the moldability of the intended resin composition is deteriorated, and conversely if it exceeds 0.1 parts by weight, the appearance of the molded product is deteriorated.
In order to adjust the content of the phosphoric acid compound (B), the concentration of the phosphoric acid compound (B) aqueous solution, the moisture content of the EVOH (A), the contact time, the temperature, the stirring speed, etc. during the contact treatment described above There is no particular limitation.
[0019]
According to the method of the present invention as described above, a resin composition excellent in thermal stability, long run moldability and the like can be obtained. In addition, if necessary, the resin composition further includes a plasticizer and a heat stabilizer. It is also possible to use additives such as ultraviolet absorbers, antioxidants, colorants, antibacterial agents, fillers and other resins. In particular, hydrotalcite compounds, hindered phenols, hindered amine heat stabilizers, and metal salts of higher aliphatic carboxylic acids can also be added as gel generation inhibitors.
Also, as EVOH (A), two or more different types of EVOH can be used. In this case, a blend of EVOH having an ethylene content of 5 mol% or more and / or a saponification degree of 1 mol% or more is different. By using the product, the stretchability at the time of high stretching and the secondary workability such as vacuum / pressure forming and deep drawing are improved while maintaining the gas barrier property.
[0020]
The resin composition thus obtained is frequently used for molded products, and is formed into pellets, films, sheets, containers, fibers, rods, tubes, various molded products by melt molding, etc., and these pulverized products ( (When reusing the recovered product) and pellets can be used for melt molding again. The melt molding methods include extrusion molding (T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion). Etc.), the injection molding method is mainly adopted. The melt molding temperature is often selected from the range of 150 to 300 ° C.
In addition, the resin composition obtained in the present invention can be used as a single layer, but as described above, the effect of the present invention can be sufficiently exhibited particularly when it is used for a laminate. Specifically, it is useful to laminate a thermoplastic resin layer or the like on at least one side of the layer made of the resin composition and use it as a multilayer laminate.
[0021]
In producing the laminate, another substrate is laminated on one side or both sides of the layer of the resin composition. As a lamination method, for example, a thermoplastic resin is applied to a film or sheet of the resin composition. A method of melt extrusion, conversely a method of melt-extruding the resin composition on a substrate such as a thermoplastic resin, a method of co-extrusion of the resin composition and another thermoplastic resin, and further obtained by the present invention Examples include a method of dry laminating a film or sheet of a resin composition and a film or sheet of another substrate using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound.
[0022]
The other resin in the case of coextrusion is linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ionomer, ethylene-propylene copolymer, ethylene-acrylic acid. Ester copolymers, polypropylene, propylene-α-olefin (α-olefins having 4 to 20 carbon atoms) copolymers, olefins such as polybutene and polypentene, or copolymers thereof, or these olefins alone or copolymers In a broad sense, such as those grafted with unsaturated carboxylic acids or esters thereof, polyesters, polyamides, copolymerized polyamides, polyvinyl chloride, polyvinylidene chloride, acrylic resins, polystyrene, vinyl ester resins, polyester elastomers , Poly Examples include urethane elastomers, chlorinated polyethylene, and chlorinated polypropylene. EVOH can also be coextruded. Among these, polypropylene, polyamide, polyethylene, ethylene-vinyl acetate copolymer, polystyrene, and PET are preferably used from the viewpoint of ease of coextrusion film formation and practicality of film physical properties (particularly strength).
[0023]
Furthermore, a molded product such as a film or a sheet is once obtained from the resin composition obtained in the present invention, and another substrate is extrusion coated thereon, or a film or sheet of another substrate is laminated using an adhesive. In this case, any base material (paper, metal foil, uniaxial or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metallic cotton, wood, etc.) can be used in addition to the thermoplastic resin.
[0024]
The layer structure of the laminate is the same as that of the resin composition layer obtained in the present invention. 1 , A 2 ,..., B (b 1 , B 2 ,..., If it is a film, sheet or bottle shape, not only a / b two-layer structure but also b / a / b, a / b / a, a 1 / A 2 / B, a / b 1 / B 2 , B 2 / B 1 / A / b 1 / B 2 Any combination such as a and b is bimetal type, core (a) -sheath (b) type, core (b) -sheath (a) type, or eccentric core-sheath type is possible. Is possible.
[0025]
The laminate is used in various shapes as it is, but it is also preferable to perform a stretching treatment in order to further improve the physical properties of the laminate, and the stretching may be either uniaxial stretching or biaxial stretching. It may be possible to obtain a stretched film or stretched sheet that has better physical properties when stretched at as high a magnification as possible and does not cause pinholes, cracks, stretch unevenness, delamination, or the like during stretching.
[0026]
As the stretching method, a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, and the like, as well as a deep drawing method, a vacuum forming method, and the like that have a high stretching ratio can be employed. In the case of biaxial stretching, both a simultaneous biaxial stretching method and a sequential biaxial stretching method can be employed. The stretching temperature is selected from the range of about 80 to 170 ° C, preferably about 100 to 160 ° C.
[0027]
After stretching is completed, heat setting is then performed. The heat setting can be carried out by a known means, and the heat treatment is performed at 80 to 170 ° C., preferably 100 to 160 ° C. for about 2 to 600 seconds while keeping the stretched film in a tension state.
In addition, when used for heat shrink packaging applications such as raw meat, processed meat, cheese, etc., after heat stretching after stretching, it is a product film, and after storing the above raw meat, processed meat, cheese, etc. in the film, The film is heat-shrinked at 50 to 130 ° C., preferably 70 to 120 ° C. for about 2 to 300 seconds, and the film is heat-shrinked for close-packaging.
[0028]
The shape of the laminate thus obtained may be any shape, and examples thereof include films, sheets, tapes, bottles, pipes, filaments, profile cross-section extrudates, and the like. In addition, the obtained laminate can be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing, tube processing, split processing, etc. It can be carried out.
The film, sheet or container obtained as described above is useful as various packaging materials such as foods, pharmaceuticals, industrial chemicals and agricultural chemicals.
[0029]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
In the examples, “parts” and “%” are based on weight unless otherwise specified.
Example 1
EVOH [ethylene content 35 mol%, saponification degree 99.5 mol%, MI 12 g / 10 min (210 ° C., load 2160 g)] (A) in water / methanol (water / methanol = 40/60 mixing weight ratio) solution (60 ° C, EVOH concentration 45%) was extruded in a strand form into a water tank maintained at 5 ° C and solidified, and then cut with a cutter to obtain EVOH in the form of pellets (diameter 4 mm, length 4 mm). The EVOH was added to warm water at 30 ° C. and stirred for about 4 hours to obtain a porous precipitate (having a uniform microporous diameter of 4 μm in diameter) having a water content of 50%.
Next, 100 parts of the obtained porous precipitate was put into 200 parts of a 0.06% magnesium dihydrogen phosphate (B) aqueous solution (magnesium dihydrogen phosphate (B) was added to the total water of 100 parts by 0.1%. 048 parts), and the mixture is stirred at 30 ° C. for 5 hours, and the resin composition comprising EVOH (A) and the phosphoric acid compound (B) [the phosphoric acid compound (B) is added to 100 parts by weight of the EVOH (A) 0.012 parts by weight in terms of conversion] was obtained.
The obtained resin composition was dried by the following method.
[0030]
<Fluid drying process>
The resin composition obtained above is dried for about 3 hours while flowing nitrogen gas at 75 ° C. using a batch fluidized bed dryer (column type) to obtain a resin composition having a water content of 20%. It was.
The water content of the resin composition before fluid drying was 50%, and the difference in water content between the resin compositions before and after fluid drying was 30%.
<Standing drying process>
Next, the resin composition after the fluidized drying treatment is dried with nitrogen gas at 125 ° C. for about 18 hours using a batch type box dryer (aeration type), and the target resin having a water content of 0.3% is obtained. A composition [containing 0.012 parts by weight of the phosphoric acid compound (B) in terms of phosphate radicals with respect to 100 parts by weight of EVOH (A)] was obtained.
[0031]
Subsequently, the obtained resin composition was supplied to a multi-layer extrusion apparatus equipped with a feed block 5-layer T-die, and a polyethylene layer ("Novatech LD LF525H" manufactured by Mitsubishi Chemical Corporation) / adhesive resin layer ("Modic" manufactured by Mitsubishi Chemical Corporation). AP240H ”) / resin composition layer / adhesive resin layer (same as left) / polyethylene layer (same as left) of 3 layers / multilayer laminate (thickness: 50/10/20/10/50 (μm)) Generation | occurrence | production of the fine fish eye whose diameter is less than 0.1 mm and the long run moldability were evaluated in the following way.
(Fish eye)
About the film (10 cm x 10 cm) immediately after shaping | molding, the appearance condition of the fish eye whose diameter is less than 0.01-0.1 mm was visually observed, and it was set as the following evaluation.
◎ --- 0 to 3
○ --- 4 to 10
△ --- 11-50 pieces
× --- 51 or more
(Long run formability)
Moreover, said shaping | molding was performed continuously for 10 days, the increase state of the fish eye was similarly observed visually about the molding film at that time, and it evaluated as follows.
○ −−− No increase was observed
△ ---- Slight increase was observed
× −−− Significant increase was observed
[0032]
Example 2
EVOH [ethylene content 40 mol%, saponification degree 99.0 mol%, MI 6 g / 10 min (210 ° C., load 2160 g)] (A) in water / methanol (water / methanol = 20/80 mixing weight ratio) solution (60 ° C) was extruded into a strand of water in a water tank maintained at 5 ° C and solidified, and then cut with a cutter to obtain a pellet-shaped (diameter 4 mm, length 4 mm) EVOH. After washing with warm water, the mixture was poured into an aqueous acetic acid solution and stirred for about 2 hours to obtain a porous precipitate having a moisture content of 55% (microporous particles having an average diameter of 5 μm exist uniformly).
Next, 100 parts of the obtained porous precipitate was put into 300 parts of a 0.007% aqueous solution of calcium dihydrogen phosphate (B) (calcium dihydrogen phosphate (B) was added to the total water content of 100 parts by 0.1%. 006 parts) at 30 ° C. for 5 hours, and the resin composition comprising EVOH (A) and the phosphoric acid compound (B) [the phosphoric acid compound (B) is added to the phosphoric acid radical with respect to 100 parts by weight of EVOH (A). 0.002 parts by weight in terms of conversion] was obtained.
The obtained resin composition was dried by the following method.
[0033]
<Fluid drying process>
The resin composition obtained above was dried for about 3 hours while flowing nitrogen gas at 75 ° C. using a fluidized bed dryer (continuous horizontal multi-chamber type) to obtain a resin composition having a water content of 20%. Obtained.
The moisture content of the resin composition before fluid drying was 55%, and the difference in moisture content of the resin composition before and after fluid drying was 35%.
<Standing drying process>
Next, the resin composition after the fluidized drying treatment is dried with nitrogen gas at 120 ° C. for about 24 hours using a batch type box dryer (aeration type) to obtain a target resin having a moisture content of 0.2%. A composition [containing 0.002 parts by weight of the phosphoric acid compound (B) in terms of phosphate radicals with respect to 100 parts by weight of EVOH (A)] was obtained.
The obtained resin composition was evaluated in the same manner as in Example 1.
[0034]
Example 3
In Example 1, the drying treatment method was changed as follows and the drying treatment was carried out in the same manner as described above, and the phosphoric acid compound (B) was added to 100 parts by weight of the target resin composition [EVOH (A). Was obtained in the same manner by obtaining 0.011 part by weight in terms of phosphate radical.
<Standing drying process>
The obtained resin composition was dried with nitrogen gas at 70 ° C. for about 5 hours using a batch box dryer (aeration type) to obtain a resin composition having a water content of 30%.
In addition, the moisture content of the resin composition before stationary drying was 50%, and the moisture content difference of the resin composition before and after stationary drying was 20%.
<Fluid drying process>
Next, the resin composition after the stationary drying treatment was dried for about 18 hours while flowing nitrogen gas at 120 ° C. using a batch-type box dryer (aeration type) to obtain a moisture content of 0.2%. The intended resin composition was obtained.
[0035]
Example 4
In Example 1, instead of magnesium dihydrogen phosphate (B), 0.03 part of sodium dihydrogen phosphate was used, and phosphate compound (B) was added to phosphate group with respect to 100 parts by weight of EVOH (A). A resin composition before drying containing 0.009 parts by weight in terms of conversion was obtained, and the same procedure was followed except that the drying treatment method was changed as follows to obtain the desired resin composition. Evaluation was performed in the same manner.
<Standing drying process>
The obtained resin composition was dried with nitrogen gas at 70 ° C. for about 5 hours using a batch box dryer (aeration type) to obtain a resin composition having a water content of 30%.
In addition, the moisture content of the resin composition before stationary drying was 50%, and the moisture content difference of the resin composition before and after stationary drying was 20%.
<Fluid drying process>
Next, the resin composition after the stationary drying treatment was dried for about 18 hours while flowing nitrogen gas at 120 ° C. using a batch-type box dryer (aeration type) to obtain a moisture content of 0.2%. The objective resin composition [containing 0.009 parts by weight of the phosphoric acid compound (B) in terms of phosphate radicals with respect to 100 parts by weight of EVOH (A)] was obtained.
[0036]
Example 5
EVOH [ethylene content 30 mol%, saponification degree 99.6 mol%, MI 12 g / 10 min (210 ° C., load 2160 g)] (A) water / methanol (water / methanol = 50/50 mixing weight ratio) solution (60 ° C.) was extruded in a strand form in a water bath maintained at 5 ° C. and solidified, then cut with a cutter to obtain pellet-shaped (diameter 4 mm, length 5 mm) EVOH. After washing with warm water, the mixture was poured into an acetic acid aqueous solution and stirred for about 2 hours to obtain a porous precipitate having a water content of 50% (microporous particles having an average diameter of 4 μm exist uniformly).
Next, 100 parts of the obtained porous precipitate was put into 250 parts of a 0.06% magnesium dihydrogen phosphate (B) aqueous solution, stirred at 30 ° C. for about 4 hours, and then EVOH (A) and phosphoric acid diphosphate. A resin composition comprising magnesium hydride (B) [containing 0.010 parts by weight of phosphate compound (B) in terms of phosphate group with respect to 100 parts by weight of EVOH (A)] was obtained.
The obtained resin composition was dried by the following method.
[0037]
<Standing drying process>
The obtained resin composition was dried with nitrogen gas at 70 ° C. for about 8 hours using a batch-type ventilated flow box dryer to obtain a resin composition having a water content of 25%.
In addition, the moisture content of the resin composition before stationary drying was 50%, and the moisture content difference of the resin composition before and after stationary drying was 25%.
<Fluid drying process>
Subsequently, the resin composition after the stationary drying treatment was dried for about 18 hours while flowing a nitrogen gas at 125 ° C. using a batch tower type fluidized bed dryer, and the water content was 0.3%. A resin composition [containing 0.010 parts by weight of the phosphate compound (B) in terms of phosphate group with respect to 100 parts by weight of EVOH (A)] was obtained.
The obtained resin composition was evaluated in the same manner as in Example 1.
[0038]
Comparative Example 1
In Example 1, it carried out similarly except having adjusted the moisture content of the porous precipitate of EVOH (A) to 10%, and with respect to 100 weight part of resin compositions [EVOH (A), phosphoric acid compound (B ) Was obtained under the same conditions and evaluated in the same manner.
However, the water content of the resin composition after the fluidized drying treatment was 6%, and the resin composition after the stationary drying treatment [the phosphate compound (B) was converted to phosphate radicals with respect to 100 parts by weight of EVOH (A). The final water content was 0.1%.
[0039]
Comparative Example 2
In Example 1, the same procedure was followed except that the water content of the porous precipitate of the water / methanol solution after saponification of EVOH (A) was adjusted to 90%. Resin composition [100 parts by weight of EVOH (A)] On the other hand, after obtaining the phosphoric acid compound (B) containing 0.002 parts by weight in terms of phosphate radical], a drying treatment was performed under the same conditions, and evaluation was performed in the same manner. However, the moisture content of the resin composition after fluid drying treatment is 30%, and the phosphate compound (B) is converted into phosphate radicals with respect to 100 parts by weight of the resin composition [EVOH (A) after stationary drying treatment] The final water content was 0.3%.
[0040]
Comparative Example 3
In Example 1, it carried out similarly except having adjusted the phosphoric acid compound (B) with respect to 100 parts of water to 0.00005, and the phosphoric acid compound (B with respect to 100 weight part of EVOH (A) resin composition. ) Was obtained in the same manner, and then subjected to a drying treatment under the same conditions and evaluated in the same manner.
However, the water content of the resin composition after fluid drying treatment is 20%, and the phosphate composition (B) is converted into phosphate radicals with respect to 100 parts by weight of the EVOH (A) resin composition after stationary drying treatment. The final water content was 0.3%.
[0041]
Comparative Example 4
In Example 1, it carried out similarly except having adjusted 2 parts of phosphoric acid compounds (B) with respect to 100 parts of the total water | moisture content, and the phosphoric acid compound (B) with respect to 100 weight part of resin compositions [EVOH (A). Was obtained under the same conditions and evaluated in the same manner.
However, the water content of the resin composition after fluid drying treatment is 20%, and the phosphate composition (B) is converted into phosphate radicals with respect to 100 parts by weight of the EVOH (A) resin composition after stationary drying treatment. The final water content was 0.3%.
The evaluation results of the examples and comparative examples are summarized in Table 1.
[0042]
[Table 1]
【The invention's effect】
When the resin composition obtained by the method of the present invention is a multi-layer laminate, there is no generation of fine fish eyes having a diameter of less than 0.1 mm, and excellent long-run moldability. It is very useful for foods, pharmaceuticals, agricultural chemicals, films for industrial chemical packaging, sheets, tubes, bags, containers and the like, and can be suitably used for secondary processed products with stretching.
Claims (3)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11418498A JP4082780B2 (en) | 1998-04-08 | 1998-04-08 | Manufacturing method of resin composition |
| US09/269,222 US6174949B1 (en) | 1997-07-25 | 1998-07-24 | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
| PCT/JP1998/003310 WO1999005213A1 (en) | 1997-07-25 | 1998-07-24 | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
| AU83576/98A AU741372B2 (en) | 1997-07-25 | 1998-07-24 | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
| EP98933923A EP0930339B1 (en) | 1997-07-25 | 1998-07-24 | Resin composition, process for preparing the same, and laminate containing layer of said resin composition |
| CA002267756A CA2267756C (en) | 1997-07-25 | 1998-07-24 | Resin composition, production thereof, and laminate comprising a layer composed of said resin composition |
| DE69821905T DE69821905T2 (en) | 1997-07-25 | 1998-07-24 | RESIN COMPOSITION, METHOD FOR THE PRODUCTION THEREOF AND LAMINATES CONTAINING A LAYER OF THIS RESIN COMPOSITION |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11418498A JP4082780B2 (en) | 1998-04-08 | 1998-04-08 | Manufacturing method of resin composition |
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| Publication Number | Publication Date |
|---|---|
| JPH11293077A JPH11293077A (en) | 1999-10-26 |
| JP4082780B2 true JP4082780B2 (en) | 2008-04-30 |
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| JP11418498A Expired - Fee Related JP4082780B2 (en) | 1997-07-25 | 1998-04-08 | Manufacturing method of resin composition |
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| JP4164151B2 (en) * | 1998-04-08 | 2008-10-08 | 日本合成化学工業株式会社 | Manufacturing method of resin composition |
| JP4125417B2 (en) * | 1998-04-08 | 2008-07-30 | 日本合成化学工業株式会社 | Manufacturing method of resin composition |
| JP3841943B2 (en) * | 1997-10-09 | 2006-11-08 | 日本合成化学工業株式会社 | Production method of resin composition |
| WO2022168840A1 (en) | 2021-02-02 | 2022-08-11 | 株式会社クラレ | Ethylene-vinyl alcohol copolymer porous pellets and manufacturing method for same |
| KR20230170681A (en) | 2021-04-12 | 2023-12-19 | 주식회사 쿠라레 | Method for producing acetalized product of ethylene vinyl alcohol copolymer |
| WO2022220085A1 (en) | 2021-04-12 | 2022-10-20 | 株式会社クラレ | Product of acetalization of ethylene/vinyl alcohol copolymer and composition containing said acetalization product |
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| JPS5714381B2 (en) * | 1973-04-26 | 1982-03-24 | ||
| JP3665085B2 (en) * | 1993-09-16 | 2005-06-29 | 株式会社クラレ | Structure comprising an ethylene-vinyl alcohol copolymer layer |
| JPH1067897A (en) * | 1996-06-19 | 1998-03-10 | Kuraray Co Ltd | Resin composition |
| JP3590498B2 (en) * | 1996-06-19 | 2004-11-17 | 株式会社クラレ | Saponified ethylene-vinyl ester copolymer composition and co-extruded multilayer molded article using the same |
| JP4164151B2 (en) * | 1998-04-08 | 2008-10-08 | 日本合成化学工業株式会社 | Manufacturing method of resin composition |
| JP3841941B2 (en) * | 1997-10-09 | 2006-11-08 | 日本合成化学工業株式会社 | Production method of resin composition |
| JP4125417B2 (en) * | 1998-04-08 | 2008-07-30 | 日本合成化学工業株式会社 | Manufacturing method of resin composition |
| JP3841942B2 (en) * | 1997-10-09 | 2006-11-08 | 日本合成化学工業株式会社 | Production method of resin composition |
| JP3895011B2 (en) * | 1997-07-28 | 2007-03-22 | 日本合成化学工業株式会社 | Resin composition and laminate thereof |
| JP3841943B2 (en) * | 1997-10-09 | 2006-11-08 | 日本合成化学工業株式会社 | Production method of resin composition |
| JP3976212B2 (en) * | 1997-11-21 | 2007-09-12 | 日本合成化学工業株式会社 | Continuous treatment of saponified ethylene-vinyl acetate copolymer |
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