JP3976212B2 - Continuous treatment of saponified ethylene-vinyl acetate copolymer - Google Patents
Continuous treatment of saponified ethylene-vinyl acetate copolymer Download PDFInfo
- Publication number
- JP3976212B2 JP3976212B2 JP33809697A JP33809697A JP3976212B2 JP 3976212 B2 JP3976212 B2 JP 3976212B2 JP 33809697 A JP33809697 A JP 33809697A JP 33809697 A JP33809697 A JP 33809697A JP 3976212 B2 JP3976212 B2 JP 3976212B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- vinyl acetate
- acetate copolymer
- salt
- evoh
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【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）の連続処理法に関し、更に詳しくは、成形時の加熱により着色の促進等が起こるなどの性能のばらつきが防止でき、ロングラン成形性等に優れたＥＶＯＨを安定して連続的に得るための処理法に関する。
【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、かかる成形性や熱安定性（耐加熱変色性）等を向上させるために、ＥＶＯＨに酢酸、ホウ酸、リン酸やその金属塩等で処理することが試みられており、その具体的な処理法としては、例えば、特開昭６２−１４３９５４号公報には、スラリー状のＥＶＯＨを酢酸及びリン酸カルシウムの水溶液中で撹拌する方法や特開昭６４−６６２６２号公報にもペレット状のＥＶＯＨを酢酸及び酢酸塩等を含有した水溶液に浸漬する方法が記載されている。
【０００３】
【発明が解決しようとする課題】
しかしながら、上記の如きバッチ方式では、ＥＶＯＨの性能がバッチ毎で水溶液の処理薬剤の調製や処理条件の制御に左右されるところが多く、処理されたＥＶＯＨの性能にばらつきが生じることは否めず、例えば溶融成形時の熱によるＥＶＯＨの変色が促進されたり、あるいは成形性等の性能にばらつきが生じて、良好な成形性が得られない恐れもあり、均一な性能のＥＶＯＨを得るための処理法が望まれるところである。
【０００４】
【課題を解決するための手段】
そこで、本発明者は、かかる現況に鑑みて鋭意研究を重ねた結果、ＥＶＯＨ（Ａ）を酸（Ｂ）および／またはその塩（Ｃ）で処理するにあたり、塔型反応器頂部よりＥＶＯＨ（Ａ）を仕込むと共に該反応器の中部より水を仕込み、かつ該反応器の下部より酸（Ｂ）および／またはその塩（Ｃ）の水溶液を仕込んで、（Ａ）と水、（Ｂ）および／または（Ｃ）の水溶液を向流接触せしめ、余剰の水と酸（Ｂ）および／またはその塩（Ｃ）の水溶液を該反応器の上部より取り出し、該反応器底部より処理されたＥＶＯＨを連続的に取り出すことにより、性能のばらつきが少なく、またフィッシュアイ等の発生を抑制することができ、かつロングラン成形時においても良好なＥＶＯＨが連続的に得られることを見出し、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。
本発明の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、成形物の機械強度が不足して好ましくない。
【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、溶液重合、懸濁重合、エマルジョン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】
上記のＥＶＯＨ（Ａ）の処理に用いられる酸（Ｂ）としては、酢酸、ホウ酸、リン酸、アジピン酸、安息香酸、クエン酸等を挙げることができ、好適には酢酸、ホウ酸、リン酸が用いられる。
また、その塩（Ｃ）としては、上記（Ｂ）のアルカリ金属塩、アルカリ土類金属塩等が挙げられ、具体的には、酢酸塩としては酢酸ナトリウム、酢酸カリウム、酢酸カルシウム、酢酸マグネシウム、酢酸マンガン、酢酸銅、酢酸コバルト、酢酸亜鉛などが挙げられ、好適には酢酸ナトリウム、酢酸カルシウム、酢酸マグネシウムが用いられ、ホウ酸塩としてはホウ砂、ホウ酸カルシウムなどが挙げられ、またリン酸塩としては、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があり、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ＥＶＯＨ（Ａ）を酸（Ｂ）やその塩（Ｃ）で処理するにあたり、塔型反応器頂部よりＥＶＯＨ（Ａ）を仕込むと共に該反応器の中部より水を仕込み、かつ該反応器の下部より酸（Ｂ）および／またはその塩（Ｃ）の水溶液を仕込んで、（Ａ）と水、（Ｂ）および／または（Ｃ）の水溶液を向流接触せしめ、余剰の水と酸（Ｂ）および／またはその塩（Ｃ）の水溶液を該反応器の上部より取り出し、該反応器底部より処理されたエチレン−酢酸ビニル共重合体ケン化物を連続的に取り出すことを最大の特徴とするもので、かかる方法について具体的に説明する。
【０００９】
本発明の塔型反応器とは、特に限定されないが、反応器の高さと直径の比（高さ／直径）が４〜１２程度の反応器（缶）で、その頂部、上部、中部、下部、底部等に原料や処理品等の供給や排出のための開口部が設けられたもので、反応器内の水や酸（Ｂ）および／またはその塩（Ｃ）の水溶液の温度調節が可能な温調設備または温調ジャケット等が付随しているもので、撹拌装置等が付いていても構わない。
【００１０】
本発明においては、上記の塔型反応器の頂部よりＥＶＯＨ（Ａ）を仕込むのであるが、かかる仕込みにあたっては、ＥＶＯＨをペレット状にして水を含水させた状態で仕込むことが好ましく、このときのＥＶＯＨの含水率は４０〜７５重量％が好ましく、かかる含水率が４０重量％未満ではＥＶＯＨに酸や塩が含有されにくくなり、逆に７５重量％を越えるとＥＶＯＨに過剰に酸や塩が含有されやすくなって好ましくない。この際、含水させる水にあらかじめメタノール、エタノール、プロパノール等のアルコールや酢酸メチル、酢酸エチル等の溶剤を含有していても差し支えない。尚、（含水）ＥＶＯＨ（Ａ）の仕込み速度は、０．１〜５ｍ3／ｈｒ程度が好ましい。
【００１１】
また、該反応器の中部より水を仕込むのであるが、仕込み位置は反応器底部より１／３〜１／２の高さで、特に３／５〜１／２の高さが好ましい。このときの水の仕込み量は上記ＥＶＯＨ（Ａ）の２．５〜２５倍が好ましく、２．５倍未満ではＥＶＯＨ（Ａ）中に不純物が存在した場合に該不純物の除去が困難となり、ＥＶＯＨに酸や塩が含有されにくくなり、逆に２５倍を越えると膨大な量の水が必要となったり、ＥＶＯＨの処理量が極めて少なくなったりして、工業的に好ましくない。
このときの水はイオン交換水等の金属イオンをほとんど含まない水であることが好ましい。
【００１２】
更に該反応器の下部より酸（Ｂ）および／またはその塩（Ｃ）の水溶液を仕込むのであるが、このときの該水溶液の仕込み量は上記ＥＶＯＨ（Ａ）の２〜１２倍が好ましく、２倍未満ではＥＶＯＨに必要量の酸や塩が含有されなかったり、酸や塩の含有量が不均一になる恐れがあり、逆に１２倍を越えるとＥＶＯＨに過剰の酸や塩が含有される恐れがあり好ましくない。
【００１３】
また、上記の水、酸（Ｂ）および／またはその塩（Ｃ）の水溶液の塔型反応器内での流速は０．０１〜０．３ｍ／ｍｉｎであることが好ましく、該流速が０．０１ｍ／ｍｉｎ未満ではＥＶＯＨに含有される酸や塩の量にばらつきが生じやすく、逆に０．３ｍ／ｍｉｎを越えるとＥＶＯＨ（Ａ）が浮遊する恐れがあり、この場合もＥＶＯＨに含有される酸や塩の量にばらつきが生じやすく好ましくない。
【００１４】
本発明においては、上記の酸（Ｂ）および／またはその塩（Ｃ）の水溶液濃度は、特に限定されず、その種類によっても異なり一概にいえないが、０．０００１〜１重量％が適当である。更に具体的には、酸（Ｂ）の場合は、０．００５〜１重量％（更には０．０１〜０．８重量％）が好ましく、０．００５重量％未満では酸の添加効果が発揮されなくなり、逆に１重量％を越えると塩を併用したときの塩の添加効果が発揮されず好ましくない。また、その塩（Ｃ）の場合は、０．０００１〜０．５重量％（更には０．００１〜０．３重量％）が好ましく、０．０００１重量％未満では塩の添加効果が発揮されなくなり、逆に０．５重量％を越えると酸を併用したときの酸の添加効果が発揮されず好ましくない。
【００１５】
また、上記の処理において、余剰となった水と酸（Ｂ）および／またはその塩（Ｃ）の水溶液は該反応器の上部より取り出すことが必要で、かかる取り出しにあたっては、（Ａ）〜（Ｃ）及び水の仕込み量や（Ｂ）、（Ｃ）の含有量により、適宜取り出し量を調整すればよい。
また、該反応器中の処理時の温度は、コントロールすることが好ましく、反応器内の液及び該反応器に仕込まれる上記の水、（Ｂ）や（Ｃ）の水溶液の温度を１０〜５０℃（特に２０〜４０℃）になるようにすることが好ましく、かかる温度が１０℃未満ではＥＶＯＨに酸や塩を含有させることが困難となり、逆に５０℃を越えると、ＥＶＯＨが溶出しやすくなって好ましくない。ＥＶＯＨの滞留時間は、１〜１０時間程度の範囲から選択される。
【００１６】
かくして処理されたＥＶＯＨは、反応器底部より連続的に取り出され、７０〜１３０℃で、６〜２４時間程度乾燥処理が行われる。かかるＥＶＯＨには、更に、必要に応じて、可塑剤、熱安定化剤、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配合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やヒンダードアミン系の熱安定化剤、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。
本発明の処理法で得られたＥＶＯＨ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が多い。
【００１７】
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、１５０〜２５０℃の範囲から選ぶことが多い。
また、該ＥＶＯＨは、積層体用途にも多用され、特に該ＥＶＯＨからなる層の少なくとも片面に熱可塑性樹脂層を積層してなる積層体として用いられる。
【００１８】
該積層体を製造するに当たっては、本発明の方法で処理されたＥＶＯＨ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ＥＶＯＨのフィルム、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ＥＶＯＨを溶融押出する方法、該ＥＶＯＨ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ＥＶＯＨのフィルム、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。
【００１９】
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。エチレン−酢酸ビニル共重合体ケン化物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。
【００２０】
更に、本発明の方法で処理されたＥＶＯＨから一旦フィルム、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。
積層体の層構成は、本発明の方法で処理されたＥＶＯＨ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。
【００２１】
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。
【００２２】
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。
【００２３】
かくして延伸が終了した後、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。
【００２４】
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。
【００２５】
【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
含水率５５％のペレット状のＥＶＯＨ（Ａ）を塔型反応器（高さ７ｍ、直径１ｍ）の頂部より、０．６ｍ3／ｈｒの速度で仕込みながら、該反応器の中部（高さ３ｍの位置）から水（３０℃）を５．５ｍ3／ｈｒの速度で仕込み、かつ該反応器の下部より０．１０％の酢酸（Ｂ）及び０．００９％のリン酸二水素カルシウム（Ｃ）を含有する水溶液（３０℃）を４．７ｍ3／ｈｒの速度で仕込んで、余剰の水と該水溶液（の混合液）を該反応器の上部より取り出すと同時に該反応器底部より、処理されたＥＶＯＨを連続的に取り出して、取り出し開始６時間後（ａ）、同１２時間後（ｂ）及び同１８時間後（ｃ）のＥＶＯＨについて、１１０℃で１２時間乾燥した後に以下の評価を行った。
（加熱変色）
上記（ａ）〜（ｃ）を１５０℃で５時間放置後、変色度（ＹＩ値）を測定して、（ａ）に対する（ｂ）及び（ｃ）の性能を評価したが、いずれも±２．５％以内であり、安定して性能のばらつきの少ないＥＶＯＨが得られていることが判明した。
【００２６】
また、上記（ａ）〜（ｃ）をＴダイを備えた単軸押出機に供給し、下記の条件で、厚さ１２０μｍのＥＶＯＨフィルムの成形を行って、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を調べた。
上記の成形直後のフィルム（１０ｃｍ×１０ｃｍ）について、直径が０．１ｍｍ未満のフィッシュアイの発生状況を目視観察したが、（ａ）〜（ｃ）いずれもフィッシュアイの発生個数は３個以下で、ばらつきはなく良好であった。
（ロングラン成形性）
また、上記の（Ａ）〜（Ｃ）のＥＶＯＨを上記に準じて順次成形を行って、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たが、（ａ）〜（ｃ）いずれもフィッシュアイの増加は認められず、ばらつきはなく良好であった。
【００２７】
実施例２
実施例１において、反応器の下部からの仕込みを０．１０％の酢酸（Ｂ）の水溶液のみを４．７ｍ3／ｈｒの速度で仕込んだ以外は同様に行って、連続的にＥＶＯＨを得て、同様に評価を行ったが、実施例１と同様に良好な結果であった。
【００２８】
実施例３
実施例１において、反応器の中部からの水の仕込み量を８．３ｍ3／ｈｒの速度とした以外は同様に行って、連続的にＥＶＯＨを得て、同様に評価を行ったが、実施例１と同様に良好な結果であった。
【００２９】
実施例４
実施例１において、反応器の下部より０．３６％の酢酸（Ｂ）、０．０１７％のリン酸（Ｂ）及び０．０１２％のリン酸二水素カルシウム（Ｃ）を含有する水溶液を４．７ｍ3／ｈｒの速度で仕込んだ以外は同様に行って、連続的にＥＶＯＨを得て、同様に評価を行ったが、実施例１と同様に良好な結果であった。
【００３０】
実施例５
実施例１において、反応器の下部より０．０２８％の酢酸（Ｂ）、０．０５５％のホウ酸（Ｂ）及び０．０３５％の酢酸ナトリウム（Ｃ）、０．００５％の酢酸マグネシウム（Ｃ）を含有する水溶液を４．７ｍ3／ｈｒの速度で仕込んだ以外は同様に行って、連続的にＥＶＯＨを得て、同様に評価を行ったが、実施例１と同様に良好な結果であった。
【００３１】
実施例６
実施例１において、含水率６５％のペレット状のＥＶＯＨ（Ａ）を塔型反応器の頂部より、０．８ｍ3／ｈｒの速度で仕込んだ以外は同様に行って、連続的にＥＶＯＨを得て、同様に評価を行ったが、実施例１と同様に良好な結果であった。
【００３２】
【発明の効果】
本発明の処理法においては、性能のばらつきが少なく、ロングラン成形性等に優れたＥＶＯＨを安定して連続的に得ることができ、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ある。
【図面の簡単な説明】
【図１】 本発明の処理法の概念図
【符号の説明】
（ａ）エチレン−酢酸ビニル共重合体ケン化物（Ａ）の供給
（ｂ）水の供給
（ｃ）酸（Ｂ）および／またはその塩（Ｃ）の水溶液の供給
（ｄ）水、酸（Ｂ）および／またはその塩（Ｃ）の水溶液の取り出し
（ｅ）処理されたエチレン−酢酸ビニル共重合体ケン化物の取り出し[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a continuous processing method for a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH), and more specifically, it can prevent variation in performance such as promotion of coloring due to heating during molding. The present invention relates to a treatment method for stably and continuously obtaining EVOH excellent in long-run moldability and the like.
[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. (Formability) is very important, and in order to improve such moldability and thermal stability (heat discoloration resistance), it is attempted to treat EVOH with acetic acid, boric acid, phosphoric acid or a metal salt thereof. As a specific treatment method, for example, JP-A-62-143954 discloses a method of stirring slurry EVOH in an aqueous solution of acetic acid and calcium phosphate, and JP-A-64-66262. Also describes a method of immersing pellet-like EVOH in an aqueous solution containing acetic acid and acetate.
[0003]
[Problems to be solved by the invention]
However, in the batch system as described above, the performance of EVOH is often affected by the preparation of the treatment chemical of the aqueous solution and the control of the processing conditions for each batch, and there is no denying that the performance of the processed EVOH varies. Disposal of EVOH due to heat at the time of melt molding is promoted, or there is a possibility that good moldability may not be obtained due to variations in performance such as moldability. This is what is desired.
[0004]
[Means for Solving the Problems]
Therefore, the present inventor has conducted extensive studies in view of the present situation, and as a result, in treating EVOH (A) with an acid (B) and / or a salt thereof (C), EVOH (A ) And water from the middle of the reactor, and an aqueous solution of acid (B) and / or its salt (C) from the bottom of the reactor, and (A) and water, (B) and / or Alternatively, the aqueous solution of (C) is brought into countercurrent contact, the excess water and the aqueous solution of acid (B) and / or its salt (C) are taken out from the top of the reactor, and the treated EVOH is continuously added from the bottom of the reactor. In order to complete the present invention, it has been found that, by taking out in a continuous manner, there is little variation in performance, generation of fish eyes and the like can be suppressed, and good EVOH can be continuously obtained even during long run molding. It came.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
Although it does not specifically limit as EVOH (A) of this invention, Ethylene content is 20-60 mol% (more 25-55 mol%), Saponification degree is 90 mol% or more (further 95 mol% or more). When the ethylene content is less than 20 mol%, the gas barrier property and melt moldability at high humidity are deteriorated. Conversely, when the ethylene content exceeds 60 mol%, sufficient gas barrier property cannot be obtained. 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 during molding, making extrusion difficult, and if it is larger than this range, the mechanical strength of the molded product will be insufficient.
[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 solution polymerization, suspension polymerization, emulsion polymerization, etc. The ethylene-vinyl acetate copolymer 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]
Examples of the acid (B) used for the treatment of the EVOH (A) include acetic acid, boric acid, phosphoric acid, adipic acid, benzoic acid, citric acid, and the like, and preferably acetic acid, boric acid, phosphorus An acid is used.
Examples of the salt (C) include the alkali metal salts and alkaline earth metal salts of the above (B). Specifically, examples of the acetate include sodium acetate, potassium acetate, calcium acetate, magnesium acetate, Manganese acetate, copper acetate, cobalt acetate, zinc acetate and the like can be mentioned. Sodium acetate, calcium acetate and magnesium acetate are preferably used, and borates include borax and calcium borate, and phosphoric acid. Salts include sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, calcium monohydrogen phosphate, calcium dihydrogen phosphate, tricalcium phosphate, There are magnesium phosphate, magnesium hydrogen phosphate, and magnesium dihydrogen phosphate, preferably sodium dihydrogen phosphate. , Potassium dihydrogen phosphate, calcium dihydrogenphosphate, magnesium dihydrogen phosphate are used.
[0008]
In the present invention, when the EVOH (A) is treated with the acid (B) or a salt thereof (C), EVOH (A) is charged from the top of the column reactor and water is charged from the center of the reactor. In addition, an aqueous solution of acid (B) and / or a salt thereof (C) is charged from the lower part of the reactor, and the aqueous solution of (A) and water, (B) and / or (C) is brought into countercurrent contact. It is important to continuously take out an aqueous solution of water and an acid (B) and / or a salt thereof (C) from the top of the reactor and continuously remove the treated ethylene-vinyl acetate copolymer saponified product from the bottom of the reactor. This method will be described in detail.
[0009]
The tower reactor of the present invention is not particularly limited, but is a reactor (can) having a ratio of height to diameter (height / diameter) of about 4 to 12, and its top, upper, middle, lower The bottom is provided with an opening for supplying and discharging raw materials and processed products, and the temperature of water and acid (B) and / or salt (C) aqueous solution in the reactor can be adjusted. A temperature control facility or a temperature control jacket is attached, and a stirring device or the like may be attached.
[0010]
In the present invention, EVOH (A) is charged from the top of the above-mentioned column type reactor. In such charging, it is preferable to charge EVOH in the form of pellets and containing water. The water content of EVOH is preferably 40 to 75% by weight. When the water content is less than 40% by weight, it becomes difficult for EVOH to contain an acid or salt. Conversely, if it exceeds 75% by weight, EVOH contains an excessive amount of acid or salt. It is not preferable because it is easy to be done. At this time, the water to be water-containing may contain an alcohol such as methanol, ethanol or propanol or a solvent such as methyl acetate or ethyl acetate in advance. In addition, the charging rate of (hydrous) EVOH (A) is preferably about 0.1 to 5 m 3 / hr.
[0011]
In addition, water is charged from the center of the reactor, and the charging position is preferably 1/3 to 1/2 of the bottom of the reactor, particularly preferably 3/5 to 1/2. The amount of water charged at this time is preferably 2.5 to 25 times that of the EVOH (A), and if it is less than 2.5 times, when impurities are present in the EVOH (A), it becomes difficult to remove the impurities. On the contrary, if it exceeds 25 times, a huge amount of water is required or the amount of EVOH treated is extremely small, which is not industrially preferable.
The water at this time is preferably water containing almost no metal ions such as ion exchange water.
[0012]
Further, an aqueous solution of acid (B) and / or a salt thereof (C) is charged from the lower part of the reactor, and the charged amount of the aqueous solution at this time is preferably 2 to 12 times that of the EVOH (A). If it is less than double, EVOH may not contain the required amount of acid or salt, or the content of acid or salt may be uneven. Conversely, if it exceeds 12 times, EVOH contains excessive acid or salt. There is fear and it is not preferable.
[0013]
The flow rate of the aqueous solution of water, acid (B) and / or salt thereof (C) in the tower reactor is preferably 0.01 to 0.3 m / min. If it is less than 01 m / min, the amount of acid or salt contained in EVOH tends to vary, and if it exceeds 0.3 m / min, EVOH (A) may float, and in this case, it is also contained in EVOH. Variations in the amount of acid or salt are apt to occur, which is not preferable.
[0014]
In the present invention, the concentration of the aqueous solution of the acid (B) and / or its salt (C) is not particularly limited and varies depending on the type of the acid (B) and / or its salt (C). is there. More specifically, in the case of the acid (B), 0.005 to 1% by weight (more preferably 0.01 to 0.8% by weight) is preferable, and if it is less than 0.005% by weight, the effect of adding an acid is exhibited. On the other hand, if the amount exceeds 1% by weight, the effect of adding the salt when the salt is used together is not preferable. In the case of the salt (C), 0.0001 to 0.5% by weight (further 0.001 to 0.3% by weight) is preferable, and if it is less than 0.0001% by weight, the effect of adding a salt is exhibited. On the other hand, if it exceeds 0.5% by weight, the effect of adding an acid when an acid is used in combination is not preferable.
[0015]
Further, in the above treatment, it is necessary to take out the excess water and the aqueous solution of the acid (B) and / or its salt (C) from the upper part of the reactor. The amount to be taken out may be appropriately adjusted according to the amount of C) and the amount of water charged and the contents of (B) and (C).
Further, the temperature during the treatment in the reactor is preferably controlled, and the temperature of the liquid in the reactor and the water charged in the reactor, the aqueous solution (B) or (C) is 10 to 50. It is preferable that the temperature is lower than 10 ° C. (especially 20 to 40 ° C.). When the temperature is lower than 10 ° C., it becomes difficult to contain an acid or salt in EVOH. It is not preferable. The residence time of EVOH is selected from the range of about 1 to 10 hours.
[0016]
The EVOH thus treated is continuously taken out from the bottom of the reactor and dried at 70 to 130 ° C. for about 6 to 24 hours. Such EVOH may further contain additives such as a plasticizer, a heat stabilizer, an ultraviolet absorber, an antioxidant, a colorant, an antibacterial agent, a filler, and other resins as necessary. . In particular, a hydrotalcite compound, a hindered phenol-based or hindered amine-based heat stabilizer, or a metal salt of a higher aliphatic carboxylic acid can also be added as a gel generation inhibitor.
EVOH obtained by the treatment method of the present invention is widely used for molded products, and is molded into pellets, films, sheets, containers, fibers, rods, tubes, various molded products, etc. by melt molding, etc. In many cases, the pulverized product (when the recovered product is reused) or pellets are used again for melt molding.
[0017]
As the melt molding method, an extrusion molding method (T-die extrusion, inflation extrusion, blow molding, melt spinning, profile extrusion, etc.) and an injection molding method are mainly employed. The melt molding temperature is often selected from the range of 150 to 250 ° C.
The EVOH is also frequently used for laminates, and is used as a laminate in which a thermoplastic resin layer is laminated on at least one surface of a layer made of the EVOH.
[0018]
In manufacturing the laminate, another substrate is laminated on one or both sides of the EVOH layer treated by the method of the present invention. As the lamination method, for example, the EVOH film or sheet is heated. A method of melt-extruding a plastic resin, conversely a method of melt-extruding the EVOH onto a base material such as a thermoplastic resin, a method of co-extruding the EVOH and another thermoplastic resin, and the EVOH obtained in the present invention And a method of dry laminating a film and a sheet of the above and other base films and sheets using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, and a polyurethane compound.
[0019]
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 copolymer, polypropylene, propylene-α-olefin (α-olefin having 4 to 20 carbon atoms) copolymer, polybutene, polypentene and other olefins alone or copolymers, or these olefins alone or copolymers Polyolefin resins such as those obtained by graft modification 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. A saponified ethylene-vinyl acetate copolymer 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).
[0020]
Furthermore, a molded product such as a film or a sheet is once obtained from EVOH treated by the method of the present invention, and another substrate is extrusion coated thereon, or a film or sheet of another substrate is used with an adhesive. When laminating, any substrate (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.
The layer structure of the laminate is such that the EVOH layer treated by the method of the present invention is a (a 1 , a 2 ,...), And another substrate, for example, a thermoplastic resin layer is b (b 1 , b 2 ,..., If it is a film, sheet, or bottle, not only a / b two-layer structure but also b / a / b, a / b / a, a 1 / a 2 / b, Arbitrary combinations such as a / b 1 / b 2 , b 2 / b 1 / a / b 1 / b 2, etc. are possible. In the filament form, a and b are bimetal type, core (a) -sheath (b) type Arbitrary combinations, such as a core (b) -sheath (a) type or an eccentric core-sheath type, are possible.
[0021]
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 is 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.
[0022]
As the stretching method, in addition to a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, and the like, a deep drawing method, a vacuum forming method, or the like having 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.
[0023]
Thus, 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.
[0024]
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.
[0025]
【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
While charging EVOH (A) in the form of pellets having a water content of 55% from the top of the column reactor (height 7 m, diameter 1 m) at the rate of 0.6 m 3 / hr, the middle part of the reactor (height 3 m Water (30 ° C.) at a rate of 5.5 m 3 / hr and 0.10% acetic acid (B) and 0.009% calcium dihydrogen phosphate (C ) Containing an aqueous solution (30 ° C.) at a rate of 4.7 m 3 / hr, and removing excess water and the aqueous solution (mixture thereof) from the top of the reactor and simultaneously treating from the bottom of the reactor. The extracted EVOH was continuously taken out, dried for 6 hours at 110 ° C. for 12 hours (a), 12 hours (b) and 18 hours (c) after the start of removal, and evaluated as follows. went.
(Discoloration by heating)
The above (a) to (c) were allowed to stand at 150 ° C. for 5 hours, and then the degree of discoloration (YI value) was measured to evaluate the performance of (b) and (c) with respect to (a). It was found that EVOH was obtained within a range of 0.5% and with little variation in performance.
[0026]
Further, the above (a) to (c) are supplied to a single screw extruder equipped with a T die, and an EVOH film having a thickness of 120 μm is formed under the following conditions, and the diameter is 0.1 mm in the following manner. The occurrence of fine fish eyes of less than and long run moldability were investigated.
Regarding the film (10 cm × 10 cm) immediately after the above molding, the occurrence of fish eyes with a diameter of less than 0.1 mm was visually observed, but in any of (a) to (c), the number of fish eyes generated was 3 or less. There was no variation and it was good.
(Long run formability)
Further, the EVOHs of the above (A) to (C) were sequentially molded according to the above, and the increase state of fish eyes was similarly visually observed for the molded film at that time, but (a) to (c) In all cases, no increase in fish eye was observed, and there was no variation and the condition was good.
[0027]
Example 2
In Example 1, the charging from the bottom of the reactor was carried out in the same manner except that only an aqueous solution of 0.10% acetic acid (B) was charged at a rate of 4.7 m 3 / hr, and EVOH was continuously obtained. In the same manner as in Example 1, the evaluation was good.
[0028]
Example 3
In Example 1, EVOH was continuously obtained in the same manner except that the amount of water charged from the center of the reactor was changed to a speed of 8.3 m 3 / hr, and evaluation was performed in the same manner. As in Example 1, good results were obtained.
[0029]
Example 4
In Example 1, an aqueous solution containing 0.36% acetic acid (B), 0.017% phosphoric acid (B) and 0.012% calcium dihydrogen phosphate (C) was added from the bottom of the reactor. Except for charging at a rate of 0.7 m 3 / hr, the same procedure was followed to obtain EVOH continuously and the same evaluation was performed.
[0030]
Example 5
In Example 1, from the bottom of the reactor, 0.028% acetic acid (B), 0.055% boric acid (B) and 0.035% sodium acetate (C), 0.005% magnesium acetate ( The same procedure was performed except that the aqueous solution containing C) was charged at a rate of 4.7 m 3 / hr, and EVOH was continuously obtained. Met.
[0031]
Example 6
In Example 1, EVOH (A) in the form of pellets having a water content of 65% was carried out in the same manner except that it was charged at a rate of 0.8 m 3 / hr from the top of the column reactor, and EVOH was continuously obtained. In the same manner as in Example 1, the evaluation was good.
[0032]
【The invention's effect】
In the treatment method of the present invention, EVOH with little variation in performance and excellent long-run moldability can be obtained stably and continuously. Films, sheets for food and pharmaceuticals, agricultural chemicals, industrial chemicals packaging, It is very useful for applications such as tubes, bags, and containers.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram of the processing method of the present invention.
(A) Supply of saponified ethylene-vinyl acetate copolymer (A) (b) Supply of water (c) Supply of aqueous solution of acid (B) and / or its salt (C) (d) Water, acid (B ) And / or its aqueous solution of salt (C) (e) Removal of treated ethylene-vinyl acetate copolymer saponified product
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33809697A JP3976212B2 (en) | 1997-11-21 | 1997-11-21 | Continuous treatment of saponified ethylene-vinyl acetate copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33809697A JP3976212B2 (en) | 1997-11-21 | 1997-11-21 | Continuous treatment of saponified ethylene-vinyl acetate copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11152307A JPH11152307A (en) | 1999-06-08 |
| JP3976212B2 true JP3976212B2 (en) | 2007-09-12 |
Family
ID=18314878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33809697A Expired - Fee Related JP3976212B2 (en) | 1997-11-21 | 1997-11-21 | Continuous treatment of saponified ethylene-vinyl acetate copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3976212B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4082780B2 (en) * | 1998-04-08 | 2008-04-30 | 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 |
| 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 |
| JP4413350B2 (en) * | 1999-12-14 | 2010-02-10 | 日本合成化学工業株式会社 | Process for continuous treatment of saponified ethylene-vinyl acetate copolymer |
| JP4733291B2 (en) * | 2000-06-06 | 2011-07-27 | 株式会社クラレ | Process for producing ethylene-vinyl alcohol copolymer resin composition |
| DE60107486T2 (en) | 2000-06-06 | 2005-12-15 | Kuraray Co., Ltd., Kurashiki | Process for the preparation of an ethylene-vinyl alcohol copolymer resin mixture |
| JP3805685B2 (en) * | 2001-01-19 | 2006-08-02 | 株式会社クラレ | Method for producing ethylene-vinyl alcohol copolymer resin |
| US7186775B2 (en) * | 2003-06-20 | 2007-03-06 | Chang Chun Petrochemical Co., Ltd. | Method for improved the handling heat-resistance of the ethylene-vinyl alcohol copolymer |
| US9221194B2 (en) | 2007-12-28 | 2015-12-29 | The Nippon Synthetic Chemical Industry Co., Ltd. | Process for preparing ethylene-vinyl alcohol copolymer composition, and process for producing ethylene-vinyl alcohol copolymer pellets |
| EP2228405B1 (en) * | 2007-12-28 | 2012-10-31 | The Nippon Synthetic Chemical Industry Co., Ltd. | Process for preparing ethylene-vinyl alcohol copolymer composition, and process for producing ethylene-vinyl alcohol copolymer pellets |
| JP5198414B2 (en) * | 2009-11-24 | 2013-05-15 | 日本合成化学工業株式会社 | Process for producing ethylene-vinyl alcohol copolymer |
-
1997
- 1997-11-21 JP JP33809697A patent/JP3976212B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11152307A (en) | 1999-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6232382B1 (en) | Saponified ethylene-vinyl acetate copolymer resin composition and laminate having a layer of said resin composition | |
| JP3976212B2 (en) | Continuous treatment of saponified ethylene-vinyl acetate copolymer | |
| JP4107446B2 (en) | Method for drying saponified pellets of ethylene-vinyl acetate copolymer | |
| JP3998340B2 (en) | Process for producing saponified ethylene-vinyl acetate copolymer composition | |
| JP3871437B2 (en) | Method for drying saponified pellets of ethylene-vinyl acetate copolymer | |
| JP4480826B2 (en) | Method for producing ethylene-vinyl alcohol copolymer resin pellets | |
| JP3895010B2 (en) | Resin composition and laminate thereof | |
| JP4705209B2 (en) | Processing method of saponified pellet of ethylene-vinyl acetate copolymer | |
| JP2001146539A (en) | Resin composition comprising ethylene/vinyl alcohol copolymer having low odor and excellent interlaminar bonding and multilayered structure using the same | |
| JP3942125B2 (en) | Treatment of saponified ethylene-vinyl acetate copolymer | |
| JP4588146B2 (en) | Method for producing ethylene-vinyl alcohol copolymer resin and method for producing pellets | |
| JP4413350B2 (en) | Process for continuous treatment of saponified ethylene-vinyl acetate copolymer | |
| JP2000043040A (en) | Production of saponified ethylene-vinyl acetate copolymer composition pellet | |
| JP4002676B2 (en) | Resin composition and use thereof | |
| JP3841943B2 (en) | Production method of resin composition | |
| JP4082780B2 (en) | Manufacturing method of resin composition | |
| JP4017275B2 (en) | Resin composition and use thereof | |
| JP4975896B2 (en) | Saponified pellet of ethylene-vinyl acetate copolymer | |
| JP3841941B2 (en) | Production method of resin composition | |
| JP4125417B2 (en) | Manufacturing method of resin composition | |
| JP4164151B2 (en) | Manufacturing method of resin composition | |
| JP4262802B2 (en) | Process for producing saponified pellets of ethylene-vinyl acetate copolymer | |
| JP3841942B2 (en) | Production method of resin composition | |
| JP2000143736A (en) | Saponified product of ethylene-vinyl acetate copolymer | |
| JP4107447B2 (en) | Method for drying saponified pellets of ethylene-vinyl acetate copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 19990118 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20041104 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20041104 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20061018 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20061026 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070614 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070615 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100629 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100629 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110629 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120629 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120629 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130629 Year of fee payment: 6 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130629 Year of fee payment: 6 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130629 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130629 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |