JP3764196B2 - Continuous production method of high strength and high modulus polyethylene material - Google Patents

Description

などのベンゾトリアゾル系、フェニルサリチレート、４−ｔ−ブチルフェニルサリチレート、ｐ−オクチルフェニルサリチレートなどのサリチレート系、ジシアノアクリレート系等も用いることができる。また光安定剤、例えばヒンダードピペリジン系のヒンダードアミン系化合物も用いることができる。
【００４２】
その他の材料として、カーボンブラック、アルミニウム粉末、銅粉末等の金属粉末、酸化アルミニウム、酸化鉄、酸化チタン等の金属酸化物粉末が挙げられ、更にアルミナ、炭化硅素、炭酸バリウム、或いはファインセラミックス、ニューセラミックス、アドバンスドセラミックス、モダンセラミックス、ハイテクセラミックス等と呼ばれる、例えば絶縁性等の電磁気的機能を付与するためのＡｌ₂ Ｏ₃ ，ＢｅＯ，ＳｉＣ（＋ＢｅＯ）組成物、蛍光性等の光学的機能を付与するためのＹ₂ ＯＳ（Ｅｕ添加）等も用いることができる。
【００４３】
また、熱可塑性樹脂フィルムに配合することのできる帯電防止剤としては、非イオン系、アニオン系、カチオン系、両性系界面活性剤などが挙げられ、次のようなものを例示することができる。
・非イオン系
ポリオキシエチレン−アルキルアミン、ポリオキシエチレン−アルキルアミド、
【００４４】
【化２】

ポリオキシエチレングリコールアルキルエーテル、ポリオキシエチレングリコールアルキルフェニルエーテル、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ステリアリン酸グリセリンモノエステル、スエアリルジエタノールアミン、など
・アニオン系
アルキルスルホネート、アルキルベンゼンスルホネート、ＲＳＯ₃ Ｎａ、アルキルサルフェネート、ＲＯＳＯ₃ Ｎａ、アルキルホスフェート、ＲＯＰＯ₃ Ｋ₂ 、ポリフォスフェート、ペンタアルキルトリポリホスフェート、など
・カチオン系
アンモニウムクロライド、アンモニウムサルフェート、アンモニウムナイトレートなどに例示される第４級アンモニウム塩、アルキルアミン塩、高級アミンエチレンオキサイド付加体、など
・両性系
アルキルベンタイン系
【００４５】
【化３】

【００４６】
【化４】

【００４７】
【化５】

などのアミノカルボン酸誘導体、アラニン型両性界面活性剤金属塩、イミダゾリン型両性界面活性剤金属塩、ジアミン型両性界面活性剤金属塩、ＥＯ基含両性界面活性剤金属塩など、
・塩化第二銅、カーボンなど
・ポリビニルベンジル型カチオン、ポリアクリル酸型カチオン
などを挙げることができる。
【００４８】
また、熱可塑性樹脂フィルムに配合することのできる接着性付与剤としては、未硬化エポキシ樹脂（顆粒、粉末状）、未硬化不飽和ポリエステル（顆粒、粉末状）、変性ポリアミドなどを挙げることができる。上記したエポキシ樹脂としては、例えばビスフェノールＡのエピクロルヒドリンによるグリシジル誘導体であるビスフェノールＡ型エポキシ樹脂が挙げられ、例えば日本ペルノックスＫＫ製、商品名ペルパウダーＰＥ−０５，ＰＥ−１０，ＰＣＥ−２７３°等を挙げることができる。また、上記した不飽和ポリエステルとしては、例えばイソフタル酸系、水素化ビスフェノール系などを使用主原料とする所謂Ｎタイプなどが好ましく用いられる。
【００４９】
同様に配合することのできる染色性付与剤としては、ケン化度８０％以上、好ましくは９５％以上のポリビニルアルコール粉末、例えばＫクラレ製、商品名ＫクラレポバールＰＶＡ−１１７，ＰＶＡ−ＣＳ，ＰＶＡ−２１７，ＰＶＡ−２０５等、セルローズ粉末、例えばＭＦＲ（１９０℃）：０．１〜２ｇ／ｍｉｎのアセテート粉末、ポリアミド粉末などを挙げることができる。
【００５０】
同様に配合することのできる親水性付与剤としては、上記と同様のポリビニルアルコール粉末、抗菌性およびキレート性等を有するキトサン、アクリル酸などを挙げることができる。
【００５１】
本発明においては、前記したオレフィン系重合体、ナイロン系重合体、ポリエステル系重合体あるいはポリ塩化ビニル系重合体に、前記した着色剤、耐候剤帯電防止剤、親水性付与剤、接着性付与剤および染色性付与剤からなる群から選ばれる少なくとも１種の添加剤が配合され、これらの熱可塑性樹脂フィルムに成膜されるが、添加剤の重合体粉末或いはペレットへの配合マスターバッチとして高濃度に含有した成分をベースポリマーと溶融ブレンドする方法などが採用され、またフィルムないしはシートへの成膜方法については特に限定されるものではなく、通常の押出機による熔融樹脂のＴ−ダイ或いは丸−ダイから押出成形されたものがそのまま利用できる。
【００５２】
前記した熱可塑性樹脂フィルムに含有させる各種添加剤の割合は、通常熱可塑性樹脂に対して通常０．０１〜５０ｗｔ％、好ましくは、０．０５〜４０ｗｔ％である。詳しくは、接着剤の場合、通常０．５〜３０ｗｔ％、好ましくは、１〜２５ｗｔ％、耐候剤の場合、通常０．０１〜１０ｗｔ％、好ましくは、０．０５〜５ｗｔ％、帯電防止剤の場合、通常、０．０１〜１０ｗｔ％、好ましくは、０．０５〜５ｗｔ％が望ましい。親水性付与剤、接着性付与剤または染色性付与剤の場合、通常、１〜２０ｗｔ％、好ましくは、２〜１５ｗｔ％が望ましい。
【００５３】
前記した各種添加剤を配合して得られる熱可塑性樹脂フィルムの形態としては、厚さは特に限定されていないが、被圧縮成形物（または被圧延物、被延伸物）などの芯原料の厚みを超えない範囲であれば特に限定されることはなく、芯材／フィルムの厚みの比は、６０／４０〜９８／２、好ましくは７０／３０〜９５／５であることが望ましく、厚みの具体的数値を挙げれば、通常０．００５〜１ｍｍ程度が望ましい。また、幅は、芯原料と同じことが望ましいが、若干広くても狭くても支障無く実施できる。
【００５４】
圧延工程、必要により更に延伸工程において積層させる熱可塑性樹脂フィルムは、例えばオレフィン系重合体フィルムまたはナイロン系重合体フィルムを単独で積層させることも可能であり、また超高分子量ポリエチレン層を挟んで多層に積層させることも可能であり、さらにオレフィン重合体フィルム層とナイロン系重合体フィルム層またはポリエステル重合体フィルム層とを積層した状態で利用することも可能であり、この際一部のフィルム層にのみ所望の添加剤を配合することもできる。
【００５５】
すなわち、目的および製品形態に合わせて、例えば製品の着色、耐候性付与、帯電性付与等、或いは高強度・高弾性率ポリエチレン材料の積層利用、すなわち、積層時における接着性等を考慮して適宜変更することができる。
【００５６】
次に高強度・高弾性率ポリエチレン材料の製造方法について詳述する。本発明においては、前述したとおり超高分子量ポリエチレンフィルム状成形物の圧延工程、必要により更に延伸工程において、前記熱可塑性樹脂フィルムを介在せしめることにより高強度・高弾性率ポリエチレン材料を製造するものである。なお、本発明でいう「積層」とは、超高分子量ポリエチレン層内部および／または表面に熱可塑性樹脂フィルムを分散させることを示す。この場合、芯材としては超高分子量ポリエチレン層を必須に含有するものとする。
【００５７】
これらの代表的な例として次の方法を挙げることができる。
【００５８】
１．圧延工程において、熱可塑性樹脂フィルムを超高分子量ポリエチレンフィルム状成形物の片側もしくは両側に積層せしめて積層成形する方法。
【００５９】
２．必要により延伸工程において、更に熱可塑性樹脂フィルムを超高分子量ポリエチレンフィルム状成形物の表面の片側もしくは両側に積層せしめて積層成形する方法。
【００６０】
上記した成形方法は、前記した如く、目的とする成形物の特性および熱可塑性樹脂フィルムの多様性との関連で適宜積層方法を変更することが可能であり、例えば圧延工程と延伸工程において異なる熱可塑性樹脂フィルムをそれぞれ積層させることも可能であり、その様式は限定されるものではない。
【００６１】
次に、超高分子量ポリエチレンフィルム状成形物について説明する。かかるフィルム状物としては、前述の超高分子量ポリエチレンを溶融工程を経て押出などの方法によりフィルム状に成形する方法により得られるもの、超高分子量ポリエチレンを多量の溶媒に溶解したのちフィルム状のゲル状物を得る方法もしくはかかるフィルム状ゲル状物からフィルムを得る方法により得られるもの、および溶媒に溶解させることなくまた一度も溶融工程を経ることなく固相状態においてフィルム状に成形する方法により得られるものなどが挙げられ、特に固相状態においてフィルム状に成形する方法により得られるものが望ましい。
【００６２】
固相状態においてフィルム状に成形する方法として望ましい方法としては、超高分子量ポリエチレン粉末を圧縮成形して超高分子量ポリエチレンフィルム状成形物を製造する方法が挙げられる。かかる圧縮成形方法においては、被圧縮物であるポリエチレン粉末の融点未満の温度で圧縮成形工程が実施されることが、引き続いて実施される圧延、延伸工程を経ることによって高強度・高弾性率ポリエチレン材料を得る上で極めて重要である。しかしながら、良好な圧縮成形シートを得るためには、融点未満の温度ではあっても許容できる範囲内であること、すなわち、通常２０℃以上、融点未満、好ましくは５０℃以上融点未満、さらに好ましくは９０〜１４０℃、特に好ましくは１１０〜１３５℃の範囲内であることが望ましい。また、圧縮成型時の圧力は特に限定されないが、通常１０００ｋｇ／ｃｍ²未満、好ましくは０．１〜１０００ｋｇ／ｃｍ²の範囲内が望ましい。
【００６３】
また、圧縮成形装置としては、対向させた回転媒体で連続的に圧縮成形できる装置であれば特に限定されることなく、また、回転媒体としては、一対または二対以上対向するロールや一対以上エンドスレベルトやエンドレスベルトとロールの組み合わせなどが例示できる。以下、その好適な成形装置の１具体例を示す図１に基づいて簡略に説明する。
【００６４】
この装置は、基本的にはロール１〜４により張力がかけられた上下に対向させた一対のエンドレスベルト５，６と、このエンドレスベルトを介し、粉末試料を加圧するための加圧プレート７と、加圧プレートとエンドレスベルトとの間に回転自在で互いに連結されたチェーンローラー群８とからなる加圧手段を有している。
【００６５】
この加圧手段は、エンドレスベルトの内側に設けられた加圧プレートおよび加圧プレートとエンドレスベルトとの間に回転自在な互いに連結されたローラー群からなる。加圧プレートとエンドレスベルトとの間に介在させる回転自在な互いに連結されたチェーンローラー群としては、そのローラー群におけるローラーの回転軸がエンドレスベルトの進行方向にほぼ垂直に配置され、かつ相互に接触しない程度に密接させて多数配列させたものが適当である。
【００６６】
これらのローラーは、両端の中心軸がそれぞれチェーンで固定され、加圧プレートの前後に配設したスプロケット９、１０にこのチェーンを噛み合わせることにより、ローラー群をエンドレスベルトの走行速度の１／２程度の速度で走行させるのがよい。
【００６７】
このローラー群はエンドレスベルトと加圧プレートとの間に固定して介在させてもよいが、この場合には、ローラー群とエンドレスベルトおよび加圧プレートとの間にそれぞれスリップによる摩擦力が生じるので、装置の耐久性に問題が生じる。
【００６８】
加圧プレートとしては、ローラー群に接する面が平滑であり、かつ圧力を均一に伝達できるものである限り特に制限されない。
【００６９】
加圧プレートのエンドレスベルト走行方向の長さは、特に制限されないが、通常３０〜４００ｃｍ、好ましくは５０〜２００ｃｍ程度である。加圧プレートがエンドレスベルトに加える平均圧力は、適宜選択されるが、通常２００ｋｇ／ｃｍ² 未満、望ましくは１００ｋｇ／ｃｍ² 未満、好ましくは０．１〜５０ｋｇ／ｃｍ² 、さらに好ましくは０．１〜２０ｋｇ／ｃｍ² 、特に好ましくは０．５〜１０ｋｇ／ｃｍ² 、さらに特に好ましくは１．０〜８．０ｋｇ／ｃｍ² の圧力である。加圧プレートは、エンドレスベルトを介してポリエチレン粉末を加圧することが第一義的な役割であるが、同時に被圧縮物の加熱手段としても使用することも可能である。本発明においては、前述のとおり被圧縮物であるポリエチレン粉末の融点未満の温度で圧縮成形工程が実施されることが極めて重要であるが、好ましくは通常２０℃以上、融点未満、さらに好ましくは５０℃以上融点未満、特に好ましくは９０〜１４０℃、さらに特に好ましくは１１０〜１３５℃の範囲内であることが望ましい。
【００７０】
そのための被圧縮物の加熱手段としては、加圧部におけるエンドレスベルトを直接加熱するのが最適であるが、加圧プレート内に加熱手段を配設し、加圧プレートからローラー群、エンドレスベルトを経て被圧縮物を加熱したり、図１に示すようにエンドレスベルトに近接させて予備加熱器１１を配設して加熱するのが実際的に便宜である。
【００７１】
加圧プレートへの加熱手段の配設態様としては、断熱部を設けた上で加圧プレート内に電熱ヒーターを埋め込んでもよいし、加圧プレート内に熱媒体の循環流路を配設して熱媒体を用いて加熱してもよい。
【００７２】
この例示された装置を用いて、高強度・高弾性率ポリエチレン材料の連続的製造方法を実施するには、まず、ホッパー１２内に投入された超高分子量ポリエチレン粉末を下方のエンドレスベルト６上に落下させる。
【００７３】
エンドレスベルトの走行速度は、加圧プレートの長さ、圧縮条件にも依存するが、通常は１０〜５００ｃｍ／ｍｉｎ、好ましくは５０〜２００ｃｍ／ｍｉｎ程度である。エンドレスベルト上に乗ったポリエチレン粉末は、ドクターナイフ１６により所定の断面形状となし、必要により加熱器により予備加熱された後、上下のエンドレスベルトによる挟圧部まで移動され、次いでローラー群と加圧プレートとが配設された圧縮部へ移行される。ここで、油圧シリンダー１５からの圧力が加圧プレートへ伝達され、さらにローラー群、エンドレスベルトを経て被圧縮物に圧縮力が加えられる。このとき、加熱体からの熱も同様にローラー群、エンドレスベルトを経て被圧縮物に伝達され、被圧縮物の温度が所定の温度に保持される。
【００７４】
このようにして、超高分子量ポリエチレン粉末が圧縮成形された超高分子量ポリエチレンフィルム状成形物が巻取機１７に巻取られる。
【００７５】
超高分子量ポリエチレンフィルム状成形物を得る他の方法である超高分子量ポリエチレンを溶融工程を経て押出などの方法によりフィルム状に成形する方法については、特に限定されないが、好適な方法としては、溶融条件下スクリュー押出機（好ましくはＬ／Ｄの大きいもの）等によりチューブ状ダイやＴダイから超高分子量ポリエチレンを押し出し、必要に応じ数倍〜十倍程度に延伸する方法などが代表的なものとして挙げられる。
【００７６】
また、超高分子量ポリエチレンフィルム状成形物を得る他の方法である超高分子量ポリエチレンを多量の溶媒に溶解したのちフィルム状のゲル状物を得る方法もしくはかかるフィルム状ゲル状物からフィルムを得る方法についても特に限定されないが、好適な方法としては、超高分子量ポリエチレンが溶解された溶液（通常、３０重量％以下の超高分子量ポリエチレン濃度）から紡出口金を通じテープ状またはフィルム状に引き出し、冷却もしくはそのまま溶媒の一部もしくは溶媒全部を除去し、必要に応じて延伸する方法が挙げられる。
【００７７】
次に、超高分子量ポリエチレンフィルムのロール圧延工程において熱可塑性樹脂フィルムを積層させる方法について説明する。
【００７８】
圧縮成形して得られるフィルム状成形物のロール圧延方法としては、公知の方法を用いることができるが、前記圧縮成形シートを溶融させることなく固相状態に保持したまま、同一方向または回転方向の異なる圧延ロールにより挟圧し、圧延フィルムを得ることができる。このとき、圧延操作により材料の変形比は広く選択することができ、通常、圧延効率（圧延後の長さ／圧延前の長さ）で１．２〜２０、好ましくは１．５〜１０とするのが望ましい。このときの温度としては、通常２０℃以上本発明で用いる超高分子量ポリエチレンフィルム状成形物の融点未満の温度、好ましくは５０℃以上融点未満、さらに好ましくは９０〜１４０℃、特に好ましくは１１０〜１３５℃の温度範囲で実施される。もちろん、上記圧延操作を１回以上の多段で圧延することもできる。
【００７９】
また、この圧延工程において熱可塑性樹脂フィルムを介在させる方法は、代表的圧延成形装置である図２の繰出しロール２０から繰出された超高分子量ポリエチレンフィルム状成形物を、該フィルムの上、下または上下に設置された繰出ロール２１，２１’から繰出される熱可塑性樹脂フィルムと接触させ、予熱ロール群２２のロール表面上で予熱したのち、必要によりさらに赤外線予熱ヒーター２３により再予熱したのち圧延ロール２４で圧延し、得られる圧延シートを巻取機２５に巻取る方法が一般的に採用される。
【００８０】
このように、圧延工程において超高分子量ポリエチレン層に熱可塑性樹脂フィルムを積層させる方法は、例えば超高分子量ポリエチレン粉末の圧縮成形工程において積層させる方法に比して、例えば工程が簡素化され易いという利点もある。ロール圧延に次いで行われる延伸工程においても種々の方法が採用可能である。延伸手段としては熱風延伸、シリンダー延伸、ロール延伸、熱盤延伸などがある。しかしながら、一対のニップロール、或いはクローバーロール間で速度差をつけて延伸を行うのが一般的である。
【００８１】
代表的延伸装置として、熱盤方式を採用する延伸装置により超高分子量ポリエチレン圧延シートに必要により熱可塑性樹脂フィルムを介在させる例を図３（ａ）に示し、熱ロール方式を用いる場合の例を図３（ｂ）に示した。詳細は省略するが、図３（ａ）においては図２の場合とほぼ同様に、繰出しロールから繰出された超高分子量ポリエチレン圧延シートと、その上、下または上下に設置された繰出しロールから繰出された熱可塑性樹脂フィルムとを繰出しピンチロールで接触させ、延伸用熱盤上で引取りピンチロールで引取られながら延伸し、巻取ロールに巻取るものであり、巻取ロールへの巻取りに先立ち、所望により延伸物をスプリット加工してテープヤーンとしてもよく、あるいは、スリット加工したのちスプリット加工してスプリットヤーンにしてもよい。また、図３（ｂ）は、図３（ａ）の延伸用熱盤に代えて３本の延伸用熱ロールにより、必要によりロール回転速度を変えて、延伸する方法を図示したものである。
【００８２】
上記した延伸操作における延伸温度は、被延伸物の融点未満の範囲内、通常２０〜１６０℃、好ましくは６０〜１５０℃、さらに好ましくは９０〜１４５℃、特に好ましくは９０〜１４０℃である。また、延伸工程も１段だけでなく多段で行うこともできる。この場合、１段目より２段目の方を高い温度で行うのが好ましい。
【００８３】
延伸速度は、引張延伸の方法、ポリマー分子量、組成比により異るものであり、適宜選択可能であるが、通常１ｍｍ／ｍｉｎ〜５００ｍ／ｍｉｎ、特に、回分式延伸の場合は、通常、１〜５００ｍｍ／ｍｉｎ、好ましくは１〜１００ｍｍ／ｍｉｎ、さらに好ましくは５〜５０ｍｍ／ｍｉｎの範囲であり、連続延伸の場合には、通常、０．１〜５００ｍ／ｍｉｎ、好ましくは１〜２００ｍ／ｍｉｎ、さらに好ましくは１０〜２００ｍ／ｍｉｎの範囲内であり、経済性を考慮すれば、高速度の設定がより好ましい。
【００８４】
延伸倍率は高倍率にするほど高強度で高弾性率が達成できるため、できるだけ延伸倍率を高めることが望ましく、本発明においては圧延および引張延伸の合計の延伸倍率であるトータル延伸倍率が通常２０倍以上、好ましくは６０倍以上、さらに好ましくは８０〜２００倍とすることが可能であり、極めて高い延伸倍率の延伸が可能である。
【００８５】
上記した方法により超高分子量ポリエチレン粉末のみを圧縮成形工程、圧延工程および延伸工程に付して得られる延伸物の引張弾性率は、通常６０ＧＰａ以上、より一般的には８０ＧＰａ〜１８０ＧＰａ、さらに一般的には１２０〜１５０ＧＰａの範囲である。また引張強度は、通常０．７ＧＰａ以上、より一般的には１．０ＧＰａ〜５．０ＧＰａ、さらに一般的には１．５ＧＰａ〜３．０ＧＰａの極めて高い物性値を有するものである。
【００８６】
本発明においては、前述のように所望の特性に対応して積層させる熱可塑性樹脂粉末またはフィルムが適宜選択され、それによって延伸物の物理的特性も若干相違するが、一般的に引張弾性率は４０ＧＰａ〜１８０ＧＰａの範囲、より一般的には１００〜１５０ＧＰａの範囲であり、また引張強度は０．７ＧＰａ〜５．０ＧＰａの範囲、より一般的には１．０ＧＰａ〜３．０ＧＰａの範囲である。
【００８７】
本発明は熱可塑性樹脂粉末またはフィルムを介在させたとしても、実質的に同等かもしくは大きく低下しない物理的特性を有する延伸物を得るという大きな特徴を有する。
【００８８】
本発明の高強度・高弾性率ポリエチレン材料は、どのような用途にも利用可能であるが、ヤーンとして利用することにより、さらに優れた特性を有する高強度・高弾性率ポリエチレン材料とすることができる。以下、これについてさらに説明する。
【００８９】
ヤーンとしては、マルチフィラメントヤーン、モノフィラメントヤーン、テープ状フィラメントヤーンなどのテープヤーンとスプリットヤーンが含まれる。これらのうち、高強度・高弾性率ポリエチレン材料として特に特徴的であるスプリットヤーンとして後加工する場合について最初に詳述する。
【００９０】
本発明における高強度・高弾性率ポリエチレン材料の特性を象徴する一つの目的製品であるスプリットヤーンは、前記超高分子量ポリエチレン延伸物をスプリット化することにより製造される。スプリット化の方法としては、特に限定されるものではなく、公知の方法を用いることができる。例えば、フィルム状またはシート状などの形状の延伸物を、叩打する方法、捻転する方法、摩擦する方法、ブラッシュする方法などの機械的方法や、エアージェットによる方法、超音波により割れ目を入れる方法、爆発風により処理する爆発法などが挙げられる。
【００９１】
本発明においては、機械的方法の採用が好ましく、特に回転式機械的方法の採用が好ましい。かかる機械的な方法としては、タップネジ状スプリッター、ヤスリ状粗面体スプリッター、針ロール状スプリッターなどの各種形状のスプリッターを用いる方法を例示することができる。なお、タップネジ状スプリッターとしては、通常、５角や６角（図４）の角形であり、１インチ当たり、１０〜４０、好ましくは１５〜３５のネジ山を有するものが望ましい。また、ヤスリ状スプリッターとしては、本発明者らの考案（実公昭５１−３８９８０号）になる図５に示すものが好適である。図５において円形断面軸２６の表面２７は鉄工用丸ヤスリ目またはこれに類似の粗面体であり、その面に２条のらせん溝２８および２８’を等ピッチに削ったものである。
【００９２】
用いるスプリット化装置としては、特に限定されないが、図６に記載したように、基本的にはニップロール２９，２９’とニップロール３０，３０’の間に、回転式のスプリッター３１を配置し、延伸物の張力をかけつつ移動し、回転式のスプリッターに接触させる方法が代表例として挙げられる。このときの延伸物の移動速度は、特に限定されないが、通常１〜１０００ｍ／ｍｉｎ、好ましくは２０〜３００ｍ／ｍｉｎである。また、スプリッターの回転速度（周速度）は、延伸物の物性、移動速度、目的とするスプリットヤーンの性状により、適宜選択されるが、通常、１０〜３０００ｍ／ｍｉｎ、好ましくは５０〜１０００ｍ／ｍｉｎである。また、延伸物とスプリッターの接触角は、通常３０〜１８０度、好ましくは６０〜９０度であることが望ましい。なお、延伸テープは、滑り易いため、スプリッターの前後に設置されているニップロールにおいて、テープを所定の速度に保持することが難しい場合があるので、ニップロールとクローバーロールを併用したり、或いはネルソンロールを用いたり、さらに、これらを組み合わせるなど滑り防止策を講じることが望ましい。
【００９３】
ブラッシュする方法や回転式スプリッターを用いる方法においては、その操作は延伸物に張力をかけて行うことが好ましく、前述した延伸物の高い引張弾性率との関連において、通常延伸物が０．１〜３％、好ましくは０．５〜２％変形することが好ましい。この場合、スプリット装置にテープの張力を一定に保つために、ダンサーロールなどの張力コントローラを設置するのも有効な手段である。
【００９４】
また、スプリット化の際の温度は、通常−２０〜＋１００℃、好ましくは−５〜＋５０℃、さらに好ましくは０〜２０℃の範囲が採用される。スプリット化は１段階で行うだけではなく、多段階で行ってもよいし、また厚みが大きな材料に対しては表と裏の両面からスプリット化を行うこともできる。なお、これらの方法としては、具体的には米国特許公報第２１８５７８９号、同３２１４８９９号、同２９５４５８７号、同３６６２９３５号、同３６９３８５１号、特公昭３６−１３１１６号、特公昭４３−１６９０９号などに例示されている。
【００９５】
これらの方法により得られるスプリットヤーンにおいては、スプリットヤーンの厚みが、通常、１０〜２００μｍ、好ましくは３０〜１００μｍである。厚みが１０μｍより小さいとフィルム状またはシート状の延伸物が縦方向に裂けることがあり、またスプリット化されたフィブリルが毛羽だったり、スプリッターに巻付いたりして、品質や工程が安定しないことがある。一方、２００μｍを越えるとスプリット性が悪くなり易い。また、スプリット幅は、通常１０〜５００μｍ、好ましくは５０〜２００μｍの範囲である。
【００９６】
本発明により得られるスプリット化ヤーンは、顔料、耐候剤、帯電防止剤等の添加による効果と共に優れた柔軟性を有しかつ高い強度を有する点で特徴的である。スプリット処理後の強度としては、通常０．４ＧＰａ以上であり、撚りをかけることによりさらに強度を高めることができ、スプリットする前の強度とほぼ同等にすることができる。５０〜５００回／ｍの範囲内に撚りをかけたときの引張強度の最高値は少なくとも０．７ＧＰａ以上であり、一般的には１ＧＰａ以上、さらに一般的には１．５ＧＰａ以上であり、このような値は、約８ｇ／ｄ以上、一般的には約１１．５ｇ／ｄ以上、さらに一般的には約１７ｇ／ｄ以上の高強度に相当するものである。
【００９７】
本発明に用いられるポリエチレン延伸材料は、極性基がなく、表面が活性でないために、表面への印刷、或いは接着が一般的には困難である。したがって必要に応じてスプリット処理する前、或いは好ましくはスプリット処理後に、延伸物をコロナ放電処理、プラズマ処理、薬品酸化処理、或いは火焔処理などの表面処理を行うことも好適に行われる。
【００９８】
上記した方法により得られる、すなわち、ロール圧延工程において添加剤が配合されている熱可塑性樹脂フィルムを積層し、次いで、延伸して得られる高強度高弾性率ポリエチレン材料を、更にスリット処理またはスプリット処理して得られるポリエチレン材料の性状は、添加剤が配合されている熱可塑性樹脂粉末またはフィルムの種、積層量ないしは積層方法等によって著るしく相違するものであるが、添加剤が配合されている熱可塑性樹脂を積層しない状態で得られるスリット体またはスプリット体の性状としては次のように説明することができる。
【００９９】
すなわち、スリット体の場合は、独立した複数本の長四角型テープであり、一方、スプリット体の場合は相互に分離されておらず、逆に相互に結びついた網状体を形成する。例えば６０μｍの厚みを有するフィルムのスリット幅の限界値は１．６ｍｍ程度であり、この場合のスリット体の繊度は概略８００〜９００ｄ程度のものとなる。これに対し、スプリット体のスプリット幅は一般的に１０〜５００μｍの範囲、この値の対数平均値は７０μｍ程度であり、スプリット厚みは１０〜２００μｍの範囲、この値の対数平均値は４５μｍ程度であり、このようなスプリット体の繊度は概略３０ｄ程度のものとなる。
【０１００】
因に上記した１．６ｍｍスリット体の下記式で示される柔軟度は２６６０ｍｇ・ｃｍ程度であり、上記スプリット体の柔軟度は９８０ｍｇ・ｃｍ程度である。
【０１０１】
【数１】

但し、２５０ｔ／ｍの撚りをかけて測定
なお、スリットする前の上記ポリエチレ材料の柔軟度は３５００ｍｇ・ｃｍ程度のものであった事からも、高強度・高弾性率ポリエチレン材料を更にスリットあるいはより好ましくはスプリット加工することによって、より好ましい高強度・高弾性率・高柔軟性ポリエチレン材料とすることができる。
【０１０２】
本発明のスプリット化ポリエチレン延伸材料は、そのまま用いてもまた撚りをかけた状態で用いてもよい。撚りをかける際の回数は特に限定されないが、通常５０〜５００回／ｍ程度であり、好ましくは１００〜３００回／ｍ程度が高い強度を示すことから好ましい。また、その場合の温度は特に限定されないが、通常、０〜１００℃、好ましくは１０〜６０℃の範囲である。
【０１０３】
【実施例】
実施例１
（１）熱可塑性樹脂フィルムの製造
高密度ポリエチレン（商品名：スタフレンＥ−７１０（日本石油化学（株）製、Ｍ１：１．０））をベースポリマーとし、アゾ系レッド１５重量％を混合し、溶融押出機にかけてマスターバッチに加工した。次にこのマスターバッチ２０重量部と高密度ポリエチレン（商品名：スタフレンＥ−７１０（日本石油化学（株）製、Ｍ１：１．０））を２３０℃で混練したのち、厚さ０．０２ｍｍになるよう連続的に押出し製膜した。
（２）高強度材料の製造
（圧縮成形）
装置仕様：
１．ロール 径 ５００ｍｍ 面長 ３００ｍｍ
２．スチ−ルベルト 肉厚 ０．６ｍｍ 幅 ２００ｍｍ
３．小口径ローラー 径 １２ｍｍ 面長 ２５０ｍｍ
４．加圧プレート 長さ １０００ｍｍ 幅 ２００ｍｍ
５．油圧シリンダー 径 １２５ｍｍ
上記仕様の圧縮成形装置を用いて、一対のスチールベルトの間に超高分子量ポリエチレン粉末（１３５℃デカリン中における極限粘度［η］＝１４ｄｌ／ｇ、粘度平均分子量２００万）を挟持し、１３０℃に加熱し、材料への平均圧力約６ｋｇ／ｃｍ² で加圧（油圧シリンダ、加圧プレート、小口径ローラー、スチールベルトの順序で圧力を伝達）し、１ｍ／分の速度で連続的に圧縮成形した。
【０１０４】
その結果、肉厚１．１ｍｍ、幅１００ｍｍのシートを得た。
【０１０５】
（圧延）
上下に配置され、同一速度で反対方向に回転し、表面温度が１４０℃に調整された一対のロール（径２５０ｍｍ、面長３００ｍｍ、ロール間隙０．０７ｍｍ）の間に一対の前記アゾ系レッド配合熱可塑性樹脂フィルム（幅約１００ｍｍ）を挿入し、該一対のフィルムの間に前記圧縮成形シートを供給し、入口速度１ｍ／分、出口速度７ｍ／分にて行い、圧延倍率７倍の肉厚０．１５７ｍｍ、幅９８ｍｍの着色圧延シートを得た。
【０１０６】
（延伸）
装置仕様
１．予熱用ロール ３本 径 ２５０ｍｍ 面長 ２００ｍｍ
２．延伸用ロール 径 １２５ｍｍ 面長 ２００ｍｍ
ロール内部には熱媒体用オイルを循環
ロール間距離はいずれも３０ｍｍ
３．冷却用ロール ３本 径 ２５０ｍｍ 面長 ２００ｍｍ
ロール内部には冷却水を循環
４．ニップロール
入口側： φ２００ｍｍシリコンゴムロールが予熱用ロール２本に対してニップ
出口側： φ２００ｍｍシリコンゴムロールが冷却用ロール２本に対してニップ
得られた圧延シートを幅６ｍｍにスリットして上記仕様の延伸装置を用い、引張延伸を行った。引張延伸は次表の条件により３回繰り返し行った。
【０１０７】
延伸の結果、赤色にむら無く着色したポリエチレン延伸材料が得られた。
【０１０８】
この材料について物性を測定したところ、引張強度が２５．０ｇ／ｄ、伸度は１．８％であった。
【０１０９】
【表１】

（スプリット工程）
装置仕様
１．入口ピンチロール： φ１６０ｍｍ、面長２００ｍｍの金属ロールとウレタンゴムロール
２．出口ピンチロール： φ１６０ｍｍ、面長２００ｍｍの金属ロールとウレタンゴムロール
３．スプリッター： 断面形状が正六角形で一辺の長さが２０ｍｍのねじ切りタップ状の刃で、刃のピッチが０．６ｍｍになっている割繊具
スプリット条件
１．ニップロール速度： 入口側３０ｍ／分→出口側３０．３ｍ／分
２スプリッターの接触角度と周速度比： ９０度、２．３倍
前記赤色延伸テープ（幅約２ｍｍ）を、上記装置と運転条件でスプリットを行い、単糸幅が０．６ｍｍ、一辺の長さが１２ｍｍの菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性（１ｍ当たり１００回よりをかけて測定、１００ｔ／ｍ、以後同様）は、引張強度が２１．０ｇ／ｄ、伸度は１．６％であった。
【０１１０】
実施例２
実施例１の（１）熱可塑性樹脂フィルムの製造において、アゾ系レッドに代えてシアニンブルーを用いた以外は、実施例１と同様に行った。
【０１１１】
その結果、青色にむら無く着色した延伸ポリエチレンが得られ、その物性は引張強度が２４．３ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の青色網状スプリットヤーンが得られた。このスプリットヤーンの物性（１００ｔ／ｍ）は、引張強度が２１．０ｇ／ｄ、伸度は１．６％であった。
【０１１２】
実施例３
実施例１の（１）熱可塑性樹脂フィルムの製造において、アゾ系レッドに代えて超微粒子カーボンブラックを用いた以外は、実施例１と同様に行った。
【０１１３】
その結果、黒色にむら無く着色した延伸ポリエチレンが得られ、その物性は引張強度が２４．４ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の黒灰色網状スプリットヤーンが得られた。このスプリットヤーンの物性は、引張強度が２１．１ｇ／ｄ、伸度は１．６％であった。
【０１１４】
実施例４
実施例１の（１）熱可塑性樹脂フィルムの製造において、アゾ系レッドに代えてステアリルジエタノールアミン０．５ｗｔ％を用いた以外は、実施例１と同様に行った。
【０１１５】
その結果、延伸ポリエチレンが得られ、その物性は引張強度が２５．２ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性は、引張強度が２０．９ｇ／ｄ、伸度は１．６％であった。
【０１１６】
また、この延伸物およびスプリットヤーンを分散した灰の上部に近づけたところ、数ｃｍの距離でも灰が付着しなかったことから十分な帯電防止性能が認められた。
【０１１７】
実施例５
実施例４において、ステアリルジエタノールアミン０．５ｗｔ％に代えて、脂肪酸モノグリセライド０．５ｗｔ％を用いた以外は、実施例４と同様に行った。その結果、延伸ポリエチレンが得られ、その物性は引張強度が２４．０ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性は、引張強度が１９．８ｇ／ｄ、伸度は１．６％であった。
【０１１８】
また、この延伸物およびスプリットヤーンを分散した灰の上部に近づけたところ、数ｃｍの距離でも灰が付着しなかったことから十分な帯電防止性能が認められた。
【０１１９】
実施例６
実施例４において、ステアリルジエタノールアミン０．５ｗｔ％に代えて、ＨＡＬＳ（商品名、チヌビン６２２、チバガイギ製）０．１ｗｔ％を用いた以外は、実施例４と同様に行った。
【０１２０】
その結果、延伸ポリエチレンが得られ、その物性は引張強度が２４．０ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性は、引張強度が２０．０ｇ／ｄ、伸度は１．６％であった。
【０１２１】
また、この延伸物およびスプリットヤーンの光安定性能をテストしたところ、良好な特性を示した。
【０１２２】
実施例７
実施例４において、ステアリルジエタノールアミン０．５ｗｔ％に代えて、ＨＡＬＳ（商品名サノールＬＳ２６２６、三共製）０．１ｗｔ％を用いた以外は、実施例４と同様に行った。
【０１２３】
その結果、延伸ポリエチレンが得られ、その物性は引張強度が２４．５ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性は、引張強度が２０．１ｇ／ｄ、伸度は１．６％であった。
【０１２４】
また、この延伸物およびスプリットヤーンの光安定性能をテストしたところ、良好な特性を示した。
【０１２５】
実施例８
（１）熱可塑性樹脂フィルムの製造
高密度ポリエチレン（商品名スタフレンＥ−７１０（日本石油化学（株）製、Ｍ１：１．０））をベースポリマーとし、ポリビニルアルコール３０重量％を混合し、２３０℃で混練したのち、厚さ０．０２ｍｍになるよう連続的に押出し成膜した。
【０１２６】
（２）高強度材料の製造
上記熱可塑性樹脂フィルムを用いた以外は実施例１と同様に行った。
【０１２７】
その結果、延伸ポリエチレンが得られ、その物性は引張強度が２５．０ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性は、引張強度が２０．３ｇ／ｄ、伸度は１．６％であった。
【０１２８】
また、この延伸物の親水性を接触角を測定することにより行ったところ良好な特性を示した。
【０１２９】
実施例９
実施例８の（１）熱可塑性樹脂フィルムの製造において、ポリビニルアルコールに代えてキトサン３０重量％を用いた以外は、実施例８と同様に行った。
【０１３０】
その結果、延伸ポリエチレンが得られ、その物性は引張強度が２４．０ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性は、引張強度が２０．０ｇ／ｄ、伸度は１．６％であった。
【０１３１】
また、この延伸物の親水性を接触角を測定することにより行ったところ良好な特性を示した。
【０１３２】
実施例１０
実施例８の（１）熱可塑性樹脂フィルムの製造において、ポリビニルアルコールに代えてアクリル酸３０重量％を用いた以外は、実施例８と同様に行った。
【０１３３】
その結果、延伸ポリエチレンが得られ、その物性は引張強度が２４．２ｇ／ｄ、伸度は１．８％であった。また、この延伸ポリエチレンをスプリット処理したところ菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性は、引張強度が２０．１ｇ／ｄ、伸度は１．６％であった。
【０１３４】
また、この延伸物の親水性を接触角を測定することにより行ったところ良好な特性を示した。
【０１３５】
実施例１１
（１）熱可塑性樹脂フィルムの製造
高密度ポリエチレン（商品名 スタフレンＥ−７１０（日本石油化学（株）製、Ｍ１：１．０）をベースポリマーとし、アゾ系レッド１５重量％を混合し、溶融押出機にかけてマスターバッチに加工した。次にこのマスターバッチ２０重量部と高密度ポリエチレン（スタンフレンＥ−７１０（日本石油化学（株）製、Ｍ１：１．０）を２３０℃で混練したのち、厚さ０．０２ｍｍになるよう連続的に押出し製膜した。
【０１３６】
（２）高強度材料の製造
（押出成形）
超高分子量ポリエチレン粉末（１３５℃デカリン中における極限粘度［η］＝１４ｄｌ／ｇ、粘度平均分子量２００万）を２５０℃で連続的に押出成膜した。その結果、肉厚０．１ｍｍ、折幅９０ｍｍのシートを得た。
【０１３７】
（圧延）
上下に配置され、同一速度で反対方向に回転し、表面温度が１４０℃に調整された一対のロール（径２５０ｍｍ、面長３００ｍｍ、ロール間隙０．０７ｍｍ）の間に一対の前記アゾ系レッド配合熱可塑性樹脂フィルム（幅約９０ｍｍ）を挿入し、該一対のフィルムの間に前記圧縮成形シートを供給し、入り口速度１ｍ／分、出口速度７ｍ／分にて行い、圧延倍率３倍の肉厚０．０４７ｍｍ、幅８８ｍｍの着色圧延シートを得た。
【０１３８】
（延伸）
装置仕様：
１．予熱用ロール ３本 径 ２５０ｍｍ 面長 ２００ｍｍ
２．延伸用ロール 径 １２５ｍｍ 面長 ２００ｍｍ
ロール内部には熱媒体用オイルを循環
ロール間距離はいずれも３０ｍｍ
３．冷却用ロール ３本 径 ２５０ｍｍ 面長 ２００ｍｍ
ロール内部には冷水を循環
４．ニップロール
入口側：φ２００ｍｍシリコンゴムロールが予熱用ロール２本に対してニップ出口側：φ２００ｍｍシリコンゴムロールが冷却用ロール２本に対してニップ得られた圧延シートを幅１２ｍｍにスリットして上記仕様の延伸装置を用い、引張延伸を行った。引張延伸は次表の条件により３回繰り返し行った。
【０１３９】
延伸の結果、赤色にむら無く着色したポリエチレン延伸材料（幅２．８ｍｍ、肉厚０．０２ｍｍ）が得られた。
この材料について物性を測定したところ、引張強度が１９ｇ／ｄ、伸度は１．８％であった。
【０１４０】
【表２】

（スプリット工程）
装置仕様：
１．入口ピンチロール φ１６０ｍｍ、面長２００ｍｍの金属ロールとウレタンゴムロール
２．出口ピンチロール φ１６０ｍｍ、面長２００ｍｍの金属ロールとウレタンゴムロール
３．スプリッター ：断面形状が正六角形で、一辺の長さが２０ｍｍのねじ切りタップ状の刃で、刃のピッチが０．６ｍｍになっている割繊具
スプリット条件：
１．ニップロール速度：入口側３０ｍ／分→出口側３０．３ｍ／分
２．スプリッターの接触角度と周速比：９０度、２．３倍
前記赤色延伸テープ（幅約２．８ｍｍ）を、上記装置と運転条件でスプリットを行い、単糸幅が０．６ｍｍ、一辺の長さが１２ｍｍの菱形状の網状スプリットヤーンが得られた。このスプリットヤーンの物性（１ｍ当り１００回よりをかけて測定１００ｔ／ｍ、以後同様）は、引張強度が１７ｇ／ｄ、伸度は１．６％であった。
【０１４１】
【発明の効果】
本発明により、着色剤、耐候剤、帯電防止剤、親水性付与剤、接着性付与剤および染色性付与剤の少なくとも１種を配合して得られる熱可塑性樹脂フィルムを、超高分子量ポリエチレンフィルム状成形物のロール圧延工程において積層処理する場合は、得られる高強度・高弾性率ポリエチレン材料を、例えば容易に着色することが可能であり、また耐候性、帯電防止性等の特性を付与することが可能となり、更に染色性付与等の後加工性が容易に付与できる。
【図面の簡単な説明】
【図１】本発明の圧縮成形工程の実施に好適な装置の１例を示す。
【図２】圧延工程の実施に好適な装置の１例を示す。
【図３】延伸工程の実施に好適な装置の２つの例を示す。
【図４】実施において好適なタップネジ状スプリッターの１例。
【図５】実施において好適なヤスリ状スプリッターの１例。
【図６】ズプリット化工程の実施に好適な装置の１例。
【符号の説明】
１〜４ ロール
５〜６ エンドレスベルト
７ 加圧プレート
８ チェーンローラー群
９〜１０ スプロケット
１１ 加熱器
１２ ホッパー
１５ 油圧シリンダー
１６ ドクターナイフ
１７ シート巻取機
２０〜２１ 繰出しロール
２２ 予熱ロール
２３ 赤外線予熱ヒーター
２４ 圧延ロール
２５ 巻取機
２６ 円形断面軸
２７ 表面
２８，２８’ らせん溝
２９，２９’，３０，３０’ ニップロール
３１ スプリッター[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a continuous production method of a surface-modified high-strength and high-modulus polyethylene material, and more particularly suitable for producing ultra-high molecular weight polyethylene tape yarns and split yarns having high strength and high modulus. The present invention relates to a continuous production method of polyethylene material.
[0002]
[Prior art]
So-called ultra-high molecular weight polyolefin having a remarkably high molecular weight is used in various fields as a characteristic engineering plastic having excellent impact resistance, wear resistance and self-lubricating properties. This ultra-high molecular weight polyolefin has a much higher molecular weight than general-purpose polyolefin. Therefore, if a highly oriented product can be stably formed into a slit yarn or split yarn and the molded product can be colored efficiently, impart light resistance, or can be antistatic processed, for example, high strength and high elastic modulus. It is expected to be useful in a wide range as a rope, net or sports / leisure goods for outdoor industries having a large area.
[0003]
However, ultra-high molecular weight polyethylene has a higher melt viscosity than conventional polyethylene, remarkably poor moldability, and cannot be highly oriented by stretching in the state where an additive is added.
[0004]
As an example of this, for example, in JP-A-1-168980, polyolefin fibers are highly hydrophobic and do not have a dyeing seat. Therefore, practically, a stock solution is colored with a pigment, or a metal salt is mixed and used as a seat. It was dyed with a specific dye. However, these methods show that high-strength polyolefin fibers cannot be obtained, and provide a method of dyeing with a specific dye.
[0005]
JP-A-3-227464 also provides a method for dyeing with a specific dye having a ratio between a specific inorganic value and an organic value for the same purpose. Furthermore, JP-A-4-289213 also provides a method for producing colored high-strength and high-modulus ultrahigh-molecular-weight polyethylene fibers in which a dye is added to a fiber in a gel state containing a solvent after spinning and then stretched. Has been.
[0006]
JP-A-4-77232 also provides a method in which a mixture of ultrahigh molecular weight polyethylene and a dye and / or pigment is compression molded at a temperature below the melting point of polyethylene and then stretched.
[0007]
Furthermore, in Japanese Patent Application Laid-Open No. 4-122746, the surface properties were modified by stretching at least a main component composed of ultrahigh molecular weight polyethylene and a component containing polyvinyl chloride at a temperature below the melting point of polyethylene, A method for producing a polyethylene material with improved adhesion is provided, which also shows that powdered ultra-high molecular weight polyethylene is compression molded, rolled and stretched on an endless belt.
[0008]
Melt forming method Gel method
On the other hand, as a continuous production method of a high-strength and high-modulus polyethylene material, according to Japanese Patent Laid-Open No. 3-130116, a compression molding step and / or a method in which ultra high molecular weight polyethylene powder is compression molded and then rolled and stretched. Laminating with laminated plates or other materials by mixing or interposing olefin polymers such as polyethylene, such as polyethylene, etc. in the form of low molecular weight powder, rod, fiber, sheet, film or non-woven fabric in the rolling process. A method for facilitating conversion or combination is disclosed.
[0009]
Further, it is known from JP-A-5-214657 that a stretched polyethylene stretched material obtained by stretching ultra-high molecular weight polyethylene and then splitting it is also useful as a rope for sports and leisure. However, the methods disclosed in JP-A-1-168980 and JP-A-3-227464 require special dyeing materials and cannot satisfy a wide range of requirements. The method disclosed in JP-A-4-77232 has a stable high strength. -It is difficult to produce a high-modulus polyethylene material, and the method of Japanese Patent Laid-Open No. 4-122746 is a molding from a mixture, so that the properties as a high-strength, high-modulus polyethylene material are significantly reduced. Furthermore, in the method of Japanese Patent Laid-Open No. 3-130116, although the problem is solved to some extent, it is necessary to further exhibit the characteristics of the ultrahigh molecular weight polyolefin material itself, and a material suitable for a multifunctional slit yarn or split yarn Is required. On the other hand, although a method of splitting an ultrahigh molecular weight polyethylene stretched material is known from Japanese Patent Application Laid-Open No. 5-214657, the configuration of the present invention and the effects of the present invention described later that can be achieved by adopting the configuration can be predicted immediately. It is not a thing.
[0010]
[Problems to be solved by the invention]
That is, the present invention is easy to meet various requirements without impairing the inherent high strength and high elastic modulus characteristics of the ultrahigh molecular weight polyethylene material in the conventional method described above, and coloring and weather resistance of molded products. The present invention provides an improved method for producing a polyethylene material having an excellent high strength and a high elastic modulus, particularly a tape yarn or a split yarn having stable characteristics, together with an improvement in antistatic properties and the like.
[0011]
[Means for Solving the Problems]
That is, the present invention is a method for producing a high-strength and high-modulus polyethylene material by rolling and stretching an ultrahigh molecular weight polyethylene film-shaped product having an intrinsic viscosity of 5 to 50 dl / g in a 135 ° C. decalin solution. In the roll rolling step, at least one additive selected from the group consisting of a colorant, a weathering agent, an antistatic agent, a hydrophilicity imparting agent, an adhesion imparting agent and a dyeability imparting agent is blended. The present invention provides a continuous production method of a high-strength and high-modulus polyethylene material characterized by laminating a thermoplastic resin layer and a material to be rolled.
[0012]
[Means for Solving the Problems]
  That is, the present invention is a method for producing a high-strength and high-modulus polyethylene material by rolling and stretching an ultrahigh molecular weight polyethylene film-shaped product having an intrinsic viscosity of 5 to 50 dl / g in a 135 ° C. decalin solution. In the roll rolling step, at least one additive selected from the group consisting of a colorant, a weathering agent, an antistatic agent, a hydrophilicity imparting agent, an adhesion imparting agent and a dyeability imparting agent is blended. Laminating the thermoplastic resin layer and the material to be rolledAnd the total draw ratio in the rolling process and the drawing process should be 20 times or more.The present invention provides a continuous method for producing a high-strength and high-modulus polyethylene material.
[0013]
In the present invention described above, by further slitting after the stretching step to obtain a tape yarn or split yarn, it is possible to obtain a further excellent high-strength and high-elasticity polyethylene material. It is useful as an industrial or sports / leisure material such as a rope, golf net, longline, safety net, 2 to 4 axis softener, high-strength tying band, and the like containing a coloring agent and a coloring agent. The present invention is described in detail below.
[0014]
The ultra high molecular weight polyethylene powder used in the present invention has an intrinsic viscosity [η] in decalin of 135 ° C. of 5 to 50 dl / g, preferably 8 to 40 dl / g, more preferably 10 to 30 dl / g. The viscosity average molecular weight corresponds to 500,000 to 12 million, preferably 900,000 to 9 million, and more preferably 1.2 million to 6 million. If [η] is smaller than 5 dl / g, the mechanical properties of the stretched sheet, film, etc. are deteriorated, which is not preferable. On the other hand, if it exceeds 50 dl / g, workability such as tensile drawing is deteriorated, which is not preferable.
[0015]
The density of the ultrahigh molecular weight polyethylene powder is usually 0.920 to 0.985, preferably 0.920 to 0.980, more preferably 0.920 to 0.970 g / cm.^Three , Particularly preferably 0.935 to 0.960 g / cm^Three What is (measured based on JIS K7112B method (30 degreeC)) is used suitably.
[0016]
The ultra-high molecular weight polyethylene having the above-mentioned specific properties used in the present invention is composed of a catalyst component containing at least one compound among compounds containing transition metal elements of groups IV to VI of the periodic table and, if necessary, organic. It can be obtained by homopolymerization of ethylene or copolymerization of ethylene and α-olefin in the presence of a catalyst in combination with a metal compound.
[0017]
As the α-olefin, those having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms can be used. Specific examples include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1. Of these, propylene, butene-1,4-methylpentene-1, and hexene-1 are particularly preferable. As the comonomer, dienes such as butadiene, 1,4-hexadiene, vinyl norbornene, ethylidene-norbornene and the like may be used in combination. The α-olefin content in the ethylene / α-olefin copolymer is usually 0.001 to 10 mol%, preferably 0.01 to 5 mol%, more preferably 0.1 to 1 mol%.
[0018]
As described above, the ultrahigh molecular weight polyethylene of the present invention is a combination of a transition metal of groups IV to VI of the periodic table such as titanium compound, panadium compound, chromium compound, zirconium compound, hafnium compound and an organometallic compound as necessary. However, the method for adjusting these catalyst components is described in detail in the above-mentioned Japanese Patent Application Laid-Open No. 3-130116 and the like, and therefore the description thereof is omitted here. Although there is no restriction | limiting in particular in the usage-amount of the organometallic compound used in this case, Usually, it can be used in 0.1-1,000 mol times with respect to a transition metal compound.
[0019]
The polymerization reaction is carried out in a gas phase with substantially no oxygen, water, etc., or an aliphatic hydrocarbon such as butane, isobutane, pentane, hexane, octane, decane, dodecane, etc., inert to the catalyst. In the presence of alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, petroleum fractions, etc., or the monomer itself is used as a solvent. The polymerization temperature is usually 15 ° C. to 350 ° C., preferably 20 ° C. to 200 ° C., but when an ultra high molecular weight polyethylene film-like molded product described later is produced by a solid phase method, an ultra high molecular weight polyethylene that generates a polymerization temperature The melting point is desirably less than the melting point, and is usually −20 to + 110 ° C., preferably 0 to 90 ° C. When the polymerization temperature is higher than the melting point of the ultrahigh molecular weight polyethylene obtained, when obtaining a film-like molded product by the solid phase method, it may not be possible to stretch 20 times or more as the total stretching ratio in the subsequent stretching step. . The polymerization pressure is usually 0 to 70 kg / cm.² G, preferably 0-60 kg / cm² G is desirable.
[0020]
The molecular weight can be adjusted by changing polymerization conditions such as polymerization temperature, polymerization pressure, catalyst type, molar ratio of catalyst components, hydrogenation into the polymerization system, and the method is not particularly limited. Of course, two-stage or more multi-stage polymerization reactions having different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any trouble.
[0021]
The shape of the ultrahigh molecular weight polyethylene thus obtained is not particularly limited, but in general, granular or powdery materials are preferably used. The particle size is 2000 μm or less, preferably 1000 μm or less. Moreover, a narrower particle size distribution provides a better sheet.
[0022]
As a resin layer laminated in the rolling process of the continuous production method of the high strength and high elastic modulus polyethylene material of the present invention, if necessary, in the stretching process, a powder layer, a film, a nonwoven fabric (including a bundle of fibers), Any of woven fabrics may be used, but a film is preferable. The thermoplastic resin film is obtained by forming a film from an olefin polymer (ethylene / vinyl acetate copolymer, modified ethylene polymer, etc.), a polyamide polymer, a polyester polymer, and a polyvinyl chloride polymer. A film is mentioned as a preferable thing. Incidentally, the shape of the film is not particularly limited, but it is usually 10 to 200 μm, preferably 20 to 100 μm.
[0023]
Examples of the olefin polymer used for the production of a preferable thermoplastic resin film include (1) an ethylene polymer produced using a Ziegler catalyst, an ethylene-α-olefin copolymer, an ethylene polymer produced by high-pressure radical polymerization. (2) grafting these ethylene copolymers in the presence of unsaturated carboxylic acids and / or their derivatives and organic peroxides, such as copolymers, copolymers, and mixtures thereof, and It shows a polymer arbitrarily selected from the group consisting of a modified ethylene (co) polymer obtained by reaction. These ethylene (co) polymers have a molecular weight lower than that of the ultra-high molecular weight polyethylene powder, and usually have [η] of 0.5 to 3 dl / g, preferably 0.8 to 2 dl / g. , Melt index (based on ASTM-D1238-65T, 190 ° C. under 2.16 kg load) Usually 0.01 to 100 g / min, preferably 0.05 to 100 g / 10 min, more preferably 0.1 to 50 g / 10 min, more preferably 0.5 to 10 g / 10 min.
[0024]
As the α-olefin in the ethylene-α-olefin copolymer produced using the Ziegler-based catalyst, various types can be used, preferably 3 to 12 carbon atoms, more preferably 3 to 3 carbon atoms. 8 α-olefins are preferred, specifically propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1 and mixtures thereof. The α-olefin content in the ethylene-α-olefin copolymer is 20 mol% or less, preferably 15 mol% or less.
[0025]
The high-pressure radical polymer includes an ethylene-vinyl ester copolymer or an ethylene / acrylic acid ester copolymer having a comonomer concentration of 30% by weight or less, preferably 25% by weight or less. If the comonomer concentration exceeds 30% by weight, the degree of adhesion increases and compression molding or rolling tends to be difficult.
[0026]
These ethylene (co) polymers used in the present invention have a normal density (based on JIS K-6760) of 0.970 g / cm.^Three Or less, usually 0.935 g / cm^Three Below, preferably 0.930-0.860 g / cm^Three , More preferably 0.930-0.910 g / cm^Three (Ultra) low density polyethylene, the density is usually 0.935 g / cm^Three Over, preferably 0.940-0.970 g / cm^Three Medium high density polyethylene.
[0027]
Each of these ethylene (co) polymers such as ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, and octene-1 other than those described above is within the range not impairing the object of the present invention. A polymer or a mutual copolymer, an ethylene propylene copolymer rubber, an ethylene / propylene / diene copolymer rubber, polyisobutylene and a mixture thereof may be appropriately blended.
[0028]
The unsaturated carboxylic acid used for modifying the ethylene (co) polymer is preferably a monobasic acid or a dibasic acid, specifically, acrylic acid, propionic acid, methacrylic acid, crotonic acid, isocrotonic acid. , Oleic acid, elaidic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and mixtures thereof, and examples of unsaturated carboxylic acid derivatives include metal salts, amides, esters and anhydrides of the above unsaturated carboxylic acids. Among them, maleic anhydride is most preferable.
[0029]
Examples of the organic peroxide include benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxydiisopropyl). ) Benzene, di-t-butyl peroxide, 2,5-di (t-butylperoxy) hexyne and the like are preferably used.
[0030]
As a method of modifying the ethylene (co) polymer with an unsaturated carboxylic acid and / or a derivative thereof, an unsaturated carboxylic acid and / or a derivative thereof is added to the ethylene (co) polymer in the presence of an organic peroxide. Heat to react. In this case, the amount of the unsaturated carboxylic acid or derivative thereof added to the ethylene (co) polymer is 0.05 to 10% by weight, preferably 0.1 to 7% by weight.
[0031]
The amount of the organic peroxide used is 0.005 to 2 parts by weight, preferably 0.01 to 1.0 part by weight based on 100 parts by weight of the total amount of the ethylene (co) polymer and the unsaturated carboxylic acid. Used in range. When the addition amount of the organic peroxide is less than 0.005 parts by weight, the modification effect is not substantially exhibited, and even if added over 2.0 parts by weight, it is difficult to obtain further effects. This may cause excessive decomposition or cross-linking reaction.
[0032]
The modification reaction is a method of melting and mixing in an extruder or a kneader such as a Banbury mixer in the absence of a solvent, an aromatic hydrocarbon such as benzene, xylene or toluene, or an aliphatic hydrocarbon such as hexane, heptane or octane. There is a method of heating and mixing in a solvent such as, but there is no particular limitation, but it can be carried out in an extruder due to simplicity of operation, excellent economy, continuity with subsequent processes, etc. preferable.
[0033]
As these olefin polymers, those formed into a film having a thickness of 10 to 200 μm, preferably 20 to 100 μm, by a known method are preferably used.
[0034]
  Examples of the polyvinyl chloride polymer include all homopolymers of vinyl chloride and copolymers or terpolymers of vinyl chloride monomers and various comonomers. Such a comonomer is not particularly limited, and examples thereof include vinyl acetate.Vinyl acyl esterAcrylic acid or methacrylic acid and esters thereof, maleic acid and esters thereof, acrylonitrile, α-olefins such as ethylene or propylene, vinyl ethers and vinylidene chloride. The comonomer content is not particularly limited, but it is usually 50 mol% or less, preferably 20 mol% or less, and more preferably 0.1 to 15 mol%.
[0035]
The production method of these polyvinyl chloride polymers is not particularly limited, and for example, those obtained by any known method such as bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, precipitation polymerization are used. be able to.
[0036]
These polyvinyl chloride polymers have an average degree of polymerization of usually 50 to 10,000, preferably 100 to 5,000, and more preferably 500 to 5,000. Further, the form of use of the molded product from these polymers is not particularly limited as long as the object of the present invention is not impaired, and any of a sheet and a film may be used. The coalescence may be formed by a known method into a film having a thickness of usually 10 to 200 μm, preferably 20 to 100 μm, and this may be further stretched and used.
[0037]
Further, as the nylon polymer, 6 nylon, 11 nylon, 12 nylon system, 6-6 nylon, 6-10 nylon, 6-66 nylon, copolymer nylon and blend nylon having a low melting point are used. It can be used after it is formed into a film or sheet by a generally known method. The preferred molecular weight range of the above-mentioned nylon polymer is usually about 1000 to 30000.
[0038]
A thermoplastic polyester polymer represented by polyethylene terephthalate (PET) can also be used. For the purpose of the present invention, by adopting a processing temperature in consideration of the glass transition temperature of PET, the ultrahigh molecular weight polyethylene layer is formed in any of the compression molding process, rolling process and stretching process of ultrahigh molecular weight polyethylene powder. Although it is possible to intervene, it is also possible to laminate more easily by replacing a part of terephthalic acid with isophthalic acid. Specific examples include polyethylene terephthalate and polyethylene 2,6-naphthalate, and the molecular weight is not particularly limited as long as it is various film grades and fiber grades.
[0039]
Examples of the colorant, weathering agent, antistatic agent, hydrophilicity-imparting agent, adhesion-imparting agent, and dyeability-imparting agent blended in the thermoplastic resin film described above include the following. The colorant used in the present invention is not particularly limited, and a wide variety of pigments that are usually used for coloring resins or fibers can be exemplified. Colorants can be roughly classified into organic pigments and inorganic pigments. Organic pigments include nitroso, nitro, azo, phthalocyanine, basic dye, acid dye, textile dye, and mordant dyes. Specifically, Hansa Yellow, Benzidine Yellow, Benzidine Orange, C.I. P. Toluidine Red Med, C.I. P. Para Pred Lt, Chlorinated Para Red, Ba Ritol Toner, Ritol Rubin, Permanent Red 28, Bon Red OK, Bon Maroon Lt, Pigment Scarlet Lake, Mader Lake, Thioindigo Red, Pyrazolone Red, Given Zantrone Violet, Helio Fast Ruby , Diazo green, diazo yellow, cyanine fluid, cyanine green, phthalocyanine blue, phthalocyanine green, indanthrene blue, quinacridone, first yellow, brilliant carmine 68, azo red, lake red, lake bordeaux, first sky blue, etc. Examples of inorganic pigments include chromic acid, ferrocyanide, sulfide, sulfate, oxide, hydroxide, silicate, and carbon black. Specific examples include cobalt pigments such as aureolin, cobalt green, cerulean blue, cobalt blue and cobalt violet, iron pigments such as ocher, chenar, bengara and Prussian blue, chromium oxide, chrome lead and pyridian. Chromium pigments, manganese pigments such as mineral violet, copper pigments such as emerald green, vanadium pigments such as vanadium yellow and vanadium blue, mercury pigments such as shrimp, lead pigments such as red lead, sulfides such as cadmium yellow and ultramarine Examples thereof include pigments, selenide pigments such as cadmium red, and fine particle aluminum powder. These pigments have particle sizes of several μ to several tens of μm, and there are various shapes such as a spherical shape, a block shape, a rod shape, a needle shape, and a flake shape. Any particle size and shape can be used in the present invention. Can do. These pigments may be used alone or in combination.
[0040]
  Examples of weathering agents that can be blended in the thermoplastic resin film in the present invention include radical chain inhibitors, antioxidants such as peroxide decomposers, ultraviolet absorbers, and the like.Such as the followingThings can be illustrated.
·Antioxidant
  Radical chain inhibitor:Phenyl-α-naphthylamine, phenyl-β-naphthylamine, Diphenylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, p-hydroxydiphenylamine, p-hydroxyphenyl-β-naphthylamine, 2,2 , 4-trimethyldihydroquinoline, di-β-naphthyl-p-phenylenediamine, N-phenyl-N′-cyclohexylparaphenylene-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine,Aldol-α-naphthylamine, etc.Amine compounds, p-hydroxyphenylcyclohexane, di-p-hydroxyphenylcyclohexane, 2,6-di-t-butylphenol, styrenated phenol, 1,1'-methylenebis (4-hydroxy-3,5-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol),2,6- (2-tert-butyl-4-methyl-6-methylphenol) -p-cresol2,2'-thiobis- (4-methyl-6-tert-butylphenol), 4,4'-thiobis- (4-methyl-6-tert-butylphenol),4,4′-butylidenebis (4-methyl-6-tert-butylphenol), etc.Phenolic compoundsSuch,
  Peroxide decomposer:4,4′-thiobis (3-methyl-6-tert-butylphenol), thiobis (β-naphthol), thiobis (N-phenyl-β-naphthylamine),Mercaptobenzothiazole, mercaptobenzimidazole, dodecyl mercaptan, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, trinonylphenyl phosphite, dilauryl thiodipropionate, distearyl thiodipropionate, etc.
・ UV absorber:
  2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-chlorobenzophenone, 2,2′-dihydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2,4-dibenzoyl-resorcinol, resorcinol monobenzoate, 5-chloro-2-hydroxybenzophenone, 2,2′-dihydroxy-4,4 '-Dimethoxybenzophenone, 4-dodecyl-2-hydroxybenzophenone,2,2 ', 4,4'-tetrahydroxybenzophenoneBenzophenone series such as 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, alkylated hydroxyphenylbenzotriazole,
[0041]
[Chemical 1]

Benzotriazoles such as benzotriazole, phenyl salicylates, 4-t-butylphenyl salicylates, salicylates such as p-octylphenyl salicylates, dicyanoacrylates, and the like can also be used. Light stabilizers such as hindered piperidine-based hindered amine compounds can also be used.
[0042]
Other materials include metal powders such as carbon black, aluminum powder and copper powder, and metal oxide powders such as aluminum oxide, iron oxide and titanium oxide. Furthermore, alumina, silicon carbide, barium carbonate, fine ceramics, Al, which is called ceramics, advanced ceramics, modern ceramics, high-tech ceramics, etc., for imparting electromagnetic functions such as insulation₂ O_Three , BeO, SiC (+ BeO) composition, Y for imparting optical functions such as fluorescence₂ OS (Eu addition) or the like can also be used.
[0043]
Examples of the antistatic agent that can be blended in the thermoplastic resin film include nonionic, anionic, cationic, and amphoteric surfactants, and the following can be exemplified.
・ Non-ionic
Polyoxyethylene-alkylamine, polyoxyethylene-alkylamide,
[0044]
[Chemical formula 2]

Polyoxyethylene glycol alkyl ether, polyoxyethylene glycol alkyl phenyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, stereria phosphate glycerin monoester, diallyl diethanolamine, etc.
・ Anionic
Alkyl sulfonate, alkyl benzene sulfonate, RSO_Three Na, alkyl sulfenate, ROSO_Three Na, alkyl phosphate, ROPO_Three K₂ , Polyphosphate, pentaalkyltripolyphosphate, etc.
・ Cation system
Quaternary ammonium salts, alkylamine salts, higher amine ethylene oxide adducts exemplified by ammonium chloride, ammonium sulfate, ammonium nitrate, etc.
・ Bisexual system
Alkyl bentine type
[0045]
[Chemical Formula 3]

[0046]
[Formula 4]

[0047]
[Chemical formula 5]

Aminocarboxylic acid derivatives such as, alanine type amphoteric surfactant metal salt, imidazoline type amphoteric surfactant metal salt, diamine type amphoteric surfactant metal salt, EO group amphoteric surfactant metal salt, etc.
・ Cupric chloride, carbon, etc.
・ Polyvinylbenzyl type cations, polyacrylic acid type cations
And so on.
[0048]
Examples of the adhesion-imparting agent that can be blended in the thermoplastic resin film include uncured epoxy resin (granule, powder), uncured unsaturated polyester (granule, powder), and modified polyamide. . Examples of the above-mentioned epoxy resin include bisphenol A type epoxy resin which is a glycidyl derivative of epichlorohydrin of bisphenol A. Can be mentioned. Further, as the above-mentioned unsaturated polyester, for example, so-called N type using isophthalic acid type, hydrogenated bisphenol type or the like as a main raw material is preferably used.
[0049]
As dyeing property imparting agents that can be blended in the same manner, polyvinyl alcohol powder having a saponification degree of 80% or more, preferably 95% or more, for example, K Kuraray, trade names K Kuraray Poval PVA-117, PVA-CS, PVA -217, PVA-205, etc., cellulose powder, for example, MFR (190 ° C.): 0.1-2 g / min acetate powder, polyamide powder, and the like.
[0050]
  As a hydrophilicity imparting agent that can be blended in the same manner,Polyvinyl alcoholExamples thereof include powder, chitosan having antibacterial properties and chelating properties, and acrylic acid.
[0051]
In the present invention, the above-mentioned olefin polymer, nylon polymer, polyester polymer or polyvinyl chloride polymer is added to the colorant, weather resistance antistatic agent, hydrophilicity imparting agent, and adhesion imparting agent. And at least one additive selected from the group consisting of a dyeability imparting agent is blended and formed into a film of these thermoplastic resin films, but a high concentration as a blending master batch of the additive into polymer powder or pellets The method of melt blending the components contained in the base polymer with the base polymer is employed, and the film forming method on the film or sheet is not particularly limited. A material extruded from a die can be used as it is.
[0052]
The ratio of the various additives contained in the thermoplastic resin film is usually 0.01 to 50 wt%, preferably 0.05 to 40 wt% with respect to the thermoplastic resin. Specifically, in the case of an adhesive, usually 0.5 to 30 wt%, preferably 1 to 25 wt%, and in the case of a weathering agent, usually 0.01 to 10 wt%, preferably 0.05 to 5 wt%, an antistatic agent. In this case, it is usually 0.01 to 10 wt%, preferably 0.05 to 5 wt%. In the case of a hydrophilicity imparting agent, an adhesion imparting agent or a dyeability imparting agent, it is usually 1 to 20 wt%, preferably 2 to 15 wt%.
[0053]
  The thickness of the thermoplastic resin film obtained by blending the various additives described above is not particularly limited, but the thickness of the core raw material such as a compression-molded product (or a rolled product or a stretched product) As long as it does not exceed the range, there is no particular limitation,Core materialThe film thickness ratio is desirably 60/40 to 98/2, and preferably 70/30 to 95/5, and a specific numerical value of thickness is generally desirably about 0.005 to 1 mm. Further, the width is preferably the same as that of the core raw material, but it can be carried out without any problem even if it is slightly wide or narrow.
[0054]
The thermoplastic resin film to be laminated in the rolling process and, if necessary, in the stretching process, for example, can be laminated with an olefin polymer film or a nylon polymer film alone, and a multilayer with an ultrahigh molecular weight polyethylene layer interposed therebetween. It is also possible to use it in a state in which an olefin polymer film layer and a nylon polymer film layer or a polyester polymer film layer are laminated. Only the desired additives can be blended.
[0055]
That is, according to the purpose and product form, for example, coloring of the product, imparting weather resistance, imparting chargeability, etc., or use of lamination of high-strength / high modulus polyethylene material, that is, adhesiveness at the time of lamination, etc. Can be changed.
[0056]
Next, a method for producing a high strength / high modulus polyethylene material will be described in detail. In the present invention, as described above, a high-strength and high-modulus polyethylene material is produced by interposing the thermoplastic resin film in the rolling process of the ultra-high molecular weight polyethylene film-like molded product, and if necessary, in the stretching process. is there. The term “lamination” as used in the present invention means that a thermoplastic resin film is dispersed inside and / or on the surface of an ultrahigh molecular weight polyethylene layer. In this case, the ultra-high molecular weight polyethylene layer is essential as a core material.
[0057]
The following method can be mentioned as a typical example of these.
[0058]
1. A method in which a thermoplastic resin film is laminated on one side or both sides of an ultra-high molecular weight polyethylene film-like molded product in a rolling process.
[0059]
2. A method in which a thermoplastic resin film is further laminated on one side or both sides of the surface of an ultra-high molecular weight polyethylene film-like molded product in a stretching step, if necessary, and laminated.
[0060]
In the molding method described above, as described above, the lamination method can be appropriately changed in relation to the characteristics of the target molded product and the diversity of the thermoplastic resin film. It is also possible to laminate each plastic resin film, and the mode is not limited.
[0061]
Next, an ultrahigh molecular weight polyethylene film-like molded product will be described. Examples of such a film-like material include those obtained by a method of forming the above ultrahigh molecular weight polyethylene into a film by a method such as extrusion through a melting step, and a film gel after dissolving the ultra high molecular weight polyethylene in a large amount of solvent. Obtained by a method for obtaining a film-like material or a method for obtaining a film from such a film-like gel-like material, and a method for forming a film in a solid phase without dissolving it in a solvent and without undergoing a melting step. In particular, those obtained by a method of forming a film in the solid phase are desirable.
[0062]
A desirable method for forming a film in the solid phase is a method of producing an ultra-high molecular weight polyethylene film-like product by compression molding ultra-high molecular weight polyethylene powder. In such a compression molding method, the compression molding process is performed at a temperature lower than the melting point of the polyethylene powder that is the object to be compressed, and the high-strength and high-modulus polyethylene is obtained through subsequent rolling and stretching processes. It is extremely important in obtaining the material. However, in order to obtain a good compression-molded sheet, it is within an acceptable range even at a temperature below the melting point, that is, usually 20 ° C. or higher and lower than the melting point, preferably 50 ° C. or higher and lower than the melting point, more preferably It is desirable to be within the range of 90 to 140 ° C, particularly preferably 110 to 135 ° C. The pressure at the time of compression molding is not particularly limited, but is usually 1000 kg / cm²Less, preferably 0.1 to 1000 kg / cm²The range of is desirable.
[0063]
Further, the compression molding apparatus is not particularly limited as long as it is an apparatus that can continuously perform compression molding with an opposed rotating medium, and the rotating medium may be a pair or two or more opposing rolls or a pair or more ends. Examples include a combination of sliverto, endless belt and roll. Hereinafter, it will be briefly described based on FIG. 1 showing one specific example of the suitable molding apparatus.
[0064]
This apparatus basically includes a pair of endless belts 5 and 6 that are vertically opposed to each other by tension applied by rolls 1 to 4, and a pressure plate 7 for pressing a powder sample through the endless belts. And a pressurizing means comprising a chain roller group 8 which is rotatable and connected to each other between the pressurizing plate and the endless belt.
[0065]
The pressurizing means includes a pressurizing plate provided inside the endless belt and a group of rollers connected to each other between the pressurizing plate and the endless belt so as to be rotatable. As a group of rotatable chain rollers that are interposed between the pressure plate and the endless belt, the rotation shafts of the rollers in the roller group are arranged substantially perpendicular to the direction of travel of the endless belt and contact each other. It is appropriate to arrange a large number of such closely arranged layers.
[0066]
These rollers are fixed at their center axes at both ends, and the chain is engaged with sprockets 9 and 10 disposed before and after the pressure plate, so that the roller group is ½ of the travel speed of the endless belt. It is better to run at a moderate speed.
[0067]
This roller group may be fixedly interposed between the endless belt and the pressure plate, but in this case, frictional force due to slip is generated between the roller group, the endless belt and the pressure plate, respectively. Problems with the durability of the device arise.
[0068]
The pressure plate is not particularly limited as long as the surface in contact with the roller group is smooth and can transmit pressure uniformly.
[0069]
The length of the pressure plate in the endless belt running direction is not particularly limited, but is usually about 30 to 400 cm, preferably about 50 to 200 cm. The average pressure applied by the pressure plate to the endless belt is appropriately selected, but is usually 200 kg / cm.² Less, preferably 100 kg / cm² Less, preferably 0.1-50 kg / cm² More preferably, 0.1-20 kg / cm² , Particularly preferably 0.5 to 10 kg / cm² More particularly preferably, 1.0 to 8.0 kg / cm² Pressure. The primary role of the pressure plate is to press the polyethylene powder through an endless belt, but it can also be used as a heating means for the object to be compressed. In the present invention, as described above, it is extremely important that the compression molding process is performed at a temperature lower than the melting point of the polyethylene powder that is the object to be compressed, but it is preferably 20 ° C. or higher and lower than the melting point, more preferably 50. It is desirable that it is in the range of not lower than the melting point and lower than the melting point, particularly preferably in the range of 90 to 140 ° C., more preferably 110 to 135 ° C.
[0070]
As a heating means for the object to be compressed, it is optimal to directly heat the endless belt in the pressure unit. However, the heating means is arranged in the pressure plate, and the roller group and the endless belt are arranged from the pressure plate. After that, it is practically convenient to heat the object to be compressed or to arrange and heat the preheater 11 in the vicinity of the endless belt as shown in FIG.
[0071]
As an arrangement mode of the heating means to the pressure plate, an electric heater may be embedded in the pressure plate after providing a heat insulating part, or a circulation path of the heat medium is arranged in the pressure plate. You may heat using a heat medium.
[0072]
In order to carry out a continuous production method of a high-strength and high-modulus polyethylene material using this exemplified apparatus, first, ultra high molecular weight polyethylene powder charged into the hopper 12 is placed on the lower endless belt 6. Drop it.
[0073]
The running speed of the endless belt is usually about 10 to 500 cm / min, preferably about 50 to 200 cm / min, although it depends on the length of the pressure plate and the compression conditions. The polyethylene powder on the endless belt has a predetermined cross-sectional shape by a doctor knife 16, and is preheated by a heater if necessary, and then moved to a pressing part by upper and lower endless belts, and then pressed by a roller group and pressure It moves to the compression part by which the plate was arrange | positioned. Here, the pressure from the hydraulic cylinder 15 is transmitted to the pressure plate, and a compression force is further applied to the object to be compressed through the roller group and the endless belt. At this time, the heat from the heating body is similarly transmitted to the object to be compressed through the roller group and the endless belt, and the temperature of the object to be compressed is maintained at a predetermined temperature.
[0074]
In this way, the ultra-high molecular weight polyethylene film-like molded product obtained by compression-molding the ultra-high molecular weight polyethylene powder is wound around the winder 17.
[0075]
Although there is no particular limitation on the method of forming ultrahigh molecular weight polyethylene into a film shape by a method such as extrusion through a melting step, which is another method for obtaining an ultrahigh molecular weight polyethylene film-shaped product, a preferred method is melting Typical methods include extruding ultrahigh molecular weight polyethylene from a tubular die or T die using a screw extruder (preferably having a large L / D), etc., and stretching it several times to ten times as necessary. As mentioned.
[0076]
Another method for obtaining an ultra-high molecular weight polyethylene film-shaped product is a method for obtaining a film-like gel after dissolving ultra-high molecular weight polyethylene in a large amount of solvent, or a method for obtaining a film from such a film-like gel. Although there is no particular limitation, the preferred method is to draw from a solution in which ultrahigh molecular weight polyethylene is dissolved (usually, an ultrahigh molecular weight polyethylene concentration of 30% by weight or less) into a tape or film through a spout gold, and then cool. Alternatively, a method of removing a part of the solvent or the whole solvent as it is and stretching as necessary may be mentioned.
[0077]
Next, a method for laminating the thermoplastic resin film in the roll rolling process of the ultrahigh molecular weight polyethylene film will be described.
[0078]
As a roll rolling method of the film-like molded product obtained by compression molding, a known method can be used, but the compression molded sheet is kept in the solid state without melting, and the same or rotational direction is maintained. A rolled film can be obtained by clamping with different rolling rolls. At this time, the deformation ratio of the material can be widely selected by rolling operation, and is usually 1.2 to 20, preferably 1.5 to 10 in terms of rolling efficiency (length after rolling / length before rolling). It is desirable to do. The temperature at this time is usually 20 ° C. or higher and a temperature lower than the melting point of the ultrahigh molecular weight polyethylene film-like molded product used in the present invention, preferably 50 ° C. or higher and lower than the melting point, more preferably 90 to 140 ° C., particularly preferably 110 to 110 ° C. It is carried out in the temperature range of 135 ° C. Of course, the above-described rolling operation can be rolled in one or more stages.
[0079]
In addition, a method of interposing a thermoplastic resin film in this rolling step is a method in which an ultrahigh molecular weight polyethylene film-shaped product fed from the feeding roll 20 of FIG. The rolls are brought into contact with the thermoplastic resin films fed from the feed rolls 21 and 21 ′ installed at the top and bottom, preheated on the roll surface of the preheat roll group 22, and further re-preheated by the infrared preheat heater 23 as necessary. Generally, a method of rolling at 24 and winding the resulting rolled sheet on a winder 25 is generally employed.
[0080]
Thus, the method of laminating the thermoplastic resin film on the ultra high molecular weight polyethylene layer in the rolling process is, for example, easier to simplify the process than the method of laminating in the compression molding process of ultra high molecular weight polyethylene powder, for example. There are also advantages. Various methods can also be employed in the stretching step performed after roll rolling. Examples of stretching means include hot air stretching, cylinder stretching, roll stretching, and hot platen stretching. However, stretching is generally performed with a speed difference between a pair of nip rolls or clover rolls.
[0081]
As a typical stretching device, an example in which a thermoplastic resin film is interposed in an ultrahigh molecular weight polyethylene rolled sheet as necessary by a stretching device employing a hot platen method is shown in FIG. This is shown in FIG. Although details are omitted, in FIG. 3 (a), in the same manner as in FIG. 2, the ultrahigh molecular weight polyethylene rolled sheet fed from the feeding roll and the feeding roll installed above, below or vertically are fed out. The drawn thermoplastic resin film is brought into contact with a feeding pinch roll, stretched while being taken up with a take-up pinch roll on a drawing hot platen, and taken up on a take-up roll. If desired, the stretched product may be split to give a tape yarn, or it may be slit and then split to give a split yarn. FIG. 3B illustrates a method of stretching by using three stretching hot rolls instead of the stretching hot plate in FIG.
[0082]
The stretching temperature in the stretching operation described above is in the range of less than the melting point of the material to be stretched, usually 20 to 160 ° C., preferably 60 to 150 ° C., more preferably 90 to 145 ° C., and particularly preferably 90 to 140 ° C. The stretching process can be performed not only in one stage but also in multiple stages. In this case, the second stage is preferably performed at a higher temperature than the first stage.
[0083]
The stretching speed varies depending on the tensile stretching method, the polymer molecular weight, and the composition ratio, and can be appropriately selected, but is usually 1 mm / min to 500 m / min, and particularly 1 to 1 in the case of batch stretching. 500 mm / min, preferably 1 to 100 mm / min, more preferably 5 to 50 mm / min. In the case of continuous stretching, usually 0.1 to 500 m / min, preferably 1 to 200 m / min. More preferably, it is in the range of 10 to 200 m / min, and the high speed setting is more preferable in consideration of economy.
[0084]
The higher the draw ratio, the higher the strength and the higher the elastic modulus. Therefore, it is desirable to increase the draw ratio as much as possible. In the present invention, the total draw ratio, which is the total draw ratio of rolling and tensile drawing, is usually 20 times. As described above, preferably 60 times or more, more preferably 80 to 200 times, and stretching at a very high stretching ratio is possible.
[0085]
The tensile elastic modulus of the stretched product obtained by subjecting only the ultrahigh molecular weight polyethylene powder to the compression molding process, rolling process and stretching process by the above-described method is usually 60 GPa or more, more generally 80 GPa to 180 GPa, more generally Is in the range of 120 to 150 GPa. Further, the tensile strength is usually 0.7 GPa or more, more generally 1.0 GPa to 5.0 GPa, and more generally 1.5 GPa to 3.0 GPa.
[0086]
In the present invention, as described above, the thermoplastic resin powder or film to be laminated corresponding to the desired properties is appropriately selected, and the physical properties of the stretched product are slightly different. It is in the range of 40 GPa to 180 GPa, more generally in the range of 100 to 150 GPa, and the tensile strength is in the range of 0.7 GPa to 5.0 GPa, more typically in the range of 1.0 GPa to 3.0 GPa.
[0087]
The present invention has a great feature of obtaining a stretched product having physical properties that are substantially the same or not significantly reduced even when a thermoplastic resin powder or film is interposed.
[0088]
The high-strength and high-modulus polyethylene material of the present invention can be used for any application, but by using it as a yarn, it can be made into a high-strength and high-modulus polyethylene material having further excellent characteristics. it can. This will be further described below.
[0089]
Examples of the yarn include a tape yarn such as a multifilament yarn, a monofilament yarn, and a tape filament yarn, and a split yarn. Of these, the case of post-processing as a split yarn, which is particularly characteristic as a high-strength and high-modulus polyethylene material, will be described in detail first.
[0090]
A split yarn, which is one target product symbolizing the characteristics of the high-strength and high-modulus polyethylene material in the present invention, is produced by splitting the ultra-high molecular weight polyethylene stretched product. The splitting method is not particularly limited, and a known method can be used. For example, a stretched product in the form of a film or sheet, a method of tapping, a method of twisting, a method of rubbing, a mechanical method such as a method of brushing, a method using an air jet, a method of making a crack by ultrasonic waves, Explosion method that treats with explosive wind.
[0091]
In the present invention, it is preferable to employ a mechanical method, and it is particularly preferable to employ a rotary mechanical method. Examples of the mechanical method include a method using a splitter having various shapes such as a tap screw splitter, a filed rough surface splitter, and a needle roll splitter. The tapped screw-type splitter is usually a pentagon or hexagon (FIG. 4) and has a thread of 10 to 40, preferably 15 to 35, per inch. As the file-shaped splitter, the one shown in FIG. 5 which is the device of the present inventors (Japanese Utility Model Publication No. 51-38980) is suitable. In FIG. 5, a surface 27 of the circular cross-section shaft 26 is a round file for ironwork or a rough surface similar thereto, and two spiral grooves 28 and 28 'are cut on the surface at equal pitches.
[0092]
The splitting device to be used is not particularly limited. As shown in FIG. 6, basically, a rotary splitter 31 is disposed between the nip rolls 29 and 29 ′ and the nip rolls 30 and 30 ′, and a stretched product is obtained. As a representative example, a method of moving while applying a tension of and contacting with a rotary splitter can be given. The moving speed of the stretched product at this time is not particularly limited, but is usually 1 to 1000 m / min, and preferably 20 to 300 m / min. The rotation speed (circumferential speed) of the splitter is appropriately selected depending on the physical properties of the stretched product, the moving speed, and the properties of the target split yarn, but is usually 10 to 3000 m / min, preferably 50 to 1000 m / min. It is. The contact angle between the stretched product and the splitter is usually 30 to 180 degrees, preferably 60 to 90 degrees. Since the stretched tape is slippery, it may be difficult to keep the tape at a predetermined speed in the nip rolls installed before and after the splitter, so the nip roll and the clover roll may be used in combination, or the Nelson roll It is desirable to take anti-slip measures such as using them or combining them.
[0093]
In the method of brushing and the method using a rotary splitter, the operation is preferably performed by applying tension to the stretched product. In relation to the high tensile elastic modulus of the stretched product described above, the stretched product is usually 0.1 to It is preferable to deform 3%, preferably 0.5-2%. In this case, it is also an effective means to install a tension controller such as a dancer roll in order to keep the tension of the tape constant in the split device.
[0094]
The temperature for splitting is usually in the range of -20 to + 100 ° C, preferably -5 to + 50 ° C, more preferably 0 to 20 ° C. Splitting may be performed not only in one stage but also in multiple stages, and for a material having a large thickness, splitting can be performed from both the front and back sides. Specific examples of these methods include U.S. Pat. Nos. 2,185,789, 3,214,899, 2,954,587, 3,662,935, 3,693,851, JP-B 36-13116, and JP-B 43-16909. Illustrated.
[0095]
In the split yarn obtained by these methods, the thickness of the split yarn is usually 10 to 200 μm, preferably 30 to 100 μm. If the thickness is less than 10 μm, the stretched film or sheet may tear in the longitudinal direction, and the split fibrils may be fuzzy or wound around a splitter, resulting in unstable quality and process. is there. On the other hand, if it exceeds 200 μm, the split property tends to deteriorate. The split width is usually in the range of 10 to 500 μm, preferably 50 to 200 μm.
[0096]
The split yarn obtained by the present invention is characteristic in that it has excellent flexibility and high strength as well as the effects of adding pigments, weathering agents, antistatic agents and the like. The strength after the split treatment is usually 0.4 GPa or more, and the strength can be further increased by twisting, and can be made substantially equal to the strength before splitting. The maximum value of the tensile strength when twisted in the range of 50 to 500 times / m is at least 0.7 GPa, generally 1 GPa or more, more generally 1.5 GPa or more. Such a value corresponds to a high strength of about 8 g / d or more, generally about 11.5 g / d or more, and more typically about 17 g / d or more.
[0097]
Since the polyethylene stretched material used in the present invention has no polar groups and the surface is not active, it is generally difficult to print or adhere to the surface. Therefore, it is also preferable to subject the stretched product to surface treatment such as corona discharge treatment, plasma treatment, chemical oxidation treatment, or flame treatment before the split treatment, or preferably after the split treatment, if necessary.
[0098]
A high-strength, high-modulus polyethylene material obtained by the above-described method, that is, by laminating a thermoplastic resin film in which an additive is blended in a roll rolling process and then stretching is further slitted or splitted. The properties of the polyethylene material thus obtained vary greatly depending on the type of thermoplastic resin powder or film in which the additive is blended, the amount of lamination or the lamination method, but the additive is blended. The properties of the slit body or the split body obtained in the state where the thermoplastic resin is not laminated can be described as follows.
[0099]
That is, in the case of the slit body, it is a plurality of independent long rectangular tapes, while in the case of the split body, it is not separated from each other, and conversely, a reticulated body is formed. For example, the limit value of the slit width of a film having a thickness of 60 μm is about 1.6 mm, and the fineness of the slit body in this case is about 800 to 900 d. On the other hand, the split width of the split body is generally in the range of 10 to 500 μm, the logarithmic average value of this value is about 70 μm, the split thickness is in the range of 10 to 200 μm, and the logarithmic average value of this value is about 45 μm. Yes, the fineness of such a split body is about 30d.
[0100]
For example, the flexibility of the 1.6 mm slit body expressed by the following formula is about 2660 mg · cm, and the flexibility of the split body is about 980 mg · cm.
[0101]
[Expression 1]

However, measured with a twist of 250 t / m
Since the flexibility of the polyethylene material before slitting was about 3500 mg · cm, it is more preferable to further slit or more preferably split the high strength / high elastic modulus polyethylene material. Strength, high elastic modulus, and high flexibility polyethylene material.
[0102]
The split polyethylene stretched material of the present invention may be used as it is or in a twisted state. The number of times of twisting is not particularly limited, but is usually about 50 to 500 times / m, and preferably about 100 to 300 times / m because high strength is exhibited. The temperature in that case is not particularly limited, but is usually in the range of 0 to 100 ° C, preferably 10 to 60 ° C.
[0103]
【Example】
Example 1
(1) Production of thermoplastic resin film
High-density polyethylene (trade name: Stafrene E-710 (manufactured by Nippon Petrochemical Co., Ltd., M1: 1.0)) is used as a base polymer, mixed with 15% by weight of azo red, and processed into a masterbatch using a melt extruder. did. Next, 20 parts by weight of this master batch and high-density polyethylene (trade name: Stafrene E-710 (manufactured by Nippon Petrochemical Co., Ltd., M1: 1.0)) are kneaded at 230 ° C., and then the thickness is 0.02 mm. The film was continuously formed by extrusion.
(2) Production of high-strength materials
(Compression molding)
Equipment specifications:
1. Roll diameter 500mm Surface length 300mm
2. Steel belt Thickness 0.6mm Width 200mm
3. Small diameter roller Diameter 12mm Surface length 250mm
4). Pressure plate Length 1000mm Width 200mm
5). Hydraulic cylinder diameter 125mm
Using a compression molding apparatus having the above specifications, an ultra high molecular weight polyethylene powder (intrinsic viscosity [η] in decalin at 135 ° C. = 14 dl / g, viscosity average molecular weight of 2 million) is sandwiched between a pair of steel belts at 130 ° C. The average pressure on the material is about 6 kg / cm² (Pressure was transmitted in the order of a hydraulic cylinder, a pressure plate, a small-diameter roller, and a steel belt) and compression-molded continuously at a speed of 1 m / min.
[0104]
As a result, a sheet having a thickness of 1.1 mm and a width of 100 mm was obtained.
[0105]
(rolling)
A pair of the above azo reds is placed between a pair of rolls (diameter 250 mm, surface length 300 mm, roll gap 0.07 mm) which are arranged one above the other and rotate in the opposite direction at the same speed and whose surface temperature is adjusted to 140 ° C. A thermoplastic resin film (width of about 100 mm) is inserted, and the compression-molded sheet is supplied between the pair of films, and the inlet speed is 1 m / min and the outlet speed is 7 m / min. A colored rolled sheet having a width of 0.157 mm and a width of 98 mm was obtained.
[0106]
(Stretching)
Equipment specifications
1. 3 rolls for preheating Diameter 250mm Surface length 200mm
2. Stretching roll Diameter 125mm Surface length 200mm
Heat medium oil circulates inside the roll
The distance between rolls is 30mm
3. 3 rolls for cooling Diameter 250mm Surface length 200mm
Cooling water circulates inside the roll
4). Nip roll
Entrance side: φ200mm silicon rubber roll is niped against two preheating rolls
Outlet side: φ200mm silicon rubber roll nips against 2 cooling rolls
The obtained rolled sheet was slit into a width of 6 mm and subjected to tensile stretching using a stretching apparatus having the above specifications. Tensile stretching was repeated three times under the conditions shown in the following table.
[0107]
As a result of stretching, a polyethylene stretched material colored uniformly in red was obtained.
[0108]
When the physical properties of this material were measured, the tensile strength was 25.0 g / d and the elongation was 1.8%.
[0109]
[Table 1]

(Split process)
Equipment specifications
1. Inlet pinch roll: φ160mm, surface length 200mm metal roll and urethane rubber roll
2. Outlet pinch roll: φ160mm, surface length 200mm metal roll and urethane rubber roll
3. Splitter: A split-tipping tool with a threaded tap-shaped blade with a regular hexagonal cross section and a side length of 20 mm, and the pitch of the blade is 0.6 mm
Split condition
1. Nip roll speed: 30 m / min on the inlet side → 30.3 m / min on the outlet side
2 splitter contact angle and peripheral speed ratio: 90 degrees, 2.3 times
The red stretched tape (width: about 2 mm) was split using the above apparatus and operating conditions to obtain a rhombus-like net-like split yarn having a single yarn width of 0.6 mm and a side length of 12 mm. The properties of this split yarn (measured over 100 times per meter, measured at 100 t / m, and so on) were a tensile strength of 21.0 g / d and an elongation of 1.6%.
[0110]
Example 2
Example 1 (1) Production of the thermoplastic resin film was carried out in the same manner as Example 1 except that cyanine blue was used instead of azo red.
[0111]
As a result, a stretched polyethylene that was uniformly colored in blue was obtained. Its physical properties were a tensile strength of 24.3 g / d and an elongation of 1.8%. Further, when this stretched polyethylene was split, a rhombus blue mesh split yarn was obtained. Regarding the physical properties (100 t / m) of this split yarn, the tensile strength was 21.0 g / d and the elongation was 1.6%.
[0112]
Example 3
Example 1 (1) Production of the thermoplastic resin film was carried out in the same manner as Example 1 except that ultrafine carbon black was used instead of azo red.
[0113]
As a result, a stretched polyethylene that was uniformly colored black was obtained, and the physical properties were a tensile strength of 24.4 g / d and an elongation of 1.8%. Further, when this stretched polyethylene was split, rhombus-shaped black-gray mesh split yarn was obtained. As for the physical properties of this split yarn, the tensile strength was 21.1 g / d and the elongation was 1.6%.
[0114]
Example 4
Example 1 (1) Production of the thermoplastic resin film was carried out in the same manner as in Example 1 except that 0.5 wt% of stearyl diethanolamine was used instead of azo red.
[0115]
As a result, stretched polyethylene was obtained, and as for its physical properties, the tensile strength was 25.2 g / d and the elongation was 1.8%. Further, when this stretched polyethylene was split, a rhombic reticulated split yarn was obtained. As for the physical properties of this split yarn, the tensile strength was 20.9 g / d and the elongation was 1.6%.
[0116]
Further, when the stretched product and the split yarn were brought close to the top of the dispersed ash, the ash did not adhere even at a distance of several centimeters, so that sufficient antistatic performance was recognized.
[0117]
Example 5
In Example 4, it replaced with stearyl diethanolamine 0.5 wt%, and performed similarly to Example 4 except having used fatty acid monoglyceride 0.5 wt%. As a result, a stretched polyethylene was obtained. Its physical properties were a tensile strength of 24.0 g / d and an elongation of 1.8%. Further, when this stretched polyethylene was split, a rhombic reticulated split yarn was obtained. As for the physical properties of this split yarn, the tensile strength was 19.8 g / d and the elongation was 1.6%.
[0118]
Further, when the stretched product and the split yarn were brought close to the top of the dispersed ash, the ash did not adhere even at a distance of several centimeters, so that sufficient antistatic performance was recognized.
[0119]
Example 6
In Example 4, it replaced with stearyl diethanolamine 0.5 wt%, and it carried out like Example 4 except having used 0.1 wt% of HALS (Brand name, Tinuvin 622, Ciba-Gigi).
[0120]
As a result, a stretched polyethylene was obtained. Its physical properties were a tensile strength of 24.0 g / d and an elongation of 1.8%. Further, when this stretched polyethylene was split, a rhombic reticulated split yarn was obtained. As for the physical properties of this split yarn, the tensile strength was 20.0 g / d and the elongation was 1.6%.
[0121]
Further, when the stretched product and split yarn were tested for light stability, they showed good characteristics.
[0122]
Example 7
In Example 4, it replaced with stearyl diethanolamine 0.5 wt%, and it carried out like Example 4 except having used 0.1 wt% of HALS (brand name Sanol LS2626, Sankyo make).
[0123]
As a result, a stretched polyethylene was obtained. The physical properties were a tensile strength of 24.5 g / d and an elongation of 1.8%. Further, when this stretched polyethylene was split, a rhombic reticulated split yarn was obtained. As for the physical properties of this split yarn, the tensile strength was 20.1 g / d and the elongation was 1.6%.
[0124]
Further, when the stretched product and split yarn were tested for light stability, they showed good characteristics.
[0125]
Example 8
(1) Production of thermoplastic resin film
A high-density polyethylene (trade name: STAFLENE E-710 (manufactured by Nippon Petrochemical Co., Ltd., M1: 1.0)) is used as a base polymer, 30% by weight of polyvinyl alcohol is mixed, kneaded at 230 ° C, and the thickness is 0. The film was continuously extruded to have a thickness of 0.02 mm.
[0126]
(2) Production of high-strength materials
It carried out similarly to Example 1 except having used the said thermoplastic resin film.
[0127]
As a result, a stretched polyethylene was obtained. The physical properties were a tensile strength of 25.0 g / d and an elongation of 1.8%. Further, when this stretched polyethylene was split, a rhombic reticulated split yarn was obtained. As for the physical properties of this split yarn, the tensile strength was 20.3 g / d and the elongation was 1.6%.
[0128]
Further, when the hydrophilicity of this stretched product was measured by measuring the contact angle, good characteristics were shown.
[0129]
Example 9
Example 8 (1) Production of the thermoplastic resin film was carried out in the same manner as Example 8 except that 30% by weight of chitosan was used instead of polyvinyl alcohol.
[0130]
As a result, a stretched polyethylene was obtained. Its physical properties were a tensile strength of 24.0 g / d and an elongation of 1.8%. Further, when this stretched polyethylene was split, a rhombic reticulated split yarn was obtained. As for the physical properties of this split yarn, the tensile strength was 20.0 g / d and the elongation was 1.6%.
[0131]
Further, when the hydrophilicity of this stretched product was measured by measuring the contact angle, good characteristics were shown.
[0132]
Example 10
In the production of the thermoplastic resin film of Example 8 (1), the same procedure as in Example 8 was carried out except that 30% by weight of acrylic acid was used instead of polyvinyl alcohol.
[0133]
As a result, a stretched polyethylene was obtained. The physical properties were a tensile strength of 24.2 g / d and an elongation of 1.8%. Further, when this stretched polyethylene was split, a rhombic reticulated split yarn was obtained. As for the physical properties of this split yarn, the tensile strength was 20.1 g / d and the elongation was 1.6%.
[0134]
Further, when the hydrophilicity of this stretched product was measured by measuring the contact angle, good characteristics were shown.
[0135]
Example 11
(1) Production of thermoplastic resin film
A high-density polyethylene (trade name: STAFLENE E-710 (manufactured by Nippon Petrochemical Co., Ltd., M1: 1.0)) was used as a base polymer, 15 wt% of azo red was mixed, and processed into a master batch using a melt extruder. Next, 20 parts by weight of this master batch and high-density polyethylene (Stamfrene E-710 (manufactured by Nippon Petrochemical Co., Ltd., M1: 1.0)) are kneaded at 230 ° C. and continuously to a thickness of 0.02 mm. To form a film.
[0136]
(2) Production of high-strength materials
(Extrusion molding)
Ultra high molecular weight polyethylene powder (intrinsic viscosity [η] in 135 ° C. decalin = 14 dl / g, viscosity average molecular weight 2 million) was continuously formed by extrusion at 250 ° C. As a result, a sheet having a wall thickness of 0.1 mm and a folding width of 90 mm was obtained.
[0137]
(rolling)
A pair of the above azo reds is placed between a pair of rolls (diameter 250 mm, surface length 300 mm, roll gap 0.07 mm) which are arranged one above the other and rotate in the opposite direction at the same speed and whose surface temperature is adjusted to 140 ° C. A thermoplastic resin film (width of about 90 mm) is inserted, and the compression-molded sheet is supplied between the pair of films. The inlet speed is 1 m / min and the outlet speed is 7 m / min. A colored rolled sheet having a width of 0.047 mm and a width of 88 mm was obtained.
[0138]
(Stretching)
Equipment specifications:
1. 3 rolls for preheating Diameter 250mm Surface length 200mm
2. Stretching roll Diameter 125mm Surface length 200mm
Heat medium oil circulates inside the roll
The distance between rolls is 30mm
3. 3 rolls for cooling Diameter 250mm Surface length 200mm
Cool water circulates inside the roll
4). Nip roll
Entrance side: φ200 mm silicon rubber roll is nip exit side with respect to two preheating rolls: φ200 mm silicon rubber roll is niped against two cooling rolls, the rolled sheet obtained by slitting to a width of 12 mm, and using the stretching device of the above specifications Used and stretched. Tensile stretching was repeated three times under the conditions shown in the following table.
[0139]
As a result of stretching, a polyethylene stretched material (width 2.8 mm, wall thickness 0.02 mm) that was uniformly colored red was obtained.
When the physical properties of this material were measured, the tensile strength was 19 g / d and the elongation was 1.8%.
[0140]
[Table 2]

(Split process)
Equipment specifications:
1. Entrance pinch roll φ160mm, surface length 200mm metal roll and urethane rubber roll
2. Outlet pinch roll φ160mm, surface length 200mm metal roll and urethane rubber roll
3. Splitter: A splitting tool having a regular hexagonal cross-section, a threaded tap-shaped blade with a side length of 20 mm, and a blade pitch of 0.6 mm
Split condition:
1. Nip roll speed: 30 m / min on the inlet side → 30.3 m / min on the outlet side
2. Splitter contact angle and peripheral speed ratio: 90 degrees, 2.3 times
The red stretched tape (width: about 2.8 mm) was split with the above-mentioned apparatus and operating conditions, and a rhombus-like net-like split yarn having a single yarn width of 0.6 mm and a side length of 12 mm was obtained. As for the physical properties of this split yarn (measured over 100 times per meter, measured at 100 t / m, and so on), the tensile strength was 17 g / d and the elongation was 1.6%.
[0141]
【The invention's effect】
According to the present invention, a thermoplastic resin film obtained by blending at least one of a colorant, a weathering agent, an antistatic agent, a hydrophilicity-imparting agent, an adhesion-imparting agent, and a dyeability-imparting agent is obtained as an ultrahigh molecular weight polyethylene film. When laminating in the roll rolling process of a molded product, the obtained high-strength and high-modulus polyethylene material can be easily colored, for example, and imparts characteristics such as weather resistance and antistatic properties. In addition, post-processability such as dyeability can be easily imparted.
[Brief description of the drawings]
FIG. 1 shows an example of an apparatus suitable for carrying out the compression molding process of the present invention.
FIG. 2 shows an example of an apparatus suitable for carrying out a rolling process.
FIG. 3 shows two examples of an apparatus suitable for carrying out the stretching process.
FIG. 4 shows an example of a tap screw splitter suitable for implementation.
FIG. 5 shows an example of a file-type splitter suitable for implementation.
FIG. 6 shows an example of an apparatus suitable for carrying out a sprit formation step.
[Explanation of symbols]
1-4 rolls
5-6 Endless belt
7 Pressure plate
8 Chain roller group
9-10 Sprocket
11 Heater
12 Hopper
15 Hydraulic cylinder
16 Doctor knife
17 Sheet winder
20-21 feeding roll
22 Preheating roll
23 Infrared preheater
24 Rolling roll
25 Winder
26 Circular section axis
27 Surface
28, 28 'spiral groove
29, 29 ', 30, 30' nip roll
31 Splitter

Claims (4)

In a method of producing a high-strength and high-modulus polyethylene material by roll-rolling an ultrahigh molecular weight polyethylene film-shaped product having an intrinsic viscosity of 5 to 50 dl / g in a 135 ° C. decalin solution, At least one thermoplastic resin layer containing at least one additive selected from the group consisting of a colorant, a weathering agent, an antistatic agent, a hydrophilicity-imparting agent, an adhesion-imparting agent, and a dyeability-imparting agent; A continuous production method of a high-strength and high-modulus polyethylene material, characterized by laminating a material to be rolled and a total draw ratio of 20 times or more in a rolling step and a drawing step .   The continuous high-strength and high-modulus polyethylene material according to claim 1, wherein a thermoplastic resin film is laminated in a roll rolling step of an ultra-high molecular weight polyethylene film-like product obtained by a melt molding method or a gel method. Manufacturing method.   2. The continuous production method for a high-strength / high-modulus polyethylene material according to claim 1, wherein the yarn is further slitted after the drawing step to form a tape yarn.   The continuous production method of a high-strength and high-modulus polyethylene material according to claim 1, wherein the yarn is further split after the drawing step to form a split yarn.

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