JP3686737B2 - POLYOLEFIN RESIN COMPOSITION AND LAMINATE USING SAME - Google Patents

Description

上記化学式中、Ｃｐは前記シクロペンタジエニル骨格を有する配位子、Ｘは水素、ハロゲン、炭素数１〜２０のアルキル基、アリールシリル基、アリールオキシ基、アルコキシ基、アミド基、シリルオキシ基等を表し、ＹはＳｉＲ₂、ＣＲ₂、ＳｉＲ₂ＳｉＲ₂、ＣＲ₂ＣＲ₂、ＣＲ＝ＣＲ、ＳｉＲ₂ＣＲ₂、ＢＲ₂、ＢＲからなる群から選ばれる２価基、Ｚは−Ｏ−、−Ｓ−、−ＮＲ−、−ＰＲ−またはＯＲ、ＳＲ、ＮＲ₂、ＰＲ₂からなる群から選ばれる２価中性リガンドを示す。ただし、Ｒは水素または炭素数１〜２０のアルキル基、アリール基、シリル基、ハロゲン化アルキル基、ハロゲン化アリール基、またはＹ、ＺまたはＹとＺの双方からの２個またはそれ以上のＲ基は縮合環系を形成するものである。Ｍは周期律表第IV族の遷移金属原子を表す。
【００５２】
この化学式で表される化合物の例としては、（ｔ−ブチルアミド）（テトラメチルシクロペンタジエニル）−１,２−エタンジイルジルコニウムジクロライド、（ｔ−ブチルアミド）（テトラメチルシクロペンタジエニル）−１,２−エタンジイルチタンジクロライド、（メチルアミド）（テトラメチルシクロペンタジエニル）−１,２−エタンジイルジルコニウムジクロライド、（メチルアミド）（テトラメチルシクロペンタジエニル）−１,２−エタンジイルチタンジクロライド、（エチルアミド）（テトラメチルシクロペンタジエニル）メチレンタンジクロライド、（ｔ−ブチルアミド）ジメチル（テトラメチルシクロペンタジエニル）シランチタンジクロライド、（ｔ−ブチルアミド）ジメチル（テトラメチルシクロペンタジエニル）シランジルコニウムジベンジル、（ベンジルアミド）ジメチル（テトラメチルシクロペンタジエニル）シランチタンジクロライド、（フェニルホスフイド）ジメチル（テトラメチルシクロペンタジエニル）シランチタンジクロライドなどが挙げられる。
【００５３】
本発明でいう助触媒としては、前記周期律表第IV族の遷移金属化合物を重合触媒として有効になし得る、または触媒的に活性化された状態のイオン性電荷を均衡させうるものをいう。
本発明において用いられる助触媒としては、有機アルミニウムオキシ化合物のベンゼン可溶のアルミノキサンやベンゼン不溶の有機アルミニウムオキシ化合物、ホウ素化合物、酸化ランタンなどのランタノイド塩、酸化スズ等が挙げられる。これらの中でもアルミノキサンが最も好ましい。
【００５４】
また、触媒は無機または有機化合物の担体に担持して使用されてもよい。該担体としては無機または有機化合物の多孔質酸化物が好ましい。具体的には、ＳｉＯ₂、Ａｌ₂Ｏ₃、ＭｇＯ、ＺｒＯ₂、ＴｉＯ₂、Ｂ₂Ｏ₃、ＣａＯ、ＺｎＯ、ＢａＯ、ＴｈＯ₂等またはこれらの混合物が挙げられ、ＳｉＯ₂−Ａｌ₂Ｏ３、ＳｉＯ₂−Ｖ₂Ｏ₅、ＳｉＯ₂−ＴｉＯ₂、ＳｉＯ₂−ＭｇＯ、ＳｉＯ₂−Ｃｒ₂Ｏ₃等が挙げられる。
【００５５】
有機アルミニウム化合物として、トリエチルアルミニウム、トリイソプロピルアルミニウム等のトリアルキルアルミニウム；ジアルキルアルミニウムハライド；アルキルアルミニウムセスキハライド；アルキルアルミニウムジハライド；アルキルアルミニウムハイドライド、有機アルミニウムアルコキサイド等が挙げられる。
【００５６】
《製造方法》
本発明のエチレン（共）重合体（Ｉ）の製造方法は、前記触媒の存在下、実質的に溶媒の存在しない気相重合法、スラリー重合法、溶液重合法等で製造され、実質的に酸素、水等を断った状態で、ブタン、ペンタン、ヘキサン、ヘプタン等の脂肪族炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素等に例示される不活性炭化水素溶媒の存在下または不存在下で製造される。重合条件は特に限定されないが、重合温度は通常１５〜３５０℃、好ましくは２０〜２００℃、さらに好ましくは５０〜１１０℃であり、重合圧力は低中圧法の場合、通常、常圧〜７０kg/cm²G、好ましくは常圧〜２０kg/cm²Gであり、高圧法の場合通常１５００kg/cm²G以下が望ましい。重合時間は低中圧法の場合通常３分〜１０時間、好ましくは５分〜５時間程度が望ましい。高圧法の場合、通常１分〜３０分、好ましくは２分〜２０分程度が望ましい。また、重合は一段重合法はもちろん、水素濃度、モノマー濃度、重合圧力、重合温度、触媒等の重合条件が互いに異なる２段階以上の多段重合法など特に限定されるものではない。
【００５７】
本発明のエチレン（共）重合体において、重合時の触媒成分を実質的に塩素等のハロゲンを含まないものとすると、得られる重合体にもこれらハロゲンが含まれず、したがって化学的安定性、衛生性が優れ、食品、衛生、医療関連用途に好適である。また電気部品、電線部材、電子レンジに関する包装材料および容器に適用した場合、周辺の金属部品等の錆の発生が抑えられるといった特徴を有する。
【００５８】
尚、エチレン（共）重合体（Ｉ）に対しては、有機あるいは無機フィラー、粘着付与剤、酸化防止剤、防曇剤、有機あるいは無機系顔料、分散剤、核剤、発泡剤、難燃剤、架橋剤、紫外線防止剤、（不）飽和脂肪酸アミド、（不）飽和高級脂肪酸の金属塩等の滑剤などの公知の添加剤を、本願発明の特性を本質的に阻害しない範囲で添加することができる。
これらの添加剤の中でも、滑剤、粘着付与剤、無機フィラーは作業性をより向上させるために好適に用いられる。
滑剤としては、オレイン酸アミド、ステアリン酸アミド、エルカ酸アミド、等の脂肪酸アミド；ステアリン酸モノグリセライド、ステアリン酸ジグリセライド、オレイン酸モノグリセライド、オレイン酸ジグリセライド等の脂肪酸グリセリンエステル化合物およびそれらのポリエチレングリコール付加物等が挙げられる。
また無機フィラーとしては、軽質および重質炭酸カルシウム、タルク、シリカ、ゼオライト、炭酸マグネシウム、長石等が挙げられる。
粘着付与剤としては、ポリブテン、ヒマシ油誘導体、ソルビタン脂肪酸エステル、ロジンおよびロジン誘導体、石油樹脂およびそれらの水添物等のタッキファイヤー、ゴム等が挙げられる。これら粘着付与剤は０.５〜２０重量部の範囲で配合することができる。
顔料としてはカーボンブラック、チタン白等の他、市販の各種着色剤マスターバッチが好適に用いられる。
【００５９】
さらに適度の滑り性、帯電防止性、防曇性を得るための添加剤についても配合することができる。
具体的には、ソルビタン脂肪酸エステルとして、ソルビタンモノオレート、ソルビタンモノラウレート、ソルビタンモノベヘネート、ソルビタンモノステアレート等；グリセリン脂肪酸エステルとして、グリセリンモノオレート、グリセリンモノステアレート、グリセリンモノラウレート、グリセリンモノベヘネート等；ポリグリセリン脂肪酸エステルとして、ジグリセリンモノラウレート、ジグリセリンモノステアレート、ジグリセリンモノオレート、テトラグリセリンモノオレート、テトラグリセリンモノステアレート、ヘキサグリセリンモノラウレート、ヘキサグリセリンモノオレート、デカグリセリンモノラウレート、デカグリセリンモノステアレート、デカグリセリンモノオレート等の他、多価アルコールの脂肪酸エステルおよびこれらのエチレンオキサイド付加物、高級脂肪酸アミドおよびこれらのエチレンオキサイド付加物、高級脂肪酸アルカノールアミド等が挙げられるがこれらに限定されるものではない。
これらの添加剤は単独あるいは混合組成物として使用されるが、添加量としては通常０.０１〜０.５重量％、好ましくは０.０５〜０.３重量％である。添加量が０.０１重量％未満では添加剤による改質効果が十分ではなく、０.５重量％を越える場合には添加剤の表面への浮き出し量が多く、べたつき、その結果、作業性が著しく低下するなどの問題が起こるため好ましくない。
【００６０】
〈（II）エポキシ化合物〉
本発明のポリオレフィン系樹脂組成物においては、成分（II）として、分子内にエポキシ基を２個以上有し、分子量が３０００以下であるエポキシ化合物を含有する。
このエポキシ化合物において、分子内にエポキシ基を２個以上有する必要があり、１個では、積層体に用いた場合に、他層との接着性の向上効果が充分でない。エポキシ化合物の分子量は３０００以下であることが必要であり、１５００以下であればより好ましい。分子量が３０００を超えると、やはり他層との接着強度が不十分となる。
エポキシ化合物としてはフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、トリメチロールプロパンポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ブタンジオールジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル、フェノールノボラックポリグリシジルエーテル、エポキシ化植物油等が挙げられる。なかでも、エポキシ化植物油は安全性の面から食品などの包装材料用途の積層体には最も好ましい。
【００６１】
ここでのエポキシ化植物油とは、天然植物油の不飽和二重結合を過酸などを用いてエポキシ化したものであり、エポキシ化大豆油、エポキシ化オリーブ油、エポキシ化亜麻仁油、エポキシ化サフラワー油、エポキシ化コーン油などを挙げることができる。
尚、植物油をエポキシ化する際に若干副生するエポキシ化されていない若しくはエポキシ化が不十分な油分の存在は本発明の効果をなんら妨げるものではない。
これらのエポキシ化合物（II）の配合量は、樹脂成分に対して、即ち、樹脂成分が成分（Ｉ）と成分（II）だけであれば、それらの合計に対して、０.０１〜５重量％、好ましくは０.０１〜０.９重量％の範囲で添加される。添加量が０.０１重量％未満では接着強度向上効果が充分でなく、５重量％を超えると成形体に臭いがつく他、表面がべたつき、また、光学特性の低下という問題が生じる為、好ましくない。
【００６２】
〈（III）オレフィン系重合体〉
本発明においては、成分（III）として、エポキシ基と反応する官能基を有するオレフィン系重合体をさらに含有していることが望ましい。この成分（III）は必須成分ではないが、添加することにより、接着性をさらに向上させることができる。
エポキシ基と反応する官能基としては、酸無水物基、カルボキシル基、またはカルボン酸金属塩のうちのいずれか１種以上の基を分子内に有することが好ましい。これらの官能基は共重合法またはグラフト法によりポリオレフィン分子中に導入される。
共重合法によって製造されるエポキシ基と反応する官能基を有するオレフィン系共重合体としては、エチレンと共重合可能な化合物とエチレンとの多元共重合体が挙げられる。共重合に用いるエチレンと共重合可能な化合物としては、（メタ）アクリル酸等のα，β−不飽和カルボン酸、（メタ）アクリル酸ナトリウム塩等のα，β−不飽和カルボン酸金属塩、および無水マレイン酸、無水イタコン酸、無水シトラコン酸等の不飽和カルボン酸無水物等が挙げられる。この他にも、ヒドロキシエチル（メタ）アクリレート、（メタ）アリルアルコール等の水酸基含有化合物、アリルアミン等の不飽和アミノ化合物等が例示されるが、この限りではない。
また、これらのエポキシ基と反応可能な官能基を有する不飽和化合物に加えて、（メタ）アクリル酸エステル、酢酸ビニル、ビニルアルコールエステル等を共重合した多元共重合体を使用することができる。また、これらの化合物とエチレンとの共重合体は、２種類以上を併用することもできる。
【００６３】
グラフト変性によってエポキシ基と反応可能な官能基を導入したポリオレフィンは、ポリオレフィンとラジカル発生剤と変性用の化合物とを溶融もしくは溶液状で作用させて製造するのが一般的である。
グラフト変性用のポリオレフィンとしては、高圧法低密度ポリエチレン、線状低密度ポリエチレン、高密度ポリエチレン、ポリプロピレンなどのホモポリマーの他、プロピレン−エチレン共重合体、プロピレン−ブテン−１共重合体、エチレン−酢酸ビニル共重合体、エチレン−（メタ）アクリル酸エステル共重合体、エチレン−酢酸ビニル−（メタ）アクリル酸エステル共重合体などの共重合体や、それらの混合物などが挙げられる。
また、例えば、エチレン−（メタ）アクリル酸エステル−無水マレイン酸共重合体のように、エポキシ基と反応可能な酸あるいは酸無水物基などを既に含むような共重合体をさらにグラフト変性したものを用いても良い。
【００６４】
変性に使用するラジカル発生剤の種類については特に限定はないが、一般に、有機過酸化物が用いられ、例えば、ジｔ−ブチルパーオキシド、ジクミルパーオキシド、ｔ−ブチルクミルパーオキシド等のジアルキルパーオキシド類、ｉ−ブチルパーオキシド等のジアシルパーオキシド類、ジｉ−プロピルパーオキシジカーボネート等のパーオキシジカーボネート類、ｔ−ブチルパーオキシピバレート等のパーオキシエステル類、メチルエチルケトンパーオキシド等のケトンパーオキシド類、１,１−ビス−ｔ−ブチルパーオキシシクロヘキサン等のパーオキシケタール類、ｔ−ブチルハイドロパーオキシド等のハイドロパーオキシド類が例示される。中でも、ジクミルパーオキシド、２，５−ジメチル−２，５−ビス（ｔ−ブチルパーオキシ）ヘキサン、１，３−ビス（２−ｔ−ブチルパーオキシイソプロピル）ベンゼン、ベンゾイルパーオキサイド等が好ましい。
変性用の不飽和化合物としては、上記エチレンと共重合可能な化合物と同様の不飽和化合物が用いられる。
【００６５】
（III）成分であるエポキシ基と反応する官能基を有するオレフィン系重合体の使用量は、樹脂成分に対して、すなわち、樹脂成分が成分（Ｉ）と成分（II）と成分（III）だけであれば、それらの合計に対して５０重量％未満であり、２〜２５重量％が好ましく、５〜２０重量％が特に好ましい。５０重量％よりも多いと、接着強度が向上するものの、成分（Ｉ）のエチレン（共）重合体に基づく機械特性、光学特性、熱特性が低下する上に、コストアップとなる。
本発明においては、その特性を本質的に損なわない範囲において、造核剤、滑剤、帯電防止剤、防曇剤、顔料、紫外線吸収剤、分散剤などの公知の添加剤を添加することができる。
本発明のポリオレフィン系樹脂組成物を製造するには、上記各成分をヘンシェルミキサー、リボンミキサー等により混合するか、混合したものをさらにオープンロール、バンバリーミキサー、ニーダー、押出機等を使用して混練する方法を適宜利用すればよい。溶融混練の温度は、通常１１０〜３５０℃、扱い易さから１２０〜３００℃が好ましい。
【００６６】
〔積層体〕
本発明のポリオレフィン系樹脂組成物は、接着性が良好なため、各種積層体として用いると、特にその特性を発揮することができる。
このポリオレフィン系樹脂組成物からなる層と隣接する層（以下、基材層とする）としては、ポリアミド６、ポリアミド６６、ポリアミド１２等のポリアミド、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル、エチレン−酢酸ビニル共重合体鹸化物等の熱可塑性樹脂のフィルムまたはシートの他、珪素酸化物やアルミニウム等の薄膜を蒸着した樹脂フィルム、鉄、アルミニウム等の金属箔、紙等、一般にフィルムまたはシートとして用いられているものを使用できる。また、織布、不織布、板体のいずれでもかまわない。また、これらの基材層は必要に応じてコロナ放電処理、フレーム処理、プラズマ処理、紫外線処理等の表面処理が行なわれていても良い。
これらの基材層の中でも、ポリアミド、ポリエステルのフィルムまたはシート、アルミ箔が包装材料等で多量に使用されており、本発明における樹脂組成物はこれらの基材に対して特に優れた接着性を発揮する。
尚、積層体としては、当該ポリオレフィン系樹脂組成物層と基材層の他にも、種々の層を設けていてもかまわない。
【００６７】
本発明の積層体を成形するには、押出しラミネート成形、共押出し成形、感熱接着法、カレンダー成形、中空成形、インフレーション成形等の方法を用いることができる。特に押出しラミネート成形においては従来依然のものに比して著しい接着強度の改善効果がみられる。
ここでいう押出ラミネート成形とは、熱可塑性樹脂を押出機を用いて加熱、溶融、Ｔダイより膜状に押出し、各種フィルム、箔等の基材の上に載せ、製膜と接着とを同時に行なう方法であり、生産性の特長を活かして包装材料や剥離紙等の分野で広く行なわれているものである。
【００６８】
押出ラミネート成形における成形温度は、従来のチーグラー触媒によるエチレン・α−オレフィン共重合体およびメタロセン系エチレン・α−オレフィン共重合体の場合、成形性の点から、２００〜３００℃の範囲が一般的であるが、本発明のポリオレフィン系樹脂組成物では２００〜３５０℃の範囲での成形が可能である。
これは、従来のエチレン・α−オレフィン共重合体では３００℃を超えると、熱分解を起こし、ラミネート時に溶融張力の低下に伴い、高速成形性が低下し、同時にネックインが大きくなるのに対して、本発明のポリオレフィン系樹脂組成物では、２８０℃以上の温度でエポキシ化合物が介在した架橋反応が起こり、安定した高速成形性および低ネックインを発現することができる為である。３００℃以上の高温で成形することにより、各種基材に対する接着強度は大きく改善される。
また、押出ラミネート成形の場合には、溶融膜にオゾンを含む空気を吹きつけて溶融膜表面を酸化させるオゾン処理や、溶融膜を圧着する直前に基材の接着面側にコロナ放電処理、プラズマ処理、フレーム処理等の前処理を行なうことでさらに接着強度を向上させることもできる。また、得られた積層体を４０℃以上、樹脂の融点以下の温度で熱処理を行なうことでさらに強固な接着強度を得ることもできる。
【００６９】
【実施例】
以下に実施例および比較例に基づいて本発明を具体的に説明するが、本発明はこれらによって限定されるものではない。
〔試験方法〕
密度：
JIS K6760に準拠した。
ＭＦＲ：
JIS K6760に準拠した。
ＤＳＣ測定：
厚さ０.２mmのシートを熱プレスで成形し、約５mgの試料を打抜き、２３０℃で１０分間保持後、２℃／分で０℃迄冷却後、再び、１０℃／分で１７０℃まで昇温し、表れた最高温ピークの頂点の温度を最高ピーク温度Ｔｍとした。
【００７０】
分子量分布Ｍｗ／Ｍｎ：
ＧＰＣ装置（ウォータース１５０型）を用い、溶媒として１３５℃のＯＤＣＢを使用した。カラムは東ソーのGMHHR-H(S)を用いた。
高速成形性（ＤＤ）：
９０mmφ（５０rpm）の押出機を用いて、Ｔダイ幅８００mm、Ｔダイからロール迄のエアギャップ１２０mmの条件下、温度３００℃で引取速度を増速し、溶融膜の安定性を観察し、耐用できる最高速度を測定した。
ネックイン：
上記押出機により膜厚２５μｍ、引取速度１５０ｍ／分で成形し、基材上のコート幅を測定し、ダイス幅との差（mm）を測定した。
【００７１】
接着強度：
ネックイン測定時と同じ条件で基材に押出ラミネート法により積層して積層体を製造し、その得られた積層体を１５mm幅の短冊状にカットし、３００mm／分の速度で１８０℃剥離を行い、その強度（g/15mm）を測定した。
基材としては、二軸延伸ポリアミドフィルム（オリエンテッドナイロン（ＯＮｙ）：東洋紡績（株）製「ハーデンフィルムN1100」、幅８６０mm、厚さ１５μｍ）と、二軸延伸ポリエチレンテレフタレートフィルム（ＰＥＴ：二村化学工業（株）製「太閣ポリエステルフィルムFE2001」、幅８６０mm、厚さ１２μｍ）とを用いた。
透明性：
幅８６０mm、厚み２０μｍの二軸延伸ポリプロピレンフィルム（ＯＰＰ）を基材とし、上記条件で製造した積層体のヘイズを測定した。測定は、JIS K7105に準じた。
【００７２】
〔エチレン（共）重合体（Ｉ-1）の製造〕
▲１▼固体触媒の調製
窒素下で電磁誘導攪拌機付き触媒調製器（No.１）に精製トルエンを加え、ついでジプロポキシジクロロジルコニウム（Ｚｒ（ＯＰｒ）₂Ｃｌ₂）２８ｇおよびメチルシクロペンタジエン４８ｇを加え、０℃に系を保持しながらトリデシルアルミニウムを４５ｇを滴下した。滴下終了後、反応系を５０℃に保持して１６時間攪拌した。この溶液をＡ液とした。
次に、窒素下で別の攪拌器付き触媒調製器（No.２）に精製トルエンを加え、前記Ａ溶液と、ついでメチルアルミノキサン６.４ｍｏｌのトルエン溶液を添加し反応させた。これをＢ液とした。
次に、窒素下で攪拌器付き調製器（No.１）に精製トルエンを加え、次いで予め４００℃で所定時間焼成処理したシリカ（富士デビソン社製、グレード＃９５２、表面積３００ｍ²／ｇ）１４００ｇを加えた後、前記Ｂ溶液の全量を添加し、室温で攪拌した。ついで窒素ブローにて溶媒を除去して流動性の良い固体触媒粉末を得た。これを触媒Ｃとした。
【００７３】
▲２▼試料の重合
連続式の流動床気相法重合装置を用い、重合温度７０℃、全圧２０kgf／cm²Gでエチレンと１−ヘキセンの共重合を行った。前記触媒Ｃを連続的に供給して重合を行い、系内のガス組成を一定に保つため、各ガスを連続的に供給しながら重合を行い、共重合体（Ｉ−▲１▼）を製造した。
（Ｉ−▲１▼）エチレン・１−ヘキセン共重合体
密度：０.９１１g/cm³
ＭＦＲ：１１g/10分
分子量分布（Ｍｗ／Ｍｎ）：２.６
組成分布パラメーターＣｂ：１.１９
ＴＲＥＦピーク温度：８３.２、９６.５℃
ｄ−０.００８logＭＦＲ：０.９０３
【００７４】
〔エチレン（共）重合体（Ｉ-2）の製造〕
攪拌機を付したステンレス製オートクレーブを窒素置換し精製トルエンを入れた。次いで、ブテン−１を添加し、更にビス１,３ジメチル（シクロペンタジエニル）ジルコニウムジクロライド（Ｚｒとして０.０２ｍモル）とメチルアルモキサン［ＭＡＯ］（ＭＡＯ／Ｚｒ＝１００［モル比］）の混合溶液を加えた後、１２０℃に昇温した。次ぎにエチレンを張り込み重合を開始した。エチレンを連続的に重合しつつ全圧を維持して１時間重合を行い、エチレン・ブテン−１共重合体（Ｉ−▲２▼）を得た。
（Ｉ−▲２▼）エチレン・ブテン−▲１▼共重合体
密度：０.９１８g/cm³
ＭＦＲ：３.８g/10分
分子量分布（Ｍｗ／Ｍｎ）：２.３
組成分布パラメーター（Ｃｂ）：１.０５
ＴＲＥＦピーク温度：９４.７℃
ｄ−０.００８logＭＦＲ：０.９０１
（Ｉ−▲３▼）エチレン・ブテン−１共重合体
気相法チーグラー触媒品（日本ポリオレフィン（株）製）
密度：０.９２０g/cm³
ＭＦＲ：７.０g/10分
【００７５】
〔成分（III）〕
エポキシ基と反応する官能基を有するオレフィン系共重合体として以下のものを使用した。
（III−▲１▼）エチレン−アクリル酸共重合体（ＥＡＡ）
三菱油化（株）製「ユカロンＡ２２１Ｍ」
ＭＦＲ：７.０g/10分
アクリル酸：８.５重量％
（III−▲２▼）無水マレイン酸変性ポリエチレン
ＭＦＲ：３６.６g/10分
無水マレイン酸：０.０９重量％
【００７６】
〔実施例１〕
成分（Ｉ）としてＩ−▲１▼のエチレン・１−ヘキセン共重合体に、成分（II）としてエポキシ化大豆油（旭電化（株）製「Ｏ−１３０Ｐ」）を０.５重量％加え、φ３０mmの二軸押出機を用いて２００℃で溶融混練してポリオレフィン系樹脂組成物を得た。
得られた樹脂組成物をφ９０mmの押出機を有する押出ラミネーターを用いてＴダイ幅８００mm、エアギャップ１２０mm、温度２８０℃で、基材上に押し出して積層体を製造した。
この実施例１のものであると、成形膜はネックインが小さく、得られた積層体は良好な接着性、透明性を発揮した。
【００７７】
〔実施例２〕
成形温度を３０５℃とする以外は実施例１と同様にして成形を行った。
エポキシ化合物を添加することにより、３００℃以上でも成形が可能となり、良好な接着強度が得られた。
〔実施例３〕
成分（II）としてエポキシ化大豆油を３.０重量％添加する以外は実施例１と同様にしてポリオレフィン系樹脂組成物を調製し、積層体を製造した。
この組成物についても、良好な成形性を示し、接着性、透明性ともに良好であった。
〔実施例４〕
成形温度を３０５℃とする以外は実施例２と同様にして成形を行った。この場合も溶融膜は安定しており、透明性、接着強度共に良好であった。
【００７８】
〔実施例５〕
成分（Ｉ）としてＩ−▲２▼を使用する以外は、実施例１と同様にしてポリオレフィン系樹脂組成物を調製し、積層体を製造した。
この組成物についても、成形性は良好であり、接着性、透明性も良好であった。
〔実施例６〕
成形温度を３０５℃とする以外は実施例５と同様にして成形を行った。この場合も溶融膜は安定しており、透明性、接着強度共に良好であった。
〔実施例７〕
成分（II）としてエポキシ化亜麻仁油を０.５重量％添加する以外は実施例１と同様にしてポリオレフィン系樹脂組成物を調製し、積層体を製造した。
この組成物についても、良好な成形性を示し、接着性、透明性ともに良好であった。
【００７９】
〔実施例８〕
成形温度を３０５℃とする以外は実施例７と同様にして成形を行った。この場合も溶融膜は安定しており、透明性、接着強度共に良好であった。
〔実施例９〕
成分Ｉ−▲１▼と成分III−▲１▼の重量比が８０：２０の割合になるように混合した組成物に、成分（II）として、エポキシ化大豆油を０.５重量％添加し、実施例１同様に、溶融混練して組成物を得た。
得られた組成物を用いて実施例１と同様に積層体を製造した。
このものにおいても、良好な成形性と優れた接着性、透明性を示した。
〔実施例１０〕
成形温度を３０５℃とする以外は実施例９と同様にして成形を行った。この場合も溶融膜は安定しており、透明性は若干低下するものの、接着強度はさらに向上した。
〔実施例１１〕
成分Ｉ−▲１▼と成分III−▲２▼の重量比が８０：２０の割合になるように混合した組成物に、成分（II）として、エポキシ化大豆油を０.５重量％添加し、実施例１同様に、溶融混練して組成物を得た。
得られた組成物を用いて実施例１と同様に積層体を製造した。
このものにおいても、良好な成形性と優れた接着性、透明性を示した。
〔実施例１２〕
成形温度を３０５℃とする以外は実施例１１と同様にして成形を行った。この場合も溶融膜は安定していた。透明性は実施例１０と同様に若干低下するものの、接着強度はさらに向上した。
【００８０】
〔比較例１〕
成分（II）のエポキシ化合物を添加せずに、エチレン（共）重合体Ｉ−▲１▼単独で実施例１と同様に、成形温度２８０℃で積層体を製造した。
このときのネックインはエポキシ化合物を添加したものよりも大きい上に、充分な接着強度も得られなかった。
〔比較例２〕
比較例１で調製した樹脂組成物を用いて、成形温度３０５℃で積層体の製造を試みた。しかしながら、Ｉ−▲１▼単独では、３０５℃で熱分解の為に溶融膜が不安定で、製膜が不可能な状態であった。
〔比較例３〕
成分（II）の代りに、エポキシ化されていない大豆油を０.５重量％添加する他は実施例１と同様にしてポリオレフィン系樹脂組成物を調製し、積層体を製造した。
このものはネックインが非常に大きく、接着強度も不十分であった。
〔比較例４〕
比較例３で調製した樹脂組成物を用いて、成形温度３０５℃で積層体の製造を試みた。しかしながら、３０５℃で熱分解の為に溶融膜が不安定で、製膜が不可能な状態であった。
〔比較例５〕
成分（Ｉ）として、Ｉ−▲３▼エチレン・ブテン−１共重合体を使用する他は実施例１と同様にして、積層体を製造した。このものでは、良好な成形性と接着強度を示したが、透明性で劣っていた。
【００８１】
【表１】

【００８２】
【発明の効果】
本発明は、優れた物性、加工性および基材との良好な接着性を有する新規なエチレン（共）重合体を含む組成物であり、分子量分布が狭いにもかかわらず、比較的広い組成分布をもち、かつ低分子量成分および非晶質成分の含有量が少なく、機械物性、成形加工性、光学特性および耐熱性に優れる。特に、押出しラミネート成形、Ｔダイ成形、インフレーションフィルム成形等によってポリエステル、ポリアミド、金属箔等と積層した際の接着強度に優れる。
また、積層体は、接着強度、透明性、ヒートシール性に優れ、溶剤抽出成分量が少ない為、食品や衣料等の各種包装材、容器等に好適である。
【図面の簡単な説明】
【図１】 成分（Ｉ-1）についての連続昇温溶出分別法による溶出温度−溶出量曲線のグラフである。
【図２】 成分（Ｉ-2）についての連続昇温溶出分別法による溶出温度−溶出量曲線のグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyolefin resin composition having excellent physical properties and processability, and having good adhesion to a substrate when used in a laminate.
[0002]
[Prior art]
Polyolefin is excellent in heat sealability and moisture resistance, and easy to process, so it is not only used as a single layer film, sheet or molded container material, but also various resin films, sheets, and metal foils such as aluminum foil It is also widely used as a laminate with paper and paper. Above all, linear low density polyethylene (LLDPE) obtained by polymerization with Ziegler-based catalysts has higher strength and toughness than high pressure method low density polyethylene (HPLDPE), and it is a film, sheet, hollow molded article, injection molded article. Used for various purposes such as body.
However, these materials are also required to have higher strength in order to reduce the thickness and weight of the molded product.
Therefore, in recent years, high-strength ethylene / α-olefin copolymers with a very narrow molecular weight distribution and composition distribution have been developed with metallocene catalysts, which show excellent performance in mechanical and optical properties. It is attracting attention as a material and container material.
[0003]
[Problems to be solved by the invention]
However, this metallocene ethylene / α-olefin copolymer also has some disadvantages.
For example, when a metallocene-based ethylene / α-olefin copolymer is laminated with a base material such as a polyester film, a polyamide film, or a metal foil by a method such as extrusion lamination, and used as a packaging material, the base material and the metallocene-based ethylene / There is a problem that the adhesive strength with the α-olefin copolymer is weak.
In addition, when HPLDPE is laminated on various substrates by an extrusion laminating method, the necessary adhesive strength is generally obtained by laminating at a high temperature of 300 ° C. or higher. However, Ziegler type LLDPE or metallocene ethylene / α-olefin is obtained. The copolymer is thermally decomposed at a high temperature and is difficult to be stably molded, and also has problems such as smoke generation during molding and odor remaining in the molded product.
For this reason, Ziegler type LLDPE and metallocene ethylene / α-olefin copolymers need to be laminated at a temperature of 300 ° C. or lower.
[0004]
Further, in order to prevent a decrease in adhesive strength, an ozone treatment method for forcibly oxidizing the surface of the molten film by spraying ozone onto the molten film before lamination (refer to Japanese Patent Application Laid-Open No. 57-157724), ozone There has been proposed a method in which treatment and an adhesive called an anchor coat agent are used in combination.
However, the ozone treatment method has problems such as ozone odor, corrosiveness, and safety to the human body, and the method using an anchor coating agent requires a coating-drying process. Since the organic solvent is used, there are problems such as a risk of fire, a deterioration of the working environment, and a residual solvent odor remaining in the product. Further, these methods are not preferable from the viewpoint of an increase in manufacturing cost.
[0005]
In view of the above circumstances, the present invention has mechanical strength and optical properties superior to those of LLDPE using Ziegler-type catalysts, and has low-temperature heat sealability and transparency equivalent to those of metallocene ethylene / α-olefin copolymers. A polyolefin-based resin composition having excellent processability than the metallocene-based ethylene / α-olefin copolymer and having excellent adhesion to various substrates without complicated processes. It aims at providing the laminated body using it.
[0006]
[Means for Solving the Problems]
As a result of earnest researches along the above-mentioned purpose, the present inventors have produced an ethylene (co) polymer with a low content of low molecular weight components and an amorphous component, and two or more epoxy groups in the molecule. By adding an epoxy compound having the above, the above-mentioned object has been achieved.
[0007]
The polyolefin-based resin composition of the present invention includes component (I): an ethylene (co) polymer that satisfies the following requirements (a) to (d):
Component (II): an epoxy compound having two or more epoxy groups in the molecule and a molecular weight of 3000 or less,
The ratio of the component (II) to the resin component is 0.01 to 5% by weight.
(A) Density is from 0.86 to 0.97 g / cm^Three
(B) Melt flow rate is 0.01-100 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) Composition distribution parameter Cb is 2.00 or less
[0008]
At this time, it is preferable that the component (III): an olefin polymer having a functional group that reacts with an epoxy group is contained, and the ratio of the component (III) to the resin component is less than 50% by weight.
In addition, the ethylene (co) polymer of component (I) comprises ethylene and a carbon number of 3 to 3 in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a group IV transition metal compound. It is desirable to be obtained by copolymerizing 20 α-olefins.
Furthermore, it is desirable that the ethylene (co) polymer of the component (I) is an ethylene / α-olefin copolymer (I-1) that satisfies the following requirements (a) to (f).
(A) Density is from 0.86 to 0.97 g / cm^Three
(B) Melt flow rate of 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) The composition distribution parameter Cb is 1.08 to 2.0.
(E) There are substantially multiple peaks in the elution temperature-elution volume curve by the continuous temperature elution fractionation method.
(F) The amount of orthodichlorobenzene soluble component X (wt%), density d and melt flow rate (MFR) at 25 ° C. satisfy the following relationship:
(A) When d−0.008logMFR ≧ 0.93
X <2.0
(B) When d−0.008logMFR <0.93
X <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
[0009]
Alternatively, in the polyolefin resin composition according to claim 1 or 2, the ethylene (co) polymer of component (I) is a ligand having a cyclopentadienyl skeleton and a group IV transition of the periodic table. Ethylene / α- which satisfies the following requirements (a) to (e) obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of at least one catalyst containing a compound The olefin copolymer (I-2) is desirable.
(A) Density is from 0.86 to 0.97 g / cm^Three
(B) Melt flow rate of 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) The composition distribution parameter Cb is 1.01 to 1.2.
(E) There is substantially one peak of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method.
[0010]
In these cases, it is desirable that the epoxy compound of component (II) is an epoxidized vegetable oil.
The olefin polymer having a functional group that reacts with the epoxy group of the component (III) contains at least one group selected from the group consisting of an acid anhydride group, a carboxyl group, and a carboxylic acid metal salt in the molecule. It is preferably a polyolefin-based resin.
The laminated body of this invention has a layer which consists of one of the polyolefin resin compositions mentioned above.
At this time, the layer adjacent to the layer made of the polyolefin resin composition is preferably made of any one of polyester, polyamide, and aluminum.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
[Polyolefin resin composition]
<(I) Ethylene (co) polymer>
In the present invention, an ethylene homopolymer or an ethylene / α-olefin copolymer (hereinafter referred to as component (I)) that satisfies the following requirements (a) to (d) is used.
(A) Density is from 0.86 to 0.97 g / cm^Three
(B) Melt flow rate of 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) Composition distribution parameter Cb is 2.00 or less
The ethylene (co) polymer (component (I)) of the present invention is a (co) polymer of ethylene or one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms. The α-olefin preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. For example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned.
In addition, the content of these α-olefins in the copolymer is desirably 30 mol% or less, preferably 3 to 20 mol%.
[0012]
The ethylene (co) polymer in the present invention has the above requirement (a), that is, a density of 0.86 to 0.97 g / cm.^ThreeIt is. Preferably, from 0.88 to 0.945 g / cm^ThreeMore preferably, 0.90 to 0.93 g / cm^ThreeMore preferably, 0.91-0.93 g / cm^ThreeIt is in the range. Density is 0.86g / cm^ThreeThose below are too soft and inferior in rigidity, in addition to poor heat resistance and inferior anti-blocking properties. 0.97g / cm^ThreeExceeding the hardness is too hard, and the tear strength and impact resistance are not sufficient.
The (b) melt flow rate (hereinafter referred to as MFR) of the ethylene (co) polymer is 0.01 to 100 g / 10 min, preferably 0.1 to 100 g / 10 min, more preferably 0.00. It is in the range of 2 to 50 g / 10 min, more preferably 0.5 to 40 g / 10 min. When the MFR is less than 0.01 g / 10 min, the workability (drawdown property, etc.) is poor, and when it exceeds 100 g / 10 min, the mechanical strength such as impact resistance is lowered.
[0013]
Component (I) (C) Molecular weight distribution Mw / Mn is in the range of 1.5 to 5.0. More preferably, it is 2.0-3.0, More preferably, it is 2.2-2.8. When Mw / Mn is less than 1.5, molding processability is inferior, and when it exceeds 5.0, mechanical strength such as impact resistance is inferior.
In addition, molecular weight distribution (Mw / Mn) calculates | requires a weight average molecular weight (Mw) and a number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculates those ratios (Mw / Mn). Desired.
[0014]
The component (I) (d) composition distribution parameter (Cb) of the component (I) of the present invention needs to be 2.00 or less. If the composition distribution parameter (Cb) is larger than 2.00, it is easy to block, heat sealability is poor, and low molecular weight or high branching component oozes out on the resin surface, resulting in hygiene problems. It is.
The composition distribution parameter (Cb) is measured as follows.
The sample was dissolved in orthodichlorobenzene (ODCB) to which an antioxidant was added by heating at 135 ° C. to a concentration of 0.2% by weight, and then transferred to a column packed with diatomaceous earth (Celite 545). Cool to 25 ° C. at a cooling rate of 0.1 ° C./min to deposit the copolymer sample on the celite surface. Next, the column temperature is raised stepwise up to 120 ° C. in steps of 5 ° C. while ODCB is allowed to flow through the column on which the sample is deposited at a constant flow rate. Then, a solution containing an elution component corresponding to each temperature is collected. The solution is cooled, methanol is added, the sample is precipitated, filtered and dried to obtain elution samples at each temperature. The weight fraction and the degree of branching (number of branches per 1000 carbon atoms) of each of the sorted samples are measured. The degree of branching¹³Measured by C-NMR.
[0015]
For each fraction collected at 30 ° C. to 90 ° C. by such a method, the degree of branching is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, the correlation is approximated to a straight line by the least square method, and a calibration curve is created. This approximate correlation coefficient is sufficiently large. The value obtained from this calibration curve is taken as the degree of branching of each fraction. For the fraction collected at an elution temperature of 95 ° C. or higher, the linear relationship is not necessarily established between the elution temperature and the degree of branching, so this correction is not performed.
[0016]
Next, the weight fraction w of each fraction_iThe degree of branching per elution temperature of 5 ° C._iChange amount (b_i-B_i-1) Divided by relative concentration c_iAnd plot the relative concentration against the degree of branching to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.
Cb = (Σc_j・ B_j ²/ Σc_j・ B_j) / (Σc_j・ B_j/ Σc_j)
Where c_jAnd b_jAre the relative concentration and the degree of branching of the jth segment, respectively. The composition distribution parameter Cb is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution increases.
[0017]
Many proposals have been made for a method for expressing the composition distribution of an ethylene (co) polymer. For example, in Japanese Patent Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (logarithmic normal distribution) with respect to the number of branches of each fractionated sample obtained by solvent fractionation of the sample. The ratio of the weight average branching degree (Cw) and the number average branching degree (Cn) is obtained. This approximate calculation is less accurate when the number of sample branches and the cumulative weight fraction deviate from the logarithmic normal distribution, and the correlation coefficient R2 is considerably low when measurements are performed on commercially available LLDPE, and the accuracy of the values is not sufficient. Further, the Cw / Cn measurement method and the numerical processing method are different from those of Cb of the present invention. However, if a numerical comparison is made, the value of Cw / Cn becomes considerably larger than Cb.
[0018]
The component (I) described above may be produced with a known catalyst such as a Ziegler catalyst or a Philips catalyst, but those prepared according to the following two embodiments are particularly suitable.
One of them is homopolymerization of ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. Those obtained by copolymerization are particularly preferred.
[0019]
Among these, an ethylene (co) polymer (hereinafter referred to as component (I-1)) that satisfies the following requirements (a) to (f) is particularly suitable.
(A) Density is from 0.86 to 0.97 g / cm^Three
(B) Melt flow rate of 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) The composition distribution parameter Cb is 1.08 to 2.0.
(E) There are substantially multiple peaks in the elution temperature-elution volume curve by the continuous temperature elution fractionation method.
(F) The amount of orthodichlorobenzene soluble component X (wt%), density d, and melt flow rate (MFR) at 25 ° C satisfy the following relationship:
(A) When d−0.008logMFR ≧ 0.93
X <2.0
(B) When d−0.008logMFR <0.93
X <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
[0020]
The other is to satisfy the following requirements (a) to (e) obtained in the presence of a ligand having a cyclopentadienyl skeleton and at least one catalyst containing a transition compound of Group IV of the periodic table. It is a satisfactory ethylene (co) polymer (hereinafter referred to as component (I-2)).
(A) Density is from 0.86 to 0.97 g / cm^Three
(B) Melt flow rate of 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) The composition distribution parameter Cb is 1.01 to 1.2.
(E) There is substantially one peak of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method.
[0021]
Here, as shown in FIG. 1, the component (I-1) is composed of a special ethylene having a plurality of peaks substantially in the elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF). As shown in FIG. 2, the component (I-2) is a homopolymer or a copolymer and has a peak substantially as shown in FIG. 2 in the elution temperature-elution amount curve obtained by the same continuous temperature rising elution fractionation method (TREF). Single ethylene by a typical metallocene-based catalyst obtained in the presence of at least one catalyst comprising a ligand having a cyclopentadienyl skeleton and a transition metal compound of Group IV of the Periodic Table It is a combination or copolymer, and the components (I-1) and (I-2) are clearly distinguished.
[0022]
<< Ingredient (I-1) >>
In the component (I-1), the molecular weight distribution (Mw / Mn) is in the range of 1.5 to 5.0, more preferably 1.5 to 4.5, and still more preferably 1.8 to It is desirable to be in the range of 4.0, more preferably 2.0 to 3.0.
In the component (I-1), the composition distribution parameter Cb is more preferably from 1.08 to 2.00, further preferably from 1.12 to 1.70, more preferably from 1.15 to 1. It is desirable to be in the range of .50. If it is less than 1.08, the hot tack property is inferior, and if it is more than 2.00, the transparency is lowered, and a polymer gel may be formed in the molded product.
[0023]
As described above, the special ethylene (co) polymer (I-1) in the present invention has a plurality of peaks in the elution temperature-elution amount curve obtained by (e) continuous temperature rising elution fractionation method (TREF). Exists. It is particularly preferable that the plurality of peak temperatures exist between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.
[0024]
The measuring method of TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) is added so that the sample concentration becomes 0.05% by weight, and heated and dissolved at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the glass bead surface. Next, the sample is sequentially eluted while increasing the column temperature at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent was set to a wave number of 2925 cm of asymmetric stretching vibration of methylene.^-1Is continuously detected by measuring the absorption with respect to an infrared detector. From this value, the concentration of the ethylene (co) polymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate.
According to the TREF analysis, since a change in elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, it is possible to detect a relatively fine peak that cannot be detected by a fractionation method.
[0025]
Further, as described above, in this component (I-1), (f) the relationship between the amount X (wt%) of the ODCB soluble component at 25 ° C. and the density d and MFR is such that the values of d and MFR are
When d-0.008logMFR ≧ 0.93 is satisfied,
X is less than 2% by weight, preferably less than 1% by weight,
If d-0.008logMFR <0.93,
X <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
Preferably,
X <7.4 × 10^Three× (0.9300-d + 0.008logMFR)²+1.0
More preferably,
X <5.6 × 10^Three× (0.9300-d + 0.008logMFR)²+0.5
It is desirable to satisfy this relationship.
[0026]
The amount ODCB soluble content X at 25 ° C. is measured by the following method. 0.5 g of sample is heated in 20 ml of ODCB at 135 ° C. for 2 hours to completely dissolve the sample and then cooled to 25 ° C. The solution is allowed to stand at 25 ° C. overnight and then filtered through a Teflon filter to collect the filtrate. This filtrate, which is a sample solution, was subjected to a wave number of 2,925 cm of asymmetric stretching vibration of methylene using an infrared spectrometer.^-1The absorption peak intensity in the vicinity is measured, and the sample concentration is calculated using a calibration curve prepared in advance. From this value, the amount of soluble ODCB at 25 ° C. is obtained.
[0027]
The ODCB soluble component at 25 ° C. is a high branching component and a low molecular weight component contained in the ethylene (co) polymer, causing a decrease in heat resistance and stickiness of the surface of the molded product. This content is desirable to be low because it causes blocking of the inner surface. The amount of ODCB solubles is affected by the α-olefin content and molecular weight of the entire copolymer, ie, density and MFR.
Accordingly, the fact that the density and the amount of soluble components of MFR and ODCB satisfying the above relationship indicate that the α-olefin contained in the entire copolymer is less unevenly distributed.
[0028]
Since this ethylene (co) polymer (I-1) has a narrow molecular weight distribution and composition distribution, it has a high mechanical strength, an excellent heat sealability, an antiblocking property, etc., and a good heat resistance.
This component (I-1) is particularly preferably polymerized with the following catalysts a1 to a4.
a1: General formula Me¹R¹ _pR² _q(OR^Three)_rX¹ _4-pqrA compound represented by
(Where Me¹Represents zirconium, titanium, hafnium, R¹And R^ThreeAre each a hydrocarbon group having 1 to 24 carbon atoms or a trialkylsilyl group, R²Is a 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonate ligand or derivative thereof, X¹Represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r are 0 ≦ p <4, 0 ≦ q <4, 0 ≦ r <4 and 0 ≦ p + q + r ≦ 4, respectively. An integer that satisfies the range. )
a2: General formula Me²R^Four _m(OR^Five)_nX² _zmnA compound represented by
(Where Me²Is the Group I-III element of the periodic table, R^FourAnd R^FiveAre each a hydrocarbon group having 1 to 24 carbon atoms, X²Is a halogen atom or a hydrogen atom (however, X²Me is a hydrogen atom²Is only for Group III elements of the Periodic Table), z is Me²M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z. )
a3: An organic cyclic compound having a conjugated double bond.
a4: a modified organoaluminum oxy compound and / or boron compound containing an Al—O—Al bond.
[0029]
Each of these catalyst components will be described in detail.
The catalyst component a1 has the general formula Me¹R¹ _pR² _q(OR^Three)_rX¹ _4-pqrIn the formula of the compound represented by¹Z represents zirconium, titanium, and hafnium, and a plurality of them can be used, but it is particularly preferable that zirconium having excellent weather resistance of the copolymer is included. R¹And R^ThreeThe hydrocarbon group having 1 to 24 carbon atoms preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms.
Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And aryl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofoyl group. These may be branched.
[0030]
Examples of the compound represented by the general formula of the catalyst component a1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tributoxymonochlorozirconium, Examples include dibutoxydichlorozirconium, tetrabutoxytitanium, and tetrabutoxyhafnium. Particularly, Zr (OR) such as tetrapropoxyzirconium and tetrabutoxyzirconium._FourCompounds are preferred, and two or more of these may be used in combination.
R²Specific examples of 2,4-pentanedionate ligands or derivatives thereof include tetra (2,4-pentanedionate) zirconium, tri (2,4-pentanedionate) chloride zirconium, di (2, 4-pentanedionato) dichloride zirconium, (2,4-pentandedionato) trichloride, di (2,4-pentandedionato) diethoxide zirconium, di (2,4-pentandedionato) di-n- Propoxide zirconium, di (2,4-pentanedionato) di-n-butoxide zirconium, di (2,4-pentandedionato) dibenzylzirconium, di (2,4-pentandedionato) dineo Foil zirconium,
Tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n-butoxy Examples include side zirconium, di (benzoylacetonato) diethoxide zirconium, di (dibenzoylacetonato) di-n-propoxide zirconium, di (benzoylacetonato) di-n-butoxide zirconium and the like.
[0031]
The catalyst component a2 has the general formula Me²R^Four _m(OR^Five)_nX² _zmnIn the formula of the compound represented by²Represents a group I-III element in the periodic table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. R4 and R^FiveAre each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically alkyl such as methyl group, ethyl group, propyl group, isopropyl group and butyl group. Group: alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenyl Examples include aralkyl groups such as a butyl group and a neofoyl group. These may be branched. X²Represents a halogen atom such as fluorine, iodine, chlorine and bromine or a hydrogen atom. However, X²Me is a hydrogen atom²Is limited to the group III elements of the periodic table exemplified by boron, aluminum and the like.
[0032]
Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyllithium and ethyllithium; organomagnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; dimethylzinc and diethyl Organic zinc compounds such as zinc; organic boron compounds such as trimethylboron and triethylboron; trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethyl Organoaluminum compounds such as aluminum ethoxide and diethylaluminum hydride And the like.
[0033]
The organic cyclic compound having a conjugated double bond as the catalyst component a3 has one or more rings that are cyclic and have 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. A cyclic hydrocarbon compound having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms; the cyclic hydrocarbon compound is partially a hydrocarbon residue having 1 to 6 carbon atoms (typically having 1 to A cyclic hydrocarbon compound substituted with 12 alkyl groups or an aralkyl group; having 1 or 2 rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds An organosilicon compound having a cyclic hydrocarbon group having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon group is partially a hydrocarbon residue or alkali metal salt (sodium 1-6) Or lithium salt) Organosilicon compounds are included. Particularly preferred is one having a cyclopentadiene structure in any of the molecules.
[0034]
Suitable examples of the compound include cyclopentadiene, indene, azulene, or alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Moreover, the compound which these compounds couple | bonded (bridge | crosslinked) via the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.
[0035]
The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.
A_LSiR_4-L
Here, A represents the cyclic hydrogen group exemplified by cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, and substituted indenyl group, and R represents methyl group, ethyl group, propyl group, isopropyl group, butyl group An alkyl group such as a group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group; To 24, preferably 1 to 12 hydrocarbon residues or hydrogen, L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.
[0036]
Specific examples of the organic cyclic hydrocarbon compound of component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, Cyclopolyene having 5 to 24 carbon atoms such as cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclopentadienylsilane, Examples include triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.
[0037]
The modified organoaluminum oxy compound and / or boron compound containing the Al—O—Al bond of the catalyst component a4 is reacted with an alkylaluminum compound and water to obtain a modified organoaluminum oxy compound usually referred to as aluminoxane. The molecule usually contains 1 to 100, preferably 1 to 50 Al—O—Al bonds. The modified organoaluminum oxy compound may be linear or cyclic. Examples of the boron compound include triethylaluminum tetra (pentafluorophenyl) borate (triethylammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate (dimethylanilinium tetra (pentafluorophenyl) borate), Examples thereof include butylammonium tetra (pentafluorophenyl) borate, N, N-dimethylanrinium tetra (pentafluorophenyl) borate, N, N-dimethylanolinium tetra (pentafluorophenyl) borate and the like.
[0038]
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferable.
The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) is usually from 0.25 / 1 to 1.2 / 1, preferably from 0.5 / 1 to 1/1.
[0039]
The catalyst components a1 to a4 may be used as mixed and contacted as they are, but it is preferable to use them supported on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or particulate polymer carrier (a5) include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, thermoplastic resins, thermosetting resins, and the like. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like.
Specifically, SiO₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Etc. or a mixture thereof, SiO 2₂-Al₂O_Three, SiO₂-V₂O_Five, SiO₂-TiO₂, SiO₂-V₂O_Five, SiO₂-MgO, SiO₂-Cr₂O_ThreeEtc. Among these, SiO₂And Al₂O_ThreeThe main component is at least one component selected from the group consisting of:
As the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, polystyrene, Examples include norbornene, various natural polymers, and mixtures thereof.
[0040]
The inorganic carrier and / or the particulate polymer carrier can be used as they are, but preferably the carrier is contacted with an organoaluminum compound or a modified organoaluminum oxy compound containing an Al—O—Al bond as a pretreatment. It can also be used as component a5 after the treatment.
[0041]
<Ingredient (I-2)>
In the ethylene homopolymer or ethylene / α-olefin copolymer component (I-2) by the metallocene catalyst, the molecular weight distribution is in the range of 1.5 to 5.0, and 1.5 to 4.5. It is more preferable that it is in the range of 1.8 to 3.5.
In the component (I-2), the composition distribution parameter is preferably in the range of 1.01 to 1.2, more preferably 1.02 to 1.18, and more preferably 1.03 to 1.17. It is desirable to be.
[0042]
The homopolymer or copolymer (I-2) of ethylene by this metallocene catalyst is a group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton and, if necessary, a promoter, organoaluminum It is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing a compound and a carrier.
[0043]
Cyclopenta, a transition metal compound of group IV of the periodic table, containing a ligand having a cyclopentadienyl skeleton, which is a catalyst for producing this ethylene homopolymer or ethylene / α-olefin copolymer (I-2) The dienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like. Examples of substituted cyclopentadienyl groups include hydrocarbon groups having 1 to 10 carbon atoms, silyl groups, silyl substituted alkyl groups, silyl substituted aryl groups, cyano groups, cyanoalkyl groups, cyanoaryl groups, halogen groups, haloalkyl groups, halosilyl groups. A substituted cyclopentadienyl group having at least one substituent selected from the group and the like. The substituted cyclopentadienyl group may have two or more substituents, and such substituents may be bonded to each other to form a ring.
[0044]
As said C1-C10 hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group etc. are mentioned, Specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n -Alkyl groups such as butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and decyl group; cycloalkyl groups such as cyclopentyl group and cycloalkyl group; Examples thereof include aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neofoyl group. Among these, an alkyl group is preferable.
Preferred examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, ethylcyclopentadienyl group, n-hexylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,3 Specific examples include -n-butylmethylcyclopentadienyl group and 1,3-n-propylmethylethylcyclopentadienyl group. Among these, the substituted cyclopentadienyl group of the present invention is preferably a cyclopentadienyl group substituted with an alkyl group having 3 or more carbon atoms, and particularly preferably a 1,3-substituted cyclopentadienyl group.
Examples of the substituted cyclopentadienyl group in the case where the substituents, that is, the hydrocarbons are bonded to each other to form one or more rings, include an indenyl group, a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group), etc. A substituted indenyl group, a naphthyl group, a substituted naphthyl group substituted by a substituent such as a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group), a hydrocarbon group having 1 to 8 carbon atoms ( Preferred examples include a substituted fluorenyl group substituted with a substituent such as an alkyl group).
[0045]
Examples of transition metals of Group IV transition metal compounds containing a ligand having a cyclopentadienyl skeleton include zirconium, titanium, hafnium, and the like, with zirconium being particularly preferred.
The transition metal compound usually has 1 to 3 ligands having a cyclopentadienyl skeleton, and may have two or more ligands bonded to each other via a crosslinking group. Examples of the crosslinking group include an alkylene group having 1 to 4 carbon atoms, an alkylsilanediyl group, and a silanediyl group.
[0046]
As a ligand other than the ligand having a cyclopentadienyl skeleton in the group IV transition metal compound of the periodic table, hydrogen, a hydrocarbon group having 1 to 20 carbon atoms (an alkyl group, Alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group and the like.
[0047]
Specific examples of these are as follows. Dialkylmetallocenes include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) ) Hafnium dimethyl, bis (cyclopentadienyl) hafnium diphenyl, and the like. Monoalkyl metallocenes include bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium phenyl chloride, etc. There is.
Moreover, pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride) and bis (pentamethylcyclopentadienyl) titanium diphenyl, which are monocyclopentadienyl titanocenes.
[0048]
Substituted bis (cyclopentadienyl) titanium compounds include bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or dichloride, dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentadienyl titanium Compounds include bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, bis (1,2-diethylcyclopentadienyl) titanium diphenyl or dichloride or other dihalide complexes, silicon, amine or carbon-linked cyclohexane. Pentadiene complexes include dimethylsilyl dicyclopentadienyl titanium diphenyl or dichloride, methylene dicyclopentadienyl titanium diph Cycloalkenyl or dichloride, and other dihalide complexes.
[0049]
Zirconocene compounds include pentamethylcyclopentadienyl zirconium trichloride, pentaethylcyclopentadienyl zirconium trichloride, bis (pentamethylcyclopentadienyl) zirconium diphenyl, and alkyl-substituted cyclopentadiene includes bis (ethylcyclopentadiene). Enyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, their haloalkyl or dihalide complexes, dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentadiene Bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (1,2-dimethylcyclopentadienyl) zirconium Dimethyl, and their dihalide complexes, silicon, carbon-linked cyclopentadiene complexes include dimethylsilyl dicyclopentadienyl zirconium dimethyl or dihalide, methylene dicyclopentadienyl zirconium dimethyl or dihalide, methylene dicyclopentadienyl zirconium dimethyl or Examples include dihalides.
[0050]
Still other metallocenes include bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dimethyl, bis (cyclopentadienyl) vanadium dichloride, and the like.
[0051]
As an example of a transition metal compound of Group IV of the periodic table of the present invention, a ligand having a cyclopentadienyl skeleton represented by the following chemical formula, another ligand and a transition metal atom form a ring. There are also things.
[Chemical 1]

In the above chemical formula, Cp is a ligand having the cyclopentadienyl skeleton, X is hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an arylsilyl group, an aryloxy group, an alkoxy group, an amide group, a silyloxy group, etc. Y represents SiR₂, CR₂, SiR₂SiR₂, CR₂CR₂, CR = CR, SiR₂CR₂, BR₂, Z is a —O—, —S—, —NR—, —PR— or OR, SR, NR₂, PR₂A divalent neutral ligand selected from the group consisting of: Where R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or two or more Rs from Y, Z or Y and Z. Groups form a condensed ring system. M represents a transition metal atom of Group IV of the periodic table.
[0052]
Examples of the compound represented by this chemical formula include (t-butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (t-butylamide) (tetramethylcyclopentadienyl) -1 , 2-ethanediyltitanium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride, (Ethylamide) (tetramethylcyclopentadienyl) methylenetan dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) sila Zirconium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (phenylphosphide) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, and the like.
[0053]
The co-catalyst as used in the present invention refers to a catalyst that can effectively make the group IV transition metal compound as a polymerization catalyst or can balance the ionic charge in a catalytically activated state.
Examples of the cocatalyst used in the present invention include benzene-soluble aluminoxanes of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, boron compounds, lanthanoid salts such as lanthanum oxide, tin oxide, and the like. Of these, aluminoxane is most preferred.
[0054]
The catalyst may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably an inorganic or organic porous oxide. Specifically, SiO₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Etc. or a mixture thereof, SiO 2₂-Al₂O3, SiO₂-V₂O_Five, SiO₂-TiO₂, SiO₂-MgO, SiO₂-Cr₂O_ThreeEtc.
[0055]
Examples of organoaluminum compounds include trialkylaluminums such as triethylaluminum and triisopropylaluminum; dialkylaluminum halides; alkylaluminum sesquihalides; alkylaluminum dihalides; alkylaluminum hydrides, organoaluminum alkoxides, and the like.
[0056]
"Production method"
The method for producing the ethylene (co) polymer (I) of the present invention is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method or the like substantially free of a solvent in the presence of the catalyst. Illustrated for aliphatic hydrocarbons such as butane, pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, etc. with oxygen and water turned off Produced in the presence or absence of an inert hydrocarbon solvent. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C., preferably 20 to 200 ° C., more preferably 50 to 110 ° C., and the polymerization pressure is usually from normal pressure to 70 kg / in the low-medium pressure method. cm²G, preferably normal pressure to 20 kg / cm²G, usually 1500kg / cm for high pressure method²G or less is desirable. The polymerization time is usually about 3 minutes to 10 hours, preferably about 5 minutes to 5 hours in the case of the low-medium pressure method. In the case of the high pressure method, it is usually 1 minute to 30 minutes, preferably about 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a one-stage polymerization method, but also a two-stage or more multi-stage polymerization method in which polymerization conditions such as a hydrogen concentration, a monomer concentration, a polymerization pressure, a polymerization temperature, and a catalyst are different from each other.
[0057]
In the ethylene (co) polymer of the present invention, when the catalyst component at the time of polymerization is substantially free of halogen such as chlorine, the resulting polymer does not contain these halogens, and therefore chemical stability, hygiene. Excellent in properties and suitable for food, hygiene and medical related applications. In addition, when applied to packaging materials and containers related to electric parts, electric wire members, and microwave ovens, it has a feature that the occurrence of rust on surrounding metal parts can be suppressed.
[0058]
For ethylene (co) polymer (I), organic or inorganic fillers, tackifiers, antioxidants, antifogging agents, organic or inorganic pigments, dispersants, nucleating agents, foaming agents, flame retardants Addition of known additives such as crosslinking agents, UV inhibitors, (un) saturated fatty acid amides, lubricants such as metal salts of (un) saturated higher fatty acids within a range that does not substantially impair the properties of the present invention. Can do.
Among these additives, a lubricant, a tackifier, and an inorganic filler are preferably used in order to further improve workability.
Examples of lubricants include fatty acid amides such as oleic acid amide, stearic acid amide, and erucic acid amide; fatty acid glycerin ester compounds such as stearic acid monoglyceride, stearic acid diglyceride, oleic acid monoglyceride, and oleic acid diglyceride; Is mentioned.
Examples of the inorganic filler include light and heavy calcium carbonate, talc, silica, zeolite, magnesium carbonate, feldspar and the like.
Examples of tackifiers include polybutene, castor oil derivatives, sorbitan fatty acid esters, rosin and rosin derivatives, tackifiers such as petroleum resins and hydrogenated products thereof, rubber, and the like. These tackifiers can be blended in the range of 0.5 to 20 parts by weight.
As the pigment, carbon black, titanium white and the like, and various commercially available colorant masterbatches are preferably used.
[0059]
Furthermore, additives for obtaining appropriate slipping property, antistatic property and antifogging property can also be blended.
Specifically, as sorbitan fatty acid ester, sorbitan monooleate, sorbitan monolaurate, sorbitan monobehenate, sorbitan monostearate, etc .; as glycerol fatty acid ester, glycerol monooleate, glycerol monostearate, glycerol monolaurate, glycerol Monobehenate, etc .; as polyglycerol fatty acid ester, diglycerol monolaurate, diglycerol monostearate, diglycerol monooleate, tetraglycerol monooleate, tetraglycerol monostearate, hexaglycerol monolaurate, hexaglycerol monooleate, In addition to decaglycerin monolaurate, decaglycerin monostearate, decaglycerin monooleate, etc., fatty acid esters of polyhydric alcohols and These ethylene oxide adducts, higher fatty acid amides and their ethylene oxide adducts, does not but such higher fatty acid alkanolamides as being limited thereto.
These additives are used alone or as a mixed composition, and the addition amount is usually 0.01 to 0.5% by weight, preferably 0.05 to 0.3% by weight. If the addition amount is less than 0.01% by weight, the modification effect by the additive is not sufficient. If the addition amount exceeds 0.5% by weight, the amount of the additive on the surface is large and sticky, resulting in workability. This is not preferable because problems such as a significant decrease occur.
[0060]
<(II) Epoxy compound>
In the polyolefin-type resin composition of this invention, the epoxy compound which has 2 or more of epoxy groups in a molecule | numerator and molecular weight is 3000 or less as a component (II).
In this epoxy compound, it is necessary to have two or more epoxy groups in the molecule, and when one is used, the effect of improving the adhesion with other layers is not sufficient when used in a laminate. The molecular weight of the epoxy compound needs to be 3000 or less, and more preferably 1500 or less. When the molecular weight exceeds 3000, the adhesive strength with other layers is still insufficient.
Epoxy compounds include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, adipic acid diglycidyl ester, trimethylolpropane polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, butanediol di- Examples thereof include glycidyl ether, hydrogenated bisphenol A diglycidyl ether, phenol novolac polyglycidyl ether, and epoxidized vegetable oil. Among these, epoxidized vegetable oil is most preferable for laminates for packaging materials such as foods from the viewpoint of safety.
[0061]
The epoxidized vegetable oil here is a product obtained by epoxidizing an unsaturated double bond of a natural vegetable oil using a peracid or the like, and epoxidized soybean oil, epoxidized olive oil, epoxidized flaxseed oil, epoxidized safflower oil. And epoxidized corn oil.
Incidentally, the presence of an oil component that is not epoxidized or is insufficiently epoxidized when the vegetable oil is epoxidized does not hinder the effects of the present invention.
The compounding quantity of these epoxy compounds (II) is 0.01-5 weight with respect to the resin component, ie, if the resin component is only component (I) and component (II), with respect to those sum total. %, Preferably in the range of 0.01 to 0.9% by weight. If the amount added is less than 0.01% by weight, the effect of improving the adhesive strength is not sufficient, and if it exceeds 5% by weight, the molded product may become odorous, the surface may become sticky, and the optical characteristics may deteriorate. Absent.
[0062]
<(III) Olefin polymer>
In the present invention, the component (III) preferably further contains an olefin polymer having a functional group that reacts with an epoxy group. This component (III) is not an essential component, but the adhesion can be further improved by adding it.
As a functional group which reacts with an epoxy group, it is preferable to have in the molecule any one or more of an acid anhydride group, a carboxyl group, or a carboxylic acid metal salt. These functional groups are introduced into the polyolefin molecule by copolymerization or grafting.
Examples of the olefin copolymer having a functional group that reacts with an epoxy group produced by a copolymerization method include a multi-component copolymer of ethylene and a compound copolymerizable with ethylene. As a compound copolymerizable with ethylene used for copolymerization, α, β-unsaturated carboxylic acid such as (meth) acrylic acid, α, β-unsaturated carboxylic acid metal salt such as sodium (meth) acrylate, And unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Other examples include hydroxyl-containing compounds such as hydroxyethyl (meth) acrylate and (meth) allyl alcohol, and unsaturated amino compounds such as allylamine, but are not limited thereto.
Moreover, in addition to the unsaturated compound which has a functional group which can react with these epoxy groups, the multi-component copolymer which copolymerized (meth) acrylic acid ester, vinyl acetate, vinyl alcohol ester, etc. can be used. Moreover, the copolymer of these compounds and ethylene can also use 2 or more types together.
[0063]
Polyolefins into which a functional group capable of reacting with an epoxy group is introduced by graft modification are generally produced by allowing a polyolefin, a radical generator and a modifying compound to act in the form of a melt or solution.
As polyolefin for graft modification, in addition to homopolymers such as high pressure method low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, propylene-ethylene copolymer, propylene-butene-1 copolymer, ethylene- Examples thereof include vinyl acetate copolymers, ethylene- (meth) acrylic acid ester copolymers, copolymers such as ethylene-vinyl acetate- (meth) acrylic acid ester copolymers, and mixtures thereof.
Further, for example, a copolymer that already contains an acid or acid anhydride group that can react with an epoxy group, such as an ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, is further graft-modified. May be used.
[0064]
The type of radical generator used for modification is not particularly limited, but generally organic peroxides are used, for example, dialkyl such as di-t-butyl peroxide, dicumyl peroxide, and t-butylcumyl peroxide. Peroxides, diacyl peroxides such as i-butyl peroxide, peroxydicarbonates such as dii-propyl peroxydicarbonate, peroxyesters such as t-butylperoxypivalate, methyl ethyl ketone peroxide, etc. Ketone peroxides, peroxyketals such as 1,1-bis-t-butylperoxycyclohexane, and hydroperoxides such as t-butyl hydroperoxide. Of these, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, 1,3-bis (2-t-butylperoxyisopropyl) benzene, benzoyl peroxide, and the like are preferable. .
As the unsaturated compound for modification, the same unsaturated compound as the compound copolymerizable with ethylene is used.
[0065]
The amount of the olefin polymer having a functional group that reacts with the epoxy group as the component (III) is the resin component, that is, the resin component is only component (I), component (II), and component (III). If it is, it is less than 50 weight% with respect to those sum total, 2 to 25 weight% is preferable and 5 to 20 weight% is especially preferable. If it exceeds 50% by weight, the adhesive strength is improved, but the mechanical properties, optical properties, and thermal properties based on the ethylene (co) polymer of component (I) are lowered and the cost is increased.
In the present invention, known additives such as a nucleating agent, a lubricant, an antistatic agent, an antifogging agent, a pigment, an ultraviolet absorber, and a dispersing agent can be added as long as the characteristics are not essentially impaired. .
In order to produce the polyolefin resin composition of the present invention, the above components are mixed by a Henschel mixer, a ribbon mixer, or the like, or the mixture is further kneaded using an open roll, a Banbury mixer, a kneader, an extruder, or the like. The method to do may be used appropriately. The melt kneading temperature is preferably 110 to 350 ° C., and preferably 120 to 300 ° C. for ease of handling.
[0066]
[Laminate]
Since the polyolefin resin composition of the present invention has good adhesiveness, it can exhibit its characteristics particularly when used as various laminates.
As a layer adjacent to the layer made of this polyolefin resin composition (hereinafter referred to as a base material layer), polyamides such as polyamide 6, polyamide 66 and polyamide 12, polyesters such as polyethylene terephthalate and polybutylene terephthalate, ethylene-acetic acid In addition to films and sheets of thermoplastic resins such as vinyl copolymer saponified products, resin films deposited with thin films such as silicon oxide and aluminum, metal foils such as iron and aluminum, paper, etc. are generally used as films or sheets. You can use what you have. Moreover, any of a woven fabric, a nonwoven fabric, and a board | plate body may be sufficient. Moreover, these base material layers may be subjected to surface treatment such as corona discharge treatment, flame treatment, plasma treatment, and ultraviolet treatment as necessary.
Among these base material layers, polyamide, polyester film or sheet, and aluminum foil are used in large quantities in packaging materials, etc., and the resin composition in the present invention has particularly excellent adhesion to these base materials. Demonstrate.
In addition to the polyolefin resin composition layer and the base material layer, various layers may be provided as the laminate.
[0067]
In order to mold the laminate of the present invention, methods such as extrusion laminate molding, coextrusion molding, heat-sensitive adhesive method, calender molding, hollow molding, inflation molding and the like can be used. Particularly in extrusion laminate molding, a remarkable effect of improving the adhesive strength is seen as compared with the conventional one.
Extrusion laminating here refers to heating and melting a thermoplastic resin using an extruder, extruding it into a film from a T-die, placing it on a substrate such as various films and foils, and simultaneously forming and bonding the film. This method is widely used in the fields of packaging materials and release papers, taking advantage of productivity.
[0068]
In the case of an ethylene / α-olefin copolymer and a metallocene ethylene / α-olefin copolymer using a conventional Ziegler catalyst, the molding temperature in the extrusion laminate molding is generally in the range of 200 to 300 ° C. from the viewpoint of moldability. However, the polyolefin resin composition of the present invention can be molded in the range of 200 to 350 ° C.
This is because when the conventional ethylene / α-olefin copolymer exceeds 300 ° C., it undergoes thermal decomposition, and as the melt tension decreases during lamination, the high-speed moldability decreases and the neck-in increases at the same time. In the polyolefin resin composition of the present invention, a crosslinking reaction involving an epoxy compound occurs at a temperature of 280 ° C. or higher, and stable high-speed moldability and low neck-in can be expressed. By molding at a high temperature of 300 ° C. or higher, the adhesive strength to various substrates is greatly improved.
In the case of extrusion lamination molding, ozone treatment that blows air containing ozone to the molten film to oxidize the surface of the molten film, or corona discharge treatment or plasma on the adhesive surface side of the substrate immediately before the molten film is pressure-bonded. Adhesive strength can be further improved by performing pretreatment such as treatment and frame treatment. Further, the obtained laminate can be heat-treated at a temperature not lower than 40 ° C. and not higher than the melting point of the resin, thereby obtaining a stronger adhesive strength.
[0069]
【Example】
Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.
〔Test method〕
density:
Conforms to JIS K6760.
MFR:
Conforms to JIS K6760.
DSC measurement:
A 0.2 mm thick sheet was formed by hot pressing, a sample of about 5 mg was punched out, held at 230 ° C. for 10 minutes, cooled to 0 ° C. at 2 ° C./minute, and then again up to 170 ° C. at 10 ° C./minute. The temperature was raised, and the temperature at the peak of the highest temperature peak that appeared was defined as the highest peak temperature Tm.
[0070]
Molecular weight distribution Mw / Mn:
A GPC apparatus (Waters 150 type) was used and ODCB at 135 ° C. was used as a solvent. The column used was Tosoh's GMHHR-H (S).
High speed formability (DD):
Using a 90mmφ (50rpm) extruder, T die width is 800mm, air gap from T die to roll is 120mm, the take-up speed is increased at 300 ° C, the stability of the molten film is observed, The highest speed possible was measured.
Neck-in:
It shape | molded by the said extruder with the film thickness of 25 micrometers and the taking-off speed of 150 m / min, the coating width on a base material was measured, and the difference (mm) with a die width was measured.
[0071]
Adhesive strength:
A laminated body is manufactured by laminating on a base material by the extrusion lamination method under the same conditions as in the neck-in measurement, and the obtained laminated body is cut into a strip of 15 mm width, and peeled at 180 ° C. at a speed of 300 mm / min. The strength (g / 15 mm) was measured.
Biaxially stretched polyamide film (Orientated nylon (ONy): “Harden film N1100” manufactured by Toyobo Co., Ltd., width 860 mm, thickness 15 μm) and biaxially stretched polyethylene terephthalate film (PET: Nimura Chemical) “Taiko Polyester Film FE2001” manufactured by Kogyo Co., Ltd., width 860 mm, thickness 12 μm) was used.
transparency:
Using a biaxially stretched polypropylene film (OPP) having a width of 860 mm and a thickness of 20 μm as a base material, the haze of the laminate produced under the above conditions was measured. The measurement conformed to JIS K7105.
[0072]
[Production of ethylene (co) polymer (I-1)]
(1) Preparation of solid catalyst
Purified toluene was added to a catalyst preparation apparatus (No. 1) equipped with an electromagnetic induction stirrer under nitrogen, and then dipropoxydichlorozirconium (Zr (OPr)₂Cl₂) 28 g and 48 g of methylcyclopentadiene were added, and 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of dropping, the reaction system was kept at 50 ° C. and stirred for 16 hours. This solution was designated as solution A.
Next, purified toluene was added to another catalyst preparation device with a stirrer (No. 2) under nitrogen, and the solution A and then a toluene solution of methylaluminoxane 6.4 mol were added and reacted. This was designated as solution B.
Next, purified toluene was added to a preparator equipped with a stirrer (No. 1) under nitrogen, and then pre-treated for a predetermined time at 400 ° C. for silica (Fuji Devison, Grade # 952, surface area 300 m²/ G) After adding 1400 g, the whole amount of the solution B was added and stirred at room temperature. Subsequently, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This was designated Catalyst C.
[0073]
(2) Sample polymerization
Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 70 ° C., total pressure 20 kgf / cm²G was copolymerized with ethylene and 1-hexene. In order to keep the gas composition in the system constant by supplying the catalyst C continuously, polymerization is performed while continuously supplying each gas to produce a copolymer (I- (1)). did.
(I- (1)) ethylene / 1-hexene copolymer
Density: 0.911 g / cm^Three
MFR: 11g / 10min
Molecular weight distribution (Mw / Mn): 2.6
Composition distribution parameter Cb: 1.19
TREF peak temperature: 83.2, 96.5 ° C
d-0.008log MFR: 0.903
[0074]
[Production of ethylene (co) polymer (I-2)]
A stainless steel autoclave equipped with a stirrer was purged with nitrogen and purified toluene was added. Next, butene-1 was added, and bis 1,3 dimethyl (cyclopentadienyl) zirconium dichloride (0.02 mmol as Zr) and methylalumoxane [MAO] (MAO / Zr = 100 [molar ratio]). After adding the mixed solution, the temperature was raised to 120 ° C. Next, ethylene was put in and polymerization was started. While continuously polymerizing ethylene, the total pressure was maintained for 1 hour to obtain an ethylene / butene-1 copolymer (I- (2)).
(I- (2)) ethylene butene- (1) copolymer
Density: 0.918g / cm^Three
MFR: 3.8g / 10min
Molecular weight distribution (Mw / Mn): 2.3
Composition distribution parameter (Cb): 1.05
TREF peak temperature: 94.7 ° C
d-0.008log MFR: 0.901
(I- (3)) ethylene butene-1 copolymer
Vapor phase Ziegler catalyst product (manufactured by Nippon Polyolefin Co., Ltd.)
Density: 0.920g / cm^Three
MFR: 7.0g / 10min
[0075]
[Ingredient (III)]
The following were used as the olefin copolymer having a functional group that reacts with an epoxy group.
(III- (1)) ethylene-acrylic acid copolymer (EAA)
Mitsubishi Yuka Co., Ltd. “Yukaron A221M”
MFR: 7.0g / 10min
Acrylic acid: 8.5% by weight
(III- (2)) Maleic anhydride modified polyethylene
MFR: 36.6g / 10min
Maleic anhydride: 0.09% by weight
[0076]
[Example 1]
0.5% by weight of epoxidized soybean oil (“O-130P” manufactured by Asahi Denka Co., Ltd.) as component (II) is added to the ethylene / 1-hexene copolymer of I- (1) as component (I). Then, it was melt-kneaded at 200 ° C. using a φ30 mm twin screw extruder to obtain a polyolefin resin composition.
The obtained resin composition was extruded onto a substrate using an extrusion laminator having a φ90 mm extruder at a T die width of 800 mm, an air gap of 120 mm, and a temperature of 280 ° C. to produce a laminate.
In the case of Example 1, the molded film had a small neck-in, and the obtained laminate exhibited good adhesion and transparency.
[0077]
[Example 2]
Molding was performed in the same manner as in Example 1 except that the molding temperature was 305 ° C.
By adding an epoxy compound, molding was possible even at 300 ° C. or higher, and good adhesive strength was obtained.
Example 3
A polyolefin resin composition was prepared in the same manner as in Example 1 except that 3.0% by weight of epoxidized soybean oil was added as component (II), and a laminate was produced.
This composition also showed good moldability, and both adhesiveness and transparency were good.
Example 4
Molding was performed in the same manner as in Example 2 except that the molding temperature was 305 ° C. Also in this case, the molten film was stable, and both transparency and adhesive strength were good.
[0078]
Example 5
A polyolefin resin composition was prepared in the same manner as in Example 1 except that I- (2) was used as component (I), and a laminate was produced.
This composition also had good moldability, and good adhesion and transparency.
Example 6
Molding was performed in the same manner as in Example 5 except that the molding temperature was 305 ° C. Also in this case, the molten film was stable, and both transparency and adhesive strength were good.
Example 7
A polyolefin resin composition was prepared in the same manner as in Example 1 except that 0.5% by weight of epoxidized linseed oil was added as component (II), and a laminate was produced.
This composition also showed good moldability, and both adhesiveness and transparency were good.
[0079]
Example 8
Molding was performed in the same manner as in Example 7 except that the molding temperature was 305 ° C. Also in this case, the molten film was stable, and both transparency and adhesive strength were good.
Example 9
Add 0.5% by weight of epoxidized soybean oil as component (II) to the composition mixed so that the weight ratio of component I- (1) and component III- (1) is 80:20. In the same manner as in Example 1, the composition was obtained by melt-kneading.
A laminate was produced in the same manner as in Example 1 using the obtained composition.
This product also showed good moldability, excellent adhesion and transparency.
Example 10
Molding was performed in the same manner as in Example 9 except that the molding temperature was 305 ° C. Also in this case, the molten film was stable, and although the transparency was slightly lowered, the adhesive strength was further improved.
Example 11
Add 0.5% by weight of epoxidized soybean oil as component (II) to the composition mixed so that the weight ratio of component I- (1) and component III- (2) is 80:20. In the same manner as in Example 1, the composition was obtained by melt-kneading.
A laminate was produced in the same manner as in Example 1 using the obtained composition.
This product also showed good moldability, excellent adhesion and transparency.
Example 12
Molding was performed in the same manner as in Example 11 except that the molding temperature was 305 ° C. Also in this case, the molten film was stable. Although the transparency slightly decreased as in Example 10, the adhesive strength was further improved.
[0080]
[Comparative Example 1]
Without adding the epoxy compound of component (II), a laminate was produced at a molding temperature of 280 ° C. in the same manner as in Example 1 by using ethylene (co) polymer I- (1) alone.
The neck-in at this time was larger than that added with an epoxy compound, and sufficient adhesive strength was not obtained.
[Comparative Example 2]
Using the resin composition prepared in Comparative Example 1, an attempt was made to produce a laminate at a molding temperature of 305 ° C. However, with I- (1) alone, the molten film was unstable due to thermal decomposition at 305 ° C., and film formation was impossible.
[Comparative Example 3]
A polyolefin resin composition was prepared in the same manner as in Example 1 except that 0.5% by weight of non-epoxidized soybean oil was added in place of component (II) to produce a laminate.
This had a very large neck-in and insufficient adhesive strength.
[Comparative Example 4]
Using the resin composition prepared in Comparative Example 3, an attempt was made to produce a laminate at a molding temperature of 305 ° C. However, the molten film was unstable due to thermal decomposition at 305 ° C., and film formation was impossible.
[Comparative Example 5]
A laminate was produced in the same manner as in Example 1 except that I- (3) ethylene / butene-1 copolymer was used as component (I). This product exhibited good moldability and adhesive strength, but was inferior in transparency.
[0081]
[Table 1]

[0082]
【The invention's effect】
The present invention is a composition comprising a novel ethylene (co) polymer having excellent physical properties, processability and good adhesion to a substrate, and a relatively wide composition distribution despite a narrow molecular weight distribution In addition, the content of the low molecular weight component and the amorphous component is small, and the mechanical properties, molding processability, optical properties, and heat resistance are excellent. In particular, the adhesive strength is excellent when laminated with polyester, polyamide, metal foil, etc. by extrusion lamination molding, T-die molding, inflation film molding or the like.
In addition, the laminate is excellent in adhesive strength, transparency, and heat sealability, and has a small amount of solvent extraction components, and thus is suitable for various packaging materials such as food and clothing, containers, and the like.
[Brief description of the drawings]
FIG. 1 is a graph of an elution temperature-elution amount curve for a component (I-1) by a continuous temperature rising elution fractionation method.
FIG. 2 is a graph of an elution temperature-elution amount curve for component (I-2) by a continuous temperature rising elution fractionation method.

Claims (8)

Component (I): an ethylene (co) polymer that satisfies the following requirements (a) to (d):
Component (II): an epoxy compound having two or more epoxy groups in the molecule and a molecular weight of 3000 or less,
Ratio is 0.01 to 5 wt% der component to the resin component (II) is,
In the presence of a catalyst in which the ethylene (co) polymer of component (I) includes at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table , ethylene and a carbon number of 3 to 20 polyolefin resin composition and Bruno α- olefins characterized der Rukoto those obtained by copolymerizing.
(A) Density is from 0.86 to 0.97 g / cm ³
(B) Melt flow rate is 0.01 to 100 g / 10 min. (C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) Composition distribution parameter Cb is 2.00 or less   The polyolefin according to claim 1, further comprising component (III): an olefin polymer having a functional group that reacts with an epoxy group, wherein the ratio of component (III) to the resin component is less than 50% by weight. -Based resin composition. 2. The ethylene (co) polymer of component (I) is an ethylene / α-olefin copolymer (I-1) that satisfies the following requirements (a) to (f): The polyolefin resin composition according to any one of to 2 .
(A) Density is from 0.86 to 0.97 g / cm ³
(B) Melt flow rate is 0.01 to 100 g / 10 min. (C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) The composition distribution parameter Cb is 1.08 to 2.0.
(E) There are substantially plural peaks of the elution temperature-elution amount curve by the continuous temperature elution fractionation method. (MFR) satisfies the following relationship (a) When d−0.008logMFR ≧ 0.93
X <2.0
(B) When d−0.008logMFR <0.93
X <9.8 × 10 ³ × (0.9300−d + 0.008 logMFR) ² +2.0 The ethylene (co) polymer of component (I) is ethylene and 3 carbon atoms in the presence of at least one catalyst comprising a ligand having a cyclopentadienyl skeleton and a group IV transition compound. An ethylene / α-olefin copolymer (I-2) satisfying the following requirements (a) to (e) obtained by copolymerizing with 20 α-olefins: Item 3. The polyolefin resin composition according to Item 1 or 2.
(A) Density is from 0.86 to 0.97 g / cm ³
(B) Melt flow rate is 0.01 to 100 g / 10 min. (C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) The composition distribution parameter Cb is 1.01 to 1.2.
(E) There is substantially one peak of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method. The polyolefin resin composition according to any one of claims 1 to 4 , wherein the epoxy compound of component (II) is an epoxidized vegetable oil.   The olefin polymer having a functional group that reacts with the epoxy group of component (III) has at least one group selected from the group consisting of an acid anhydride group, a carboxyl group, and a carboxylic acid metal salt in the molecule. The polyolefin resin composition according to claim 2, which is a polyolefin resin. It has a layer which consists of a polyolefin-type resin composition in any one of Claims 1-6 , The laminated body characterized by the above-mentioned. The layered product according to claim 7, wherein a layer adjacent to the layer made of the polyolefin resin composition is made of any one of polyester, polyamide, and aluminum.

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