JP3690867B2 - Resin composition for extrusion lamination molding - Google Patents

Description

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。
【００３４】
式１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。
【００３５】
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うる、または触媒的に活性化された状態のイオン性電荷を均衝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。
【００３６】
また、触媒は無機又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く、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。
【００３７】
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。
【００３８】
本発明の特殊なエチレン単独重合体またはエチレン・α−オレフィン共重合体（Ａ２）の製造は、好ましくは以下のＤ１〜Ｄ５の触媒で重合することが望ましい。
Ｄ１：一般式Ｍｅ¹Ｒ¹ _p（ＯＲ²）_qＸ¹ _4-p-qで表される化合物（式中Ｍｅ¹はジルコニウム、チタン、ハフニウムを示し、Ｒ1およびＲ²はそれぞれ炭素数１〜２４の炭化水素基、Ｘ1はハロゲン原子を示し、ｐおよびｑはそれぞれ０≦ｐ＜４、０≦ｐ＋ｑ≦４の範囲を満たすを整数である）。
Ｄ２：一般式Ｍｅ²Ｒ³ _m（ＯＲ⁴）_nＸ² _z-m-nで表される化合物（式中Ｍｅ²は周期律表第Ｉ〜III族元素、Ｒ³およびＲ4はそれぞれ炭素数１〜２４の炭化水素基、Ｘ²はハロゲン原子または水素原子（ただし、Ｘ²が水素原子の場合はＭｅ²は周期律表第III族元素の場合に限る）を示し、ｚはＭｅ²の価数を示し、ｍおよびｎはそれぞれ０≦ｍ≦ｚ、０≦ｎ≦ｚの範囲を満たす整数であり、かつ、０≦ｍ＋ｎ≦ｚである）。
Ｄ３：共役二重結合を持つ有機環状化合物。
Ｄ４：Ａｌ−Ｏ−Ａｌ結合を含む変性有機アルミニウムオキシ化合物。
Ｄ５：無機担体および／又は粒子状ポリマー担体を相互に接触させて得られる触媒。
【００３９】
以下、さらに詳説する。
上記触媒成分Ｄ１の一般式Ｍｅ¹Ｒ¹ _p（ＯＲ²）_qＸ¹ _4-p-qで表される化合物の式中、Ｍｅ¹はジルコニウム、チタン、ハフニウムを示し、これらの遷移金属の種類は限定されるものではなく、複数を用いることもできるが、共重合体の耐候性の優れるジルコニウムが含まれることが特に好ましい。Ｒ¹およびＲ²はそれぞれ炭素数１〜２４の炭化水素基で、好ましくは炭素数１〜１２、さらに好ましくは１〜８である。具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基などのアルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、トリル基、キシリル基、メシチル基、インデニル基、ナフチル基などのアリール基；ベンジル基、トリチル基、フェネチル基、スチリル基、ベンズヒドリル基、フェニルブチル基、ネオフイル基などのアラルキル基などが挙げられる。これらは分岐があってもよい。Ｘ¹はフッ素、ヨウ素、塩素および臭素などのハロゲン原子を示す。ｐおよびｑはそれぞれ、０≦ｐ＜４、０≦ｐ＋ｑ≦４の範囲を満たすを整数である。
【００４０】
上記触媒成分Ｄ１の一般式で示される化合物の例としては、テトラメチルジルコニウム、テトラエチルジルコニウム、テトラベンジルジルコニウム、テトラプロポキシジルコニウム、トリプロポキシモノクロロジルコニウム、テトラブトキシジルコニウム、テトラブトキシチタン、テトラブトキシハフニウムなどが挙げられ、特にテトラプロポキシジルコニウム、テトラブトキシジルコニウムなどのＺｒ（ＯＲ）₄化合物が好ましく、これらを２種以上混合して用いても差し支えない。
【００４１】
上記触媒成分Ｄ２の一般式Ｍｅ²Ｒ³ _m（ＯＲ⁴）_nＸ² _z-m-nで表される化合物の式中Ｍｅ²は周期律表第Ｉ〜III族元素を示し、リチウム、ナトリウム、カリウム、マグネシウム、カルシウム、亜鉛、ホウ素、アルミニウムなどである。Ｒ³およびＲ⁴はそれぞれ炭素数１〜２４の炭化水素基、好ましくは炭素数１〜１２、さらに 好ましくは１〜８であり、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基などのアルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、トリル基、キシリル基、メシチル基、インデニル基、ナフチル基などのアリール基；ベンジル基、トリチル基、フェネチル基、スチリル基、ベンズヒドリル基、フェニルブチル基、ネオフイル基などのアラルキル基などが挙げられる。これらは分岐があってもよい。Ｘ²はフッ素、ヨウ素、塩素および臭素 などのハロゲン原子または水素原子を示すものである。ただし、Ｘ²が水素原子の場合はＭｅ²はホウ素、アルミニウムなどに例示される周期律表第III族元素の場合に限るものである。また、ｚはＭｅ²の価数を示し、ｍおよびｎはそれぞれ、０≦ｍ≦ｚ、０≦ｎ≦ｚの範囲を満たす整数であり、かつ、０≦ｍ＋ｎ≦ｚである。
【００４２】
上記触媒成分Ｄ２の一般式で示される化合物の例としては、メチルリチウム、エチルリチウムなどの有機リチウム化合物；ジメチルマグネシウム、ジエチルマグネシウム、メチルマグネシウムクロライド、エチルマグネシウムクロライドなどの有機マグネシウム化合物；ジメチル亜鉛、ジエチル亜鉛などの有機亜鉛化合物；トリメチルボロン、トリエチルボロンなどの有機ボロン化合物；トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、トリヘキシルアルミニウム、トリデシルアルミニウム、ジエチルアルミニウムクロライド、エチルアルミニウムジクロライド、エチルアルミニウムセスキクロライド、ジエチルアルミニウムエトキサイド、ジエチルアルミニウムハイドライドなどの有機アルミニウム化合物等の誘導体が挙げられる。
【００４３】
上記触媒成分Ｄ3の共役二重結合を持つ有機環状化合物には、環状で共役二重結合を２個以上、好ましくは２〜４個、さらに好ましくは２〜３個有する環を１個または２個以上もち、全炭素数が４〜２４、好ましくは４〜１２である環状炭化水素化合物；前記環状炭化水素化合物が部分的に１〜６個の炭化水素残基（典型的には、炭素数１〜１２のアルキル基またはアラルキル基）で置換された環状炭化水素化合物；共役二重結合を２個以上、好ましくは２〜４個、さらに好ましくは２〜３個有する環を１個または２個以上もち、全炭素数が４〜２４、好ましくは４〜１２である環状炭化水素基を有する有機ケイ素化合物；前記環状炭化水素基が部分的に１〜６個の炭化水素残基またはアルカリ金属塩（ナトリウムまたはリチウム塩）で置換された有機ケイ素化合物が含まれる。特に好ましくは分子中のいずれかにシクロペンタジエン構造をもつものが望ましい。
【００４４】
上記の好適な化合物としては、シクロペンタジエン、インデン、アズレンまたはこれらのアルキル、アリール、アラルキル、アルコキシまたはアリールオキシ誘導体などが挙げられる。また、これらの化合物がアルキレン基（その炭素数は通常２〜８、好ましくは２〜３）を介して結合（架橋）した化合物も好適に用いられる。
【００４５】
環状炭化水素基を有する有機ケイ素化合物は、下記一般式で表示することができる。
Ａ_LＳｉＲ_4-L
ここで、Ａはシクロペンタジエニル基、置換シクロペンタジエニル基、インデニル基、置換インデニル基で例示される前記環状水素基を示し、Ｒはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基などのアルキル基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などのアルコキシ基；フェニル基などのアリール基；フェノキシ基などのアリールオキシ基；ベンジル基などのアラルキル基で示され、炭素数１〜２４、好ましくは１〜１２の炭化水素残基または水素を示し、Ｌは１≦Ｌ≦４、好ましくは１≦Ｌ≦３である。
【００４６】
上記成分Ｄ３の有機環状炭化水素化合物の具体例として、シクロペンタジエン、メチルシクロペンタジエン、エチルシクロペンタジエン、１,３−ジメチルシ クロペンタジエン、インデン、４−メチル−１−インデン、４,７−ジメチルイ ンデン、シクロヘプタトリエン、メチルシクロヘプタトリエン、シクロオクタテトラエン、アズレン、フルオレン、メチルフルオレンのような炭素数５〜２４のシクロポリエンまたは置換シクロポリエン、モノシクロペンタジエニルシラン、ビスシクロペンタジエニルシラン、トリスシクロペンタジエニルシラン、モノインデニルシラン、ビスインデニルシラン、トリスインデニルシランなどが挙げられる。
【００４７】
触媒成分Ｄ４のＡｌ−Ｏ−Ａｌ結合を含む変性有機アルミニウムオキシ化合物とは、アルキルアルミニウム化合物と水とを反応させることにより、通常アルミノキサンと称される変性有機アルミニウムオキシ化合物が得られ、分子中に通常１〜１００個、好ましくは１〜５０個のＡｌ−Ｏ−Ａｌ結合を含有する。また、変性有機アルミニウムオキシ化合物は線状でも環状でもいずれでもよい。
【００４８】
有機アルミニウムと水との反応は通常不活性炭化水素中で行われる。該不活性炭化水素としては、ペンタン、ヘキサン、ヘプタン、シクロヘキサン、ベンゼン、トルエン、キシレン等の脂肪族、脂環族、芳香族炭化水素が好ましい。水と有機アルミニウム化合物との反応比（水／Ａｌモル比）は通常０.２５／ １〜１.２／１、好ましくは０.５／１〜１／１であることが望ましい。
【００４９】
触媒成分Ｄ５の無機物担体および／または粒子状ポリマー担体とは、炭素質物、金属、金属酸化物、金属塩化物、金属炭酸塩またはこれらの混合物あるいは熱可塑性樹脂、熱硬化性樹脂等が挙げられる。該無機物担体に用いることができる好適な金属としては、鉄、アルミニウム、ニッケルなどが挙げられる。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−Ｖ₂Ｏ₅、ＳｉＯ₂−ＭｇＯ、ＳｉＯ₂−Ｃｒ₂Ｏ₃等が挙げられる。これらの中でもＳｉＯ₂およびＡｌ₂Ｏ₃からなる群から選択された少なくとも１種の成分を主成分とするものが好ましい。
また、有機化合物としては、熱可塑性樹脂、熱硬化性樹脂のいずれも使用でき、具体的には、粒子状のポリオレフィン、ポリエステル、ポリアミド、ポリ塩化ビニル、ポリ（メタ）アクリル酸メチル、ポリスチレン、ポリノルボルネン、各種天然高分子およびこれらの混合物等が挙げられる。
【００５０】
上記無機物担体および／または粒子状ポリマー担体は、このまま使用することもできるが、好ましくは予備処理としてこれらの担体を有機アルミニウム化合物やＡｌ−Ｏ−Ａｌ結合を含む変性有機アルミニウムオキシ化合物などに接触処理させた後に成分Ｄ５として用いることもできる。
【００５１】
上記本発明のエチレン単独重合体またはエチレン・α−オレフィン共重合体（Ａ２）は分子量分布が狭く、組成分布が適度な広さを有し、機械的強度が強く、低温ヒートシール性、ヒートシール強度、夾雑物ヒートシール性等のヒートシール特性、ホットタック性に優れ、しかも耐熱性の良い重合体である。
【００５２】
本発明のエチレン単独重合体またはエチレン・α−オレフィン共重合体（Ａ）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。
【００５３】
本発明における（Ｂ）他のエチレン系重合体とは、高圧ラジカル重合によるエチレン系重合体（Ｂ１）および／または密度が０．８６〜０．９７ｇ／cm³のエチレン−α−オレフイン共重合体（Ｂ２）を包含するものである。
【００５４】
上記（Ｂ１）高圧ラジカル重合法によるエチレン系重合体とは、高圧ラジカル重合法による密度０．９１〜０．９４ｇ／cm³のエチレン単独重合体（Ｂ１１：低密度ポリエチレン）、（Ｂ１２）エチレン・ビニルエステル共重合体および（Ｂ１３）エチレンとα,β−不飽和カルボン酸またはその誘導体との共重合体等が挙げられる。
【００５５】
該（Ｂ１１）低密度ポリエチレン（以下ＬＤＰＥと称す）は、ＭＦＲが０．０５〜５０ｇ／１０分、好ましくは０．１〜３０ｇ／１０分の範囲で選択される。この範囲内であれば組成物の溶融張力が適切な範囲となり押出ラミネート成形等が容易である。該ＬＤＰＥの密度は０．９１〜０．９４ｇ／cm³、好ましくは０．９１２〜０．９３５ｇ／cm³、さらに好ましくは０．９１２〜０．９３０ｇ／cm³の範囲で選択される。
また、分子量分布（Ｍｗ／Ｍｎ）は３．０〜１２、好ましくは４．０〜８．０である。これらＬＤＰＥの製法は、公知の高圧ラジカル重合法により製造され、チューブラー法、オートクレーブ法のいずれでもよい。
【００５６】
また、上記（Ｂ１２）エチレン・ビニルエステル共重合体とは、高圧ラジカル重合法で製造され、エチレンを主成分とし、プロピオン酸ビニル、酢酸ビニル、カプロン酸ビニル、カプリル酸ビニル、ラウリル酸ビニル、ステアリン酸ビニル、トリフルオル酢酸ビニルなどのビニルエステル単量体との共重合体である。これらの中でも特に好ましいものとしては、酢酸ビニルを挙げることができる。エチレン５０〜９９．５重量％、ビニルエステル０．５〜５０重量％、他の共重合可能な不飽和単量体０〜４９．５重量％からなる共重合体が好ましい。さらにビニルエステル含有量は３〜２０重量％、特に好ましくは５〜１５重量％の範囲で選択される。
これら共重合体のＭＦＲは、０．１〜５０ｇ／１０分、好ましくは０．３〜３０ｇ／分の範囲で選択される。
【００５７】
さらに上記（Ｂ１３）エチレンとα,β−不飽和カルボン酸またはその誘導体との共重合体の代表的な共重合体としては、エチレン・（メタ）アクリル酸またはそのアルキルエステル共重合体が挙げられ、これらのコモノマーとしては、アクリル酸、メタクリル酸、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸プロピル、メタクリル酸プロピル、アクリル酸イソプロピル、メタクリル酸イソプロピル、アクリル酸−ｎ−ブチル、メタクリル酸−ｎ−ブチル、アクリル酸シクロヘキシル、メタクリル酸シクロヘキシル、アクリル酸ラウリル、メタクリル酸ラウリル、アクリル酸ステアリル、メタクリル酸ステアリル、アクリル酸グリシジル、メタクリル酸グリシジル等を挙げることができる。この中でも特に好ましいものとして（メタ）アクリル酸のメチル、エチル等のアルキルエステルを挙げることができる。特に（メタ）アクリル酸エステル含有量は３〜２０重量％、好ましくは５〜１５重量％の範囲である。
これら共重合体のＭＦＲは、０．１〜３０ｇ／１０分、好ましくは０．２〜２０ｇ／分の範囲で選択される。
【００５８】
本発明の他のエチレン系重合体の密度が０．８６〜０．９７ｇ／cm³のエチレン−α−オレフイン共重合体（Ｂ２）とは、従来公知のチーグラー系触媒あるいはフィリップス系触媒等を用いる、高・中・低圧法およびその他の公知の方法によるエチレンと炭素数３〜１２のα−オレフィンとの共重合体である。これは、（Ａ）成分より一般的には分子量分布あるいは組成分布が広く、（Ｂ２１）密度が０．８６〜０．９１ｇ／cm³の超低密度ポリエチレン（以下ＶＬＤＰＥと称す）、（Ｂ２２）密度が０．９１〜０．９４ｇ／cm³の線状低密度ポリエチレン（以下ＬＬＤＰＥと称す）、（Ｂ２３）密度が０．９４〜０．９７の高密度ポリエチレン、（Ｂ２４）密度が０．８６〜０．９１ｇ／cm³のエチレン・プロピレン共重合体ゴム、エチレン・プロピレン・ジエン共重合体ゴム等のエチレン・α−オレフィン共重合体ゴムを包含する。
【００５９】
上記（Ｂ２１）ＶＬＤＰＥとは、密度が０．８６〜０．９１ｇ／cm³、好ましくは０．８８０〜０．９０５ｇ／cm³の範囲のエチレン−α−オレフィン共重合体であり、ＭＦＲが０．０１〜５０ｇ／１０分、好ましくは０．１〜３０ｇ／１０分の範囲で選択される。
該ＶＬＤＰＥは、線状低密度ポリエチレン（ＬＬＤＰＥ）とエチレン・α−オレフィン共重合体ゴム（ＥＰＲ、ＥＰＤＭ）の中間の性状を示すポリエチレンであり、示差走査熱量測定法（ＤＳＣ）による最大ピーク温度（Ｔm）６０℃以上、好ましくは、１００℃以上、かつ沸騰ｎ−ヘキサン不溶分１０重量％以上の性状を有する特定のエチレン・α−オレフィン共重合体であり、ＬＬＤＰＥが示す高結晶部分とエチレン・α−オレフィン共重合体ゴムが示す非晶部分とを合わせ持つ樹脂であって、前者の特徴である耐衝撃性、耐熱性などと、後者の特徴であるゴム状弾性、耐低温衝撃性などがバランスよく共存している。
【００６０】
また上記（Ｂ２２）ＬＬＤＰＥとは、密度が０．９１〜０．９４ｇ／cm³、好ましくは０．９１〜０．９３ｇ／cm³の範囲のエチレン・α−オレフィン共重合体であり、ＭＦＲが０．０５〜５０ｇ／１０分、好ましくは０．１〜３０ｇ／１０分の範囲で選択される。分子量分布（Ｍｗ／Ｍｎ）は特に限定はないが、３．０〜１３、好ましくは３. ５〜８．０の範囲にあるのが一般的である。
上記ＬＬＤＰＥのα−オレフィンは、炭素数３〜２０、好ましくは炭素数４〜１２、さらに好ましくは炭素数６〜１２の範囲のα−オレフィンであり、具体的にはプロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン等が挙げられる。上記ＭＦＲが０.０５ｇ／１０分未満では、成形加工性が悪化し、５０ｇ／１０分を超えるものは耐衝撃性やヒートシール特性等が低下するおそれを生じる。
【００６１】
また上記（Ｂ２３）高密度ポリエチレンは、密度が０．９４〜０．９７ｇ／cm3、好ましくは０．９５〜０．９７ｇ／cm³、メルトフローレートが０．０１〜５０ｇ／１０分、好ましくは０．０５〜３０ｇ／１０分、特に好ましくは０．１〜２０ｇ／１０分である。
【００６２】
また上記（Ｂ２４）エチレン・α−オレフィン共重合体ゴムとは、密度が０．８６〜０．９１ｇ／cm³未満のエチレン・プロピレン共重合体ゴム、エチレン・プロピレン・ジエン共重合体ゴム等が挙げられ、該エチレン・プロピレン系ゴムとしては、エチレンおよびプロピレンを主成分とするランダム共重合体（ＥＰＭ）、および第３成分としてジエンモノマー（ジシクロペンタジエン、エチリデンノルボルネン等）を加えたものを主成分とするランダム共重合体（ＥＰＤＭ）が挙げられる。
【００６３】
上記（Ｂ）他のエチレン系重合体のなかでも、高圧ラジカル重合による低密度ポリエチレンおよび／または密度が０．８６０〜０．９４ｇ／cm³のエチレン−α−オレフイン共重合体が好ましい。
【００６４】
本発明における樹脂組成物の（Ａ）成分と（Ｂ）成分の配合割合は、（Ａ）成分が９８〜２０重量％、（Ｂ）成分が２〜８０重量％、好ましくは（Ａ）成分が９０〜６０重量％、（Ｂ）成分が１０〜４０重量％、さらに好ましくは（Ａ）成分が８５〜７０重量％、（Ｂ）成分が１５〜３０重量％である。該組成物の（Ａ）成分の配合量が９８重量％を超える場合には、ドローダウン性、ネックイン等の成形加工性が劣るものとなり、２０重量％より少ない場合には、突刺強度、低温ヒートシール性、ヒートシール強度、夾雑物ヒートシール性等のヒートシール特性、ホットタック性等が改良されない虞がある。
【００６５】
上記本発明の組成物の具体的な例としては、（Ａ１＋Ｂ１１）、（Ａ２＋Ｂ１１）、（Ａ１＋Ｂ１１＋Ｂ２２）、（Ａ２＋Ｂ１１＋Ｂ２２）、（Ａ１＋Ｂ１２＋Ｂ２２）、（Ａ２＋Ｂ１２＋Ｂ２２）（Ａ１＋Ｂ１１＋Ｂ２１）、（Ａ２＋Ｂ１１＋Ｂ２１）（Ａ１＋Ａ２＋Ｂ１１）、（Ａ１＋Ａ２＋Ｂ１１＋Ｂ２１）、（Ａ１＋Ａ２＋Ｂ１１＋Ｂ２２）などの種々の組み合わせが挙げられる（ただし、Ａ１：本発明のエチレン−α−オレフイン共重合体、Ａ２：本発明の他のエチレン−α−オレフイン共重合体、Ｂ１１：ＬＤＰＥ、Ｂ１２：ＥＶＡ、Ｂ２１：ＶＬＤＰＥ、Ｂ２２：ＬＬＤＰＥを示す）。
特に（Ａ１またはＡ２＋Ｂ１１＋Ｂ２１）、（Ａ１＋Ｂ１１＋Ｂ２２）、すなわち、本発明のエチレン−α−オレフイン共重合体（Ａ１またはＡ２）とＬＤＰＥ、ＬＬＤＰＥの組み合わせの場合の配合量は（Ａ）成分６０〜９０重量％、（Ｂ１）成分５〜３５重量％、（Ｂ２）成分５〜３５重量％の範囲で選択されることが望ましい。
【００６６】
上記本発明の（Ａ）成分と（Ｂ）成分を含む組成物は、（ｃ1）メルトフロレート（ＭＦＲ）が１〜５０ｇ／１０分、（ｃ2）１９０℃におけるダイスウエル比（ＤＳＲ）が１．１０〜３．００、（ｃ3）１９０℃における溶融張力（ＭＴ）が０．５〜４．０ｇの範囲であることが肝要である。上記（ｃ1）ＭＦＲが１ｇ／１０分未満であると成形加工性が劣り、５０ｇ／１０分を超えるものはネックインが大きくなり、突刺強度等の機械的強度が改良されない虞がある。また、（ｃ2）ダイスウエル比（ＤＳＲ）が１．１０未満であるとネックインが大きく、３．００を超える場合には高速成形性に難が生じる。（ｃ3）溶融張力（ＭＴ）が０．５ｇ未満であるとドローダウン性が劣り、４．０ｇを超えるものは高速成形性が低下する虞がある。
【００６７】
本発明の組成物においては、上記（Ａ）成分として、（Ａ１）成分を用いた際には、（ｃ1）メルトフロレート（ＭＦＲ）が１〜５０ｇ／１０分、好ましくは１．５〜４０ｇ／１０分、さらに好ましくは２．０〜３０ｇ／１０分の範囲、（ｃ2）１９０℃におけるダイスウエル比（ＤＳＲ）が１．３０〜３．００、好ましくは１．３０〜２．８０、さらに好ましくは１．３０〜２．５０の範囲、（ｃ3）１９０℃における溶融張力（ＭＴ）が０．５〜４．０ｇ、好ましくは０．５〜３．５ｇの範囲であることが望ましい。
【００６８】
本発明の組成物においては、上記（Ａ）成分として、（Ａ２）成分を用いた際には、（ｃ1）メルトフロレート（ＭＦＲ）が１〜５０ｇ／１０分、好ましくは１．５〜４０ｇ／１０分、さらに好ましくは２．０〜３０ｇ／１０分の範囲、（ｃ2）１９０℃におけるダイスウエル比（ＤＳＲ）が１．１０〜２．００、好ましくは１．１０〜１．７０、さらに好ましくは１．１０〜１．６５の範囲、（ｃ3）１９０℃における溶融張力（ＭＴ）が０．５〜４．０ｇ、好ましくは０．５〜２．５ｇの範囲であることが望ましい。
【００６９】
本発明の組成物の配合は従来の樹脂組成物配合法として一般に用いられる公知の方法により配合することができる。その一例としては（Ａ）成分、（Ｂ）成分、およびその他の添加可能な添加剤等を単にドライブレンドすることにより行える。また、他の例としては（Ａ）成分、（Ｂ）成分および所望により各種添加剤をタンブラー、リボンブレンダーまたはヘンシェルミキサー等の混合機を使用してドライブレンドした後、単軸押出機、二軸押出機等の連続式溶融混練機をにより溶融混合し、押出してペレットを調製することによって該樹脂組成物を得ることができる。
【００７０】
本発明の組成物を用いて押出ラミネート成形する場合には、特に制限されるものではないが、特に本発明においては、基材としてクラフト紙を使用し、モダンマシナリー(株)製９０ｍｍφ押出機を用い、Ｔダイ面長８００ｍｍ、リップギャップ０．８ｍｍ、エアーギャップ、１２０ｍｍ、成形樹脂温度２７０〜２８０℃、冷却ロール温度２０℃で、押出機回転数６０ｒｐｍ、巻取速度６０ｍ／minにおけるラミネート膜の幅をＴダイの面長から差し引いた長さ（ネックイン）が１５０ｍｍ未満であり、また、ドローダウンとして、押出機回転数３０ｒｐｍにおける膜割れが起こらない最高巻取速度が９０ｍ／min以上を達成することができる。
【００７１】
本発明の押出ラミネート成形される基材としては、上質紙、クラフト紙、薄葉紙、ケント紙等の紙、アルミニウム箔等の金属箔、セロファン、織布、不織布、延伸ナイロン、無延伸ナイロン、特殊ナイロン（ＭＸＤ６等）、Ｋーナイロン（ポリフッ化ビニリデンコート）等のナイロン系基材、延伸ＰＥＴ、無延伸ＰＥＴ、ＫーＰＥＴ、アルミニウム蒸着ＰＥＴ（ＶＭＰＥＴ）等のＰＥＴ（ポリエチレンテレフタレート）系基材、延伸ＰＰ（ＯＰＰ）、無延伸ＰＰ（ＣＰＰ）、アルミニウム蒸着ＰＰ、Ｋ−ＰＰ、共押出フイルムＰＰ等のポリプロピレン系基材、ＬＤＰＥフイルム、ＬＬＤＰＥフィルム、ＥＶＡフイルム、延伸ＬＤＰＥフイルム、延伸ＨＤＰＥフイルム、ポリスチレン系フイルム等の合成樹脂フイルム系基材等が挙げられる。
【００７２】
さらに本発明においては、防曇剤、有機あるいは無機フィラー、酸化防止剤、有機あるいは無機系顔料、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、分散剤、核剤、架橋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。
【００７３】
【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。
【００７４】
（物性試験方法）
密度 ：ＪＩＳ Ｋ６７６０に準拠した。
ＭＦＲ ：ＪＩＳ Ｋ６７６０に準拠した。
ＤＳＲ ：ＪＩＳ Ｋ６７６０で使用されるメルトインデクサーを使用し、シリンダー温度１９０℃、定荷重２．１６ｋｇで行った。シリンダーにサンプルを充填し、４分間余熱の後荷重をかける。ピストンの降下が定状状態になったところでストランドを一旦カットし、そこから順次長さ約１インチのストランドを採取し、水道水を入れたビーカーの中に入れて冷却する。採取したサンプルの先端から１／２インチのところの直径（Ｄ）をマイクロメーターで測定しダイスのオリフィス径をＤ₀とし、次式によりＤＳＲを求める。
ＤＳＲ＝Ｄ／Ｄ₀
溶融張力 ：溶融させた樹脂を一定速度で延伸したときの応力をストレインゲージにて測定することにより決定される。東洋精機製作所製ＭＴ測定装置を使用して測定した。使用したオリフィスは穴径２．０９ｍｍφ、長さ８ｍｍであり、測定条件は樹脂温度１９０℃、押出ヘッドの速度２０ｍｍ／分である。引取速度を徐々に上げていくと、応力も上昇するが、ある点でそれ以上上昇しなくなったとき、その値を溶融張力とした。
Ｍｗ／Ｍｎ ：ＧＰＣ（ウオーターズ１５０型）、ＯＤＣＢ １３５℃
カラム：東ソー(株)製ＧＭＭＨＲ−Ｈ（Ｓ） ＰＳ標準試料による検量線法による。
ＮＭＲ ：日本電子(株)製 ＧＸ−２７０，ＯＤＣＢ １３５℃で測定した。
引張衝撃試験 ：ＡＳＴＭ Ｄ１８２２に準拠した。ただしサンプルは１ｍｍ厚のプレスシートにて強度を測定した。
ＭＩＴ耐揉疲労試験：１ｍｍ厚のプレスシートから、１．２７ｃｍ幅のサンプルを切り出し、５００ｇの荷重で張力をかけた状態で、裏表１３５°ずつにわたって繰り返し折り曲げる。裏表の折り曲げを１回とし、試験片が破断するまでの回数を測定する。
【００７５】
（ラミネート成形性）
ネックイン（ＮＩ） ：押出機の成形条件を６０ｒｐｍ，６０ｍ／ｍｉｎ
に固定し、紙基材にラミネートする。そのときのラミネート膜の幅（Ｗ）を測定し、ダイ幅をＷ₀として、次式よりＮＩを計算する。 ＮＩ＝Ｗ₀−Ｗ（ｍｍ）
ドローダウン（ＤＤ）：紙基材による成形において押出速度を３０ｒｐｍに固定し、引取速度を徐々に上げたとき、ラミネートフィルムが破れない最高引取速度を測定する。

【００７６】
（ラミネートフィルム評価法）
突刺衝撃試験 ：ＪＩＳ Ｐ８１３４に準拠した。ただし、貫通部は半径１．２７ｃｍの半球状のものを用いた。クラフト紙基材のサンプルを用い、衝撃荷重が６００ｋｇｆ／cm³となるように重りを調節し、１０回の試験の内、１度も破断しないものに対して○、１〜９回破断するものに対して△、１０回とも破断するものに対して×の判定とした。
低温ヒートシール性：ヒートシール試験器（テスター産業(株)製）を使用。シールバー幅５ｍｍ、圧力２ｋｇ／cm²でシール温度を５℃刻みで１秒間シール後放冷。シール部を１５ｍｍ幅に短冊状に切り出し、引張試験機にて３００ｍｍ／minでシール部を剥離し、その際の荷重が５００ｇとなる温度を内挿により求めた。この温度が低い方が低温ヒートシール性に優れたものである。
夾雑物シール性 ：前述のヒートシール試験において、サラダ油を夾雑物とし、シール部に塗布した後、１３０℃においてシールした。シールバー寸法、圧力は低温ヒートシール性の場合と同じである。剥離の際の荷重が、２．５ｋｇｆを越えたものを○、それ未満のものを×とした。
ホットタック性 ：前述のヒートシーラーを用い、圧力２ｋｇ／cm²、シール時間０．５秒でヒートシールし、シール直後、それぞれのフィルムの片端につけた重り（２３ｇ×２）荷重し、ヒートシール部の剥離が完全に止まるまで剥離し、剥離した長さを測定した。この長さが短いほどホットタック性がよい。剥離した長さが１０ｃｍ未満の温度の範囲を内挿により求めた。
衝撃破袋試験 ：４辺をシールした１４×１８ｃｍの袋に３００ｃｃの水を入れたサンプルを作成し、これに３５ｃｍの高さから１４８０ｇの鉄板を落とし、破袋するまでの回数を測定した。
【００７７】
（エチレン・α−オレフイン共重合体Ａ１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、１−ブテンを添加し、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）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、（Ａ１１）エチレン・１−ブテン共重合体を得た。また、触媒としてエチレンビス（インデニル）ジルコニウムジクロライド、重合温度８０℃、コモノマーをヘキセン−１として同様の操作を行い、（Ａ１２）エチレン・１−ヘキセン共重合体を得た。
（Ａ１１）エチレン・１−ブテン共重合体
（ａ１）密度＝０．９１２ｇ／cm³
（ａ２）ＭＦＲ＝１２ｇ／10min
（ａ３）分子量分布（Ｍｗ／Ｍｎ）＝２．４
（ａ４）組成分布パラメーター（Ｃｂ）＝１．０４
（ａ５）ＴＲＥＦピーク温度＝８３．５℃
（Ａ１２）エチレン・１−ヘキセン共重合体
（ａ１）密度＝０．９０７ｇ／cm³
（ａ２）ＭＦＲ＝１１ｇ／10min
（ａ３）分子量分布（Ｍｗ／Ｍｎ）＝２．４
（ａ４）組成分布パラメーター（Ｃｂ）＝１．０５
（ａ５）ＴＲＥＦピーク温度＝８２．９℃
【００７８】
（エチレン−α−オレフイン共重合体Ａ２の製造）
（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、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、ついであらかじめ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。
【００７９】
（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−ブテ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Ａ２１を製造した。また、同様に重合温度７０℃、全圧２０kgf／cm²Gでエチレンと１−ヘキセンの重合を行い、共重合体Ａ２２を製造した。共重合体Ａ２１およびＡ２２の物性は以下に示すとおりである。
（Ａ２１）エチレン・１−ブテン共重合体
（ａ１）密度＝０．９１５ｇ／cm³
（ａ２）ＭＦＲ＝９．５ｇ／１０ｍｉｎ
（ａ３）分子量分布（Ｍｗ／Ｍｎ）＝２．６
（ａ４）組成分布パラメーターＣｂ＝１．２０
（ａ５）ＴＲＥＦピーク温度＝８２．５、９４．３℃
（ａ６）ｄ−０．００８logＭＦＲ＝０．９０７
ODCB可溶分（％）＝
１．２＜9.8×10³×(0.9300ーd+0.008logMFR)²+2.0
（Ａ２２）エチレン・１−ヘキセン共重合体
（ａ１）密度＝０．９１０ｇ／cm³
（ａ２）ＭＦＲ＝１１ｇ／１０ｍｉｎ
（ａ３）分子量分布（Ｍｗ／Ｍｎ）＝２．６
（ａ４）組成分布パラメーターＣｂ＝１．２２
（ａ５）ＴＲＥＦピーク温度＝８３．２、９６．５℃
（ａ６）ｄ−０．００８logＭＦＲ＝０．９０２
ODCB可溶分（％）＝
１．５＜9.8×10³×(0.9300ーd+0.008logMFR)²+2.0
【００８０】
（他のエチレン系重合体）
物性値は表１に示した。
Ｂ１１ａ：高圧法低密度ポリエチレン（日本ポリオレフィン(株)製）
Ｂ１１ｂ：高圧法低密度ポリエチレン（日本ポリオレフィン(株)製）
Ｂ１２ ：高圧法エチレン−酢酸ビニル共重合体
（酢酸ビニル濃度５重量％、日本ポリオレフィン(株)製）
Ｂ１３ ：高圧法エチレン−アクリル酸エチル共重合体
（アクリル酸エチル濃度１０重量％、日本ポリオレフィン(株)製）
Ｂ２１ ：線状超低密度ポリエチレン重合体（気相法チグラー触媒品）
（コモノマー：ブテン−１、日本ポリオレフィン(株)製）
Ｂ２２ ：線状低密度ポリエチレン重合体（気相法チグラー触媒品）
（コモノマー： ブテン−１、日本ポリオレフィン(株)製）
Ｂ２３ ：高密度ポリエチレン（スラリー法チグラー触媒品）
（日本ポリオレフィン(株)製）
【００８１】
［実施例１］
樹脂（Ａ２１）成分のエチレン−α−オレフイン共重合体および表１の樹脂Ｂ成分のＬＤＰＥを表２に示した割合で配合した組成物に対して、酸化防止剤０．０９重量部、ステアリン酸カルシウム（日本油脂(株)製）０．１重量部を加え、ヘンシェルミキサーで約３０秒間均一に混合した後ペレット化し、組成物を得、ＭＦＲ、ＤＳＲ、溶融張力を測定した。また、この組成物をプレスにて厚さ１．０ｍｍのシートを作成し引張衝撃試験、耐折強度試験を行った。
前述の押出ラミネート成形装置を用い、ナイロン基材のコロナ放電処理面にＬＤＰＥ（日本ポリオレフィン(株)製 高圧法低密度ポリエチレン ＭＦＲ＝７．０，密度＝０．９１７）を樹脂温度３００℃、厚さ２０μｍ、加工速度５０ｍ／ｍｉｎでアンカーコート剤（大日精化工業(株)製 イソシアネート系 ３６００Ａ／Ｂ，配合比＝７：３）を用いて積層した。積層後、４０℃で１日間エージングした。
この積層体のＬＤＰＥ面に、前記本発明の組成物を樹脂温度２８０℃、厚さ３０μｍ、加工速度５０ｍ／ｍｉｎでシーラント層を積層した。得られたナイロン基材のサンプルを用いて低温ヒートシール性、ホットタック性を測定し、衝撃破袋試験を行った。また、紙基材にも前記組成物を３０μｍ厚、加工速度５０ｍ／ｍｉｎで直接積層した。この紙基材のサンプルを用いて突刺衝撃試験を行った。
さらに、紙基材の成形の後、押出機の回転数を６０ｒｐｍ、引取速度（加工速度）を６０ｍ／ｍｉｎとしてネックイン（ＮＩ）を測定した。その後さらに押出機の回転数を３０ｒｐｍに落とし、ドローダウン試験として引取速度を３０ｍ／ｍｉｎから５ｒｐｍ刻みで徐々に上げ、ラミ膜が破れるまで試験を行った。
【００８２】
［実施例２〜９］
前記の樹脂Ａ成分および表１に示した樹脂Ｂ成分を用い、表２〜３の配合で実施例１と全く同様の操作を行った。
【００８３】
［実施例１０〜１１］
前記の樹脂Ａ成分および樹脂Ｂ成分を表４に示した３成分による配合で実施例１と同様の操作を行った。
【表１】

【表２】

【表３】

【表４】

比較として、以下に示す各樹脂組成物を調製し、それらの物性を表５に示した。
［比較例１］
樹脂成分Ａ２２とＢ１１ｂの重量分率を１０／９０とした以外は実施例３と同様の操作を行った。強度およびドローダウン、低温ヒートシール性、夾雑物シール性が劣る。
【００８４】
［比較例２］
樹脂成分をＢ１１ｂ単独とした（混練工程を省略した）以外は実施例１と同様の操作を行った。強度およびドローダウン、低温ヒートシール性、夾雑物シール性が劣る。
【００８５】
［比較例３］
樹脂成分Ａ２１のかわりに気相法チグラー触媒による線状低密度ポリエチレンであるＢ２２を用いた以外は実施例１と同様の操作を行った。ドローダウンおよび低温ヒートシール性、夾雑物シール性が劣る。
【００８６】
［比較例４］
樹脂成分をＡ２１単独とした（ペレタイズのみ行った）以外は実施例１と同様の操作を行った。ネックインおよびドローダウンが劣る。
【００８７】
［比較例５］
樹脂成分をＢ１２単独とした（混練工程を省略した）以外は実施例５と同様の操作を行った。強度およびドローダウンが劣る。
【表５】

【００８８】
【発明の効果】
本発明の押出ラミネート成形用樹脂組成物は、透明性、衝撃強度、低温ヒートシール性、ヒートシール強度等のヒートシール特性等が良好で、抗ブロッキング性に優れ、押出ラミネート成形におけるネックイン、ドローダウン（延展性）等の成形性、突刺強度、夾雑物ヒートシール性、樹脂成分の内容物への溶出が少ない等に優れ、例えば漬物、乳製品、レトルト食品あるいは冷凍食品、調味料、菓子などの食品あるいは衣類などの各種包装材、各種液体輸送用包材等に好適に用いられるものである。
【図面の簡単な説明】
【図１】エチレン・α−オレフィン共重合体（Ａ1）についての、連続昇温溶出分別法による溶出温度−溶出量曲線を示すグラフである。
【図２】エチレン・α−オレフィン共重合体（Ａ2）についての、連続昇温溶出分別法による溶出温度−溶出量曲線を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention provides a packaging material having a sealant layer that has excellent heat seal properties such as transparency, impact strength, low-temperature heat sealability, heat seal strength, contaminant heat seal properties, etc., and excellent puncture strength by extrusion lamination molding. The resin composition for extrusion laminate molding suitable for obtaining is excellent in molding processability such as neck-in and draw-down (extensibility) in extrusion lamination. These packaging materials are suitably used, for example, for pickles, dairy products, retort foods or frozen foods, seasonings, foods such as confectionery, various packaging materials such as clothes, and various liquid transport packaging materials.
[0002]
[Prior art]
Conventionally, as a resin composition for extrusion lamination, a low density polyethylene (hereinafter referred to as LDPE) by a high pressure polymerization method, a linear low density polyethylene (hereinafter referred to as LLDPE) obtained by polymerization with a Ziegler catalyst, or a mixture thereof, etc. Is generally used.
However, although LDPE is excellent in molding processability, it has problems such as low temperature heat sealability, heat seal strength, heat seal properties such as foreign matter heat seal properties, and hot tack properties. An ethylene-vinyl acetate copolymer (EVA) or the like is used as a resin for improving the low temperature heat sealability of the LDPE, but the heat seal strength, hot tack property, etc. described above are not improved even in this EVA, and There is a problem that an odor is generated during laminating that is molded at a high temperature. On the other hand, although LLDPE has excellent heat seal strength, mechanical strength, etc., it has poor physical properties such as low-temperature heat seal properties, foreign matter heat seal properties, hot tack properties, etc. It has become. In addition, it has been proposed to blend LDPE in order to improve the moldability of LLDPE. However, since LDPE is blended, the mechanical strength is lowered.
[0003]
[Problems to be solved by the invention]
In view of the above circumstances, the present invention has good heat sealing properties such as transparency, impact strength, puncture strength, low-temperature heat sealability, heat seal strength, foreign matter heat seal properties, hot tack properties, etc., neck-in, draw An object of the present invention is to provide a resin composition for extrusion laminate molding which is excellent in moldability such as down (extensibility).
[0004]
[Means for Solving the Problems]
As a result of intensive studies, the present inventor achieves the object of the present invention by blending a specific amount of an ethylene homopolymer or ethylene / α-olefin copolymer with a specific catalyst and a conventional ethylene polymer. As a result, the present invention has been completed.
[0007]
  The present invention(A) an organic cyclic compound having at least a conjugated double bond and a periodic table IV Ethylene satisfying the following requirements (a1) to (a6) obtained by (co) polymerizing ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing a group III transition metal compound: Homopolymer or ethylene / α-olefin copolymer 98 to 20% by weight,
(A1) Density of 0.86 to 0.96 g / cm^Three,
(A2) Melt flow rate 0.1-100 g / 10 min,
(A3) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0,
(A4) Composition distribution parameter Cb is 1.08 to 2.00,
(A5) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF)And a peak on the high temperature side of the plurality of peaks is present between 85 and 100 ° C.,
(A6) The amount of orthodichlorobenzene (ODCB) soluble component X (wt%) at 25 ° C., the density d and MFR (melt flow rate) 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
(B) a resin composition comprising 2 to 80% by weight of another ethylene polymer,
  (C1) Melt flow rate of 1 to 50 g / 10 min of the composition, (c2) Die swell ratio (DSR) at 190 ° C. of 1.10 to 3.00, (c3) Melt tension (MT) at 190 ° C. of 0 In the range of 5 to 4.0 gIt is a resin composition for extrusion lamination molding characterized by the above-mentioned.
[0008]
As the other ethylene polymer (B) of the present invention, an ethylene (co) polymer by high-pressure radical polymerization and / or a density of 0.86 to 0.97 g / cm.^ThreeIt is desirable to use an ethylene-α-olefin copolymer of (B), in particular, (B) the other ethylene-based polymer is a low-density polyethylene by high-pressure radical polymerization and / or a density of 0.86-0.94 g / cm.^ThreeThe ethylene-α-olefin copolymer is preferable.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The ethylene homopolymer or ethylene / α-olefin copolymer (A) used in the present invention contains ethylene in the presence of at least one catalyst containing at least a cyclopentadiene compound and a group IV transition compound. The following requirements (a1) to (a4) obtained by copolymerizing with an α-olefin having 3 to 20 carbon atoms;
(A1) Density is 0.86-0.96 g / cm^Three,
(A2) Melt flow rate 0.1-100 g / 10 min,
(A3) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0,
(A4) Composition distribution parameter Cb is 2.00 or less
In an elution temperature-elution amount curve obtained by a continuous temperature rising elution fractionation method (TREF) as shown in FIG. 1, an ethylene homopolymer or an ethylene / α-olefin copolymer satisfying Ethylene alone by a common metallocene catalyst obtained in the presence of at least one catalyst containing a ligand having one peak and a cyclopentadienyl skeleton and a transition metal compound of Group IV of the Periodic Table There are substantially plural peaks in the elution temperature-elution amount curve obtained by the polymer or ethylene / α-olefin copolymer (A1) and / or the continuous temperature rising elution fractionation method (TREF) as shown in FIG. Including one special novel ethylene homopolymer or ethylene / α-olefin copolymer (A2).
[0010]
The α-olefin of the ethylene homopolymer or ethylene / α-olefin copolymer (A) of the present invention has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, specifically propylene, Examples include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like. The total content of these α-olefins is usually 30 mol% or less, preferably 20 mol% or less.
[0011]
The ethylene homopolymer or ethylene / α-olefin copolymer (A) of the present invention has a density (a1) of 0.86 to 0.96 g / cm.^Three, Preferably 0.890-0.95 g / cm^ThreeMore preferably, 0.900 to 0.940 g / cm^Three(A2) Melt flow rate (hereinafter referred to as MFR) is 0.1-100 g / min, preferably 0.5-50 g / min, more preferably 1.0-30 g / 10 min. is there. Density is 0.86g / cm^ThreeThose below are too soft and inferior in heat resistance. 0.96g / cm^ThreeIf it exceeds, it will be too hard and the tear strength, impact strength, etc. will be low. If the MFR is less than 0.1 g / 10 min, the moldability (drawdown property, neck-in, etc.) becomes poor. Moreover, when it exceeds 100 g / 10 minutes, mechanical strength etc. will become weak.
[0012]
In general, the molecular weight distribution (Mw / Mn) of an ethylene homopolymer or an ethylene / α-olefin copolymer is determined by gel permeation chromatography (GPC) to obtain a weight average molecular weight (Mw) and a number average molecular weight (Mn). These ratios (Mw / Mn) can be obtained by calculating, and (a3) Mw / Mn of the ethylene homopolymer or ethylene / α-olefin copolymer (A) of the present invention is 1.5 to The range is 5.0.
Moreover, in the ethylene homopolymer or ethylene / α-olefin copolymer (A1) by the general metallocene catalyst shown in FIG. 1, it is preferably 1.5 to 4.5, more preferably 1.8 to 3. It is desirable to be in the range of .5.
Furthermore, in the special ethylene homopolymer or ethylene / α-olefin copolymer (A2) shown in FIG. 2, it is preferably 1.5 to 4.5, more preferably 1.8 to 4.0, and more. Preferably it is in the range of 2.0 to 3.5. When the Mw / Mn is less than 1.5, the moldability is inferior, and when it exceeds 5.0, the mechanical strength such as impact resistance is inferior.
[0013]
The method for measuring the (a4) composition distribution parameter (Cb) of the ethylene homopolymer or ethylene / α-olefin copolymer (A) of the present invention is as follows. That is, a 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). Then, it cools to 25 degreeC with the cooling rate of 0.1 degree-C / min, and deposits a copolymer sample on the celite surface. Next, the column temperature is raised stepwise 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. Methanol is added to this solution, and the sample is precipitated, then filtered and dried to obtain eluted samples at each temperature. The weight fraction and the degree of branching (number of branches per 1000 carbon atoms) of each sample are measured. The degree of branching is determined by measuring with 13C-NMR.
[0014]
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.
[0015]
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.
[0016]
Cb = (Σc_j・ B_j ²/ Σc_j・ B_j) ÷ (Σc_j・ B_j/ Σc_j)
[0017]
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 increases as the composition distribution increases.
[0018]
The (a4) composition distribution parameter (Cb) of the ethylene homopolymer or ethylene / α-olefin copolymer (A) of the present invention is 2.00 or less, and the ethylene homopolymer or ethylene In the α-olefin copolymer (A1), it is preferably 1.01 to 1.2, more preferably 1.02 to 1.18, more preferably 1.03 to 1.16. . In the special ethylene homopolymer or ethylene / α-olefin copolymer (A2) of the present invention, it is preferably 1.08 to 2.00, more preferably 1.10 to 1.80, more preferably It is desirable to be in the range of 1.15 to 1.50.
When the composition distribution parameter (Cb) is greater than 2.00, blocking tends to occur, and bleeding of low-molecular weight or high-branching components to the resin surface is often caused, resulting in sanitary problems.
[0019]
The special ethylene homopolymer or ethylene / α-olefin copolymer (A2) of the present invention has a plurality of peaks in the elution temperature-elution amount curve obtained by (a5) continuous temperature rising elution fractionation method (TREF). It exists and is clearly distinguished from the general metallocene catalyst polymer (A1) of FIG. It is particularly preferable that the plurality of peak temperatures exist between 85 ° C and 100 ° C. The presence of this peak improves the heat resistance of the molded body.
[0020]
The TREF measurement method according to the present invention is as follows. 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 / α-olefin copolymer 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.
[0021]
The relationship between (a6) the amount of ODCB soluble content X (wt%) of the special ethylene homopolymer or ethylene / α-olefin copolymer (A2) of the present invention at 25 ° C. and the density d and MFR is: And the value of MFR is
d-0.008logMFR ≧ 0.93
X satisfies less than 2% by weight, preferably less than 1% by weight,
d-0.008logMFR <0.93
In the case of,
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 necessary to satisfy the relationship.
[0022]
The amount of soluble ODCB 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. Wavelength of the asymmetric stretching vibration of methylene in this filtrate 2925cm^-1The absorption peak area in the vicinity is obtained, 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.
[0023]
The ODCB soluble content at 25 ° C. is a highly branched component and a low molecular weight component contained in the ethylene / α-olefin copolymer, and this causes sanitary problems and blocking of the inner surface of the molded product. It is desirable that there are few. The amount of ODCB solubles is affected by comonomer content and molecular weight. 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.
[0024]
The ethylene homopolymer or ethylene / α-olefin copolymer (A1) based on the general metallocene catalyst is a group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton and, if necessary, It is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing a promoter, an organoaluminum compound and a carrier.
[0025]
Cyclopentadienyl as 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 (A1) The 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.
[0026]
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).
[0027]
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.
[0028]
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.
[0029]
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, etc. 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.
[0030]
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.
[0031]
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.
[0032]
Still other metallocenes include bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dimethyl, bis (cyclopentadienyl) vanadium dichloride, and the like.
[0033]
As another example of the transition metal group of Group IV of the present invention, a ligand having a cyclopentadienyl skeleton represented by the following general formula, a ligand other than that and a transition metal atom form a ring Something to do.
[Chemical 1]

In the 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, or the like. 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.
[0034]
Examples of the compound represented by Formula 1 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) silanesil Conium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (phenylphosphide) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, and the like.
[0035]
The co-catalyst as referred to in the present invention is one that can effectively make the transition metal compound of Group IV of the periodic table as a polymerization catalyst, or can neutralize ionic charges 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.
[0036]
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, Al.₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Etc. or a mixture thereof, SiO 2₂-Al₂O_Three, SiO₂-V₂O_Five, SiO₂-TiO₂, SiO₂-MgO, SiO₂-Cr₂O_ThreeEtc.
[0037]
Examples of organoaluminum compounds include trialkylaluminums such as triethylaluminum and triisopropylaluminum; dialkylaluminum halides; alkylaluminum sesquihalides; alkylaluminum dihalides; alkylaluminum hydrides, organoaluminum alkoxides, and the like.
[0038]
The production of the special ethylene homopolymer or ethylene / α-olefin copolymer (A2) of the present invention is preferably carried out by polymerization using the following catalysts D1 to D5.
D1: General formula Me¹R¹ _p(OR²)_qX¹ _4-pqA compound represented by the formula:¹Represents zirconium, titanium, hafnium, R1 and R²Each represents a hydrocarbon group having 1 to 24 carbon atoms, X1 represents a halogen atom, and p and q are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively).
D2: General formula Me²R^Three _m(OR^Four)_nX² _zmnA compound represented by the formula:²Is the Group I-III element of the periodic table, R^ThreeAnd R4 are 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 Me²Where m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z.
D3: An organic cyclic compound having a conjugated double bond.
D4: A modified organoaluminum oxy compound containing an Al—O—Al bond.
D5: a catalyst obtained by bringing an inorganic carrier and / or a particulate polymer carrier into contact with each other.
[0039]
Further details will be described below.
General formula Me of the catalyst component D1¹R¹ _p(OR²)_qX¹ _4-pqIn the formula of the compound represented by¹Represents zirconium, titanium, and hafnium, and the types of these transition metals are not limited, and a plurality of transition metals can be used, but it is particularly preferable that zirconium having excellent weather resistance of the copolymer is included. R¹And R²Are 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 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. X¹Represents a halogen atom such as fluorine, iodine, chlorine and bromine. p and q are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively.
[0040]
Examples of the compound represented by the general formula of the catalyst component D1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetrabutoxyzirconium, tetrabutoxytitanium, tetrabutoxyhafnium and the like. In particular, Zr (OR) such as tetrapropoxyzirconium and tetrabutoxyzirconium_FourCompounds are preferred, and two or more of these may be used in combination.
[0041]
General formula Me of the catalyst component D2²R^Three _m(OR^Four)_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. R^ThreeAnd R^FourAre 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 or hydrogen atom such as fluorine, iodine, chlorine and bromine. However, X²Me is a hydrogen atom²Is limited to the group III elements of the periodic table exemplified by boron, aluminum and the like. Z is Me²M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.
[0042]
Examples of the compound represented by the general formula of the catalyst component D2 include organic lithium compounds such as methyl lithium and ethyl lithium; organic magnesium compounds such as dimethyl magnesium, diethyl magnesium, methyl magnesium chloride, and ethyl magnesium chloride; dimethyl zinc 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 Organic aluminum compounds such as aluminum ethoxide and diethylaluminum hydride Derivatives and the like.
[0043]
The organic cyclic compound having a conjugated double bond of the catalyst component D3 is one or two cyclic rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. As described above, a cyclic hydrocarbon compound having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms; the cyclic hydrocarbon compound partially has 1 to 6 hydrocarbon residues (typically 1 carbon atom) A cyclic hydrocarbon compound substituted with ˜12 alkyl groups or aralkyl groups; one or more rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds And an organosilicon compound having a cyclic hydrocarbon group having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms; a hydrocarbon residue or alkali metal salt partially having 1 to 6 cyclic hydrocarbon groups ( Sodium or lithium salt) Organosilicon compounds are included. Particularly preferred is one having a cyclopentadiene structure in any of the molecules.
[0044]
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.
[0045]
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.
[0046]
Specific examples of the organic cyclic hydrocarbon compound of component D3 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.
[0047]
The modified organoaluminum oxy compound containing the Al—O—Al bond of the catalyst component D4 is obtained by reacting an alkylaluminum compound with water to obtain a modified organoaluminum oxy compound usually referred to as an aluminoxane. Usually, it contains 1 to 100, preferably 1 to 50 Al—O—Al bonds. The modified organoaluminum oxy compound may be linear or cyclic.
[0048]
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.
[0049]
Examples of the inorganic carrier and / or the particulate polymer carrier of the catalyst component D5 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.
[0050]
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 is also possible to use it as component D5 after having been used.
[0051]
The ethylene homopolymer or ethylene / α-olefin copolymer (A2) of the present invention has a narrow molecular weight distribution, an appropriate composition distribution, strong mechanical strength, low temperature heat sealability, and heat seal. It is a polymer excellent in heat sealing properties such as strength and foreign matter heat sealing properties, hot tack properties, and good heat resistance.
[0052]
The method for producing an ethylene homopolymer or an ethylene / α-olefin copolymer (A) of the present invention includes a gas phase polymerization method, a slurry polymerization method, a solution polymerization method and the like substantially free of a solvent in the presence of the catalyst. In the state where oxygen, water, etc. are substantially cut off, aliphatic hydrocarbons such as butane, pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and fats such as cyclohexane and methylcyclohexane It is produced in the presence or absence of an inert hydrocarbon solvent exemplified by cyclic hydrocarbons. 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 normal pressure to 70 kg / cm in the case of the low-medium pressure method.²G, 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.
[0053]
The (B) other ethylene polymer in the present invention is an ethylene polymer (B1) by high-pressure radical polymerization and / or a density of 0.86 to 0.97 g / cm.^ThreeOf ethylene-α-olefin copolymer (B2).
[0054]
The (B1) ethylene polymer obtained by the high pressure radical polymerization method means a density of 0.91 to 0.94 g / cm by the high pressure radical polymerization method.^ThreeAnd ethylene homopolymer (B11: low density polyethylene), (B12) ethylene / vinyl ester copolymer, and (B13) copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof.
[0055]
The (B11) low density polyethylene (hereinafter referred to as LDPE) is selected in the range of MFR of 0.05 to 50 g / 10 min, preferably 0.1 to 30 g / 10 min. Within this range, the melt tension of the composition becomes an appropriate range, and extrusion lamination molding and the like are easy. The density of the LDPE is 0.91 to 0.94 g / cm.^Three, Preferably 0.912 to 0.935 g / cm^ThreeMore preferably, 0.912-0.930 g / cm^ThreeThe range is selected.
Moreover, molecular weight distribution (Mw / Mn) is 3.0-12, Preferably it is 4.0-8.0. The LDPE is produced by a known high-pressure radical polymerization method, and may be either a tubular method or an autoclave method.
[0056]
The (B12) ethylene-vinyl ester copolymer is produced by a high-pressure radical polymerization method and contains ethylene as a main component, vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearin. It is a copolymer with vinyl ester monomers such as vinyl acid and vinyl trifluoroacetate. Among these, vinyl acetate is particularly preferable. A copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0 to 49.5% by weight of other copolymerizable unsaturated monomers is preferred. Furthermore, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight.
The MFR of these copolymers is selected in the range of 0.1 to 50 g / 10 min, preferably 0.3 to 30 g / min.
[0057]
Furthermore, as a typical copolymer of the copolymer of (B13) ethylene and an α, β-unsaturated carboxylic acid or derivative thereof, ethylene / (meth) acrylic acid or an alkyl ester copolymer thereof may be mentioned. These comonomers include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, acrylic acid-n- Examples thereof include butyl, methacrylic acid-n-butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. Among these, alkyl esters such as methyl and ethyl of (meth) acrylic acid are particularly preferable. In particular, the (meth) acrylic acid ester content is in the range of 3 to 20% by weight, preferably 5 to 15% by weight.
The MFR of these copolymers is selected in the range of 0.1 to 30 g / 10 minutes, preferably 0.2 to 20 g / minute.
[0058]
The density of another ethylene polymer of the present invention is 0.86 to 0.97 g / cm.^ThreeThe ethylene-α-olefin copolymer (B2) is a C3-C12 ethylene and carbon by high-, medium- and low-pressure methods and other known methods using a conventionally known Ziegler catalyst or Philips catalyst. It is a copolymer with an α-olefin. This is because the molecular weight distribution or composition distribution is generally wider than the component (A), and the density (B21) is 0.86 to 0.91 g / cm.^ThreeVery low density polyethylene (hereinafter referred to as VLDPE), (B22) density is 0.91 to 0.94 g / cm^ThreeLinear low density polyethylene (hereinafter referred to as LLDPE), (B23) high density polyethylene having a density of 0.94 to 0.97, (B24) density of 0.86 to 0.91 g / cm^ThreeAnd ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber.
[0059]
The (B21) VLDPE has a density of 0.86 to 0.91 g / cm.^Three, Preferably 0.880-0.905 g / cm^ThreeAnd an MFR of 0.01 to 50 g / 10 min, preferably 0.1 to 30 g / 10 min.
The VLDPE is a polyethylene having intermediate properties between linear low density polyethylene (LLDPE) and ethylene / α-olefin copolymer rubber (EPR, EPDM), and has a maximum peak temperature (DSC) determined by differential scanning calorimetry (DSC). Tm) A specific ethylene / α-olefin copolymer having a property of 60 ° C. or higher, preferably 100 ° C. or higher and a boiling n-hexane insoluble content of 10% by weight or more, It is a resin that has both the amorphous part of the α-olefin copolymer rubber and has the impact characteristics, heat resistance, etc., which are the features of the former, and rubbery elasticity, low temperature impact resistance, etc., which are the latter characteristics. Coexist in a balanced manner.
[0060]
The (B22) LLDPE has a density of 0.91 to 0.94 g / cm.^Three, Preferably 0.91-0.93 g / cm^ThreeThe ethylene / α-olefin copolymer has a MFR of 0.05 to 50 g / 10 minutes, preferably 0.1 to 30 g / 10 minutes. The molecular weight distribution (Mw / Mn) is not particularly limited, but is generally in the range of 3.0 to 13, preferably 3.5 to 8.0.
The α-olefin of the LLDPE is an α-olefin having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 6 to 12 carbon atoms. Specifically, propylene, 1-butene, 4 -Methyl-1-pentene, 1-hexene, 1-octene and the like. If the MFR is less than 0.05 g / 10 min, the moldability is deteriorated, and if it exceeds 50 g / 10 min, impact resistance, heat seal characteristics and the like may be deteriorated.
[0061]
The (B23) high density polyethylene has a density of 0.94 to 0.97 g / cm @ 3, preferably 0.95 to 0.97 g / cm.^ThreeThe melt flow rate is 0.01 to 50 g / 10 minutes, preferably 0.05 to 30 g / 10 minutes, and particularly preferably 0.1 to 20 g / 10 minutes.
[0062]
The (B24) ethylene / α-olefin copolymer rubber has a density of 0.86 to 0.91 g / cm.^ThreeEthylene / propylene copolymer rubber, ethylene / propylene / diene copolymer rubber, and the like. Examples of the ethylene / propylene rubber include a random copolymer (EPM) mainly composed of ethylene and propylene, and Examples of the third component include a random copolymer (EPDM) containing as a main component a diene monomer (dicyclopentadiene, ethylidene norbornene, or the like).
[0063]
Among the other ethylene polymers (B), low density polyethylene by high pressure radical polymerization and / or density is 0.860 to 0.94 g / cm.^ThreeThe ethylene-α-olefin copolymer is preferred.
[0064]
The blending ratio of the component (A) and the component (B) in the resin composition of the present invention is such that the component (A) is 98 to 20% by weight, the component (B) is 2 to 80% by weight, preferably the component (A). 90 to 60% by weight, (B) component is 10 to 40% by weight, more preferably (A) component is 85 to 70% by weight, and (B) component is 15 to 30% by weight. If the amount of component (A) in the composition exceeds 98% by weight, the moldability such as drawdown and neck-in will be inferior, and if it is less than 20% by weight, the puncture strength, low temperature There is a possibility that heat seal properties such as heat seal properties, heat seal strength, and foreign matter heat seal properties, and hot tack properties may not be improved.
[0065]
Specific examples of the composition of the present invention include (A1 + B11), (A2 + B11), (A1 + B11 + B22), (A2 + B11 + B22), (A1 + B12 + B22), (A2 + B12 + B22) (A1 + B11 + B21), (A2 + B11 + B21 + B11) + B11 + B21 + B11 + B21 + B11 + B21 + ), (A1 + A2 + B11 + B22) and the like (where A1: ethylene-α-olefin copolymer of the present invention, A2: other ethylene-α-olefin copolymer of the present invention, B11: LDPE, B12: EVA, B21: VLDPE, B22: LLDPE).
Particularly, the blending amount in the case of (A1 or A2 + B11 + B21), (A1 + B11 + B22), that is, the combination of the ethylene-α-olefin copolymer (A1 or A2) of the present invention with LDPE or LLDPE is 60 to 90% by weight of component (A). (B1) 5 to 35% by weight of the component and (B2) 5 to 35% by weight of the component are preferably selected.
[0066]
The composition containing the components (A) and (B) of the present invention has a (c1) melt flow rate (MFR) of 1 to 50 g / 10 min, (c2) a die swell ratio (DSR) at 190 ° C. of 1. It is important that the melt tension (MT) at 10 to 3.00 and (c3) 190 ° C. is in the range of 0.5 to 4.0 g. When the above (c1) MFR is less than 1 g / 10 min, the molding processability is inferior, and when it exceeds 50 g / 10 min, the neck-in becomes large, and the mechanical strength such as puncture strength may not be improved. Further, when the (c2) die swell ratio (DSR) is less than 1.10, the neck-in is large, and when it exceeds 3.00, high-speed moldability is difficult. (C3) When the melt tension (MT) is less than 0.5 g, the drawdown property is inferior, and when it exceeds 4.0 g, the high-speed moldability may be lowered.
[0067]
In the composition of the present invention, when the component (A1) is used as the component (A), the (c1) melt flow rate (MFR) is 1 to 50 g / 10 minutes, preferably 1.5 to 40 g. / 10 minutes, more preferably in the range of 2.0 to 30 g / 10 minutes, (c2) the die swell ratio (DSR) at 190 ° C. of 1.30 to 3.00, preferably 1.30 to 2.80, more preferably Is in the range of 1.30 to 2.50, and (c3) the melt tension (MT) at 190 ° C. is 0.5 to 4.0 g, preferably 0.5 to 3.5 g.
[0068]
In the composition of the present invention, when the component (A2) is used as the component (A), the (c1) melt flow rate (MFR) is 1 to 50 g / 10 minutes, preferably 1.5 to 40 g. / 10 minutes, more preferably in the range of 2.0-30 g / 10 minutes, (c2) the die swell ratio (DSR) at 190 ° C. of 1.10 to 2.00, preferably 1.10 to 1.70, more preferably Is in the range of 1.10 to 1.65, and (c3) the melt tension (MT) at 190 ° C. is 0.5 to 4.0 g, preferably 0.5 to 2.5 g.
[0069]
The composition of the present invention can be blended by a known method generally used as a conventional resin composition blending method. For example, the component (A), the component (B), and other additives that can be added can be simply dry blended. Other examples include (A) component, (B) component and optionally various additives using a tumbler, ribbon blender or Henschel mixer, and then dry blended, followed by a single screw extruder, twin screw The resin composition can be obtained by melting and mixing with a continuous melt kneader such as an extruder and extruding to prepare pellets.
[0070]
In the case of extrusion lamination molding using the composition of the present invention, it is not particularly limited. In particular, in the present invention, kraft paper is used as a base material and a 90 mmφ extruder manufactured by Modern Machinery Co., Ltd. is used. Used, T-die surface length 800 mm, lip gap 0.8 mm, air gap, 120 mm, molding resin temperature 270 to 280 ° C., cooling roll temperature 20 ° C., extruder rotation speed 60 rpm, winding speed 60 m / min. The length (neck-in) obtained by subtracting the width from the surface length of the T-die is less than 150 mm, and the maximum winding speed at which film cracking does not occur at an extruder rotation speed of 30 rpm is 90 m / min or more as drawdown. can do.
[0071]
Examples of the base material for extrusion lamination molding of the present invention include fine paper, kraft paper, thin paper, Kent paper, metal foil such as aluminum foil, cellophane, woven fabric, non-woven fabric, stretched nylon, unstretched nylon, special nylon ( MXD6, etc.), nylon base materials such as K-nylon (polyvinylidene fluoride coat), PET (polyethylene terephthalate) base materials such as stretched PET, non-stretched PET, K-PET, aluminum-deposited PET (VMPET), stretched PP ( PP base materials such as OPP), unstretched PP (CPP), aluminum vapor-deposited PP, K-PP, co-extruded film PP, LDPE film, LLDPE film, EVA film, stretched LDPE film, stretched HDPE film, polystyrene film, etc. Synthetic resin film base materials and the like.
[0072]
Further, in the present invention, anti-fogging agents, organic or inorganic fillers, antioxidants, organic or inorganic pigments, UV inhibitors, (un) saturated fatty acid amides, (un) saturated higher fatty acid metal salts and other lubricants, dispersion Known additives such as an agent, a nucleating agent, and a crosslinking agent can be added within a range that does not substantially impair the characteristics of the present invention.
[0073]
【Example】
Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.
[0074]
(Physical property test method)
Density: Conforms to JIS K6760.
MFR: Conforms to JIS K6760.
DSR: A melt indexer used in JIS K6760 was used, and the cylinder temperature was 190 ° C. and the constant load was 2.16 kg. Fill the cylinder with the sample and apply the preheat after 4 minutes of preheating. When the lowering of the piston reaches a fixed state, the strand is cut once, and then a strand having a length of about 1 inch is taken from the strand, and then placed in a beaker containing tap water and cooled. The diameter (D) at 1/2 inch from the tip of the collected sample is measured with a micrometer, and the orifice diameter of the die is D₀And DSR is obtained by the following equation.
DSR = D / D₀
Melt tension: Determined by measuring the stress when a molten resin is stretched at a constant speed with a strain gauge. It measured using MT measuring apparatus by Toyo Seiki Seisakusho. The orifice used had a hole diameter of 2.09 mmφ and a length of 8 mm. The measurement conditions were a resin temperature of 190 ° C. and an extrusion head speed of 20 mm / min. As the take-up speed is gradually increased, the stress increases, but when it does not increase any more at a certain point, the value is taken as the melt tension.
Mw / Mn: GPC (Waters 150 type), ODCB 135 ° C
Column: According to a calibration curve method using a GMMHR-H (S) PS standard sample manufactured by Tosoh Corporation.
NMR: GX-270 manufactured by JEOL Ltd., ODCB Measured at 135 ° C.
Tensile impact test: compliant with ASTM D1822. However, the strength of the sample was measured with a 1 mm thick press sheet.
MIT fatigue resistance test: A sample having a width of 1.27 cm is cut out from a 1 mm-thick press sheet, and repeatedly bent over 135 ° on both sides in a state where tension is applied with a load of 500 g. The back and front are folded once and the number of times until the test piece breaks is measured.
[0075]
(Laminate formability)
Neck-in (NI): Extruder molding conditions of 60 rpm, 60 m / min
And laminated to a paper substrate. Measure the width (W) of the laminate film at that time and set the die width to W₀NI is calculated from the following equation. NI = W₀-W (mm)
Drawdown (DD): The maximum take-up speed at which the laminate film is not broken is measured when the extrusion speed is fixed at 30 rpm and the take-up speed is gradually increased in molding with a paper base material.

[0076]
(Lamination film evaluation method)
Puncture impact test: compliant with JIS P8134. However, the penetrating part was a hemispherical one with a radius of 1.27 cm. Using a kraft paper base sample, the impact load is 600 kgf / cm^ThreeThe weight was adjusted so that, among 10 tests, ◯ for those that never broke, △ for those that broke 1-9 times, x for those that broke 10 times Judgment was made.
Low temperature heat sealability: Uses a heat seal tester (manufactured by Tester Sangyo Co., Ltd.). Seal bar width 5mm, pressure 2kg / cm²The seal temperature is sealed in 5 ° C increments for 1 second and then allowed to cool. The seal part was cut into a strip shape with a width of 15 mm, the seal part was peeled off at 300 mm / min with a tensile tester, and the temperature at which the load was 500 g was determined by interpolation. The lower the temperature, the better the low temperature heat sealability.
Contaminant sealing property: In the heat seal test described above, salad oil was made into a contaminant, applied to the seal portion, and then sealed at 130 ° C. The seal bar dimensions and pressure are the same as in the case of low temperature heat sealability. The case where the load at the time of peeling exceeded 2.5 kgf was rated as ◯, and the case where the load was less than that was rated as ×.
Hot tackiness: Using the above-mentioned heat sealer, pressure 2 kg / cm², Heat seal with a sealing time of 0.5 seconds, immediately after sealing, load the weight (23g × 2) attached to one end of each film, peel until the heat seal part completely stops peeling, and measure the peeled length did. The shorter the length, the better the hot tack. The temperature range where the peeled length was less than 10 cm was determined by interpolation.
Impact bag breaking test: A sample in which 300 cc of water was put in a 14 × 18 cm bag sealed on four sides was dropped, a 1480 g iron plate was dropped from a height of 35 cm, and the number of times until the bag was broken was measured.
[0077]
(Production of ethylene / α-olefin copolymer A1)
A stainless steel autoclave equipped with a stirrer was purged with nitrogen and purified toluene was added. Next, 1-butene is added, and further a mixed solution of bis 1,3 dimethyl (cyclopentadienyl) zirconium dichloride (0.02 mmol as Zr) methylalumoxane [MAO] (MAO / Zr = 100 [molar ratio]) Then, the temperature was raised to 120 ° C. Next, ethylene was charged to initiate polymerization, and the polymerization was continued for 1 hour while continuously polymerizing ethylene to maintain (A11) ethylene / 1-butene. The same operation was carried out using ethylenebis (indenyl) zirconium dichloride as a catalyst, a polymerization temperature of 80 ° C., and the comonomer as hexene-1 to obtain (A12) an ethylene / 1-hexene copolymer. .
(A11) Ethylene / 1-butene copolymer
(A1) Density = 0.912 g / cm^Three
(A2) MFR = 12g / 10min
(A3) Molecular weight distribution (Mw / Mn) = 2.4
(A4) Composition distribution parameter (Cb) = 1.04
(A5) TREF peak temperature = 83.5 ° C.
(A12) Ethylene / 1-hexene copolymer
(A1) Density = 0.007 g / cm^Three
(A2) MFR = 11g / 10min
(A3) Molecular weight distribution (Mw / Mn) = 2.4
(A4) Composition distribution parameter (Cb) = 1.05
(A5) TREF peak temperature = 82.9 ° C.
[0078]
(Production of ethylene-α-olefin copolymer A2)
(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, 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the dropwise addition, the reaction system was maintained 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 1400 g of silica (made by Fuji Devison, Grade # 952, surface area 300 m 2 / g) previously calcined at 400 ° C. for a predetermined time was added. After that, 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.
[0079]
(Sample polymerization)
Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 70 ° C., total pressure 20 kgf / cm²Ethylene and 1-butene were copolymerized with G. In order to keep the gas composition in the system constant by continuously supplying the catalyst C, polymerization was performed while continuously supplying each gas to produce a copolymer A21. Similarly, the polymerization temperature is 70 ° C. and the total pressure is 20 kgf / cm.²Polymerization of ethylene and 1-hexene was performed with G to produce a copolymer A22. The physical properties of the copolymers A21 and A22 are as shown below.
(A21) Ethylene / 1-butene copolymer
(A1) Density = 0.915 g / cm^Three
(A2) MFR = 9.5 g / 10 min
(A3) Molecular weight distribution (Mw / Mn) = 2.6
(A4) Composition distribution parameter Cb = 1.20
(A5) TREF peak temperature = 82.5, 94.3 ° C.
(A6) d-0.008 log MFR = 0.007
                ODCB soluble content (%) =
1.2 <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
(A22) Ethylene / 1-hexene copolymer
(A1) Density = 0.910 g / cm^Three
(A2) MFR = 11 g / 10 min
(A3) Molecular weight distribution (Mw / Mn) = 2.6
(A4) Composition distribution parameter Cb = 1.22
(A5) TREF peak temperature = 83.2, 96.5 ° C.
(A6) d-0.008 log MFR = 0.902
                ODCB soluble content (%) =
1.5 <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
[0080]
(Other ethylene polymers)
The physical property values are shown in Table 1.
B11a: High-pressure low-density polyethylene (manufactured by Nippon Polyolefin Co., Ltd.)
B11b: High-pressure low-density polyethylene (manufactured by Nippon Polyolefin Co., Ltd.)
B12: High-pressure ethylene-vinyl acetate copolymer
(Vinyl acetate concentration 5% by weight, manufactured by Nippon Polyolefin Co., Ltd.)
B13: High-pressure ethylene-ethyl acrylate copolymer
(Ethyl acrylate concentration 10% by weight, manufactured by Nippon Polyolefin Co., Ltd.)
B21: Linear ultra-low density polyethylene polymer (gas phase method Ziegler catalyst product)
(Comonomer: Butene-1, manufactured by Nippon Polyolefin Co., Ltd.)
B22: Linear low density polyethylene polymer (gas phase method Ziegler catalyst product)
(Comonomer: Butene-1, manufactured by Nippon Polyolefin Co., Ltd.)
B23: High density polyethylene (slurry method Ziegler catalyst product)
(Nippon Polyolefin Co., Ltd.)
[0081]
[Example 1]
0.09 parts by weight of antioxidant and calcium stearate with respect to composition in which ethylene-α-olefin copolymer of resin (A21) component and LDPE of resin B component of Table 1 are blended in the proportions shown in Table 2 0.1 part by weight (Nippon Yushi Co., Ltd.) was added, and the mixture was uniformly mixed for about 30 seconds with a Henschel mixer, then pelletized to obtain a composition, and MFR, DSR, and melt tension were measured. In addition, a sheet having a thickness of 1.0 mm was prepared from the composition using a press, and a tensile impact test and a bending strength test were performed.
Using the above-mentioned extrusion laminating apparatus, LDPE (High Pressure Low Density Polyethylene MFR = 7.0, Density = 0.919) manufactured by Nippon Polyolefin Co., Ltd. is used on the corona discharge treatment surface of the nylon base, and the resin temperature is 300 ° C. The film was laminated using an anchor coating agent (isocyanate-based 3600 A / B manufactured by Dainichi Seika Kogyo Co., Ltd., blending ratio = 7: 3) at a thickness of 20 μm and a processing speed of 50 m / min. After lamination, the film was aged at 40 ° C. for 1 day.
A sealant layer was laminated on the LDPE surface of this laminate at a resin temperature of 280 ° C., a thickness of 30 μm, and a processing speed of 50 m / min. Using the obtained nylon base material sample, low temperature heat sealability and hot tack property were measured, and an impact bag breaking test was conducted. The composition was directly laminated on a paper substrate at a thickness of 30 μm and a processing speed of 50 m / min. A puncture impact test was performed using a sample of this paper substrate.
Further, after forming the paper base material, the neck-in (NI) was measured by setting the rotational speed of the extruder to 60 rpm and the take-up speed (processing speed) to 60 m / min. Thereafter, the number of revolutions of the extruder was further reduced to 30 rpm, and as a draw-down test, the take-up speed was gradually increased from 30 m / min in increments of 5 rpm, and the test was performed until the laminar membrane was broken.
[0082]
[Examples 2 to 9]
Using the resin A component and the resin B component shown in Table 1, the same operations as in Example 1 were performed with the formulations shown in Tables 2 to 3.
[0083]
[Examples 10 to 11]
The same operation as in Example 1 was performed by blending the resin A component and the resin B component with the three components shown in Table 4.
[Table 1]

[Table 2]

[Table 3]

[Table 4]

For comparison, the following resin compositions were prepared, and their physical properties are shown in Table 5.
[Comparative Example 1]
The same operation as in Example 3 was performed except that the weight fraction of the resin components A22 and B11b was changed to 10/90. Inferior in strength and drawdown, low-temperature heat sealability, and foreign matter sealability.
[0084]
[Comparative Example 2]
The same operation as in Example 1 was performed except that the resin component was B11b alone (the kneading step was omitted). Inferior in strength and drawdown, low-temperature heat sealability, and foreign matter sealability.
[0085]
[Comparative Example 3]
The same operation as in Example 1 was performed except that B22, which is a linear low density polyethylene using a gas phase method Ziegler catalyst, was used instead of the resin component A21. Drawdown, low temperature heat sealability, and foreign matter sealability are poor.
[0086]
[Comparative Example 4]
The same operation as in Example 1 was performed except that the resin component was A21 alone (only pelletizing was performed). Neck-in and drawdown are inferior.
[0087]
[Comparative Example 5]
The same operation as in Example 5 was performed except that the resin component was B12 alone (the kneading step was omitted). Poor strength and drawdown.
[Table 5]

[0088]
【The invention's effect】
The resin composition for extrusion laminate molding of the present invention has excellent heat sealing properties such as transparency, impact strength, low-temperature heat sealability, heat seal strength, etc., excellent anti-blocking properties, neck-in and draw in extrusion laminate molding. Excellent in moldability such as down (extensibility), puncture strength, contaminant heat sealability, and less elution of resin components into the contents, such as pickles, dairy products, retort or frozen foods, seasonings, confectionery, etc. The present invention is suitably used for various packaging materials such as foods and clothes, packaging materials for various liquid transportation, and the like.
[Brief description of the drawings]
FIG. 1 is a graph showing an elution temperature-elution amount curve for an ethylene / α-olefin copolymer (A1) by a continuous temperature elution elution fractionation method.
FIG. 2 is a graph showing an elution temperature-elution amount curve for an ethylene / α-olefin copolymer (A2) by a continuous temperature rising elution fractionation method.

Claims (5)

(A) (Co) polymerization of ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table An ethylene homopolymer or an ethylene / α-olefin copolymer that satisfies the following requirements (a1) to (a6) :
(A1) The density is 0.86 to 0.96 g / cm ³ ,
(A2) Melt flow rate 0.1-100 g / 10 min,
(A3) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0,
(A4) Composition distribution parameter Cb is 1.08 to 2.00,
(A5) There are a plurality of elution temperature-elution amount curve peaks by the continuous temperature rising elution fractionation method (TREF), and a peak on the high temperature side of the plurality of peaks exists between 85 and 100 ° C. thing,
(A6) Orthodichlorobenzene (ODCB) soluble amount X ( wt% ) at 25 ° C. The density d and MFR (melt flow rate) satisfy the following relationship:
a) When d−0.008 log MFR ≧ 0.93
X <2.0
b) When d−0.008 log MFR <0.93
^{X <9. 8 × 10 3} × (0. 9300-d + 0. 008 logMFR) 2 +2. 0
(B) A resin composition containing 2 to 80% by weight of another ethylene polymer, (c1) Melt flow rate of 1 to 50 g / 10 min, (c2) Die swell ratio (DSR) at 190 ° C. 1.10 to 3.00, (c3) Extrusion laminate molding resin composition having a melt tension (MT) at 190 ° C. in the range of 0.5 to 4.0 g. The extrusion laminate molding resin according to claim 1, wherein the (A) ethylene homopolymer or ethylene / α-olefin copolymer is polymerized using the following catalysts D1 to D5. Composition.
D1: formula _{^{Me 1 R 1 p (OR 2}} ) q X 1 compound represented by the _4-pq (wherein Me ¹ represents zirconium, titanium, hafnium, R ¹ and R ² each having 1 to 24 carbon atoms And X ¹ represents a halogen atom, and p and q are integers satisfying the ranges of 0 ≦ p <4 and 0 ≦ p + q ≦ 4, respectively.
D2: a compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _zmn (wherein Me ² is a Group I to III element in the periodic table , R ³ and R ⁴ are each having 1 to 24 carbon atoms) X ² represents a halogen atom or a hydrogen atom (however, when X ² is a hydrogen atom, Me ² is limited to a group III element in the periodic table ), and z represents the valence of Me ² M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z).
D3: An organic cyclic compound having a conjugated double bond.
D4: Modified organoaluminum oxy compound containing an Al—O—Al bond.
D5: A catalyst obtained by bringing an inorganic carrier and / or a particulate polymer carrier into contact with each other. The (B) other ethylene polymer is an ethylene (co) polymer by high-pressure radical polymerization and / or an ethylene-α-olefin copolymer having a density of 0.86 to 0.97 g / cm ^3. The resin composition for extrusion lamination molding according to any one of claims 1 and 2 . The other ethylene polymer (B) is low-density polyethylene by high-pressure radical polymerization and / or ethylene-α-olefin copolymer having a density of 0.86 to 0.94 g / cm ^3. The resin composition for extrusion laminate molding according to claim 1 or 2 . The laminated body shape | molded by extrusion-laminating the resin composition for extrusion lamination molding in any one of Claims 1-4 to a base material.

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