JP3592816B2 - Adhesive resin composition and laminate thereof - Google Patents

Description

【００２３】
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、Ｚは−Ｏ−、−Ｓ−、−ＮＲ−、−ＰＲ−またはＯＲ、ＳＲ、ＮＲ_２ 、ＰＲ_２ からなる群から選ばれる２価中性リガンド、ＹはＳｉＲ_２ 、ＣＲ_２ 、ＳｉＲ_２ ＳｉＲ_２ 、ＣＲ_２ ＣＲ_２ 、ＣＲ＝ＣＲ、ＳｉＲ_２ ＣＲ_２ 、ＢＲ_２ 、ＢＲからなる群から選ばれる２価基を示す。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。
【００２４】
上記式Ｉの金属配位化合物としては、（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、（フェニルホスフィド）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あげられる。
【００２５】
本発明の助触媒としては、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衡させうるものをいい、具体的な助触媒としては、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、酸化スズ等があげられる。これらの中でもアルミノキサンが最も好ましい。
【００２６】
上記触媒は無機化合物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化合物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ＳｉＯ_２ 、Ａｌ_２ Ｏ_３ 、ＭｇＯ、ＺｒＯ_２ 、ＴｉＯ_２ 、Ｂ_２ Ｏ_３ 、ＣａＯ、ＺｎＯ、ＢａＯ、ＴｈＯ_２ 等またはこれらの混合物があげられ、ＳｉＯ_２ −Ａｌ_２ Ｏ_３ 、ＳｉＯ_２ −Ｖ_２ Ｏ_５ 、ＳｉＯ_２ −ＴｉＯ_２ 、ＳｉＯ_２ −Ｖ_２ Ｏ_５ 、ＳｉＯ_２ −ＭｇＯ、ＳｉＯ_２ −Ｃｒ_２ Ｏ_３ 等があげられる。これらの中でもＳｉＯ_２ およびＡｌ_２ Ｏ_３ 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。
【００２７】
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あげられる。
【００２８】
本発明の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あげられる。
【００２９】
本発明の（Ａ）エチレン（共）重合体は、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には通常常圧〜７０ｋｇ／ｃｍ^２ Ｇ、好ましくは常圧〜２０ｋｇ／ｃｍ^２ Ｇであり、高圧法の場合には通常１５００ｋｇ／ｃｍ^２ Ｇ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。
【００３０】
本発明の上記（Ａ）エチレン（共）重合体は、（ロ）密度が０．８６〜０．９７ｇ／ｃｍ^３ 、好ましくは０．８９〜０．９５ｇ／ｃｍ^３ 、より好ましくは０．９０〜０．９４ｇ／ｃｍ^３ の範囲である。密度が０．８６ｇ／ｃｍ^３ 未満では得られた接着性樹脂の耐熱性が乏しく、０．９７ｇ／ｃｍ^３ 以上では接着強度が十分でない。特に、０．９０〜０．９４ｇ／ｃｍ^３ の密度範囲であれば、耐熱性と接着強度とがバランスされる組成物が得られることから最も好ましい。
【００３１】
また、（Ａ）エチレン（共）重合体の（ハ）メルトフローレートは０．０１〜１００ｇ／１０分、好ましくは０．０３〜５０ｇ／１０分、さらに好ましくは０．１〜３０ｇ／１０分の範囲である。ＭＦＲが０．０１ｇ／１０分未満、または１００ｇ／１０分以上では接着強度が十分でない。
【００３２】
本発明の（Ａ）エチレン（共）重合体は、従来のチグラー型触媒やフイリップス型触媒で得られるエチレン（共）重合体とは性状が異なるものである。すなわち、上記触媒で得られる本発明のエチレン（共）重合体は触媒の活性点が均一であるため分子量分布および組成分布が狭く、（ニ）分子量分布Ｍｗ／Ｍｎが１．５〜５．０、（ホ）組成分布パラメーターＣｂが１．２以下のものである。この分子構造の特性から分岐の量が多くなるに従い、樹脂の結晶ラメラが薄くなり、融点が低くなる。また結晶ラメラ厚が薄くなるため、ラメラを渡るタイ分子の数が多くなり、さらに結晶サイズが小さく均一になるため溶融状態から冷却される際の固化速度が早くなるなどの特徴を有する。従って、低分子量あるいは高分岐構造による低融点成分ができにくい。これらの特徴は、本発明の接着性樹脂組成物の接着強度の向上に寄与するものとなる。
【００３３】
上記（ニ）分子量分布（Ｍｗ／Ｍｎ）の算出方法は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）により重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）を求め算出するものであるが、Ｍｗ／Ｍｎが１．５〜５．０、好ましくは１．８〜４．５の範囲である。Ｍｗ／Ｍｎが１．５未満では積層体成型時の加工性が十分でなく、５．０以上では接着強度が劣る。Ｍｗ／Ｍｎが上記範囲にあることにより、従来のポリオレフィン系樹脂を用いた場合と比較して、成形加工性と接着強度が格段に優れる接着性樹脂組成物および積層体が得られる。
【００３４】
上記（ホ）組成分布パラメーターＣｂの測定法は下記の通りである。
試料に耐熱安定剤を加え、ＯＤＣＢに濃度０．２重量％となるように１３５℃で加熱溶解する。溶液を、けい藻土（セライト５４５）を充填したカラムに移送し、０．１℃／ｍｉｎで２５℃まで冷却し、試料をセライト表面に沈着する。次に、ＯＤＣＢを一定流量で流しながら、カラム温度を５℃きざみに１２０℃まで段階的に昇温し、試料を溶出させ試料を分別する。溶液をメタノールで再沈後、濾過、乾燥し、各溶出温度の試料を得る。各試料の重量分率および分岐度（炭素数１０００個あたりの分岐数）を測定する。分岐度（測定値）は１３Ｃ−ＮＭＲにより求める。
【００３５】
このような方法で３０℃から９０℃のフラクションについては次のような、分岐度の補正を行う。すなわち、溶出温度に対して測定した分岐度をプロットし、相関関係を最小自乗法で直線に近似し、検量線を作成する。この近似の相関係数は十分大きい。この検量線により求めた値を各フラクションの分岐度とする。溶出温度９５℃以上では溶出温度と分岐度に必ずしも直線関係が成立しないのでのこの補正は行わない。
【００３６】
次にそれぞれのフラクションの重量分率ｗ_ｉ を、溶出温度５℃当たりの分岐度ｂ_ｉ の変化量（ｂ_ｉ −ｂ_ｉ−１ ）で割って相対濃度ｃ_ｉ を求め、分岐度に対して相対濃度をプロットし、組成分布曲線を得る。この組成分布曲線を一定の幅で分割し、次式より組成分布パラメーターＣｂを算出する。
【００３７】
【数２】

【００３８】
ここでｃ_ｊ とｂ_ｊ はそれぞれｊ番目の区分の相対濃度と分岐度である。組成分布パラメーターＣｂは試料の組成が均一である場合に１となり、組成分布が広がるに従って値が大きくなる。
【００３９】
エチレン・α−オレフィン共重合体の組成分布を測定する方法は多くの提案がなされている。例えば特開昭６０−８８０１６では、試料を溶剤分別して得た各分別試料の分岐数に対して、累積重量分率が特定の分布（対数正規分布）をすると仮定して数値処理を行い、重量平均分岐度（Ｃｗ）と数平均分岐度（Ｃｎ）の比を求めている。この近似計算は、試料の分岐数と累積重量分率が対数正規分布からずれると精度が下がり、市販のＬＬＤＰＥについて測定を行うと相関係数Ｒ_２ はかなり低く、値の精度は十分でない。また、Ｃｗ／Ｃｎの測定法は、本発明のＣｂのそれと異なるが、あえて数値の比較を行えば、Ｃｗ／Ｃｎの値は、Ｃｂよりかなり大きくなる。
【００４０】
前記（Ａ）エチレン（共）重合体の組成分布パラメーターＣｂは１．２以下である必要がある。組成分布パラメーターが１．２以上では接着強度の改善がみられない。
【００４１】
本発明の（Ｂ）成分は、（Ａ）成分のエチレン（共）重合体以外のすべてのポリオレフィンを用いることができ、中でも（Ｂ１）密度が０．８６〜０．９７ｇ／ｃｍ^３ のエチレン（共）重合体、（Ｂ２）高圧ラジカル重合法によるエチレン（共）重合体、（Ｂ３）ホリプロピレン系樹脂から選ばれた少なくとも１種のポリオレフィン系樹脂が好ましいものとしてあげられる。
【００４２】
前記（Ｂ１）密度が０．８６〜０．９７ｇ／ｃｍ^３ 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とは、チグラー系、フイリップス系触媒を用い高中低圧法およびその他の公知の方法により得られるエチレン単独重合体、エチレンと炭素数３〜１２のα−オレフィンとの共重合体で、密度が０．８６〜０．９１ｇ／ｃｍ^３ 未満の超低密度ポリエチレン（以下ＶＬＤＰＥと称す）、および密度が０．９１〜０．９４ｇ／ｃｍ^３ 未満の線状低密度ポリエチレン（以下ＬＬＤＰＥと称す）、密度が０．９４〜０．９７ｇ／ｃｍ^３ の中高密度ポリエチレン（以下ＭＤＰＥまたはＨＤＰＥと称す）を包含するものである。
【００４３】
具体的なα−オレフィンとしては、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、１−ドデセンなどをあげることができる。これらのうち好ましいのは１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテンであり、とくに好ましいのは１−ブテンである。
なおエチレン共重合体中のα−オレフィン含有量は０．５〜４０モル％であることが好ましい。
【００４４】
前記（Ｂ２）高圧ラジカル重合法によるエチレン（共）重合体としては、高圧ラジカル重合法による密度０．９１〜０．９４ｇ／ｃｍ^３ のエチレン単独重合体、エチレン・ビニルエステル共重合体、エチレン・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あげられる。
【００４５】
上記高圧ラジカル重合法による密度０．９１〜０．９４ｇ／ｃｍ^３ のエチレン単独重合体とは、公知の高圧法による低密度ポリエチレンである。
【００４６】
上記エチレン・ビニルエステル共重合体は、高圧ラジカル重合法で製造されるエチレンを主成分とする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および他の不飽和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、エチレン・酢酸ビニル共重合体をあげることができる。すなわち、エチレン５０〜９９．５重量％、酢酸ビニル０．５〜５０重量％および他の不飽和単量体０〜２５重量％からなる共重合体が好ましい。
【００４７】
前記他の不飽和単量体とは、プロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン等の炭素数３〜１０のオレフィン類、Ｃ_２ 〜Ｃ_３ アルカンカルボン酸のビニルエステル類、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、グリシジル（メタ）アクリレート等の（メタ）アクリル酸エステル類、（メタ）アクリル酸、マレイン酸、フマル酸および無水マレイン酸等のエチレン性不飽和カルボン酸またはその無水物類などの群から選ばれた少なくとも１種である。
【００４８】
上記エチレン・α，β−不飽和カルボン酸またはその誘導体との共重合体として高圧ラジカル重合法で製造されるもので、α，β−不飽和カルボン酸またはその誘導体には不飽和ジカルボン酸またはその無水物等も含まれこれらの少なくとも１種以上のモノマーをエチレンと共重合体するものである。これらの具体的なものとしては、エチレン・（メタ）アクリル酸メチル共重合体、エチレン・（メタ）アクリル酸エチル共重合体、エチレン・（メタ）アクリル酸メチル・無水マレイン酸共重合体、エチレン・（メタ）アクリル酸エチル・無水マレイン酸共重合体、エチレン・無水マレイン酸共重合体等をあげることができる。すなわち、エチレン５０〜９９．５重量％、（メタ）アクリル酸エステル０．５〜５０重量％および不飽和ジカルボン酸またはその無水物０〜２５重量％からなる共重合体が好ましい。またその接着性を損なわない範囲で他のモノマーを共重合させても良い。
【００４９】
前記（Ｂ１）エチレン（共）重合体、（Ｂ２）高圧ラジカル重合による低密度ポリエチレン、エチレン・ビニルエステル共重合体、エチレン・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ＭＦＲは、０．０１〜１００ｇ／１０ｍｉｎ．、好ましくは０．１〜７０ｇ／１０ｍｉｎ．、更に好ましくは１〜５０ｇ／１０ｍｉｎ．の範囲から選択される。ＭＦＲが０．０１ｇ／１０ｍｉｎ．未満では成形性が不良となり、１００ｇ／１０ｍｉｎ．を超える場合は強度が不十分となる。
【００５０】
本発明の（Ｃ）成分のゴムとしては、エチレンプロピレン系ゴム、ブタジエン系ゴム、イソブチレンゴム、イソプレン系ゴム、天然ゴム、ニトリルゴムなどがあげられ、これらは単独でも混合物でもよい。
【００５１】
上記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あるいはブテン−１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）があげられる。
【００５２】
上記ブタジエン系ゴムとしては、ブタジエンを構成要素とする共重合体をいい、スチレン−ブタジエンブロック共重合体（ＳＢＳ）およびその水添または部分水添誘導体であるスチレン−ブタジエン−エチレン共重合体（ＳＢＥＳ）、１，２−ポリブタジエン（１，２−ＰＢ）、無水マレイン酸−ブタジエン−スチレン共重合体、コアシェル構造を有する変性ブタジエンゴム等が例示される。
これらの中で、強度の向上が良好であることよりエチレン−プロピレンゴムおよびエチレン−ブテン−１ゴムが好ましい。
【００５３】
上記（Ａ）、（Ｂ）および（Ｃ）成分の配合割合は通常（Ａ）成分２０〜１００重量％、（Ｂ）成分８０重量％以下、（Ｃ）成分４０重量％以下（ただし（Ａ）＋（Ｂ）＋（Ｃ）＝１００重量％）であるが、（Ａ）成分のエチレン（共）重合体が２０重量％未満では、本願の目的である接着強度や親和性が不十分となる。また、（Ｃ）成分のゴムは、４０重量％以下の範囲で用いられる。４０重量％を超えると成形体の強度が弱くなり好ましくない。
【００５４】
上記範囲の内では、特に接着強度あるいは親和性と高温安定性を重視する場合は（Ａ）成分単独あるいは５０重量％以上で用いるのが好ましく、経済性を重視する場合は（Ｂ１）成分を上記の範囲で配合されし、さらにインフレーション法、中空成形法での成形においては加工性を向上するため（Ｂ２）成分を上記の範囲で配合するのが望ましい。
【００５５】
本発明においては上記（Ａ）、（Ｂ）、（Ｃ）各成分を目的に応じて、単独であるいは複数を組み合わせた組成物の形で特定のモノマーでグラフト変性して用いられる。
【００５６】
前記グラフト変性をする樹脂成分に関しては、接着強度を重視する場合は樹脂成分全体をグラフト変性して用いられるが、色相等の外観や経済性を重視する場合は（Ａ）、（Ｂ）、（Ｃ）の少なくとも一種類を未変性の状態で配合するのが望ましい。
これらグラフト変性樹脂と未変性樹脂との配合比は１００：０〜１：９９であり特に限定されないが、組成物中のモノマー濃度は後述する範囲に入る必要がある。
【００５７】
変性樹脂と未変性樹脂の組み合わせの方法としての第１はグラフト変性された（Ａ）成分、（Ａ＋Ｂ）成分、（Ａ＋Ｃ）成分、（Ａ＋Ｂ＋Ｃ）成分と未変性樹脂成分の組み合わせである。
【００５８】
変性樹脂と未変性樹脂の組み合わせの方法としての第２は、（Ａ）成分、（Ｂ）成分、（Ｃ）成分のいずれか一種のグラフト変性樹脂と（Ａ）成分、（Ｂ）成分、（Ｃ）成分の少なくとも一種の未変性樹脂の組み合わせである。
【００５９】
組み合わせの方法としての第３は、（Ａ＋Ｂ）成分、（Ｂ＋Ｃ）成分、（Ａ＋Ｃ）成分のいずれか一種のグラフト変性樹脂と（Ａ）成分、（Ｂ）成分、（Ｃ）成分の少なくとも一種の未変性樹脂の組み合わせである。
【００６０】
組み合わせの方法としての第４は、（Ａ＋Ｂ＋Ｃ）成分からなるグラフト変性樹脂と（Ａ）成分、（Ｂ）成分、（Ｃ）成分の少なくとも一種の未変性樹脂の組み合わせである。
【００６１】
前記のグラフト変性とは重合された樹脂成分をラジカル開始剤の存在下に反応性モノマーを押出機内で反応させる溶融法または溶液中で反応させる溶液法でグラフト変性するものである。
【００６２】
該ラジカル開始剤としては、有機過酸化物、ジヒドロ芳香族、ジクミル化合物等が挙げられる。
前記有機過酸化物としては、例えばヒドロパーオキサイド、ジクミルパーオキサイド、ｔ−ブチルクミルパーオキサイド、ジアルキル（アリル）パーオキサイド、ジイソプロピルベンゼンヒドロパーオキサイド、ジプロピオニルパーオキサイド、ジオクタノイルパーオキサイド、ベンゾイルパーオキサイド、パーオキシ琥珀酸、パーオキシケタール、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、ｔ−ブチルオキシアセテート、ｔ−ブチルパーオキシイソブチレート等が好適に用いられる。
【００６３】
ジヒドロ芳香族としては、ジヒドロキノリンまたはその誘導体、ジヒドロフラン、１，２−ジヒドロベンゼン、１，２−ジヒドロナフタレン、９，１０−ジヒドロフェナントレン等が挙げられる。
【００６４】
ジクミル化合物としては、２，３−ジメチル−２，３−ジフェニルブタン、２，３−ジエチル−２，３−ジフェニルブタン、２，３−ジエチル−２，３−ジ（ｐ−メチルフェニル）ブタン、２，３−ジエチル−２，３−ジ（ｐ−ブロモフェニル）ブタン等が例示され、特に２，３−ジエチル−２，３−ジフェニルブタンが好ましく用いられる。
【００６５】
本発明においてグラフトに用いられるモノマーは、前記の官能基を有するモノマー即ちａ：カルボン酸基または酸無水基含有モノマー、ｂ：エステル基含有モノマー、ｃ：ヒドロキシル基含有モノマー、ｄ：アミノ基含有モノマー、ｅ：シラン基含有モノマーから選択された少なくとも一種のモノマーである。
【００６６】
前記ａ：カルボン酸基または酸無水基含有モノマーとしては、マレイン酸、フマル酸、シトラコン酸、イタコン酸等のα，β−不飽和ジカルボン酸またはこれらの無水物、アクリル酸、メタクリル酸、フラン酸、クロトン酸、ビニル酢酸、ペンテン酸等の不飽和モノカルボン酸等があげられる。
【００６７】
前記ｂ：エステル基含有モノマーとしては、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、アクリル酸ブチル、メタクリル酸ブチルなどがあげられるが、特に好ましいものとしてはアクリル酸メチルをあげることができる。
【００６８】
前記ｃ：ヒドロキシル基含有モノマーとしては、ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等があげられる。
【００６９】
前記ｄ：アミノ基含有モノマーとしては、アミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、シクロヘキシルアミノエチル（メタ）アクリレート等があげられる。
【００７０】
前記ｅ：シラン基含有モノマーとしては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセチルシラン、ビニルトリクロロシラン等の不飽和シラン化合物があげられる。
【００７１】
これらグラフトモノマーの中では、ａ：カルボン酸基または酸無水基含有モノマーであるマレイン酸、フマル酸、シトラコン酸、イタコン酸等のα，β−不飽和ジカルボン酸またはこれらの無水物が好ましく、特に無水マレイン酸が接着強度、経済性等の観点から好ましく使用される。
【００７２】
前記グラフトモノマー濃度は、樹脂成分１ｇに対して１０^−８〜１０^−３ｍｏｌ、好ましくは１０^−７〜１０^−４ｍｏｌの範囲であることが必要である。これらのモノマーは（Ｂ２）成分であるエチレン・ビニルエステル共重合体またはエチレン・α，β−不飽和カルボン酸またはその共重合体を配合することによって、樹脂成分に導入されることもあるが、グラフト変性によって導入されたものは、共重合によって導入されたものより接着強度が強いものである。グラフトモノマー濃度が１０^−８ｍｏｌ未満では積層基材の接着強度や充填材との親和性が劣り、１０^−３ｍｏｌを超える濃度では、組成物中に“焼け”や“ゲル”が生じるおそれがあり、かつ経済的でない。
【００７３】
前記の接着性樹脂組成物は、またその使用目的により本発明の主旨を逸脱しない範囲において、他の熱可塑性樹脂、酸化防止剤、滑剤、顔料、紫外線吸収剤、核剤等の添加剤を配合してもよい。特に酸化防止剤は焼けやゲルの発生を抑えるために有効である。
【００７４】
本発明における接着性樹脂組成物は各種材料との接着性あるいは親和性が良好で、各種基材と積層したり、各種充填材を配合して用いるのに適したものである。積層についてはポリオレフィン、エチレン酢酸ビニル共重合体ケン化物、ポリアミド、ポリエステル、ポリウレタン、ポリスチレン、木材、繊維および金属箔から選ばれた少なくとも１種類からなる層と積層され、フィルム状、シート状、チューブ状、中空容器などの形状が形成され、食品包装材、薬品、化粧品なども分野で有効に使われるものである。
またガラス繊維、カーボンブラック、木粉、顔料などの無機または有機充填剤と熱可塑性樹脂との相溶分散剤としても有効に用いられる。
【００７５】
本発明における第２の発明である積層体は、酢酸ビニル共重合体ケン化物、ポリアミド、ポリエステル、ポリスチレン、金属箔、木材、織布、不織布などとの積層体であり、ポリオレフィンの有する良好な加工性、耐水性、耐薬品性、柔軟性等の特性と他の材料の有する特性、例えばエチレン酢酸ビニル共重合体ケン化物、ポリアミド、ポリエステル、金属箔等の良好なガス遮断性、ポリスチレン、金属箔等の剛性あるいは木材、織布、不織布など強度等を兼ね備えた材料である。
【００７６】
基材としてはまず各種のポリオレフィン樹脂が用いられ、この例としてはポリエチレン、ポリプロピレン、ポリ−１−ブテン、ポリ−４−メチル−１−ペンテンなどのオレフィン単独重合体；あるいはエチレン、プロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテンなどの相互共重合体；エチレンと酢酸ビニル共重合体などのエチレンとビニルエステルとの共重合体、エチレン−メタクリル酸共重合体、エチレン−アクリル酸エチル共重合体、エチレン−メタクリル酸エチル共重合体などのエチレンと不飽和カルボン酸、不飽和カルボン酸エステルなどとの共重合体およびそれらの混合物などがあげられる。
【００７７】
その他の基材としてエチレン酢酸ビニル共重合体ケン化物、ポリアミド、ポリエステル、ポリウレタン、ポリスチレンなどの合成樹脂類、ベニヤ、合板などの木材、炭素繊維や無機質材料から成る各種繊維、アルミニウム、鉄、亜鉛、銅などの金属類があげられる。
【００７８】
前記の中でも特にエチレン酢酸ビニル共重合体ケン化物、ポリアミド、ポリエステル、金属箔等との積層体はガス遮断性の優れた食品あるいは薬剤保存用容器、包装体等として用いられる場合にはこれらの材料との接着強度が強く最も好ましいものである。またこれらは、例えば調理や殺菌のための煮沸、あるいは用途によっては屋外、自動車内等の高温にさらされる使用にも耐える必要があり比較的高温でも接着強度の低下が少ないことが要求される。
【００７９】
本発明の積層体の形態は、フィルム状、板状、管状、箔状、織布状あるいはびん、容器、射出成形品などいずれでもよく、特に限定されない。
本発明の積層体の製造方法としては、予め成形されたフィルム、シートに押出ラミネーション法、ドライラミネーション法、サンドラミネーション法等により積層する方法、あるいは多層ダイを用いて押出機で溶融された樹脂をダイス先端で接合させ積層構造とする多層インフレーション法、多層Ｔダイなどの共押出成形法の他に、多層ブロー成形法、射出成形法などの通常の成形法が適用され、特に限定されないものである。
【００８０】
上記のうちエチレン酢酸ビニル共重合体ケン化物、ポリアミド、ポリエステルとの積層体は本発明の接着性樹脂組成物の成形性が良好であることから共押出成形が適しており、本発明の接着性樹脂組成物のヒートシール性、耐衝撃強度、耐水性、耐薬品性とエチレン酢酸ビニル共重合体ケン化物、ポリアミド、ポリエステルのガス遮断性の両者を兼ね備えたものである。また金属箔等との積層はラミネーション法で成形するのが好ましい。
【００８１】
前記積層体は外層にエチレン酢酸ビニル共重合体ケン化物や金属箔、内層に接着性樹脂組成物からなる層とすると上記特性が生かされ特に好ましい。またこれらは少なくとも上記の二層を含むものであって、さらに別の層、例えば内側にポリオレフィン樹脂からなる層を構成するなどにより経済性の上から有利となる。
【００８２】
具体的な層構成としてはＥＶＯＨ／接着、ＥＶＯＨ／接着／ＰＯ、ＰＯ／接着／ＥＶＯＨ／接着／ＰＯあるいはＥＶＯＨ／接着／ＰＯ／接着／ＥＶＯＨ等が考えられる（ただしＥＶＯＨ：エチレン酢酸ビニル共重合体ケン化物や金属箔等、接着：本願発明の接着性樹脂組成物、ＰＯ：ポリオレフィン樹脂を表す）。
【００８３】
【実施例】
以下本発明を実施例により、具体的に説明するが、本発明はこれら実施例によって限定されるものではない。
（Ａ）エチレン・α−オレフィン共重合体
〔製造例１〕
Ａ１：エチレン・ブテン−１共重合体の重合
攪拌機付ステンレス製オートクレーブを窒素置換した後溶媒として所定量の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（ｎ−ブ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＝５００〔モル比〕の混合溶液を加えた後、８０℃に昇温し、エチレンを供給して、連続的に重合しつつ圧力を一定圧に維持して重合を行った。得られたエチレン・ブテン−１共重合体（Ａ１）の物性は以下の通りであった。
ＭＦＲ ：４．４ｇ／１０ｍｉｎ．
密 度 ：０．９１８ｇ／ｃｍ^３
分子量分布（Ｍｗ／Ｍｎ） ：２．５
組成分布パラメーター（Ｃｂ）：１．０３
【００８４】
〔製造例２〕
Ａ２：エチレン・ブテン−１共重合体の重合
製造例１と同様にして、ＭＦＲの異なるエチレン・α−オレフィン共重合体を得た。
ＭＦＲ ：２．０ｇ／１０ｍｉｎ．
密 度 ：０．９２１ｇ／ｃｍ^３
分子量分布（Ｍｗ／Ｍｎ） ：２．６
組成分布パラメーター（Ｃｂ）：１．０２
【００８５】

【００８６】
（Ｃ）ゴム
Ｃ１：エチレン−プロピレンゴム（ＥＰ−０１、日本合成ゴム（株））
ムーニー粘度ＭＬ_１＋４ （１００℃）＝１９
プロピレン含有量 ＝２２ｗｔ％
型さ（ＪＩＳ−Ａ） ＝７３
【００８７】
（評価法）
評価に当たり以下の条件にて、ＬＬＤＰＥ／接着性樹脂／エチレン−酢酸ビニルケン化物／接着性樹脂／ＬＬＤＰＥよりなる３種５層のＴダイフィルムを成形し、各種測定した。

【００８８】
実施例１
製造例１に記したエチレン・ブテン−１共重合体（Ａ１）７０重量％、エチレン−プロピレンゴム（ＥＰ０１）３０重量％からなる樹脂成分１００重量部に、無水マレイン酸０．２５重量部、２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン０．０２重量部、酸化防止剤イルガノックス１０１０（チバガイギー社）０．１重量部、イルガフォス１６８（チバガイギー社）０．１重量部を加えヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度２３０℃で混練し変性を行った。得られた樹脂組成物のＭＦＲは３．１ｇ／１０分、無水マレイン酸の付加率は１．８×１０^−５ｍｏｌ／ｇであった。
【００８９】
実施例２
製造例２に記したエチレン・ブテン−１共重合体（Ａ２）５０重量％、ＬＬＤＰＥ（Ｂ１−１）３０重量％、エチレン−プロピレンゴム（ＥＰ０１）２０重量％からなる樹脂成分１００重量部に、無水マレイン酸０．２５重量部、２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン０．０２重量部、酸化防止剤イルガノックス１０１０（チバガイギー社）０．１重量部、イルガフォス１６８（チバガイギー社）０．１重量部を加えヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度２３０℃で混練し変性を行った。得られた樹脂組成物のＭＦＲは１．３ｇ／１０分、無水マレイン酸の付加率は１．８×１０^−５ｍｏｌ／ｇであった。
【００９０】
実施例３
製造例２で得られたエチレン・ブテン−１共重合体（Ａ２）７０重量％、エチレン−プロピレンゴム（ＥＰ０１）３０重量％からなる樹脂成分１００重量部に、無水マレイン酸０．２重量部、２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン０．０１５重量部、酸化防止剤イルガノックス１０１０（チバガイギー社）０．１重量部、イルガフォス１６８（チバガイギー社）０．１重量部を加えヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度２３０℃で混練し変性を行った。得られた樹脂組成物のＭＦＲは１．２ｇ／１０分、無水マレイン酸の付加率は１．８×１０^−５ｍｏｌ／ｇであった。
【００９１】
参考例１
ＬＬＤＰＥ（Ｂ１−２）７６０ｇを、トルエン７リットルとともに、攪拌機付きの１５リットルオートクレーブに入れ、攪拌しながら昇温し、１２７℃に達したところで、トルエン４８３ｇに溶かした無水マレイン酸４２ｇ、およびトルエン３２０ｇに溶かしたジクミルペルオキシド５．６ｇをそれぞれ別の口から６時間かけて加える。滴下後３時間反応を行い、ついで冷却して生成物を析出回収した後アセトンで数回洗浄し無水マレイン酸変性エチレン・ブテン−１共重合体（マレイン化率＝０．９％、ＭＦＲ＝４ｇ／１０分）を得た。
【００９２】
この無水マレイン酸変性エチレン・ブテン−１共重合体を７重量％、製造例２に記したエチレン・ブテン−１共重合体（Ａ２）６３重量％、エチレン−プロピレンゴム（ＥＰ０１）３０重量％からなる樹脂成分１００重量部に、酸化防止剤イルガノックス１０１０（チバガイギー社）０．１重量部、イルガフォス１６８（チバガイギー社）０．１重量部を加えヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度１８０℃で混練した。得られた樹脂組成物のＭＦＲは２．０ｇ／１０分、無水マレイン酸の付加率は７×１０^−６ｍｏｌ／ｇであった。
【００９３】
比較例１
ＬＬＤＰＥ（Ｂ１−１）７０重量％、エチレン−プロピレンゴム（ＥＰ０１）３０重量％からなる樹脂成分１００重量部に、無水マレイン酸０．２５重量部、２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン０．０２重量部、酸化防止剤イルガノックス１０１０（チバガイギー社）０．１重量部、イルガフォス１６８（チバガイギー社）０．１重量部を加えヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度２３０℃で混練し変性を行った。得られた樹脂組成物のＭＦＲは１．４ｇ／１０分、無水マレイン酸の付加率は１．８×１０^−５ｍｏｌ／ｇであった。
【００９４】
比較例２
製造例２に記したエチレン・ブテン−１共重合体（Ａ２）１５重量％、ＬＬＤＰＥ（Ｂ１−１）６５重量％、エチレン−プロピレンゴム（ＥＰ０１）２０重量％からなる樹脂成分１００重量部に、無水マレイン酸０．２５重量部、２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン０．０２重量部、酸化防止剤イルガノックス１０１０（チバガイギー社）０．１重量部、イルガフォス１６８（チバガイギー社）０．１重量部を加えヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度２３０℃で混練し変性を行った。得られた樹脂組成物のＭＦＲは１．４ｇ／１０分、無水マレイン酸の付加率は１．８×１０^−５ｍｏｌ／ｇであった。
【００９５】
比較例３
ＬＤＰＥ（Ｂ１−３）７０重量％、エチレン−プロピレンゴム（ＥＰ０１）３０重量％からなる樹脂成分１００重量部に、無水マレイン酸０．２５重量部、２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン０．０２重量部、酸化防止剤イルガノックス１０１０（チバガイギー社）０．１重量部、イルガフォス１６８（チバガイギー社）０．１重量部を加えヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度２３０℃で混練し変性を行った。得られた樹脂組成物のＭＦＲは０．７ｇ／１０分、無水マレイン酸の付加率は１．８×１０^−５ｍｏｌ／ｇであった。
【００９６】
比較例４
製造例２に記したエチレン・ブテン−１共重合体（Ａ２）よりなる樹脂組成物１００重量部、無水マレイン酸０．２重量部、２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン０．０１５重量部、および酸化防止剤イルガノックス１０７６（チバガイギー社）０．２重量部を加えヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度２３０℃で混練し変性を行った。
【００９７】
この変性樹脂０．１重量％、未変性のエチレン・ブテン−１共重合体（Ａ２）６９．９重量％および、エチレン−プロピレンゴム（ＥＰ０１）３０重量％からなる樹脂組成物１００重量部に、酸化防止剤イルガノックス１０１０（チバガイギー社）０．１重量部、イルガフォス１６８（チバガイギー社）０．１重量部を加え、ヘンシェルミキサーで十分混合後、５０ｍｍ単軸押出機を用い、設定温度１８０℃で混練した。得られた樹脂組成物のＭＦＲは１．９ｇ／１０分、無水マレイン酸の付加率は３×１０^−９ｍｏｌ／ｇであった。
【００９８】
（接着強度の測定）
常温および６０℃雰囲気における接着強度を表１および２にまとめるが、本出願請求項を満足する実施例１〜３の接着性樹脂組成物は比較例に比べ、１０〜３０％の接着強度の向上を得た。
【００９９】
【発明の効果】
本発明の接着性樹脂組成物は、特定の触媒により製造されたエチレン（共）重合体または該（共）重合体を含む組成物をグラフト変性したものであり、他の基材との高い接着強度、強い親和性を保持し、高速成型時や薄膜形成時での良好な接着強度をもつ積層体を得ることが可能となる。また本組成物からなる層と他の基材からなる層を積層することにより本組成物の有する特性と他の基材の特性を兼ね備えた積層体を提供することが可能となる。
【０１００】
【表１】

【０１０１】
【表２】

【図面の簡単な説明】
【図１】本発明の共重合体の溶出温度−溶出量曲線を示す。
【図２】代表的なメタロセン触媒による共重合体の溶出温度−溶出量曲線を示す。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an adhesive resin composition having excellent adhesion to various substrates and a laminate comprising the same and various substrates.
[0002]
[Prior art]
In general, polyethylene resin is used for a wide range of applications such as films, containers, blow bottles, etc. in injection molding, extrusion molding, blow molding, etc. because it has high strength, chemical resistance, corrosion resistance, inexpensive etc. I have.
Further, by further laminating with a specific substrate such as a gas barrier material, a container having gas barrier properties in addition to the above characteristics can be obtained. However, at the time of lamination, since the polyethylene resin does not have a polar group in the molecule, there is a disadvantage that the adhesion to other kinds of adhesive materials such as other synthetic resins and metal wood is extremely low. In order to improve these, an attempt has been made to add an unsaturated carboxylic acid or the like to introduce a functional group to impart adhesiveness (for example, JP-A-50-4144).
[0003]
Further, a composition obtained by modifying a polyolefin-based polymer with a solid rubber or an unsaturated carboxylic acid to further improve the adhesiveness (for example, JP-A-50-7848, JP-A-54-12408) or ethylene α -A composition in which an olefin copolymer rubber is modified with an unsaturated carboxylic acid (JP-A-52-49289) has been proposed.
However, although these have achieved some results, the high adhesive strength at the time of high-speed molding and under the thin film thickness, which has recently been required, is not sufficiently satisfied.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an adhesive resin composition having high adhesive strength during high-speed molding and under a thin film thickness while improving the above-mentioned disadvantages, and to provide a laminate using the same.
[0005]
[Means for Solving the Problems]
Thus, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composition containing a specific ethylene (co) polymer and a graft-modified resin produced by a specific catalyst gives excellent adhesive strength. And completed the present invention.
[0006]
That is, the present invention firstly provides (A) (a) ethylene or ethylene and carbon number in the presence of a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton. (B) Density of 0.86 to 0.97 g / cm, obtained by (co) polymerizing 3 to 20 α-olefins³(C) a melt flow rate of 0.01 to 100 g / 10 min, (d) a molecular weight distribution Mw / Mn of 1.5 to 5.0, and (e) a composition distribution parameter Cb of 1.2 or less.Ethylene (co) polymer (however, the melt flow ratio (MI ₁₀ / MI _2.16 ) Has a long-chain branch corresponding to 7 or more)In a composition (A + B + C = 100% by weight) comprising at least 20% by weight, (B) 80% by weight or less of a polyolefin resin other than the ethylene (co) polymer of the component (A), and (C) 40% by weight or less of rubber, The resin composition contains the components (A) and (C) as essential components, andAt least the components (A) and (C)It is graft-modified with at least one monomer containing a functional group selected from carboxylic acid groups, acid anhydride groups, ester groups, hydroxyl groups, amino groups and silane groups.^-8-10^-3The present invention relates to an adhesive resin composition characterized in that it is mol.Where MI ₁₀ Indicates a melt index at a load of 10 kg at 190 ° C., and MI _2.16 Indicates a melt index at 190 ° C. under a load of 2.16 kg.
[0007]
Secondly, the present invention comprises a layer comprising the adhesive resin composition according to the first aspect as a single layer, comprising a polyolefin, a saponified ethylene-vinyl acetate copolymer, a polyamide, a polyester, a polyurethane, a polystyrene, a wood, a fiber and a metal foil. A laminated body including at least two layers in which at least one type of layer selected from the group consisting of:
[0008]
Hereinafter, the present invention will be described in detail.
The (A) ethylene (co) polymer of the present invention comprises a transition metal compound belonging to Group IV of the periodic table containing the above-mentioned ligand having a cyclopentadienyl skeleton, and, if necessary, a cocatalyst, an organoaluminum compound and / or (B) Density 0.86 to 0.97 g / cm obtained by homopolymerizing ethylene or copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing a carrier.³(C) an ethylene (co) polymer having a melt flow rate of 0.01 to 100 g / 10 min.
Moreover, what is obtained by preliminarily polymerizing ethylene and / or the α-olefin onto the catalyst may be used as the catalyst.
[0009]
The α-olefin has 3 to 20, preferably 3 to 12 carbon atoms, and specifically includes propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene and the like. -1, dodecene-1 and the like. It is desirable that the content of these α-olefins used as a conomer of the copolymer be selected in the range of usually 30 mol% or less, preferably 20 mol% or less.
[0010]
The (A) cyclopentadienyl skeleton of a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, which is a catalyst for producing the ethylene (co) polymer of the present invention, And a cyclopentadienyl group and a substituted cyclopentadienyl group. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 10 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. And a substituted cyclopentadienyl group having at least one substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may combine with each other to form a ring.
[0011]
Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. Specific examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group, alkyl group such as decyl group; cycloalkyl group such as cyclopentyl group and cycloalkyl group; phenyl group And aralkyl groups such as a benzyl group and a neophyl group. Among these, an alkyl group is preferable.
[0012]
Preferred examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-hexylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1,3 Specific examples include -n-butylmethylcyclopentadienyl group and 1,3-n-propylmethylethylcyclopentadienyl group. As the substituted cyclopentadienyl group of the present invention, among these, a cyclopentadienyl group substituted by an alkyl group having 3 or more carbon atoms is preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable.
[0013]
When the substituents, that is, the hydrocarbons are bonded to each other to form one or more rings, the substituted cyclopentadienyl group includes an indenyl group, a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group), and the like. A substituted naphthyl group substituted with a substituent such as a substituted indenyl group, a naphthyl group, 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.
[0014]
Examples of the transition metal of the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton include zirconium, titanium, hafnium and the like, with zirconium being particularly preferred.
[0015]
The transition metal compound usually has 1 to 3 ligands having a cyclopentadienyl skeleton, and when having 2 or more ligands, they may be bonded to each other by a crosslinking group. In addition, examples of such a crosslinking group include an alkylene group having 1 to 4 carbon atoms, an alkylsilanediyl group, and a silanediyl group.
[0016]
Typical examples of the ligand other than the ligand having a cyclopentadienyl skeleton in the transition metal compound of Group IV of the periodic table include hydrogen, a hydrocarbon group having 1 to 20 carbon atoms (alkyl group, Alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group and the like.
[0017]
Specific examples of the transition metal compounds belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton include the following. Examples of the monoalkyl metallocene include bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, and bis (cyclopentadienyl) zirconium phenyl chloride There is. Examples of the dialkyl metallocene include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) Enyl) hafnium dimethyl and bis (cyclopentadienyl) hafnium diphenyl. Trialkyl metallocenes include cyclopentadienyl titanium trimethyl, cyclopentadienyl zirconium trimethyl, cyclopentadienyl zirconium triphenyl, cyclopentadienyl zirconium trineopentyl, cyclopentadienyl hafkonium trimethyl, cyclopentadienyl hafnium And triphenyl.
[0018]
Examples of the monocyclopentadienyl titanocene include pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride, and bis (pentamethylcyclopentadienyl) titanium diphenyl.
[0019]
Examples of the substituted bis (cyclopentadienyl) titanium compound include bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or dihalolide; 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 complex; silicon, amine or carbon-linked cycloalkyl. Examples of the pentadiene complex include dimethylsilyldicyclopentadienyltitaniumdiphenyl or dichloride, methylenedicyclopentadienyltitaniumdiphenyl. Eniru or dichloride, other dihalide complexes, and the like.
[0020]
Examples of zirconocene compounds include pentamethylcyclopentadienyl zirconium trichloride, pentaethylcyclopentadienyl zirconium trichloride, and bis (pentamethylcyclopentadienyl) zirconium diphenyl. As the alkyl-substituted cyclopentadiene, bis (ethylcyclopentadiene) is used. 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 And dimethylsilyldicyclopentadienyl zirconium dimethyl or dihalide, methylene dicyclopentadienyl zirconium dimethyl or dihalide, methylene dicyclopentadienyl zirconium dimethyl or Dihalide and the like.
[0021]
Further, as another example of a transition metal compound belonging to Group IV of the periodic table, a ligand having a cyclopentadienyl skeleton represented by the following general formula and other ligands and transition metal atoms form a ring. There are also things.
[0022]
(Equation 1)

[0023]
In the formula, Cp represents a ligand having the cyclopentadienyl skeleton, X represents 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. And Z is -O-, -S-, -NR-, -PR- or OR, SR, NR₂, PR₂A divalent neutral ligand selected from the group consisting of₂, CR₂, SiR₂SiR₂, CR₂CR₂, CR = CR, SiR₂CR₂, BR₂, BR. Wherein 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 R from Y, Z or both Y and Z; The groups form a fused ring system. M represents a transition metal atom of Group IV of the periodic table.
[0024]
Examples of the metal coordination compound of the above formula I include (t-butylamide) (tetramethyl-cyclopentadienyl) -1,2-ethanediylzirconium dichloride and (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) silanetitanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) Lanzirconium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl- (tetramethylcyclopentadienyl) silanetitanium dichloride, (phenylphosphido) dimethyl- (tetra Methylcyclopentadienyl) silane titanium dichloride.
[0025]
The co-catalyst of the present invention refers to a co-catalyst that can effectively use the transition metal compound of Group IV of the periodic table as a polymerization catalyst or balance ionic charges in a catalytically activated state. Typical cocatalysts include benzene-soluble aluminoxanes of organic aluminum oxy compounds, benzene-insoluble organic aluminum oxy compounds, boron compounds, lanthanide salts such as lanthanum oxide, and tin oxide. Of these, aluminoxanes are most preferred.
[0026]
The catalyst may be used by being supported on a carrier of an inorganic compound or an organic compound. As the carrier, a porous oxide of an inorganic compound or an organic compound is preferable.₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂And mixtures thereof.₂-Al₂O₃, SiO₂-V₂O₅, SiO₂-TiO₂, SiO₂-V₂O₅, SiO₂-MgO, SiO₂−Cr₂O₃And the like. Among them, SiO₂And Al₂O₃The main component is preferably at least one component selected from the group consisting of:
[0027]
In addition, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, poly Examples include norbornene, various natural polymers, and mixtures thereof.
[0028]
Examples of the organoaluminum compound of the present invention include trialkylaluminums such as triethylaluminum and triisopropylaluminum; dialkylaluminum halides; alkylaluminum sesquihalides; alkylaluminum dihalides; alkylaluminum hydrides and organoaluminum alkoxides.
[0029]
The (A) ethylene (co) polymer of the present invention is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, or the like substantially in the absence of a solvent in the presence of the catalyst, and substantially contains oxygen, water, and the like. In a state where the above-mentioned conditions have been refused, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Produced in the presence of an active 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 normal pressure to 70 kg / kg in the case of the low and medium pressure method. cm²G, preferably normal pressure to 20 kg / cm²G, usually 1500 kg / cm in the case of the high pressure method²G or less is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high-pressure method, it is usually 1 minute to 30 minutes, preferably 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a one-stage polymerization method and a multi-stage polymerization method of two or more stages 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.
[0030]
The (A) ethylene (co) polymer of the present invention has a (b) density of 0.86 to 0.97 g / cm.³, Preferably 0.89 to 0.95 g / cm³, More preferably 0.90 to 0.94 g / cm³Range. 0.86g / cm density³If less than 0.97 g / cm, the heat resistance of the obtained adhesive resin is poor.³Above, the adhesive strength is not sufficient. In particular, 0.90 to 0.94 g / cm³When the density is within the range, a composition in which the heat resistance and the adhesive strength are balanced can be obtained, which is the most preferable.
[0031]
Further, (A) the melt flow rate of the ethylene (co) polymer is 0.01 to 100 g / 10 min, preferably 0.03 to 50 g / 10 min, and more preferably 0.1 to 30 g / 10 min. Range. If the MFR is less than 0.01 g / 10 min or 100 g / 10 min or more, the adhesive strength is not sufficient.
[0032]
The ethylene (co) polymer (A) of the present invention is different in properties from the ethylene (co) polymer obtained with a conventional Ziegler-type catalyst or a Phillips-type catalyst. That is, the ethylene (co) polymer of the present invention obtained with the above catalyst has a narrow molecular weight distribution and composition distribution because the active sites of the catalyst are uniform, and (d) the molecular weight distribution Mw / Mn is 1.5 to 5.0. , (E) the composition distribution parameter Cb is 1.2 or less. From the characteristics of this molecular structure, as the amount of branching increases, the crystalline lamella of the resin becomes thinner and the melting point becomes lower. Further, the thickness of the crystal lamella is reduced, the number of tie molecules across the lamella is increased, and the crystal size is small and uniform, so that the solidification rate when cooled from a molten state is increased. Therefore, it is difficult to form a low melting point component having a low molecular weight or a highly branched structure. These features contribute to improving the adhesive strength of the adhesive resin composition of the present invention.
[0033]
The method for calculating (d) the molecular weight distribution (Mw / Mn) is to determine and calculate the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC). Mn is in the range of 1.5 to 5.0, preferably 1.8 to 4.5. If Mw / Mn is less than 1.5, the workability during molding of the laminate is insufficient, and if Mw / Mn is 5.0 or more, the adhesive strength is poor. When the Mw / Mn is in the above range, an adhesive resin composition and a laminate having significantly excellent moldability and adhesive strength as compared with the case of using a conventional polyolefin-based resin can be obtained.
[0034]
The method (E) for measuring the composition distribution parameter Cb is as follows.
A heat-resistant stabilizer is added to the sample, and the sample is heated and dissolved at 135 ° C. to a concentration of 0.2% by weight in ODCB. The solution is transferred to a column filled with diatomaceous earth (Celite 545), cooled to 25 ° C at 0.1 ° C / min, and the sample is deposited on the Celite surface. Next, while flowing the ODCB at a constant flow rate, the column temperature is increased stepwise to 120 ° C. in steps of 5 ° C. to elute the sample and separate the sample. The solution is reprecipitated with methanol, filtered and dried to obtain samples at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of each sample are measured. The degree of branching (measured value) is determined by 13C-NMR.
[0035]
With such a method, the branching degree is corrected as follows for the fraction at 30 ° C. to 90 ° C. That is, the degree of branching measured with respect to the elution temperature is plotted, and the correlation is approximated to a straight line by the least squares method to create a calibration curve. The correlation coefficient of this approximation is large enough. The value obtained from this calibration curve is defined as the degree of branching of each fraction. At a dissolution temperature of 95 ° C. or higher, a linear relationship is not always established between the dissolution temperature and the degree of branching, so this correction is not performed.
[0036]
Next, the weight fraction w of each fraction_iWith the degree of branching b per 5 ° C. of elution temperature_i(B)_i-B_i-1) Divided by the relative density c_iIs obtained, and the relative concentration is plotted 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.
[0037]
(Equation 2)

[0038]
Where c_jAnd b_jIs the relative density and branching degree of the j-th section, respectively. The composition distribution parameter Cb becomes 1 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.
[0039]
Many methods have been proposed for measuring the composition distribution of the ethylene / α-olefin copolymer. For example, in Japanese Patent Application Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (log normal distribution) with respect to the number of branches of each separated sample obtained by solvent separation of the sample. The ratio between the average branching degree (Cw) and the number average branching degree (Cn) is determined. The accuracy of this approximation calculation decreases when the number of branches of the sample and the cumulative weight fraction deviate from the lognormal distribution, and when the measurement is performed on a commercially available LLDPE, the correlation coefficient R₂Is quite low and the value is not accurate enough. The method of measuring Cw / Cn is different from that of Cb of the present invention, but if numerical values are compared, the value of Cw / Cn becomes considerably larger than Cb.
[0040]
The composition distribution parameter Cb of the (A) ethylene (co) polymer needs to be 1.2 or less. When the composition distribution parameter is 1.2 or more, no improvement in adhesive strength is observed.
[0041]
As the component (B) of the present invention, all polyolefins other than the ethylene (co) polymer of the component (A) can be used. Among them, the (B1) density is 0.86 to 0.97 g / cm.³And at least one polyolefin resin selected from (B2) an ethylene (co) polymer obtained by a high-pressure radical polymerization method and (B3) a polypropylene resin.
[0042]
(B1) Density of 0.86 to 0.97 g / cm³The ethylene homopolymer or ethylene-α-olefin copolymer is an ethylene homopolymer obtained by a Ziegler-based, Phillips-based catalyst by a high-medium-low pressure method and other known methods, ethylene and C3 to C12. A copolymer with α-olefin, having a density of 0.86 to 0.91 g / cm³Less than very low density polyethylene (hereinafter referred to as VLDPE) and a density of 0.91 to 0.94 g / cm³Linear low-density polyethylene (hereinafter referred to as LLDPE) having a density of 0.94 to 0.97 g / cm³Medium-density polyethylene (hereinafter referred to as MDPE or HDPE).
[0043]
Specific α-olefins include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecene and the like. Of these, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferred, and 1-butene is particularly preferred.
The α-olefin content in the ethylene copolymer is preferably 0.5 to 40 mol%.
[0044]
The (B2) ethylene (co) polymer obtained by the high-pressure radical polymerization method has a density of 0.91 to 0.94 g / cm by the high-pressure radical polymerization method.³And ethylene / vinyl ester copolymers, and copolymers with ethylene / α, β-unsaturated carboxylic acids or derivatives thereof.
[0045]
Density 0.91-0.94 g / cm by the high pressure radical polymerization method³The ethylene homopolymer is a low-density polyethylene obtained by a known high-pressure method.
[0046]
The above-mentioned ethylene / vinyl ester copolymer is a vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trifluoroacetate containing ethylene as a main component produced by a high-pressure radical polymerization method. And other unsaturated monomers. Among them, particularly preferred is an ethylene / vinyl acetate copolymer. That is, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl acetate and 0 to 25% by weight of another unsaturated monomer is preferable.
[0047]
The other unsaturated monomers include olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene;₂~ C₃Vinyl esters of alkanecarboxylic acids, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylates such as glycidyl (meth) acrylate, (meth) acrylic acid, It is at least one selected from the group of ethylenically unsaturated carboxylic acids such as maleic acid, fumaric acid and maleic anhydride or anhydrides thereof.
[0048]
It is produced by a high-pressure radical polymerization method as a copolymer with the above-mentioned ethylene / α, β-unsaturated carboxylic acid or its derivative, and the α, β-unsaturated carboxylic acid or its derivative is unsaturated dicarboxylic acid or its derivative. An anhydride and the like are included, and at least one of these monomers is copolymerized with ethylene. Specific examples thereof include ethylene / methyl (meth) acrylate copolymer, ethylene / ethyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate / maleic anhydride copolymer, ethylene -Ethyl (meth) acrylate / maleic anhydride copolymer, ethylene / maleic anhydride copolymer and the like. That is, a copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a (meth) acrylate ester and 0 to 25% by weight of an unsaturated dicarboxylic acid or an anhydride thereof is preferable. Further, other monomers may be copolymerized as long as the adhesiveness is not impaired.
[0049]
(B1) MFR of ethylene (co) polymer, (B2) low density polyethylene by high pressure radical polymerization, ethylene / vinyl ester copolymer, copolymer with ethylene / α, β-unsaturated carboxylic acid or derivative thereof Is 0.01 to 100 g / 10 min. , Preferably 0.1 to 70 g / 10 min. , More preferably 1 to 50 g / 10 min. Is selected from the range. MFR is 0.01 g / 10 min. If less than 100 g / 10 min. If it exceeds, the strength becomes insufficient.
[0050]
Examples of the rubber as the component (C) of the present invention include ethylene propylene rubber, butadiene rubber, isobutylene rubber, isoprene rubber, natural rubber, nitrile rubber and the like, and these may be used alone or as a mixture.
[0051]
As the ethylene-propylene rubber, a random copolymer (EPM) containing ethylene and propylene or butene-1 as main components and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) as a third component are mainly used. A random copolymer (EPDM) as a component is exemplified.
[0052]
The butadiene-based rubber refers to a copolymer containing butadiene as a constituent element, and includes a styrene-butadiene block copolymer (SBS) and a styrene-butadiene-ethylene copolymer (SBES) which is a hydrogenated or partially hydrogenated derivative thereof. ), 1,2-polybutadiene (1,2-PB), a maleic anhydride-butadiene-styrene copolymer, a modified butadiene rubber having a core-shell structure, and the like.
Of these, ethylene-propylene rubber and ethylene-butene-1 rubber are preferred because of their good strength improvement.
[0053]
The mixing ratio of the above components (A), (B) and (C) is usually 20 to 100% by weight of component (A), 80% by weight or less of component (B), and 40% by weight or less of component (C) (provided that (A) + (B) + (C) = 100% by weight), but if the ethylene (co) polymer of the component (A) is less than 20% by weight, the adhesive strength and affinity which are the objects of the present application will be insufficient. . The rubber as the component (C) is used in a range of 40% by weight or less. If it exceeds 40% by weight, the strength of the molded article is undesirably reduced.
[0054]
Within the above range, the component (A) is preferably used alone or in an amount of 50% by weight or more when importance is attached to the adhesive strength or affinity and high-temperature stability, and the component (B1) is used when importance is attached to economy. In the molding by the inflation method or the hollow molding method, the component (B2) is desirably compounded in the above range in order to improve workability.
[0055]
In the present invention, the above components (A), (B), and (C) are used, depending on the purpose, by graft modification with a specific monomer in the form of a composition singly or in combination.
[0056]
The resin component to be graft-modified is used by graft-modifying the entire resin component when importance is attached to adhesive strength, but (A), (B), and (B) when importance is attached to appearance and economics such as hue. It is desirable to blend at least one of the compounds (C) in an unmodified state.
The blending ratio between the graft-modified resin and the unmodified resin is from 100: 0 to 1:99 and is not particularly limited, but the monomer concentration in the composition needs to fall within the range described later.
[0057]
The first method of combining the modified resin and the unmodified resin is a combination of the graft-modified component (A), the component (A + B), the component (A + C), and the combination of the component (A + B + C) and the unmodified resin.
[0058]
The second method of combining the modified resin and the unmodified resin is a graft modified resin of any one of the component (A), the component (B) and the component (C), the component (A), the component (B), It is a combination of at least one unmodified resin of component (C).
[0059]
A third method of combination is a graft-modified resin of any one of the components (A + B), (B + C), and (A + C) and at least one of the components (A), (B), and (C). It is a combination of unmodified resins.
[0060]
A fourth combination method is a combination of a graft-modified resin composed of the component (A + B + C) and at least one unmodified resin of the components (A), (B) and (C).
[0061]
The above-mentioned graft modification refers to graft modification of a polymerized resin component by a melting method in which a reactive monomer is reacted in an extruder in the presence of a radical initiator or a solution method in which a reactive monomer is reacted in a solution.
[0062]
Examples of the radical initiator include organic peroxides, dihydroaromatics, dicumyl compounds and the like.
Examples of the organic peroxide include hydroperoxide, dicumyl peroxide, t-butylcumyl peroxide, dialkyl (allyl) peroxide, diisopropylbenzene hydroperoxide, dipropionyl peroxide, dioctanoyl peroxide, and benzoyl. Peroxide, peroxysuccinic acid, peroxyketal, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane , T-butyloxyacetate, t-butylperoxyisobutyrate and the like are preferably used.
[0063]
Examples of the dihydroaromatic include dihydroquinoline or a derivative thereof, dihydrofuran, 1,2-dihydrobenzene, 1,2-dihydronaphthalene, and 9,10-dihydrophenanthrene.
[0064]
Examples of the dicumyl compound include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-di (p-methylphenyl) butane, Examples thereof include 2,3-diethyl-2,3-di (p-bromophenyl) butane, and in particular, 2,3-diethyl-2,3-diphenylbutane is preferably used.
[0065]
In the present invention, the monomer used for grafting is a monomer having the above-mentioned functional group, that is, a: a carboxylic acid group or acid anhydride group-containing monomer, b: an ester group-containing monomer, c: a hydroxyl group-containing monomer, and d: an amino group-containing monomer. , E: at least one monomer selected from silane group-containing monomers.
[0066]
A: a, β-unsaturated dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, itaconic acid or anhydride thereof, acrylic acid, methacrylic acid, furic acid And unsaturated monocarboxylic acids such as crotonic acid, vinyl acetic acid, and pentenoic acid.
[0067]
B: Examples of the ester group-containing monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like. Particularly preferred is methyl acrylate. Can be.
[0068]
Examples of the c: hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.
[0069]
Examples of the d: amino group-containing monomer include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and cyclohexylaminoethyl (meth) acrylate.
[0070]
E: Examples of the silane group-containing monomer include unsaturated silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, and vinyltrichlorosilane.
[0071]
Among these graft monomers, a: α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, which are monomers containing a carboxylic acid group or an acid anhydride group, or anhydrides thereof are particularly preferable. Maleic anhydride is preferably used from the viewpoint of adhesive strength, economy and the like.
[0072]
The graft monomer concentration was 10 to 1 g of the resin component.^-8-10^-3mol, preferably 10^-7-10^-4It must be in the range of mol. These monomers may be introduced into the resin component by blending the ethylene / vinyl ester copolymer or the ethylene / α, β-unsaturated carboxylic acid or the copolymer thereof as the component (B2), Those introduced by graft modification have higher adhesive strength than those introduced by copolymerization. Graft monomer concentration is 10^-8If it is less than 10 mol, the adhesive strength of the laminated base material and the affinity with the filler are inferior.^-3If the concentration exceeds mol, "burn" or "gel" may occur in the composition, and it is not economical.
[0073]
The adhesive resin composition further contains additives such as other thermoplastic resins, antioxidants, lubricants, pigments, ultraviolet absorbers, and nucleating agents without departing from the gist of the present invention depending on the purpose of use. May be. In particular, antioxidants are effective for suppressing burning and gel formation.
[0074]
The adhesive resin composition of the present invention has good adhesiveness or affinity with various materials, and is suitable for laminating with various base materials and blending and using various fillers. For lamination, it is laminated with at least one layer selected from polyolefin, saponified ethylene vinyl acetate copolymer, polyamide, polyester, polyurethane, polystyrene, wood, fiber and metal foil, and is in the form of a film, sheet, or tube. In addition, a shape such as a hollow container is formed, and food packaging materials, medicines, cosmetics, and the like are effectively used in the field.
It is also effectively used as a compatible dispersant of an inorganic or organic filler such as glass fiber, carbon black, wood flour, and pigment, and a thermoplastic resin.
[0075]
The laminate according to the second invention of the present invention is a laminate of a saponified vinyl acetate copolymer, polyamide, polyester, polystyrene, metal foil, wood, woven fabric, non-woven fabric, etc. Properties such as water resistance, water resistance, chemical resistance, flexibility, etc. and properties of other materials, for example, good gas barrier properties such as saponified ethylene vinyl acetate copolymer, polyamide, polyester, metal foil, polystyrene, metal foil It is a material having both rigidity and the like and strength such as wood, woven cloth and non-woven cloth.
[0076]
Various polyolefin resins are used as a base material, and examples thereof include olefin homopolymers such as polyethylene, polypropylene, poly-1-butene, and poly-4-methyl-1-pentene; Mutual copolymers such as butene, 4-methyl-1-pentene, 1-hexene, and 1-octene; copolymers of ethylene and vinyl esters such as ethylene and vinyl acetate copolymer, and ethylene-methacrylic acid copolymer And copolymers of ethylene with unsaturated carboxylic acids and unsaturated carboxylic esters, such as ethylene-ethyl acrylate copolymer and ethylene-ethyl methacrylate copolymer, and mixtures thereof.
[0077]
Other substrates include saponified ethylene-vinyl acetate copolymer, polyamide, polyester, polyurethane, synthetic resins such as polystyrene, wood such as veneer and plywood, various fibers made of carbon fibers and inorganic materials, aluminum, iron, zinc, Examples include metals such as copper.
[0078]
Among the above, in particular, when a laminate with a saponified ethylene-vinyl acetate copolymer, polyamide, polyester, or metal foil is used as a food or container for preserving medicine or a package having excellent gas barrier properties, these materials are used. Is the most preferred because of its strong adhesive strength to Further, they need to withstand, for example, boiling for cooking and sterilization or, depending on the use, exposure to high temperatures such as outdoors or in automobiles, and are required to have a small decrease in adhesive strength even at relatively high temperatures.
[0079]
The form of the laminate of the present invention may be any of a film form, a plate form, a tubular form, a foil form, a woven cloth form, a bottle, a container, an injection molded product and the like, and is not particularly limited.
As a method for producing a laminate of the present invention, a pre-formed film, a method of laminating on a sheet by an extrusion lamination method, a dry lamination method, a sand lamination method, or a resin melted by an extruder using a multilayer die. In addition to the co-extrusion method such as a multilayer inflation method and a multilayer T-die which are joined at the die tip to form a laminated structure, a normal molding method such as a multilayer blow molding method and an injection molding method is applied, and is not particularly limited. .
[0080]
Among the above, a laminate of saponified ethylene-vinyl acetate copolymer, polyamide, and polyester is suitable for co-extrusion molding because the moldability of the adhesive resin composition of the present invention is good, and The resin composition has both heat sealability, impact strength, water resistance, chemical resistance, and gas barrier properties of saponified ethylene vinyl acetate copolymer, polyamide, and polyester. The lamination with a metal foil or the like is preferably formed by a lamination method.
[0081]
It is particularly preferable that the laminate be a layer made of a saponified ethylene-vinyl acetate copolymer or a metal foil for the outer layer and a layer made of the adhesive resin composition for the inner layer because the above characteristics can be utilized. These include at least the two layers described above, and are advantageous from the viewpoint of economic efficiency by forming another layer, for example, a layer made of a polyolefin resin inside.
[0082]
As a specific layer configuration, EVOH / adhesion, EVOH / adhesion / PO, PO / adhesion / EVOH / adhesion / PO or EVOH / adhesion / PO / adhesion / EVOH can be considered (however, EVOH: ethylene-vinyl acetate copolymer) Adhesion such as saponified product and metal foil: adhesive resin composition of the present invention, PO: polyolefin resin).
[0083]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.
(A) Ethylene / α-olefin copolymer
[Production Example 1]
A1: Polymerization of ethylene / butene-1 copolymer
After replacing the autoclave made of stainless steel with a stirrer with nitrogen, a predetermined amount of purified toluene was added as a solvent. Then, butene-1 was added, and a mixed solution of bis (n-butylcyclopentadienyl) zirconium dichloride (0.02 mmol as Zr) methylalumoxane [MAO] (MAO / Zr = 500 [molar ratio]) was further added. After the addition, the temperature was raised to 80 ° C., ethylene was supplied, and polymerization was carried out while maintaining the pressure at a constant pressure while continuously polymerizing the obtained ethylene / butene-1 copolymer (A1). Its physical properties are as follows.
MFR: 4.4 g / 10 min.
Density: 0.918 g / cm³
Molecular weight distribution (Mw / Mn): 2.5
Composition distribution parameter (Cb): 1.03
[0084]
[Production Example 2]
A2: Polymerization of ethylene / butene-1 copolymer
In the same manner as in Production Example 1, ethylene / α-olefin copolymers having different MFRs were obtained.
MFR: 2.0 g / 10 min.
Density: 0.921 g / cm³
Molecular weight distribution (Mw / Mn): 2.6
Composition distribution parameter (Cb): 1.02
[0085]

[0086]
(C) Rubber
C1: Ethylene-propylene rubber (EP-01, Nippon Synthetic Rubber Co., Ltd.)
Mooney viscosity ML_{1 + 4}(100 ° C.) = 19
Propylene content = 22 wt%
Type (JIS-A) = 73
[0087]
(Evaluation method)
In the evaluation, three types and five layers of a T-die film composed of LLDPE / adhesive resin / ethylene-saponified vinyl acetate / adhesive resin / LLDPE were molded under the following conditions, and various measurements were made.

[0088]
Example 1
0.25 parts by weight of maleic anhydride was added to 100 parts by weight of a resin component comprising 70% by weight of ethylene / butene-1 copolymer (A1) and 30% by weight of ethylene-propylene rubber (EP01) described in Production Example 1. , 5-di (t-butylperoxy) hexyne, 0.02 parts by weight of the antioxidant Irganox 1010 (Ciba-Geigy) and 0.1 parts by weight of Irgafos 168 (Ciba-Geigy) were added, and the mixture was mixed with a Henschel mixer. After sufficient mixing, denaturation was performed by kneading at a set temperature of 230 ° C. using a 50 mm single screw extruder. The MFR of the obtained resin composition was 3.1 g / 10 minutes, and the addition ratio of maleic anhydride was 1.8 × 10^-5mol / g.
[0089]
Example 2
To 100 parts by weight of a resin component composed of 50% by weight of ethylene / butene-1 copolymer (A2), 30% by weight of LLDPE (B1-1), and 20% by weight of ethylene-propylene rubber (EP01) described in Production Example 2, 0.25 parts by weight of maleic anhydride, 0.02 parts by weight of 2,5-di (t-butylperoxy) hexine, 0.1 parts by weight of antioxidant Irganox 1010 (Ciba-Geigy), Irgafoss 168 (Ciba-Geigy) 0.1 part by weight was added, and the mixture was sufficiently mixed with a Henschel mixer, and kneaded at a set temperature of 230 ° C. using a 50 mm single screw extruder for denaturation. The MFR of the obtained resin composition was 1.3 g / 10 minutes, and the addition ratio of maleic anhydride was 1.8 × 10^-5mol / g.
[0090]
Example 3
0.2 parts by weight of maleic anhydride was added to 100 parts by weight of a resin component composed of 70% by weight of the ethylene / butene-1 copolymer (A2) and 30% by weight of ethylene-propylene rubber (EP01) obtained in Production Example 2. 0.015 parts by weight of 2,5-di (t-butylperoxy) hexine, 0.1 parts by weight of an antioxidant Irganox 1010 (Ciba-Geigy) and 0.1 parts by weight of Irgafos 168 (Ciba-Geigy) are added, and a Henschel mixer is added. , And kneaded at a set temperature of 230 ° C. for denaturation using a 50 mm single screw extruder. The MFR of the obtained resin composition was 1.2 g / 10 min, and the addition ratio of maleic anhydride was 1.8 × 10^-5mol / g.
[0091]
Reference Example 1
760 g of LLDPE (B1-2) was put into a 15 liter autoclave equipped with a stirrer together with 7 liters of toluene, and the temperature was raised while stirring. When the temperature reached 127 ° C., 42 g of maleic anhydride dissolved in 483 g of toluene and 320 g of toluene 5.6 g of dicumyl peroxide dissolved in the above are added via separate mouths over 6 hours. After the dropwise addition, the reaction was carried out for 3 hours, followed by cooling to precipitate and recover the product, followed by washing with acetone several times, and maleic anhydride-modified ethylene / butene-1 copolymer (maleation ratio = 0.9%, MFR = 4 g). / 10 min).
[0092]
7% by weight of the maleic anhydride-modified ethylene / butene-1 copolymer, 63% by weight of the ethylene / butene-1 copolymer (A2) described in Production Example 2, and 30% by weight of ethylene-propylene rubber (EP01). 0.1 parts by weight of the antioxidant Irganox 1010 (Ciba-Geigy) and 0.1 parts by weight of Irgafos 168 (Ciba-Geigy) were added to 100 parts by weight of the resulting resin component, and the mixture was sufficiently mixed with a Henschel mixer. And kneaded at a set temperature of 180 ° C. The MFR of the obtained resin composition was 2.0 g / 10 min, and the addition ratio of maleic anhydride was 7 × 10^-6mol / g.
[0093]
Comparative Example 1
100 parts by weight of a resin component comprising 70% by weight of LLDPE (B1-1) and 30% by weight of ethylene-propylene rubber (EP01), 0.25 part by weight of maleic anhydride, 2,5-di (t-butylperoxy) Add 0.02 parts by weight of hexine, 0.1 parts by weight of antioxidant Irganox 1010 (Ciba-Geigy) and 0.1 parts by weight of Irgafos 168 (Ciba-Geigy), mix well with a Henschel mixer, and use a 50 mm single screw extruder. At a set temperature of 230 ° C. for denaturation. The MFR of the obtained resin composition was 1.4 g / 10 minutes, and the addition ratio of maleic anhydride was 1.8 × 10^-5mol / g.
[0094]
Comparative Example 2
To 100 parts by weight of a resin component composed of 15% by weight of ethylene / butene-1 copolymer (A2), 65% by weight of LLDPE (B1-1), and 20% by weight of ethylene-propylene rubber (EP01) described in Production Example 2, 0.25 parts by weight of maleic anhydride, 0.02 parts by weight of 2,5-di (t-butylperoxy) hexine, 0.1 parts by weight of antioxidant Irganox 1010 (Ciba-Geigy), Irgafoss 168 (Ciba-Geigy) 0.1 part by weight was added, and the mixture was sufficiently mixed with a Henschel mixer, and kneaded at a set temperature of 230 ° C. using a 50 mm single screw extruder for denaturation. The MFR of the obtained resin composition was 1.4 g / 10 minutes, and the addition ratio of maleic anhydride was 1.8 × 10^-5mol / g.
[0095]
Comparative Example 3
100 parts by weight of a resin component consisting of 70% by weight of LDPE (B1-3) and 30% by weight of ethylene-propylene rubber (EP01), 0.25 part by weight of maleic anhydride, 2,5-di (t-butylperoxy) Add 0.02 parts by weight of hexine, 0.1 parts by weight of antioxidant Irganox 1010 (Ciba-Geigy) and 0.1 parts by weight of Irgafos 168 (Ciba-Geigy), mix well with a Henschel mixer, and use a 50 mm single screw extruder. At a set temperature of 230 ° C. for denaturation. The MFR of the obtained resin composition was 0.7 g / 10 min, and the addition ratio of maleic anhydride was 1.8 × 10^-5mol / g.
[0096]
Comparative Example 4
100 parts by weight of the resin composition comprising the ethylene / butene-1 copolymer (A2) described in Production Example 2, 0.2 parts by weight of maleic anhydride, and 2,5-di (t-butylperoxy) hexine 0.1 part by weight. After adding 015 parts by weight and 0.2 parts by weight of an antioxidant Irganox 1076 (Ciba Geigy), the mixture was sufficiently mixed with a Henschel mixer, and then kneaded at a set temperature of 230 ° C. using a 50 mm single screw extruder for denaturation.
[0097]
To 100 parts by weight of a resin composition comprising 0.1% by weight of this modified resin, 69.9% by weight of an unmodified ethylene / butene-1 copolymer (A2) and 30% by weight of ethylene-propylene rubber (EP01), 0.1 parts by weight of an antioxidant Irganox 1010 (Ciba-Geigy) and 0.1 parts by weight of Irgafos 168 (Ciba-Geigy) are added, and after sufficiently mixing with a Henschel mixer, a 50 mm single screw extruder is used at a set temperature of 180 ° C. Kneaded. The MFR of the obtained resin composition was 1.9 g / 10 min, and the addition ratio of maleic anhydride was 3 × 10^-9mol / g.
[0098]
(Measurement of adhesive strength)
Tables 1 and 2 summarize the adhesive strength at room temperature and at 60 ° C., but the examples satisfy the claims of the present application.1-3The adhesive resin composition of (1) obtained an improvement in adhesive strength of 10 to 30% as compared with the comparative example.
[0099]
【The invention's effect】
The adhesive resin composition of the present invention is obtained by graft-modifying an ethylene (co) polymer produced by a specific catalyst or a composition containing the (co) polymer, and has a high adhesion to other base materials. It is possible to obtain a laminate that maintains strength and strong affinity and has good adhesive strength during high-speed molding or thin film formation. In addition, by laminating a layer composed of the present composition and a layer composed of another substrate, it is possible to provide a laminate having both the characteristics of the present composition and the characteristics of another substrate.
[0100]
[Table 1]

[0101]
[Table 2]

[Brief description of the drawings]
FIG. 1 shows an elution temperature-elution amount curve of a copolymer of the present invention.
FIG. 2 shows an elution temperature-elution amount curve of a copolymer with a typical metallocene catalyst.

Claims (5)

(A) (a) ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing a transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton; (B) a density of 0.86 to 0.97 g / cm ³ , (c) a melt flow rate of 0.01 to 100 g / 10 min, and (d) a molecular weight distribution Mw / Mn obtained by (co) polymerization. (E) an ethylene (co) polymer having a composition distribution parameter Cb of 1.2 or less (provided that the melt flow ratio (MI ₁₀ / MI _2.16 ) is 7 or more). A composition comprising 20% by weight or more, (B) 80% by weight or less of a polyolefin resin other than the ethylene (co) polymer of the component (A), and (C) 40% by weight or less of rubber ( excluding those having chain branching) A + B + C = 100% by weight In includes as an essential component (A) and component (C) of the resin composition, and at least components (A) and component (C) a carboxylic acid group, acid anhydride group, an ester group, a hydroxyl group, an amino group And an adhesive resin which is graft-modified with at least one kind of monomer containing a functional group selected from silane groups, and the amount of the graft monomer is 10 ⁻⁸ to 10 ⁻³ mol per 1 g of the resin composition. Composition. 2. The adhesive resin composition according to claim 1, wherein the composition comprises any of the (A + C) component and the ( A + B + C) component that has been graft-modified. 3. Wherein the composition, the graft-modified resin and (A), (B), the adhesive resin composition according to claim 1 or 2 comprising at least one non-modified product of component (C). The polyolefin resin (B) has a (B1) density of 0.86 to 0.97 g / cm. ³ Selected from ethylene / α-olefin copolymers, (B2) low-density polyethylene by high-pressure radical polymerization, ethylene / vinyl ester copolymers, and copolymers with ethylene / α, β-unsaturated carboxylic acids or derivatives thereof. The adhesive resin composition according to any one of claims 1 to 3, wherein the adhesive resin composition is at least one kind. A layer comprising the adhesive resin composition according to any one of claims 1 to 4, comprising a single layer, a polyolefin, a saponified ethylene vinyl acetate copolymer, a polyamide, a polyester, a polyurethane, a polystyrene, a wood, a fiber, and a metal foil. A laminate comprising at least two layers in which at least one layer selected from the group consisting of:

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