JP3872141B2 - Barrier packaging material - Google Patents

Description

化学式中、Ｃｐは前記シクロペンタジエニル骨格を有する配位子、Ｘは水素、ハロゲン、炭素数１〜２０のアルキル基、アリールシリル基、アリールオキシ基、アルコキシ基、アミド基、シリルオキシ基等を表し、ＹはＳｉＲ₂、ＣＲ₂、ＳｉＲ₂ＳｉＲ₂、ＣＲ₂ＣＲ₂、ＣＲ＝ＣＲ、ＳｉＲ₂ＣＲ₂、ＢＲ₂、ＢＲからなる群から選ばれる２価基、Ｚは−Ｏ−、−Ｓ−、−ＮＲ−、−ＰＲ−またはＯＲ、ＳＲ、ＮＲ₂、ＰＲ₂からなる群から選ばれる２価中性リガンドを示す。ただし、Ｒは水素または炭素数１〜２０のアルキル基、アリール基、シリル基、ハロゲン化アルキル基、ハロゲン化アリール基、またはＹ、ＺまたはＹとＺの双方からの２個またはそれ以上のＲ基は縮合環系を形成するものである。Ｍは周期律表第IV族の遷移金属原子を表す。
【００４８】
上記化学式で表される化合物の例としては、（ｔ−ブチルアミド）（テトラメチルシクロペンタジエニル）−１,２−エタンジイルジルコニウムジクロライド、（ｔ−ブチルアミド）（テトラメチルシクロペンタジエニル）−１,２−エタンジイルチタンジクロライド、（メチルアミド）（テトラメチルシクロペンタジエニル）−１,２−エタンジイルジルコニウムジクロライド、（メチルアミド）（テトラメチルシクロペンタジエニル）−１,２−エタンジイルチタンジクロライド、（エチルアミド）（テトラメチルシクロペンタジエニル）メチレンタンジクロライド、（ｔ−ブチルアミド）ジメチル（テトラメチルシクロペンタジエニル）シランチタンジクロライド、（ｔ−ブチルアミド）ジメチル（テトラメチルシクロペンタジエニル）シランジルコニウムジベンジル、（ベンジルアミド）ジメチル（テトラメチルシクロペンタジエニル）シランチタンジクロライド、（フェニルホスフイド）ジメチル（テトラメチルシクロペンタジエニル）シランチタンジクロライドなどが挙げられる。
【００４９】
本発明でいう助触媒としては、前記周期律表第IV族の遷移金属化合物を重合触媒として有効になし得る、または触媒的に活性化された状態のイオン性電荷を均衡させうるものをいう。
本発明において用いられる助触媒としては、有機アルミニウムオキシ化合物のベンゼン可溶のアルミノキサンやベンゼン不溶の有機アルミニウムオキシ化合物、ホウ素化合物、酸化ランタンなどのランタノイド塩、酸化スズ等が挙げられる。これらの中でもアルミノキサンが最も好ましい。
【００５０】
また、触媒は無機または有機化合物の担体に担持して使用されてもよい。該担体としては無機または有機化合物の多孔質酸化物が好ましい。具体的には、ＳｉＯ₂、Ａｌ₂Ｏ₃、ＭｇＯ、ＺｒＯ₂、ＴｉＯ₂、Ｂ₂Ｏ₃、ＣａＯ、ＺｎＯ、ＢａＯ、ＴｈＯ₂等またはこれらの混合物が挙げられ、ＳｉＯ₂−Ａｌ₂Ｏ₃、ＳｉＯ₂−Ｖ₂Ｏ₅、ＳｉＯ₂−ＴｉＯ₂、ＳｉＯ₂−ＭｇＯ、ＳｉＯ₂−Ｃｒ₂Ｏ₃等が挙げられる。
【００５１】
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。
【００５２】
《製造方法》
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（成分（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において、重合時の触媒成分を実質的に塩素等のハロゲンを含まないものとすると、得られる重合体にもこれらハロゲンが含まれず、したがって化学的安定性、衛生性が優れ、食品、衛生、医療関連用途に好適である。また電気部品、電線部材、電子レンジに関する包装材料および容器に適用した場合、周辺の金属部品等の錆の発生が抑えられるといった特徴を有する。
【００５４】
〈（Ｂ）他のエチレン系重合体〉
本発明でのシーラント層を構成する樹脂としては、上述した成分（Ａ）に加えて、他のエチレン系重合体を（成分（Ｂ））を混合しておくことが望ましい。
そのような他のエチレン系重合体としては、高圧ラジカル重合法によるエチレン系重合体（Ｂ1）及び又は密度が０.８６〜０.９７g/cm³のエチレン−α−オレフィン共重合体（Ｂ2）が好ましい。
【００５５】
上記（Ｂ1）高圧ラジカル重合法によるエチレン系重合体としては、高圧ラジカル重合法による密度が０.９１〜０.９４g/cm³のエチレン単独重合体（低密度ポリエチレン（ＬＤＰＥ）：Ｂ11）、エチレン・ビニルエステル共重合体（Ｂ12）、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（Ｂ13）等が挙げられる。
【００５６】
（Ｂ11）低密度ポリエチレンは、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。
【００５７】
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。
【００５８】
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/10分の範囲で選択される。
【００５９】
また、上記密度が０.８６〜０.９７g/cm³のエチレン−α−オレフイン共重合体（Ｂ2）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、密度が０.９４〜０.９７g/cm³の高密度ポリエチレン、０.９１〜０.９４g/cm³の線状低密度ポリエチレン（ＬＬＤＰＥ）、密度が０.８６〜０.９１g/cm³の超低密度ポリエチレン（以下、ＶＬＤＰＥと称する）、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。
【００６０】
その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。
【００６１】
上記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虞を生じる。
【００６２】
また上記ＶＬＤＰＥとは、密度が０.８６〜０.９１g/cm³、好ましくは０.８８〜０.９０５g/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。
【００６３】
上記エチレン・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。
【００６４】
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及び／又は密度が０.８６〜０.９５g/cm³のエチレン−α−オレフイン共重合体が好ましい。
【００６５】
シーラント層を構成する樹脂組成物を（Ａ）成分と（Ｂ）成分とで構成した場合、その配合割合は、（Ａ）成分が９８〜１０重量％、（Ｂ）成分が２〜９０重量％、好ましくは（Ａ）成分が９５〜６０重量％、（Ｂ）成分が５〜４０重量％、さらに好ましくは（Ａ）成分が９０〜７０重量％、（Ｂ）成分が１０〜３０重量％である。該組成物の（Ｂ）成分が存在することにより、ドローダウン性、ネックイン等の成形加工性が向上するものの、（Ａ）成分が１０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、ホットタック性等の改良効果が小さくなってしまう。
【００６６】
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＋Ｂ21）、（Ａ2＋Ｂ11＋Ｂ21）、（Ａ1＋Ｂ12＋Ｂ21）、（Ａ2＋Ｂ12＋Ｂ21）、（Ａ1＋Ｂ11＋Ｂ22）、（Ａ2＋Ｂ11＋Ｂ22）（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：，Ａ2：上述した成分（Ａ）の２態様、Ｂ11：ＬＤＰＥ、Ｂ12：ＥＶＡ、Ｂ21：ＬＬＤＰＥ、Ｂ22：ＶＬＤＰＥを示す）。
特に（（Ａ1またはＡ2）＋Ｂ11＋（Ｂ21または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５０〜９０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。
【００６７】
この（Ａ）成分と（Ｂ）成分を含む組成物は、（ｃ1）メルトフローレート（ＭＦＲ）が１〜１００g/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望ましい。上記（ｃ1）ＭＦＲが１g/10分未満であると成形加工性が劣り、１００g/10分を超えるものは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ある。（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。
【００６８】
この際、（Ａ）成分として上述した（Ａ1）成分を用いた場合には、メルトフローレートは、１〜５０g/10分とすることがより好ましく、さらには、１.５〜４０g/10分、さらに好ましくは２.０〜３０g/10分である。
さらに、１９０℃におけるダイスウエル比（ＤＳＲ）は、１.１０〜２.００とすることがより好ましく、さらには１.１０〜１.７０、さらに好ましくは１.１０〜１.６５である。
また、１９０℃における溶融張力（ＭＴ）は、０.５〜４.０ｇとすることがより好ましく、さらには０.５〜２.５ｇの範囲であることが望ましい。
【００６９】
また（Ａ）成分として上述した（Ａ2）成分を用いた場合には、メルトフローレート（ＭＦＲ）は、１〜５０g/10分であることがより好ましく、さらには１.５〜４０g/10分、さらに好ましくは２.０〜３０g/10分の範囲であることが好ましい。
さらに、１９０℃におけるダイスウエル比（ＤＳＲ）が１.３０〜３.００であることが好ましく、より好ましくは１.３０〜２.８０、さらに好ましくは１.３０〜２.５０である。
また、１９０℃における溶融張力（ＭＴ）は、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。
【００７０】
尚、ＤＳＲは例えば次のようにして求めることができる。
JIS K6760で使用されるメルトインデクサーを使用し、シリンダーにサンプルを充填し、シリンダー温度１９０℃で４分間予熱の後、定荷重２.１６ｋｇをかける。ピストンの降下が定常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、次式により求まる。
ＤＳＲ＝Ｄ／Ｄ₀
【００７１】
成分（Ａ）と成分（Ｂ）の配合は樹脂組成物の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ポリオレフィン樹脂等をフィルム成形時に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。また、必要に応じて、バンバリーミキサー等のバッチ式溶融混練機を併用しても良い。
【００７２】
尚、シーラント層を構成する樹脂層には、有機あるいは無機フィラー、粘着付与剤、酸化防止剤、帯電防止剤、防曇剤、有機あるいは無機系顔料、分散剤、核剤、発泡剤、難燃剤、架橋剤、紫外線防止剤、（不）飽和脂肪酸アミド、（不）飽和高級脂肪酸の金属塩等の滑剤などの公知の添加剤を本願発明の特性を本質的に阻害しない範囲で添加することができる。
これらの添加剤の中でも、滑剤、粘着付与剤、無機フィラーは作業性をより向上させるために好適に用いられる。
滑剤としては、オレイン酸アミド、ステアリン酸アミド、エルカ酸アミド、等の脂肪酸アミド；ステアリン酸モノグリセライド、ステアリン酸ジグリセライド、オレイン酸モノグリセライド、オレイン酸ジグリセライド等の脂肪酸グリセリンエステル化合物およびそれらのポリエチレングリコール付加物等が挙げられる。
また無機フィラーとしては、軽質および重質炭酸カルシウム、タルク、シリカ、ゼオライト、炭酸マグネシウム、長石等が挙げられる。
粘着付与剤としては、ポリブテン、ヒマシ油誘導体、ソルビタン脂肪酸エステル、ロジンおよびロジン誘導体、石油樹脂およびそれらの水添物等のタッキファイヤー、ゴム等が挙げられる。これら粘着付与剤は０.５〜２０重量部の範囲で配合することができる。
顔料としてはカーボンブラック、チタン白等の他、市販の各種着色剤マスターバッチが好適に用いられる。
【００７３】
さらに適度の滑り性、帯電防止性、防曇性を得るための添加剤についても配合することができる。
具体的には、ソルビタン脂肪酸エステルとして、ソルビタンモノオレート、ソルビタンモノラウレート、ソルビタンモノベヘネート、ソルビタンモノステアレート等；グリセリン脂肪酸エステルとして、グリセリンモノオレート、グリセリンモノステアレート、グリセリンモノラウレート、グリセリンモノベヘネート等；ポリグリセリン脂肪酸エステルとして、ジグリセリンモノラウレート、ジグリセリンモノステアレート、ジグリセリンモノオレート、テトラグリセリンモノオレート、テトラグリセリンモノステアレート、ヘキサグリセリンモノラウレート、ヘキサグリセリンモノオレート、デカグリセリンモノラウレート、デカグリセリンモノステアレート、デカグリセリンモノオレート等の他、多価アルコールの脂肪酸エステルおよびこれらのエチレンオキサイド付加物、高級脂肪酸アミドおよびこれらのエチレンオキサイド付加物、高級脂肪酸アルカノールアミド等が挙げられるがこれらに限定されるものではない。
これらの添加剤は単独あるいは混合組成物として使用されるが、添加量としては通常０.０１〜０.５重量％、好ましくは０.０５〜０.３重量％である。添加量が０.０１重量％未満ではフィルムの改質効果が十分ではなく、０.５重量％を越える場合にはフィルム表面への浮き出し量が多く、フィルムがべたつき、その結果、作業性が著しく低下するなどの問題が起こるため好ましくない。
【００７４】
〔基材層〕
本発明の基材層としては、セロファン、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）、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。
また、電子レンジ加熱適性を必要としない用途に用いる場合には、アルミニウム蒸着ＰＥＴ（ＶＭＰＥＴ）や、アルミニウム蒸着ＰＰなども用いることができる。
これらは印刷がなされていても差し支えない。
また必要に応じて、コロナ処理、フレーム処理、プラズマ処理、紫外線処理、アンカーコート処理、オゾン処理等の各種前処理がなされていても良い。
【００７５】
〔バリヤー性材料層〕
本発明でのバリヤー性材料層は、酸素等の気体類あるいは水蒸気等を遮断して内容物の劣化を防ぐ材料で構成されるもので、ポリビニルアルコール、エチレン−酢酸ビニル共重合体のケン化物、アルミニウム箔などの金属箔等が挙げられる。特に、気体透過性および水蒸気透過性が小さく、押出ラミネート成形性が良好なエチレン−酢酸ビニル共重合体のケン化物が好ましい。
これらの材料は、上述した基材、例えば、アルミニウム蒸着ＰＥＴ（ＶＭＰＥＴ）、アルミニウム蒸着ＰＰなどのバリヤー性を有する基材と重複させてもよい。
【００７６】
〔積層構成〕
本発明の積層体においては、上述した基材層、バリヤー性材料層、シーラント層を有していれば、他の層をさらに有していてもよく、例えば、基材層とバリヤー性材料層の間に、及び又は、バリヤー性材料層とシーラント層の間などに接着層を設けることが望ましい。
基材層（「第Ｉ層」とする）とバリヤー性材料層（「第III層」とする）の間に介在させる接着層（「第II層」とする）は、基材層とは共押出ラミネーション成形法により冷却ロールとニップロールで圧着される際に積層し、バリヤー性材料層とは共押出の際に流路の合流部分で両層とも溶融状態で積層することが望ましい。
このような接着層（第II層）としては、エチレンと酸もしくは酸無水物とのランダム共重合体、あるいはポリエチレンやポリエチレン系共重合体を酸もしくは酸無水物で変性したものが好適である。ここで、酸としては、アクリル酸、メタクリル酸、マレイン酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸等の分子内に不飽和二重結合をもつ酸が望ましい。酸無水物としては、これらの酸の無水物等が好適である。これら酸、または酸無水物は単独もしくは２種以上を組み合わせて共重合あるいは変性に用いることができる。また、他の共重合性モノマーと組み合わせて用いることもできる。ここで、ポリエチレン系共重合体としては、ＥＶＡ、エチレン−プロピレン共重合体、エチレン−１−ブテン共重合体等がある。これらの樹脂は単独あるいは必要により他の樹脂と混合して使用され得る。
【００７７】
また、バリヤー性材料層（第III層）とシーラント層（「第Ｖ層」とする）との間に介在させる接着層（「第IV層」とする）は、共押出の際に流路の合流部分で各層と溶融状態で積層することが望ましい。
このような接着層（第IV層）としては、上記第II層と同種の材料を適用することができる。また、それらの樹脂を単独あるいは必要により他の樹脂と混合して使用することもできる。
第II層と第IV層とを異なる樹脂材料として、それぞれ別個の押出機から供給するようにしても良いが、同一の樹脂材料とすれば、１つの押出機から分流して用いることができるので効率が良い。
【００７８】
また、本発明の積層体としては、これらの第Ｉ層〜第Ｖ層だけでなく、さらに他の層を積層させてもよい。
例えば、第Ｉ層と第II層の間、あるいは第Ｉ層の外側にさらに、ポリエチレン等のポリオレフィン層や、アイオノマー樹脂、各種のポリオレフィン及び又はゴムに不飽和カルボン酸またはその誘導体をグラフト変性させた酸変性ポリオレフィン層等を設けてもよい。
例えば、ＯＮｙ／（酸変性ＰＥ／ＥＶＯＨ／酸変性ＰＥ／ＳＳ）、ＯＮｙ／（共重合体１／ＥＶＯＨ／共重合体１／ＳＳ）、ＯＮｙ／（共重合体２／ＥＶＯＨ／共重合体２／ＳＳ）、ＯＮｙ／（共重合体３／ＥＶＯＨ／共重合体３／ＳＳ）、ＯＮｙ／（共重合体１／ＥＶＯＨ／共重合体３／ＳＳ）、ＯＮｙ／（ＰＥ／酸変性ＰＥ／ＥＶＯＨ／酸変性ＰＥ／ＳＳ）、ＰＥＴ／（共重合体２／ＥＶＯＨ／共重合体２／ＳＳ）、ＯＮｙ／（ＬＤＰＥ／共重合体２／ＥＶＯＨ／共重合体２／ＳＳ）等が挙げられる。ここで、ＯＮｙ：延伸ナイロン、ＰＥ：ポリエチレン系樹脂、酸変性ＰＥ：酸または酸無水物変性ポリエチレン、共重合体１：エチレン−不飽和酸または酸無水物共重合体、共重合体２：エチレン−不飽和酸または酸無水物−エステル共重合体、共重合体３：エチレン−不飽和酸または酸無水物共重合体の金属塩、ＳＳ：シーラント層を示す。
尚、シーラント層は最内層に位置させることが好適である。
【００７９】
本発明の積層体を製造する方法としては、第Ｉ層に第II層〜第Ｖ層を共押出ラミネーション成形法により積層する方法が好適である。
本発明の積層体を製造する共押出ラミネート装置は、第II層から第Ｖ層までの少なくとも４層を同時に共押出できる装置が好ましい。また樹脂として最低３種類（第II層と第IV層に同一の樹脂を使用した場合）の樹脂を別個に押し出すための最低３台の押出機を備えていることが好ましい。これらを共押出する方式は、フィードブロック方式、ブラックボックス方式等のダイ前合流型共押出とマルチマニホールド方式などのダイ内合流型共押出、マルチスロット方式などのダイ外合流型共押出などを用いることができる。
【００８０】
【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。
【００８１】
実施例および比較例における試験法は以下のとおりである。
（物性試験方法）
密度：
JIS K6760に準拠した。
ＭＦＲ：
JIS K6760に準拠した。
Ｍｗ／Ｍｎ：
ＧＰＣ（ウオーターズ１５０型）ＯＤＣＢ １３５℃ カラムには東ソー(株)製ＧＭＭＨＲ−Ｈ（Ｓ）を使用した。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。
【００８２】
（積層体評価法）
酸素透過率：
MOCON10/50酸素透過率試験機により湿度９０％、温度２３℃における酸素透過率を測定した。積層体の第Ｉ層の外側を酸素で飽和させ、積層体の第Ｖ層の内側にキャリヤーガス（窒素＋水素１％混合ガス）を流して５０cm²の積層体を透過する酸素量を測定し、１ｍ²当たりで、２４時間当たりの透過量の数値に換算した。
ヘイズ：
JIS K7105に準じて測定した。
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）を使用し、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、放冷した。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。
ヒートシール強度：
上記ヒートシール試験器を用い、圧力２ｋｇ／ｃｍ²、シール温度１５０℃、シール時間３秒でヒートシールした後、放冷した。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、強度を求めた。
【００８３】
（エチレン・α−オレフイン共重合体Ａ1の製造）
▲１▼固体触媒の調製
窒素下で電磁誘導攪拌機付き触媒調製器（No.１）に精製トルエンを加え、ついでジプロポキシジクロロジルコニウム（Ｚｒ（ＯＰｒ）₂Ｃｌ₂）２８ｇおよびメチルシクロペンタジエン４８ｇを加え、０℃に系を保持しながらトリデシルアルミニウムを４５ｇを滴下し、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Ｄとした。
【００８４】
▲２▼試料の重合
連続式の流動床気相法重合装置を用い、重合温度７０℃、全圧２０kgf／cm²Gでエチレンと１−ヘキセンの共重合を行った。前記触媒Ｄ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った。生成した共重合体を樹脂成分Ａ1とする。樹脂成分Ａ1の物性は以下に示すとおりである。
（Ａ1）エチレン・１−ヘキセン共重合体
（イ）密度：０.９１０g/cm³
（ロ）ＭＦＲ：１１g/10分
（ハ）分子量分布（Ｍｗ／Ｍｎ）：２.６
（ニ）組成分布パラメーターＣｂ：１.２２
（ホ）ＴＲＥＦピーク温度：８３.２、９６.５℃
（ヘ）ｄ−０.００８logＭＦＲ：０.９０２
ODCB可溶分(%)＝１.５＜9.8×10³×(0.9300ーd+0.008logMFR)²+2.0
【００８５】
（エチレン−α−オレフィン共重合体Ａ2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−ヘキセンを添加し、更にエチレンビス（インデニル）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、８０℃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、（Ａ2）エチレン・１−ヘキセン共重合体を得た。 （Ａ2）エチレン・１−ヘキセン共重合体
（イ）密度：０.９０７g/cm³
（ロ）ＭＦＲ：１１g/10分
（ハ）分子量分布（Ｍｗ／Ｍｎ）：２.４
（ニ）組成分布パラメーター（Ｃｂ）：１.０５
（ホ）ＴＲＥＦピーク温度：８２.９℃
【００８６】
（他のエチレン系重合体（Ｂ））
Ｂ11：高圧法低密度ポリエチレン（ＭＦＲ：８.５g/cm³、密度：０.９１９g/cm³、日本ポリオレフィン（株）製）；ＬＤＰＥ
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％、ＭＦＲ：５.０g/cm³、密度：０.９２３g/cm³、日本ポリオレフィン（株）製）；ＥＶＡ
Ｂ13：高圧法エチレン−メチルメタクリレート−無水マレイン酸共重合体（メチルメタクリレート濃度：５重量％、無水マレイン酸濃度：１％）
Ｂ14：高圧法低密度ポリエチレン（ＭＦＲ：２１g/10分、密度：０.９１７g/cm³、日本ポリオレフィン（株）製）に無水マレイン酸０.５重量部と、有機過酸化物０.１重量部を加え、押出機にて２４０℃で溶融混練して得られた酸無水物変性ポリエチレン。
Ｂ21：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、ＭＦＲ：７.０g/10分、密度：０.９２０g/cm³、日本ポリオレフィン（株）製）；ＬＬＤＰＥ
Ｂ31：エチレン−酢酸ビニル共重合体けん化物（ＭＦＲ：５g/10分、密度：１.１９g/cm³、クラレ（株）製）
【００８７】
［実施例１］
樹脂成分（Ａ1）のエチレン−α−オレフィン共重合体および樹脂成分（Ｂ11）のＬＤＰＥを重量比で７５：２５の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Ｃ1を得た。
第Ｉ層として厚さが１５μｍ、片面にコロナ処理の施された２軸延伸ポリアミドフィルムであって、このフィルムのコロナ処理面に、イソシアネート系アンカーコート剤（大日精化工業製、３６００Ａ／Ｂ、配合比７：３）とオゾン処理を併用したもの、第II層及び第IV層に（Ｂ13）を各々５μｍ、第III層に（Ｂ31）を１０μｍ、第Ｖ層に上記調製した組成物Ｃ1を２５μｍとした層構成で樹脂温度２４６℃、総層厚が４５μｍ、速度５０ｍ／分で共押出ラミネートして積層体を得た。
【００８８】
［実施例２］
樹脂成分（Ａ2）のエチレン−α−オレフィン共重合体、樹脂成分（Ａ1）のエチレン−α−オレフィン共重合体、樹脂成分（Ｂ12）のＥＶＡを、重量比が各々３０、４０、３０となるように配合し、それ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Ｃ2を得た。
この組成物Ｃ2を第Ｖ層として用いたこと以外は実施例１と同様にして、積層体を製造し、評価した。
【００８９】
［実施例３］
第II層及び第IV層として、（Ｂ14）を用いたこと以外は実施例１と同様にして、積層体を製造し、評価した。
［実施例４］
第Ｉ層として、コロナ処理の施された１２μｍ厚のＰＥＴを用い、そのコロナ処理面にイソシアネート系アンカーコート剤（大日精化工業製、３６００Ａ／Ｂ、配合比７：３）を塗工した。このアンカーコート面上に、第II層の第Ｉ層側に組成物Ｃ1を５μｍ、第II層及び第IV層に（Ｂ14）を各々５μｍ、第III層として（Ｂ31）を１０μｍ、第Ｖ層として組成物Ｃ1を２０μｍ、即ち、ＰＥＴ／Ｃ1／Ｂ14／Ｂ31／Ｂ14／Ｃ1の４種６層構成とし、樹脂温度２４０℃でオゾン処理を行いながら、共押出ラミネートした。
【００９０】
［比較例１］
第Ｖ層として（Ｂ12）のＥＶＡを使用したこと以外は実施例１と同様にして共押出ラミネートして積層体を製造した。
ヒートシール強度が劣るものであった。
【００９１】
［比較例２］
樹脂成分（Ｃ1）の代りに、樹脂成分（Ｂ21）のＬＬＤＰＥを使用したこと以外は、実施例１と同様の操作を行った。評価結果を表１に示す。
ヒートシール強度が劣ることがわかる。
【００９２】
【表１】

【００９３】
【発明の効果】
本発明の積層体は、透明性、衝撃強度、低温ヒートシール性、ヒートシール強度、夾雑物ヒートシール性等のヒートシール特性、突刺強度等に優れ、共押出成形した際にネックイン、ドローダウン（延展性）等の成形性に優れる。また、樹脂成分の溶出が少なく、本積層体を使用して製袋した場合に、内容物への滲み出しが少なく、例えば、浸物、乳製品、レトルト食品、冷凍食品、調味料、菓子などの食品に代表される各種包装材料、各種液体輸送用包材に好適である。また、製袋したときに、電子レンジによる内容物の加熱に適応し、また、共押出成形に行った際に、偏肉精度、層間の界面の安定性に優れている。
【図面の簡単な説明】
【図１】 成分（Ａ1）についての連続昇温溶出分別法による溶出温度−溶出量曲線のグラフである。
【図２】 成分（Ａ2）についての連続昇温溶出分別法による溶出温度−溶出量曲線のグラフである。[0001]
BACKGROUND OF THE INVENTION
  The present invention is excellent in heat seal properties such as low temperature heat sealability and heat seal strength, transparency, impact strength, puncture strength, etc., and has a gas barrier property with a strong waist.Packaging materialIt is about.
[0002]
[Prior art]
In recent laminates used for food packaging materials and food packaging bags, heat sealing properties such as high heat-sealing strength, low-temperature heat-sealing properties, and contaminant heat-sealing properties during high-speed bag making, high gas against oxygen and water vapor Barrier properties, flexibility, puncture resistance, impact resistance, etc. are required.
Therefore, conventionally, an aluminum foil, a film on which aluminum, silicon oxide, aluminum oxide or the like is deposited is used as the barrier material layer in order to improve the gas barrier property.
[0003]
[Problems to be solved by the invention]
However, recently, along with the diversification of eating habits, there is a demand for suitability for heating by a microwave oven, visibility of contents from the outside, suitability for incineration due to environmental problems, suitability for recycling, and the like.
Conventionally, as a sealant layer, a low density polyethylene (hereinafter referred to as LDPE) obtained by polymerization by a high pressure method, an ethylene-vinyl acetate copolymer (hereinafter referred to as EVA), a linear chain obtained by polymerization with a Ziegler catalyst. In general, a low-density polyethylene (hereinafter referred to as LLDPE), ethylene-propylene, 1-butene copolymer or the like is used alone or in combination.
However, although LDPE is excellent in molding processability, heat sealing properties such as low-temperature heat sealing properties, heat sealing strength, foreign matter heat sealing properties, hot tack properties, etc. are inferior, resulting in insufficient strength and suitability for high-speed filling. have.
EVA has improved heat seal characteristics, hot tack properties, etc. compared to LDPE, but is insufficient in terms of suitability for high-speed filling, and there are handling problems such as requiring labor to replace the resin. In addition, there is a problem that odor is generated during lamination processing which is molded at a high temperature.
In addition, LLDPE obtained by polymerization with Ziegler catalyst has excellent heat seal strength, mechanical strength, etc., but has insufficient physical properties such as low temperature heat seal properties, foreign matter heat seal properties, hot tack properties, and high-speed filling suitability. However, molding processability is also a problem.
[0004]
  The present invention has been made to solve the above problems, and has high heat seal strength and low temperature heat seal properties during high-speed bag making, heat seal properties such as foreign matter heat seal properties, and high gas barrier properties against oxygen, water vapor, and the like. Gas barrier properties with good flexibility, puncture resistance, impact strength, microwave heating suitability, transparency, etc.Packaging materialIs to provide. In addition, it has excellent moldability such as neck-in and draw-down (extensibility) at the time of co-extrusion lamination molding, thickness deviation accuracy, and interlayer stability.Packaging materialIs intended to provide.
[0005]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have determined a specific ethylene homopolymer or ethylene-α / olefin copolymer as a sealant layer of a laminate comprising a base material and a barrier material for use as a packaging material or packaging bag. Or a layer using an ethylene homopolymer or ethylene / α-olefin copolymer using a specific catalyst and a gas barrier material layer to achieve the above object. As a result, the present invention has been completed.
[0006]
  Barrier properties of the present inventionPackaging materialIs
  Laminated body having at least a base material layer, a barrier material layer, and a sealant layerPackaging material (excluding inner bag for bag-in-box)Because
  The sealant layer is(F)The ethylene homopolymer or the ethylene / α-olefin copolymer (A) satisfying the requirements ofThe
  The ethylene homopolymer or ethylene / α-olefin copolymer (A) includes at least an organic cyclic compound having a conjugated double bond and a periodic table. IV Obtained by (co) polymerizing ethylene or ethylene and α-olefin in the presence of a catalyst containing a transition metal compound of group IIIIt is characterized by this.
  (A) Density is 0.86 to 0.97 g / cm^Three,
  (B) Melt flow rate is 0.01-100 g / 10 min.
  (C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0,
  (D) The composition distribution parameter Cb is1 . 08-2 . 00,
  (E) There are substantially a plurality of peaks in the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method,
  (F) Orthodichlorobenzene-soluble amount X ( wt% ), Density d and MFR (melt flow rate) satisfy the following relationship:
  d-0 . 008 log MFR ≧ 0 . In case of 93
  X <2 . 0
  d-0 . 008 log MFR <0 . In case of 93
  X <9 . 8x Ten ^Three × ( 0 . 9300-d + 0 . 008 logMFR) ² +2 . 0
  At this time, the ethylene homopolymer or ethylene / α-olefin copolymer (A)The temperature on the high temperature side of a plurality of peaks in the elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF) is between 85 and 100 ° C.It is desirable.
  Further, the ethylene homopolymer or ethylene / α-olefin copolymer (A)Is polymerized using the following catalysts a1 to a4It is desirable that
  a 1 : General formula Me ¹ R ¹ _p R ² _q (OR ^Three ) _r X ¹ _4-pqr A compound represented by
  (Where Me ¹ Represents zirconium, titanium, hafnium, R ¹ And R ^Three Are each a hydrocarbon group having 1 to 24 carbon atoms or a trialkylsilyl group, R ² Is 2,4- Pentandionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonate ligand or derivative thereof, X ¹ Represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r are 0 ≦ p <4, 0 ≦ q <4, 0 ≦ r <4 and 0 ≦, respectively. p + q + r It is an integer satisfying the range of ≦ 4. )
  a 2 : General formula Me ² R ^Four _m (OR ^Five ) _n X ² _zmn A compound represented by
  (Where Me ² Is periodic table I ~ III Group element, R ^Four And R ^Five Are each a hydrocarbon group having 1 to 24 carbon atoms, X ² Is a halogen atom or a hydrogen atom (however, X ² Me is a hydrogen atom ² Is the periodic table III Z is Me) ² M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z. )
  a Three : An organic cyclic compound having a conjugated double bond.
a Four : A modified organoaluminum oxy compound containing an Al-O-Al bond and / Or a boron compound.
  The sealant layer is composed of 98 to 10% by weight of the ethylene homopolymer or ethylene / α-olefin copolymer (A) and 2 to 90% by weight of the other ethylene polymer (B). It is desirable that
  At this time, it is desirable that the composition satisfies the following requirements (c1) to (c3).
  (C1) Melt flow rate of 1 to 100 g / 10 min
  (C2) The die swell ratio (DSR) at 190 ° C. is 1.10-3.00.
  (C3) Melt tension (MT) at 190 ° C. is 0.5 to 4.0 g
  In addition, these barrier propertiesPackaging materialIn this case, it is desirable that the barrier material layer and the sealant layer are simultaneously formed by coextrusion lamination.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a packaging material used for a bag or the like containing various contents, and the packaging material is a laminate having at least three layers of a base material layer, a barrier material layer, and a sealant layer. .
[Sealant layer]
<(A) Ethylene homopolymer or ethylene / α-olefin copolymer>
In the laminate of the present invention, an ethylene resin composition containing a specific ethylene homopolymer or ethylene / α-olefin copolymer or another ethylene polymer together with the specific ethylene homopolymer or ethylene / α-olefin copolymer is used for the sealant layer.
This ethylene homopolymer or ethylene / α-olefin copolymer in the present invention satisfies the following requirements (a) to (d).
(A) Density is from 0.86 to 0.97 g / cm^Three,
(B) Melt flow rate is 0.01-100 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0,
(D) Composition distribution parameter Cb is 2.00 or less
[0008]
The α-olefin in the ethylene / α-olefin copolymer (A) of the present invention preferably has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. For example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned.
In addition, the content of these α-olefins in the copolymer is desirably 30 mol% or less, preferably 3 to 20 mol%.
[0009]
The ethylene homopolymer or ethylene / α-olefin copolymer (A) in the present invention has a density of 0.86 to 0.97 g / cm.^ThreeIt is. Preferably 0.90 to 0.945 g / cm^ThreeMore preferably, 0.91-0.935 g / cm^ThreeIt is in the range. Density is 0.86g / cm^ThreeIf it is less than 1, the heat resistance is poor and the anti-blocking property is poor. 0.97g / cm^ThreeIf it exceeds, it will be too hard and the tear strength, impact drop strength, etc. will be low.
The melt flow rate of component (A) (hereinafter referred to as MFR) is 0.01-100 g / 10 min, preferably 0.1-50 g / 10 min, more preferably 0.5-30 g / 10 min. More preferably, it is the range of 1.0-20 g / 10min. When the MFR is less than 0.01 g / 10 min, the workability (drawdown property, etc.) is poor, and when it exceeds 100 g / 10 min, the mechanical strength is weak.
[0010]
The molecular weight distribution Mw / Mn of the component (A) is in the range of 1.5 to 5.0. When Mw / Mn is less than 1.5, molding processability is inferior, and when it exceeds 5.0, mechanical strength such as impact resistance is inferior.
In addition, molecular weight distribution (Mw / Mn) calculates | requires a weight average molecular weight (Mw) and a number average molecular weight (Mn) by gel permeation chromatography (GPC), and calculates those ratios (Mw / Mn). Desired.
[0011]
The composition distribution parameter (Cb) of the component (A) of the present invention needs to be 2.00 or less. If the composition distribution parameter (Cb) is larger than 2.00, it is easy to block, heat sealability is poor, and low molecular weight or high branching component oozes out on the resin surface, resulting in hygiene problems. It is.
The composition distribution parameter (Cb) is measured as follows.
The sample was dissolved in orthodichlorobenzene (ODCB) to which an antioxidant was added by heating at 135 ° C. to a concentration of 0.2% by weight, and then transferred to a column packed with diatomaceous earth (Celite 545). Cool to 25 ° C. at a cooling rate of 0.1 ° C./min to deposit the copolymer sample on the celite surface. Next, the column temperature is raised stepwise up to 120 ° C. in steps of 5 ° C. while ODCB is allowed to flow through the column on which the sample is deposited at a constant flow rate. Then, a solution containing an elution component corresponding to each temperature is collected. The solution is cooled, methanol is added, the sample is precipitated, filtered and dried to obtain elution samples at each temperature. The weight fraction and the degree of branching (number of branches per 1000 carbon atoms) of each of the sorted samples are measured. The degree of branching¹³Measured by C-NMR.
[0012]
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.
[0013]
Next, the weight fraction w of each fraction_iThe degree of branching per elution temperature of 5 ° C._iChange amount (b_i-B_i-1) Divided by relative concentration c_iAnd plot the relative concentration against the degree of branching to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.
Cb = (Σc_j・ B_j ²/ Σc_j・ B_j) / (Σc_j・ B_j/ Σc_j)
Where c_jAnd b_jAre the relative concentration and the degree of branching of the jth segment, respectively. The composition distribution parameter Cb becomes 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution widens.
[0014]
Many proposals have been made for the method of expressing the composition distribution of the ethylene / α-olefin copolymer. For example, in Japanese Patent Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (logarithmic normal distribution) with respect to the number of branches of each fractionated sample obtained by solvent fractionation of the sample. The ratio of the weight average branching degree (Cw) and the number average branching degree (Cn) is obtained. This approximate calculation is less accurate when the number of sample branches and the cumulative weight fraction deviate from the logarithmic normal distribution, and the correlation coefficient R2 is considerably low when measurements are performed on commercially available LLDPE, and the accuracy of the values is not sufficient. Further, the Cw / Cn measurement method and the numerical processing method are different from those of Cb of the present invention. However, if a numerical comparison is made, the value of Cw / Cn becomes considerably larger than Cb.
[0015]
The component (A) described above may be produced using a known catalyst such as a Ziegler catalyst or a Philips catalyst, but those prepared by the following two embodiments are particularly suitable.
One of them is homopolymerization of ethylene in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table, or ethylene and an α- having 3 to 20 carbon atoms. Those obtained by copolymerizing with olefins are preferred.
Among them, an ethylene homopolymer or an ethylene / α-olefin copolymer (hereinafter referred to as component (A1)) that satisfies the following requirements (a) to (f) is particularly suitable.
(A) Density is from 0.86 to 0.97 g / cm^Three
(B) Melt flow rate of 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) The composition distribution parameter Cb is 1.08 to 2.0.
(E) There are substantially multiple peaks in the elution temperature-elution volume curve by the continuous temperature elution fractionation method.
(F) The amount of orthodichlorobenzene soluble component X (wt%), density d, and melt flow rate (MFR) at 25 ° C. satisfy the following relationship:
(A) When d−0.008logMFR ≧ 0.93
X <2.0
(B) When d−0.008logMFR <0.93
X <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
[0016]
The other is to satisfy the following requirements (a) to (e) obtained in the presence of a ligand having a cyclopentadienyl skeleton and at least one catalyst containing a transition compound of Group IV of the periodic table. A satisfactory ethylene homopolymer or ethylene / α-olefin copolymer (hereinafter referred to as component (A2)).
(A) Density is from 0.86 to 0.97 g / cm^Three
(B) Melt flow rate of 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0.
(D) The composition distribution parameter Cb is 1.01 to 1.2.
(E) There is substantially one peak of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method.
[0017]
Here, as shown in FIG. 1, the component (A1) is composed of a special novel ethylene single weight having a plurality of peaks substantially in the elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF). As shown in FIG. 2, the component (A2) is substantially an elution temperature-elution amount curve obtained by the same continuous temperature rising elution fractionation method (TREF). Ethylene alone with a typical metallocene catalyst obtained in the presence of at least one catalyst having a peak and having a cyclopentadienyl skeleton and a group IV transition metal compound in the periodic table It is a polymer or an ethylene / α-olefin copolymer, and the components (A1) and (A2) are clearly distinguished.
[0018]
<< Ingredient (A1) >>
In the component (A1), the molecular weight distribution (Mw / Mn) is in the range of 1.5 to 5.0, more preferably 1.5 to 4.5, and still more preferably 1.8 to 4. It is desirable to be in the range of 0, more preferably 2.0 to 3.5.
In the component (A1), the composition distribution parameter Cb is more preferably from 1.08 to 2.00, further preferably from 1.10 to 1.80, more preferably from 1.15 to 1.50. It is desirable to be in the range.
[0019]
As described above, the special ethylene homopolymer or ethylene / α-olefin copolymer (A1) in the present invention is (e) in the elution temperature-elution amount curve determined by the continuous temperature rising elution fractionation method (TREF). There are multiple peaks. It is particularly preferable that the plurality of peak temperatures exist between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.
[0020]
The measuring method of TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) is added so that the sample concentration becomes 0.05% by weight, and heated and dissolved at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the glass bead surface. Next, the sample is sequentially eluted while increasing the column temperature at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent was set to a wave number of 2925 cm of asymmetric stretching vibration of methylene.^-1Is continuously detected by measuring the absorption with respect to an infrared detector. From this value, the concentration of the ethylene / 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, a relatively fine peak that cannot be detected by a fractionation method can be detected.
[0021]
Further, as described above, in this component (A1), (f) the relationship between the amount X (% by weight) of the ODCB soluble content at 25 ° C. and the density d and MFR is such that the values of d and MFR are:
When d-0.008logMFR ≧ 0.93 is satisfied,
X is less than 2% by weight, preferably less than 1% by weight,
If d-0.008logMFR <0.93,
X <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
Preferably,
X <7.4 × 10^Three× (0.9300-d + 0.008logMFR)²+1.0
More preferably,
X <5.6 × 10^Three× (0.9300-d + 0.008logMFR)²+0.5
It is desirable to satisfy this relationship.
[0022]
The amount ODCB soluble content X at 25 ° C. is measured by the following method. 0.5 g of sample is heated in 20 ml of ODCB at 135 ° C. for 2 hours to completely dissolve the sample and then cooled to 25 ° C. The solution is allowed to stand at 25 ° C. overnight and then filtered through a Teflon filter to collect the filtrate. The filtrate was subjected to an asymmetric stretching vibration wavenumber of methylene of 2925 cm using an infrared spectrometer.^-1The absorption peak intensity in the vicinity is measured, and the sample concentration is calculated using a calibration curve prepared in advance. From this value, the amount of soluble ODCB at 25 ° C. is obtained.
[0023]
The ODCB soluble content at 25 ° C. is a high branching component and a low molecular weight component contained in the ethylene / α-olefin copolymer, which causes a decrease in heat resistance and stickiness of the molded product surface, This content is preferably small because it causes blocking of the inner surface of the molded product. 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]
This ethylene homopolymer or ethylene / α-olefin copolymer (A1) has a narrow molecular weight distribution, an appropriate composition distribution, strong mechanical strength, and excellent heat sealability and antiblocking properties. Moreover, it is a polymer with good heat resistance.
This component (A1) is preferably polymerized with the following catalysts a1 to a4.
a1: General formula Me¹R¹ _pR² _q(OR^Three)_rX¹ _4-pqrA compound represented by
(Where Me¹Represents zirconium, titanium, hafnium, R¹And R^ThreeAre each a hydrocarbon group having 1 to 24 carbon atoms or a trialkylsilyl group, R²Is a 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonate ligand or derivative thereof, X¹Represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r are 0 ≦ p <4, 0 ≦ q <4, 0 ≦ r <4 and 0 ≦ p + q + r ≦ 4, respectively. An integer that satisfies the range. )
a2: General formula Me²R^Four _m(OR^Five)_nX² _zmnA compound represented by
(Where Me²Is the Group I-III element of the periodic table, R^FourAnd R^FiveAre each a hydrocarbon group having 1 to 24 carbon atoms, X²Is a halogen atom or a hydrogen atom (however, X²Me is a hydrogen atom²Is only for Group III elements of the Periodic Table), z is Me²M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z. )
a3: An organic cyclic compound having a conjugated double bond.
a4: a modified organoaluminum oxy compound and / or boron compound containing an Al—O—Al bond.
[0025]
Each of these catalyst components will be described in detail.
The catalyst component a1 has the general formula Me¹R¹ _pR² _q(OR^Three)_rX¹ _4-pqrIn the formula of the compound represented by¹Z represents zirconium, titanium, and hafnium, and a plurality of them can be used, but it is particularly preferable that zirconium having excellent weather resistance of the copolymer is included. R¹And R^ThreeThe hydrocarbon group having 1 to 24 carbon atoms preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms.
Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And aryl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofoyl group. These may be branched.
[0026]
Examples of the compound represented by the general formula of the catalyst component a1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tributoxymonochlorozirconium, Examples include dibutoxydichlorozirconium, tetrabutoxytitanium, and tetrabutoxyhafnium. Particularly, Zr (OR) such as tetrapropoxyzirconium and tetrabutoxyzirconium._FourCompounds are preferred, and two or more of these may be used in combination.
R²Specific examples of 2,4-pentanedionate ligands or derivatives thereof include tetra (2,4-pentanedionate) zirconium, tri (2,4-pentanedionate) chloride zirconium, di (2, 4-pentanedionato) dichloride zirconium, (2,4-pentandedionato) trichloride, di (2,4-pentandedionato) diethoxide zirconium, di (2,4-pentandedionato) di-n- Propoxide zirconium, di (2,4-pentanedionato) di-n-butoxide zirconium, di (2,4-pentandedionato) dibenzylzirconium, di (2,4-pentandedionato) dineo Foil zirconium,
Tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n-butoxy Examples include side zirconium, di (benzoylacetonato) diethoxide zirconium, di (dibenzoylacetonato) di-n-propoxide zirconium, di (benzoylacetonato) di-n-butoxide zirconium and the like.
[0027]
The catalyst component a2 has the general formula Me²R^Four _m(OR^Five)_nX² _zmnIn the formula of the compound represented by²Represents a group I-III element in the periodic table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. R4 and R^FiveAre each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically alkyl such as methyl group, ethyl group, propyl group, isopropyl group and butyl group. Group: alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenyl Examples thereof include aralkyl groups such as a butyl group and a neofoyl group. These may be branched. X²Represents a halogen atom such as fluorine, iodine, chlorine and bromine or a hydrogen atom. However, X²Me is a hydrogen atom²Is limited to the group III elements of the periodic table exemplified by boron, aluminum and the like.
[0028]
Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyllithium and ethyllithium; organomagnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; dimethylzinc and diethyl Organic zinc compounds such as zinc; organic boron compounds such as trimethylboron and triethylboron; trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethyl Organoaluminum compounds such as aluminum ethoxide and diethylaluminum hydride And the like.
[0029]
The organic cyclic compound having a conjugated double bond of the catalyst component a3 has one or more rings which are cyclic and have 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. A cyclic hydrocarbon compound having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms; the cyclic hydrocarbon compound is partially a hydrocarbon residue having 1 to 6 carbon atoms (typically having 1 to 12 alkyl groups or aralkyl groups) substituted with 2 or more, preferably 2 to 4 and more preferably 2 to 3 rings having 1 or 2 conjugated double bonds. An organosilicon compound having a cyclic hydrocarbon group having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon group is partially a hydrocarbon residue or alkali metal salt (sodium 1-6) Or lithium salt) Organosilicon compounds are included. Particularly preferred is one having a cyclopentadiene structure in any of the molecules.
[0030]
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.
[0031]
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.
[0032]
Specific examples of the organic cyclic hydrocarbon compound of component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, Cyclopolyene having 5 to 24 carbon atoms such as cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclopentadienylsilane, Examples include triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.
[0033]
The modified organoaluminum oxy compound and / or boron compound containing the Al—O—Al bond of the catalyst component a4 is reacted with an alkylaluminum compound and water to obtain a modified organoaluminum oxy compound usually referred to as aluminoxane. The molecule usually contains 1 to 100, preferably 1 to 50 Al—O—Al bonds. The modified organoaluminum oxy compound may be linear or cyclic. Examples of the boron compound include triethylaluminum tetra (pentafluorophenyl) borate (triethylammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate (dimethylanilinium tetra (pentafluorophenyl) borate), Examples thereof include butylammonium tetra (pentafluorophenyl) borate, N, N-dimethylanolinium tetra (pentafluorophenyl) borate, N, N-dimethylanrinium tetra (pentafluorophenyl) borate and the like.
[0034]
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 (water / Al molar ratio) between water and the organoaluminum compound is usually 0.25 / 1 to 1.2 / 1, preferably 0.5 / 1 to 1/1.
[0035]
The catalyst components a1 to a4 may be used as mixed and contacted as they are, but it is preferable to use them supported on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or particulate polymer carrier (a5) include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, thermoplastic resins, thermosetting resins, and the like. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like.
Specifically, SiO₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Etc. or a mixture thereof, SiO 2₂-Al₂O_Three, SiO₂-V₂O_Five, SiO₂-TiO₂, SiO₂-V₂O_Five, SiO₂-MgO, SiO₂-Cr₂O_ThreeEtc. Among these, SiO₂And Al₂O_ThreeThe main component is at least one component selected from the group consisting of:
As the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, polystyrene, Examples include norbornene, various natural polymers, and mixtures thereof.
[0036]
The inorganic carrier and / or the particulate polymer carrier can be used as they are, but preferably the carrier is contacted with an organoaluminum compound or a modified organoaluminum oxy compound containing an Al—O—Al bond as a pretreatment. It can also be used as component a5 after the treatment.
[0037]
<< Ingredient (A2) >>
In the ethylene homopolymer or ethylene / α-olefin copolymer component (A2) by the metallocene catalyst, the molecular weight distribution is in the range of 1.5 to 5.0, and is 1.5 to 4.5. It is more preferable that it is in the range of 1.8 to 3.5.
In the component (A2), the composition distribution parameter is desirably in the range of 1.01 to 1.2, preferably 1.02 to 1.18, more preferably 1.03 to 1.16.
[0038]
This metallocene-based ethylene homopolymer or ethylene / α-olefin copolymer (A2) is a group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton and, if necessary, a promoter. It is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing an organoaluminum compound and a support.
[0039]
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 (A2) 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.
[0040]
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).
[0041]
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.
[0042]
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.
[0043]
Specific examples of these are as follows. Dialkylmetallocenes include bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) ) Hafnium dimethyl, bis (cyclopentadienyl) hafnium diphenyl, and the like. Monoalkyl metallocenes include bis (cyclopentadienyl) titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, bis (cyclopentadienyl) zirconium phenyl chloride, etc. There is.
Moreover, pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride) and bis (pentamethylcyclopentadienyl) titanium diphenyl, which are monocyclopentadienyl titanocenes.
[0044]
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.
[0045]
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.
[0046]
Still other metallocenes include bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dimethyl, bis (cyclopentadienyl) vanadium dichloride, and the like.
[0047]
As an example of the transition metal compound of Group IV of the periodic table of the present invention, a ligand having a cyclopentadienyl skeleton represented by the following chemical formula, another ligand and a transition metal atom form a ring. There are also things.
[Chemical 1]

In the chemical formula, Cp is a ligand having the cyclopentadienyl skeleton, X is hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an arylsilyl group, an aryloxy group, an alkoxy group, an amide group, a silyloxy group, 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.
[0048]
Examples of the compound represented by the above chemical formula include (t-butylamide) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (t-butylamide) (tetramethylcyclopentadienyl) -1 , 2-ethanediyltitanium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride, (Ethylamide) (tetramethylcyclopentadienyl) methylenetan dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) sila Zirconium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (phenylphosphide) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, and the like.
[0049]
The co-catalyst as used in the present invention refers to a catalyst that can effectively make the transition metal compound of Group IV of the periodic table as a polymerization catalyst or can balance the ionic charge in a catalytically activated state.
Examples of the cocatalyst used in the present invention include benzene-soluble aluminoxanes of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, boron compounds, lanthanoid salts such as lanthanum oxide, tin oxide, and the like. Of these, aluminoxane is most preferred.
[0050]
The catalyst may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably an inorganic or organic porous oxide. Specifically, SiO₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Etc. or a mixture thereof, SiO 2₂-Al₂O_Three, SiO₂-V₂O_Five, SiO₂-TiO₂, SiO₂-MgO, SiO₂-Cr₂O_ThreeEtc.
[0051]
Examples of organoaluminum compounds include trialkylaluminums such as triethylaluminum and triisopropylaluminum; dialkylaluminum halides; alkylaluminum sesquihalides; alkylaluminum dihalides; alkylaluminum hydrides and organoaluminum alkoxides.
[0052]
"Production method"
The method for producing an ethylene homopolymer or ethylene / α-olefin copolymer (component (A)) according to the present invention comprises a gas phase polymerization method, a slurry polymerization method, a solution substantially free of a solvent in the presence of the catalyst. Manufactured by a polymerization method, etc., with substantially no oxygen, water, etc., but with aliphatic hydrocarbons such as butane, pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane and methylcyclohexane It is produced in the presence or absence of an inert hydrocarbon solvent exemplified by alicyclic hydrocarbons and the like. The polymerization conditions are not particularly limited, but the polymerization temperature is usually from 15 to 350 ° C., preferably from 20 to 200 ° C., more preferably from 50 to 110 ° C. The polymerization pressure is usually from normal pressure to 70 kg / in the low-medium pressure method. cm²G, preferably normal pressure to 20 kg / cm²G, usually 1500kg / cm for high pressure method²G or less is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from about 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 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 hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other.
[0053]
In the ethylene homopolymer or ethylene / α-olefin copolymer of the present invention, if the catalyst component at the time of polymerization is substantially free of halogen such as chlorine, the resulting polymer does not contain these halogens, Therefore, it is excellent in chemical stability and hygiene, and is suitable for food, hygiene and medical related applications. In addition, when applied to packaging materials and containers related to electric parts, electric wire members, and microwave ovens, it has a feature that the occurrence of rust on surrounding metal parts can be suppressed.
[0054]
<(B) Other ethylene polymer>
As the resin constituting the sealant layer in the present invention, in addition to the component (A) described above, it is desirable to mix (component (B)) with another ethylene polymer.
Examples of such other ethylene polymers include an ethylene polymer (B1) obtained by a high pressure radical polymerization method and / or a density of 0.86 to 0.97 g / cm.^ThreeThe ethylene-α-olefin copolymer (B2) is preferred.
[0055]
The ethylene polymer obtained by the above (B1) high pressure radical polymerization method has a density of 0.91 to 0.94 g / cm by the high pressure radical polymerization method.^ThreeEthylene homopolymer (low density polyethylene (LDPE): B11), ethylene / vinyl ester copolymer (B12), copolymer of ethylene and α, β-unsaturated carboxylic acid or its derivative (B13), etc. Can be mentioned.
[0056]
(B11) The low density polyethylene 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 from 0.91 to 0.94 g / cm.^Three, Preferably 0.912 to 0.935 g / cm^ThreeMore preferably, 0.912 to 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.
[0057]
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.
[0058]
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 / 10 minutes.
[0059]
The density is from 0.86 to 0.97 g / cm.^ThreeThe ethylene-α-olefin copolymer (B2) of the present invention is a high-, medium- and low-pressure method using a conventionally known Ziegler-type catalyst or Phillips-type catalyst, and other known methods. -Copolymers with olefins. This generally has a broader molecular weight distribution or composition distribution than component (A), and a density of 0.94 to 0.97 g / cm.^ThreeHigh density polyethylene, 0.91-0.94g / cm^ThreeLinear low density polyethylene (LLDPE), density 0.86-0.91 g / cm^ThreeUltra low density polyethylene (hereinafter referred to as VLDPE), density 0.86-0.91 g / cm^ThreeAnd ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber.
[0060]
The high density polyethylene has a density of 0.94 to 0.97 g / cm.^Three, Preferably 0.95 to 0.97 g / cm^ThreeThe melt flow rate is from 0.01 to 50 g / 10 min, preferably from 0.05 to 30 g / 10 min, particularly preferably from 0.1 to 20 g / 10 min.
[0061]
The LLDPE has a density of 0.91 to 0.94 g / cm.^Three, Preferably 0.91-0.93 g / cm^ThreeAnd an MFR of 0.05 to 50 g / 10 min, preferably 0.1 to 30 g / 10 min. 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 deteriorates, and if it exceeds 50 g / 10 min, the impact resistance and heat seal characteristics may be lowered.
[0062]
The VLDPE has a density of 0.86 to 0.91 g / cm.^Three, Preferably 0.88-0.905 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.
[0063]
The 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).
[0064]
Among the above (B) other ethylene polymers, low density polyethylene by high pressure radical polymerization and / or density of 0.86 to 0.95 g / cm.^ThreeThe ethylene-α-olefin copolymer is preferred.
[0065]
When the resin composition constituting the sealant layer is composed of the component (A) and the component (B), the blending ratio is 98 to 10% by weight for the component (A) and 2 to 90% by weight for the component (B). The component (A) is preferably 95 to 60% by weight, the component (B) is 5 to 40% by weight, more preferably the component (A) is 90 to 70% by weight, and the component (B) is 10 to 30% by weight. is there. The presence of the component (B) of the composition improves the moldability such as drawdown and neck-in, but when the component (A) is less than 10% by weight, the puncture strength, low temperature heat seal Effects, heat seal properties such as heat seal strength, foreign matter heat seal properties, and hot tack properties are reduced.
[0066]
Specific examples of the composition of the present invention include (A1 + B11), (A2 + B11), (A1 + B11 + B21), (A2 + B11 + B21), (A1 + B12 + B21), (A2 + B12 + B21), (A1 + B11 + B22), (A2 + B11 + B11) (B1 + A11) (A1 + A2 + B11 + B21) (A1 + A2 + B11 + B22) and the like (where A1 :, A2: two aspects of component (A) described above, B11: LDPE, B12: EVA, B21: LLDPE, B22: VLDPE).
In particular, the blending amount in the case of ((A1 or A2) + B11 + (B21 or B22)), that is, the combination of the ethylene-α-olefin copolymer (A1 or A2) of the present invention with LDPE or LLDPE is (A) component 50 It is desirable to select within a range of ˜90 wt%, (B1) component 5 to 35 wt%, and (B2) component 5 to 35 wt%.
[0067]
The composition containing the component (A) and the component (B) has (c1) a melt flow rate (MFR) of 1 to 100 g / 10 minutes, (c2) a die swell ratio (DSR) at 190 ° C. of 1.10 to 3 .00, (c3) The melt tension (MT) at 190 ° C. is preferably in the range of 0.5 to 4.0 g. When the above (c1) MFR is less than 1 g / 10 min, molding processability is inferior, and when it exceeds 100 g / 10 min, 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.
[0068]
At this time, when the component (A1) described above is used as the component (A), the melt flow rate is more preferably 1 to 50 g / 10 minutes, and more preferably 1.5 to 40 g / 10 minutes. More preferably, it is 2.0-30 g / 10 min.
Further, the die swell ratio (DSR) at 190 ° C. is more preferably 1.10 to 2.00, further 1.10 to 1.70, and further preferably 1.10 to 1.65.
Further, the melt tension (MT) at 190 ° C. is more preferably 0.5 to 4.0 g, and further preferably in the range of 0.5 to 2.5 g.
[0069]
Further, when the component (A2) described above is used as the component (A), the melt flow rate (MFR) is more preferably 1 to 50 g / 10 minutes, and further preferably 1.5 to 40 g / 10 minutes. More preferably, it is in the range of 2.0 to 30 g / 10 min.
Furthermore, the die swell ratio (DSR) at 190 ° C. is preferably 1.30 to 3.00, more preferably 1.30 to 2.80, and still more preferably 1.30 to 2.50.
Further, the melt tension (MT) at 190 ° C. is preferably in the range of 0.5 to 4.0 g, preferably 0.5 to 3.5 g.
[0070]
The DSR can be obtained as follows, for example.
Using the melt indexer used in JIS K6760, the cylinder is filled with the sample, preheated at a cylinder temperature of 190 ° C. for 4 minutes, and then a constant load of 2.16 kg is applied. When the lowering of the piston reaches a steady state, the strand is cut once, and then a strand having a length of about 1 inch is collected 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 is obtained by the following equation.
DSR = D / D₀
[0071]
The component (A) and the component (B) can be blended by a known method generally used as a blending method of the resin composition. For example, the component (A), the component (B), and other addable polyolefin resins can be simply dry blended during film formation. 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. Moreover, you may use batch type melt-kneaders, such as a Banbury mixer, as needed.
[0072]
The resin layer constituting the sealant layer includes an organic or inorganic filler, a tackifier, an antioxidant, an antistatic agent, an antifogging agent, an organic or inorganic pigment, a dispersant, a nucleating agent, a foaming agent, and a flame retardant. , Known additives such as cross-linking agents, UV inhibitors, (un) saturated fatty acid amides, metal salts of (un) saturated higher fatty acids, etc. may be added within a range that does not substantially impair the properties of the present invention. it can.
Among these additives, a lubricant, a tackifier, and an inorganic filler are preferably used in order to further improve workability.
Examples of lubricants include fatty acid amides such as oleic acid amide, stearic acid amide, and erucic acid amide; fatty acid glycerin ester compounds such as stearic acid monoglyceride, stearic acid diglyceride, oleic acid monoglyceride, and oleic acid diglyceride; Is mentioned.
Examples of the inorganic filler include light and heavy calcium carbonate, talc, silica, zeolite, magnesium carbonate, feldspar and the like.
Examples of tackifiers include polybutene, castor oil derivatives, sorbitan fatty acid esters, rosin and rosin derivatives, tackifiers such as petroleum resins and hydrogenated products thereof, rubber, and the like. These tackifiers can be blended in the range of 0.5 to 20 parts by weight.
As the pigment, carbon black, titanium white and the like, and various commercially available colorant masterbatches are preferably used.
[0073]
Furthermore, additives for obtaining appropriate slipping property, antistatic property and antifogging property can also be blended.
Specifically, as sorbitan fatty acid ester, sorbitan monooleate, sorbitan monolaurate, sorbitan monobehenate, sorbitan monostearate, etc .; as glycerol fatty acid ester, glycerol monooleate, glycerol monostearate, glycerol monolaurate, glycerol Monobehenate, etc .; as polyglycerol fatty acid ester, diglycerol monolaurate, diglycerol monostearate, diglycerol monooleate, tetraglycerol monooleate, tetraglycerol monostearate, hexaglycerol monolaurate, hexaglycerol monooleate, In addition to decaglycerin monolaurate, decaglycerin monostearate, decaglycerin monooleate, etc., fatty acid esters of polyhydric alcohols and These ethylene oxide adducts, higher fatty acid amides and their ethylene oxide adducts, does not but such higher fatty acid alkanolamides as being limited thereto.
These additives are used alone or as a mixed composition, and the addition amount is usually 0.01 to 0.5% by weight, preferably 0.05 to 0.3% by weight. If the amount added is less than 0.01% by weight, the effect of modifying the film is not sufficient. If the amount added exceeds 0.5% by weight, the amount of protrusion on the surface of the film is large and the film becomes sticky. This is not preferable because a problem such as reduction occurs.
[0074]
[Base material layer]
As the base material layer of the present invention, cellophane, stretched nylon, non-stretched nylon, special nylon (MXD6 etc.), nylon base materials such as K-nylon (polyvinylidene fluoride coat), stretched PET, unstretched PET, K-PET Such as PET (polyethylene terephthalate) base material, expanded PP (OPP), unstretched PP (CPP), K-PP, co-extruded film PP and other polypropylene base materials, LDPE film, LLDPE film, EVA film, stretched LDPE Examples thereof include synthetic resin film base materials such as films, stretched HDPE films, and polystyrene films.
Moreover, when using for the use which does not require the microwave heating aptitude, aluminum vapor deposition PET (VMPET), aluminum vapor deposition PP, etc. can also be used.
These can be printed.
If necessary, various pretreatments such as corona treatment, flame treatment, plasma treatment, ultraviolet ray treatment, anchor coat treatment, and ozone treatment may be performed.
[0075]
[Barrier material layer]
The barrier material layer in the present invention is composed of a material that blocks gas such as oxygen or water vapor to prevent deterioration of the contents, and is a saponified product of polyvinyl alcohol, ethylene-vinyl acetate copolymer, Examples thereof include metal foils such as aluminum foil. In particular, a saponified product of an ethylene-vinyl acetate copolymer having low gas permeability and water vapor permeability and good extrusion laminate moldability is preferred.
These materials may be overlapped with the above-described base materials, for example, base materials having barrier properties such as aluminum vapor-deposited PET (VMPET) and aluminum vapor-deposited PP.
[0076]
(Laminated structure)
The laminated body of the present invention may further have other layers as long as it has the above-described base material layer, barrier material layer, and sealant layer. For example, the base material layer and the barrier material layer It is desirable to provide an adhesive layer between the barrier material layer and the sealant layer.
The adhesive layer (referred to as “layer II”) interposed between the base material layer (referred to as “layer I”) and the barrier material layer (referred to as “layer III”) is the same as the base material layer. It is desirable that the layers be laminated when they are pressure-bonded by a cooling roll and a nip roll by an extrusion lamination molding method, and the barrier material layer is laminated in a molten state at the joining portion of the flow path at the time of co-extrusion.
As such an adhesive layer (II layer), a random copolymer of ethylene and an acid or an acid anhydride, or a polyethylene or polyethylene copolymer modified with an acid or an acid anhydride is suitable. Here, the acid is preferably an acid having an unsaturated double bond in the molecule, such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. As the acid anhydride, anhydrides of these acids are suitable. These acids or acid anhydrides can be used alone or in combination of two or more for copolymerization or modification. Moreover, it can also be used in combination with another copolymerizable monomer. Here, examples of the polyethylene copolymer include EVA, an ethylene-propylene copolymer, and an ethylene-1-butene copolymer. These resins may be used alone or in combination with other resins as necessary.
[0077]
In addition, an adhesive layer (referred to as “IVth layer”) interposed between the barrier material layer (IIIth layer) and the sealant layer (referred to as “Vth layer”) is used for the flow path during coextrusion. It is desirable to laminate in a molten state with each layer at the junction.
As such an adhesive layer (IV layer), the same material as that of the above-mentioned II layer can be applied. Moreover, those resins can be used alone or in combination with other resins if necessary.
The II layer and the IV layer may be supplied from different extruders as different resin materials, but if they are the same resin material, they can be used by diverting from one extruder. Efficiency is good.
[0078]
Moreover, as a laminated body of this invention, you may laminate | stack not only these 1st layer-Vth layer, but another layer.
For example, an unsaturated carboxylic acid or a derivative thereof is graft-modified between a polyolefin layer such as polyethylene, an ionomer resin, various polyolefins and / or rubber between the I layer and the II layer or outside the I layer. An acid-modified polyolefin layer or the like may be provided.
For example, ONy / (acid-modified PE / EVOH / acid-modified PE / SS), ONy / (copolymer 1 / EVOH / copolymer 1 / SS), ONy / (copolymer 2 / EVOH / copolymer 2) / SS), ONy / (copolymer 3 / EVOH / copolymer 3 / SS), ONy / (copolymer 1 / EVOH / copolymer 3 / SS), ONy / (PE / acid-modified PE / EVOH) / Acid-modified PE / SS), PET / (copolymer 2 / EVOH / copolymer 2 / SS), ONy / (LDPE / copolymer 2 / EVOH / copolymer 2 / SS) and the like. Here, ONy: stretched nylon, PE: polyethylene resin, acid-modified PE: acid or acid anhydride-modified polyethylene, copolymer 1: ethylene-unsaturated acid or acid anhydride copolymer, copolymer 2: ethylene —Unsaturated acid or acid anhydride—ester copolymer, copolymer 3: Metal salt of ethylene-unsaturated acid or acid anhydride copolymer, SS: sealant layer.
The sealant layer is preferably located in the innermost layer.
[0079]
As a method for producing the laminate of the present invention, a method of laminating the II layer to the V layer on the I layer by a coextrusion lamination molding method is suitable.
The coextrusion laminating apparatus for producing the laminate of the present invention is preferably an apparatus capable of simultaneously coextruding at least four layers from the II layer to the V layer. Further, it is preferable to provide at least three extruders for extruding at least three types of resins (when the same resin is used for the II layer and the IV layer) separately. Co-extrusion methods such as feed block method and black box method such as pre-die co-extrusion type and multi-manifold type co-extrusion co-extrusion method and multi-slot co-extrusion type co-extrusion method are used. be able to.
[0080]
【Example】
Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.
[0081]
Test methods in Examples and Comparative Examples are as follows.
(Physical property test method)
density:
Conforms to JIS K6760.
MFR:
Conforms to JIS K6760.
Mw / Mn:
GMMHR-H (S) manufactured by Tosoh Corporation was used for the GPC (Waters 150 type) ODCB 135 ° C. column. According to a calibration curve method using a PS standard sample.
NMR:
GX-270 manufactured by JEOL Ltd., ODCB Measured at 135 ° C.
[0082]
(Laminate evaluation method)
Oxygen transmission rate:
The oxygen transmission rate at a humidity of 90% and a temperature of 23 ° C. was measured with a MOCON 10/50 oxygen transmission rate tester. Saturate the outside of the layer I layer with oxygen and flow a carrier gas (nitrogen + 1% hydrogen mixed gas) inside the layer V layer 50 cm.²Measure the amount of oxygen permeating through the laminate of 1 m²It was converted into a numerical value of permeation amount per 24 hours.
Hayes:
Measured according to JIS K7105.
Low temperature heat sealability:
Using a heat seal tester (manufactured by Tester Sangyo Co., Ltd.), seal bar width 5 mm, pressure 2 kg / cm²The seal temperature was sealed at 5 ° C. for 1 second and allowed to cool. The seal part was cut into a strip shape with a width of 15 mm, and 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.
Heat seal strength:
Using the above heat seal tester, pressure 2 kg / cm²After heat sealing at a sealing temperature of 150 ° C. and a sealing time of 3 seconds, the mixture was allowed to cool. The seal part was cut into a strip shape with a width of 15 mm, and the seal part was peeled off at 300 mm / min with a tensile tester to determine the strength.
[0083]
(Production of ethylene / α-olefin copolymer A1)
(1) Preparation of solid catalyst
Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen, followed by dipropoxydichlorozirconium (Zr (OPr)₂Cl₂) 28 g and 48 g of methylcyclopentadiene were added and 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the 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 under nitrogen (No. 1), and then pre-baked at 400 ° C. for a predetermined time in advance (Fuji Devison, grade # 952, surface area 300 m).²/ G) After adding 1400 g, the whole amount of the solution B was added and stirred at room temperature. Subsequently, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This was designated Catalyst D.
[0084]
(2) Sample polymerization
Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 70 ° C., total pressure 20 kgf / cm²G was copolymerized with ethylene and 1-hexene. Polymerization was carried out by continuously supplying the catalyst D, and the polymerization was carried out while continuously supplying each gas in order to keep the gas composition in the system constant. The produced copolymer is designated as resin component A1. The physical properties of the resin component A1 are as follows.
(A1) Ethylene / 1-hexene copolymer
(I) Density: 0.910 g / cm^Three
(B) MFR: 11g / 10min
(C) Molecular weight distribution (Mw / Mn): 2.6
(D) Composition distribution parameter Cb: 1.22
(E) TREF peak temperature: 83.2, 96.5 ° C
(F) d-0.008 log MFR: 0.902
ODCB soluble content (%) = 1.5 <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
[0085]
(Production of ethylene-α-olefin copolymer A2)
A stainless steel autoclave equipped with a stirrer was purged with nitrogen and purified toluene was added. Next, 1-hexene was added, and further a mixed solution of ethylenebis (indenyl) zirconium dichloride (0.02 mmol as Zr) methylalumoxane [MAO] (MAO / Zr = 100 [molar ratio]) was added, and then 80 The temperature was raised to ° C. Next, polymerization was started by adding ethylene, and polymerization was continued for 1 hour while maintaining the total pressure while continuously polymerizing ethylene to obtain (A2) an ethylene / 1-hexene copolymer. (A2) Ethylene / 1-hexene copolymer
(I) Density: 0.907 g / cm^Three
(B) MFR: 11g / 10min
(C) Molecular weight distribution (Mw / Mn): 2.4
(D) Composition distribution parameter (Cb): 1.05
(E) TREF peak temperature: 82.9 ° C
[0086]
(Other ethylene polymer (B))
B11: High-density low-density polyethylene (MFR: 8.5 g / cm^Three, Density: 0.919 g / cm^ThreeManufactured by Nippon Polyolefin Co., Ltd.); LDPE
B12: High-pressure ethylene-vinyl acetate copolymer (vinyl acetate concentration: 5% by weight, MFR: 5.0 g / cm^Three, Density: 0.923 g / cm^Three, Manufactured by Nippon Polyolefin Co., Ltd.); EVA
B13: High-pressure ethylene-methyl methacrylate-maleic anhydride copolymer (methyl methacrylate concentration: 5% by weight, maleic anhydride concentration: 1%)
B14: High-pressure method low density polyethylene (MFR: 21 g / 10 min, density: 0.917 g / cm^ThreeAcid polyolefin modified polyethylene obtained by adding 0.5 parts by weight of maleic anhydride and 0.1 parts by weight of organic peroxide to 240 ° C. in an extruder. .
B21: linear low density polyethylene polymer (gas phase method Ziegler catalyst product, comonomer: butene-1, MFR: 7.0 g / 10 min, density: 0.920 g / cm^Three, Manufactured by Nippon Polyolefin Co., Ltd.); LLDPE
B31: Saponified ethylene-vinyl acetate copolymer (MFR: 5 g / 10 min, density: 1.19 g / cm^Three, Manufactured by Kuraray Co., Ltd.)
[0087]
[Example 1]
0.09 parts by weight of an antioxidant and a steer for a composition in which the ethylene-α-olefin copolymer of the resin component (A1) and the LDPE of the resin component (B11) are blended at a weight ratio of 75:25 0.1 part by weight of calcium phosphate (manufactured by NOF Corporation) was added, mixed uniformly with a Henschel mixer for about 30 seconds, and then pelletized to obtain a composition C1.
A biaxially stretched polyamide film having a thickness of 15 μm as the first layer and having a corona treatment on one surface, and an isocyanate anchor coating agent (manufactured by Dainichi Seika Kogyo Co., Ltd., 3600 A / B, Mixing ratio 7: 3) combined with ozone treatment, (B13) is 5 μm for each of the II and IV layers, (B31) is 10 μm for the III layer, and the above prepared composition C1 is used for the V layer. A laminated body was obtained by coextrusion laminating at a resin temperature of 246 ° C., a total layer thickness of 45 μm, and a speed of 50 m / min.
[0088]
[Example 2]
The weight ratio of the ethylene-α-olefin copolymer of the resin component (A2), the ethylene-α-olefin copolymer of the resin component (A1), and the EVA of the resin component (B12) is 30, 40, and 30, respectively. Then, 0.09 part by weight of antioxidant and 0.1 part by weight of calcium stearate (manufactured by Nippon Oil & Fats Co., Ltd.) are added to it, and mixed uniformly with a Henschel mixer for about 30 seconds, then pelletized, Composition C2 was obtained.
A laminate was manufactured and evaluated in the same manner as in Example 1 except that this composition C2 was used as the Vth layer.
[0089]
[Example 3]
A laminate was manufactured and evaluated in the same manner as in Example 1 except that (B14) was used as the II layer and the IV layer.
[Example 4]
As the first layer, 12 μm-thick PET subjected to corona treatment was used, and an isocyanate anchor coating agent (manufactured by Dainichi Seika Kogyo Co., Ltd., 3600 A / B, blending ratio 7: 3) was applied to the corona-treated surface. On this anchor coat surface, the composition C1 is 5 .mu.m on the I-layer side of the II layer, (B14) is 5 .mu.m on each of the II and IV layers, and (B31) is 10 .mu.m on the III layer. The composition C1 was 20 μm, that is, a PET / C1 / B14 / B31 / B14 / C1 four-layered six-layer structure, and coextruded and laminated while performing ozone treatment at a resin temperature of 240 ° C.
[0090]
[Comparative Example 1]
A laminate was produced by coextrusion laminating in the same manner as in Example 1 except that EVA of (B12) was used as the V layer.
The heat seal strength was inferior.
[0091]
[Comparative Example 2]
The same operation as in Example 1 was performed except that LLDPE of the resin component (B21) was used instead of the resin component (C1). The evaluation results are shown in Table 1.
It can be seen that the heat seal strength is inferior.
[0092]
[Table 1]

[0093]
【The invention's effect】
The laminate of the present invention is excellent in heat sealing properties such as transparency, impact strength, low temperature heat sealability, heat seal strength, foreign matter heat seal properties, puncture strength, etc., and neck-in, drawdown when co-extrusion molding Excellent formability such as (extensibility). In addition, there is little elution of the resin component, and when the laminate is used to make a bag, there is little oozing into the contents, for example, soaking, dairy products, retort food, frozen food, seasoning, confectionery, etc. It is suitable for various packaging materials typified by foods and various liquid transport packaging materials. In addition, when the bag is made, it is suitable for heating the contents by a microwave oven, and when it is subjected to coextrusion molding, it is excellent in thickness deviation accuracy and stability of the interface between layers.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a graph of an elution temperature-elution amount curve for a component (A1) by a continuous temperature rising elution fractionation method.
FIG. 2 is a graph of an elution temperature-elution amount curve for a component (A2) by a continuous temperature rising elution fractionation method.

Claims (6)

A packaging material (excluding an inner bag for a bag-in-box) comprising a laminate having at least a base material layer, a barrier material layer, and a sealant layer,
The ethylene homopolymer or an ethylene · alpha-olefin copolymer sealant layer satisfies the following requirements (a) to (f) (A) Tona is,
The ethylene homopolymer or ethylene / α-olefin copolymer (A) is ethylene or ethylene in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a group IV transition metal compound. A packaging material obtained by (co) polymerizing ethylene and α-olefin .
(A) Density is from 0.86 to 0.97 g / cm ³ ,
(B) Melt flow rate is 0.01-100 g / 10 min.
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0,
(D) the composition distribution parameter Cb is from 1.08 to 2.00,
(E) There are substantially a plurality of peaks in the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method,
(F) The amount of orthodichlorobenzene soluble component X ( wt% ) at 25 ° C. , the density d and MFR (melt flow rate) satisfy the following relationship:
d-0. 008 log MFR ≧ 0. In the case of 93
X <2. 0
d-0. 008 log MFR < 0. In the case of 93
^{X <9. 8 × 10 3} × (0. 9300-d + 0. 008 logMFR) 2 +2. 0 The temperature on the high temperature side of a plurality of peaks of the elution temperature-elution amount curve by the continuous temperature rising elution fractionation method (TREF) of the ethylene homopolymer or ethylene / α-olefin copolymer (A) is between 85 and 100 ° C. The packaging material according to claim 1, wherein The packaging material according to claim 1 or 2, wherein the ethylene homopolymer or the ethylene / α-olefin copolymer (A) is polymerized using the following catalysts a1 to a4.
a 1 : General formula Me ¹ R ¹ _p R ² _q (OR ^Three ) _r X ¹ _4-p-q-r A compound represented by
(Where Me ¹ Represents zirconium, titanium, hafnium, R ¹ And R ^Three Are each a hydrocarbon group having 1 to 24 carbon atoms or a trialkylsilyl group, R ² Is 2,4- Pentandionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonate ligand or derivative thereof, X ¹ Represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r are 0 ≦ p <4, 0 ≦ q <4, 0 ≦ r <4 and 0 ≦, respectively. p + q + r It is an integer satisfying the range of ≦ 4. )
a 2 : General formula Me ² R ^Four _m (OR ^Five ) _n X ² _z-m-n A compound represented by
(Where Me ² Is periodic table I ~ III Group element, R ^Four And R ^Five Are each a hydrocarbon group having 1 to 24 carbon atoms, X ² Is a halogen atom or a hydrogen atom (however, X ² Me is a hydrogen atom ² Is the periodic table III Z is Me) ² M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z. )
a Three : An organic cyclic compound having a conjugated double bond.
  a Four : A modified organoaluminum oxy compound containing an Al-O-Al bond and / Or a boron compound. The sealant layer is composed of 98 to 10% by weight of the ethylene homopolymer or ethylene / α-olefin copolymer (A) and 2 to 90% by weight of the other ethylene polymer (B). The packaging material according to any one of claims 1 to 3 . The packaging material according to claim 4 , wherein the composition satisfies the following requirements (c1) to (c3).
(C1) Melt flow rate is 1 to 100 g / 10 min. (C2) Die swell ratio (DSR) at 190 ° C. is 1.10 to 3.00.
(C3) Melt tension (MT) at 190 ° C. is 0.5 to 4.0 g The packaging material according to any one of claims 1 to 5 , wherein the barrier material layer and the sealant layer are simultaneously formed by coextrusion lamination molding.

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