JP4774142B2 - Polyolefin resin - Google Patents

Description

【００４８】
【化２】

【００４９】
一般式（２）または（３）において、Ｒは炭素数が、１〜６、好ましくは１〜４のアルキル基であり、メチル基、エチル基、プロピル基、ブチル基、イソブチル基が挙げられる。これらのうち特に好ましいのはメチル基であり、一部炭素数２〜６のアルキル基を含んでいてもよい。ｍは、４〜１００の整数であり、好ましくは、６〜８０、特に好ましくは１０〜６０である。
【００５０】
上記のアルミノキサン化合物の製造方法は、公知の種々の方法を採用すればよく、例えば、トリアルキルアルミニウムを炭化水素溶媒中、直接水と反応させる方法、結晶水を有する硫酸銅水和物、硫酸アルミニウム水和物、含水させたシリカゲル等を用いて炭化水素溶媒中で吸着した水分とトリアルキルアルミニウムを反応させる方法等が例示できる。
【００５１】
非配位性イオン化化合物は、前記アルミノキサン化合物以外の非配位性イオン化化合物であれば公知のものが特に制限なく使用される。特にホウ素原子を含有するイオン化化合物が好適に用いることができる。
【００５２】
ホウ素原子を含有するイオン化化合物を具体的に例示すればホウ素原子を含有するルイス酸及びホウ素原子を含有するイオン性化合物が挙げられる。
【００５３】
上記ホウ素原子を含有するルイス酸としては一般式（４）で表される化合物が例示できる。
【００５４】
ＢＲ₃ （４）
上記一般式中、Ｒは、フッ素、メチル基、トリフルオロメチル基等の置換基を有していてもよいフェニル基またはフッ素である。
【００５５】
かかる一般式（４）で表される化合物として具体的には、トリフルオロボラン、トリフェニルボラン、トリス（４−フルオロフェニル）ボラン、トリス（３，５−ジフルオロフェニル）ボラン、トリス（４−フルオロメチルフェニル）ボラン、トリス（ペンタフルオロフェニル）ボラン、トリス（ｐ−トリル）ボラン、トリス（ｏ−トリル）ボラン、トリス（３，５−ジメチルフェニル）ボラン等が挙げられる。中でも、トリス（ペンタフルオロ）ボランが好適に用いられる。
【００５６】
ホウ素を含有するイオン性化合物としては、トリアルキル置換アンモニウム塩、Ｎ，Ｎ−ジアルキルアニリニウム塩、ジアルキルアンモニウム塩、トリアリールホスフォニウム塩などを挙げられる。
【００５７】
具体的には、トリアルキル置換アンモニウム塩としては、トリエチルアンモニウムテトラ（フェニル）ホウ素、トリプロピルアンモニウムテトラ（フェニル）ホウ素、トリ（ｎ−ブチル）アンモニウムテトラ（フェニル）ホウ素、トリメチルアンモニウム（ｐ−トリル）ホウ素、トリメチルアンモニウムテトラ（ｏ−トリル）ホウ素、トリブチルアンモニウムテトラ（ペンタフルオロフェニル）ホウ素、トリプロピルアンモニウムテトラ（ｏ，ｐ−ジメチルフェニル）ホウ素、トリブチルアンモニウムテトラ（ｍ，ｍ−ジメチルフェニル）ホウ素、トリブチルアンモニウムテトラ（ｐ−トリフルオロメチルフェニル）ホウ素、トリ（ｎ−ブチル）アンモニウムテトラ（ｏ−トリル）ホウ素などが挙げられ、Ｎ，Ｎ−ジアルキルアニリニウム塩としては、Ｎ，Ｎ−ジメチルアニリニウムテトラ（フェニル）ホウ素、Ｎ，Ｎ−ジエチルアニリニウムテトラ（フェニル）ホウ素、Ｎ，Ｎ−２，４，６−ペンタメチルアニリニウムテトラ（フェニル）ホウ素などが挙げられ、ジアルキルアンモニウム塩としては、ジ（１−プロピル）アンモニウムテトラ（ペンタフルオロフェニル）ホウ素、ジシクロヘキシルアンモニウムテトラ（フェニル）ホウ素などが挙げられ、トリアリールホスフォニウム塩としては、トリフェニルホスフォニウムテトラ（フェニル）ホウ素、トリ（メチルフェニル）ホスフォニウムテトラ（フェニル）ホウ素、トリ（ジメチルフェニル）ホスフォニウムテトラ（フェニル）ホウ素などが挙げられる。
【００５８】
上記ホウ素原子を含有するルイス酸またはホウ素原子を含有するイオン性化合物のうち、トリフェニルカルボニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ−ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレート、フェロセニウムテトラ（ペンタフルオロフェニル）ボレートも挙げることができる。中でもトリフェニルカルボニウムテトラキス（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ−ジメチルアニリニウムテトラキス（ペンタフルオロフェニル）ボレートが好適に用いられる。
【００５９】
成分［Ｉ］および成分［ＩＩ］の使用量は任意であるが、成分［ＩＩ］にアルミノキサン化合物を用いた場合の該成分［ＩＩ］の使用量（成分［ＩＩ］中のＡｌ原子のモル量）は、成分［Ｉ］中の遷移金属１モルに対して、０．１〜１００，０００モルが好ましく、より好ましくは１〜５０，０００モル、さらに好ましくは１０〜３０，０００モルが好適である。また、成分［ＩＩ］に非配位性イオン化化合物を用いた場合の成分［ＩＩ］の使用量（成分［ＩＩ］中の第３Ｂ族原子のモル量）は、成分［Ｉ］中の遷移金属１モルに対して、０．０１〜１０，０００モルが好ましく、より好ましくは０．１〜５，０００モル、さらに好ましくは１〜３，０００モルが好適である。
【００６０】
成分［Ｉ］および成分［ＩＩ］からなる触媒の存在下にポリプロピレン成分（ａ）とプロピレンとエチレンの共重合体成分（ｂ）を段階的に製造する方法において必要に応じて有機アルミニウム化合物（以下成分［III］と略す）を併用することもできる。成分［III］は、一般式（５）で表わされる化合物である。
【００６１】
ＡｌＲ_mＸ_3-m （５）
（式中、Ｒは、炭素数１〜１０のアルキル基、アリール基等の炭化水素基またはアルコキシ基を示す。Ｘはハロゲン原子を示す。ｍは、Ａｌの原子価で１〜３の整数である。）
【００６２】
上記、一般式（５）で表わされる化合物として具体的には、トリメチルアルミニウム、トリエチルアルミニウム、トリｎ−プロピルアルミニウム、トリイソプロピルアルミニウム、トリｎ−ブチルアルミニウム、トリイソブチルアルミニウムトリｎ−ヘキシルアルミニウム、トリｎ−オクチルアルミニウム、トリｎ−デシルアルミニウム等のトリアルキルアルミニウム類、ジエチルアルミニウムモノクロライド、ジエチルアルミニウムモノブロマイド、ジエチルアルミニウムモノフルオライド等のジアルキルアルミニウムモノハライド類、メチルアルミニウムセスキクロライド、エチルアルミニウムセスキクロライド、エチルアルミニウムジクロライド類のアルキルアルミニウムハライド類、ジエチルアルミニウムモノエトキシド、エチルアルミニウムジエトキシド等のアルコキシアルミニウム類が挙げられる。中でも、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム等のトリアルキルアルミニウムが好適に用いられる。
【００６３】
成分［III］の使用量は、特に制限されないが、一般には、成分［Ｉ］中の遷移金属原子１モルに対して、好ましくは１〜５０，０００モルであり、より好ましくは５〜１０，０００モルである。特に好ましくは１０〜５，０００モルである。
【００６４】
成分［Ｉ］及び／または成分［ＩＩ］は、微粒子状担体(以下成分［IV］と略す)に担持して使用することも可能である。担体に上記触媒成分を担持すると得られる重合体の粒子性状が向上し、反応器への重合スケールの防止等、樹脂製造におけるプロセス適合性を大幅に改良することができる。
【００６５】
微粒子状担体は、担体としての機能を有するものが制限なく使用されるが、特に無機酸化物が好ましい。
【００６６】
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例えば、ＳｉＯ₂−Ａｌ₂Ｏ₃、ＳｉＯ₂−ＭｇＯ、ＳｉＯ₂−ＴｉＯ₂、ＳｉＯ₂−Ｖ₂Ｏ₅、ＳｉＯ₂−Ｃｒ₂Ｏ₃、ＳｉＯ₂−ＴｉＯ₂−ＭｇＯなどが好適に用いることができる。これらの中でも特にＳｉＯ₂およびＡｌ₂Ｏ₃からなる群から選ばれたすくなくとも１種の成分を主成分として含有する担体がより好ましい。
【００６７】
担体はその種類および製法により性状は異なるが、本発明に好ましく用いられる担体は粒径が１０〜３００μｍ、より好ましくは２０〜２００μｍ、比表面積が好ましくは５０〜１０００ｍ³／ｇ、より好ましくは１００〜７００ｍ³／ｇ、細孔容積が好ましくは０．３〜３．０ｃｍ³／ｇ、より好ましくは０．５〜２．５ｃｍ³／ｇである。
【００６８】
無機微粒子担体は、通常１５０〜１０００℃、好ましくは２００〜８００℃で焼成して用いられる。
【００６９】
これら担体の粒径は、一般に０．１〜５００μｍであり、好ましくは１〜２００μｍ、さらに好ましくは１０〜１００μｍである。粒径が小さいと生成粒子が微粉状の重合体になり、また大きすぎると粗大な粒子となるために粉体の取り扱いが困難となる。
【００７０】
これら担体の細孔容積は通常０．１〜５ｃｍ³／ｇであり、好ましくは０．３〜３ｃｍ³／ｇである。細孔容積はＢＥＴ法や水銀圧入法などにより測定することができる。
【００７１】
上記微粒子担体[IV]１ｇに対するメタロセン化合物[Ｉ]の使用量は、遷移金属原子で０．００５〜１ｍｍｏｌ、好ましくは０．０５〜０．５ｍｍｏｌの割合が望ましい。また、成分［ＩＩ］としてアルミノキサン化合物を使用する場合には、メタロセン化合物［Ｉ］に対するアルミノキサン化合物の使用量は、Ａｌ原子のモル量に換算して、成分［Ｉ］中の遷移金属原子１モルに対して好ましくは１〜２００モルであり、より好ましくは１５〜１５０モルである。
【００７２】
非配位性イオン化化合物を用いる場合には、メタロセン化合物［Ｉ］に対する非配位性イオン化化合物の使用量は、非配位性イオン化化合物中の第５Ａ族原子のモル量に換算して、成分［Ｉ］中の遷移金属原子１モルに対して好ましくは０．１〜２０モルであり、より好ましくは１〜１５モルである。
【００７３】
得られる重合体を更に優れた粒子性状で得るために以下の方法を採用することもできる。 即ち、前記成分［Ｉ］、成分［ＩＩ］、成分［IV］及び必要に応じて成分［III］の各成分の存在下に、先ず、オレフィンの予備重合が行われる。予備重合における成分［III］の使用量は、特に制限されないが、成分［Ｉ］中の遷移金属原子１モルに対して、好ましくは１〜５０，０００モルであり、より好ましくは５〜１０，０００モルである。特に好ましくは１０〜５，０００モルである。
【００７４】
予備重合で用いる上記の各成分は一成分ずつ逐次添加してもよく、混合したものを一括添加してもよい。好ましくは触媒成分［IV］に成分［Ｉ］及び［IV］をあらかじめ接触させる方法が採用される。より好ましくは触媒成分［IV］に成分［ＩＩ］を担持せしめた後、成分［Ｉ］を担持せしめる方法がより優れた嵩比重でランダム共重合体を得るために有効である。
【００７５】
予備重合触媒成分の調製で用いられるオレフィンとしては、エチレン、プロピレン、１−ブテン、１−ペンテン、３−メチル−１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、４，４−ジメチル−１−ペンテン、１−ヘプテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、３−エチル−１−ヘキセン、４−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン等のα−オレフィン；シクロペンテン、シクロヘプテン、ノルボルネン、５−メチル−２−ノルボルネン、テトラシクロドデセン、２−メチル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン等の環状オレフィンが挙げられる。
【００７６】
さらにスチレン、ジメチルスチレン類、アリルノルボルナン、アリルベンゼン、アリルナフタレン、アリルトルエン類、ビニルシクロペンタン、ビニルシクロヘキサン、ビニルシクロペプタン、ジエンなどを用いることもできる。
【００７７】
好ましくは、エチレン、プロピレン、１−ブテン、１−ペンテン、３−メチル−１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、４，４−ジメチル−１−ペンテン、１−ヘプテン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ヘキセン、３−エチル−１−ヘキセン、４−エチル−１−ヘキセン、１−オクテン、１−デセン、シクロペンテン、ビニルシクロヘキサンであり、特に好ましくは、エチレン、プロピレン、１−ブテン、１−ヘプテン、３−メチル−１−ブテン、１−ヘキセン、４−メチル−１−ペンテンである。
【００７８】
予備重合はオレフィンが９５モル％以上の実質的に単独重合を行なうことが好ましい。
【００７９】
本発明の予備重合で最初に施こされるオレフィンの重合量は、触媒成分［Ｉ］、［ＩＩ］及び［IV］から形成される触媒１ｇ当り好ましくは０．１〜１０００ｇ、より好ましくは１〜５０ｇの範囲から選べばよい。
【００８０】
また、特に好ましい予備重合の実施形態としては、上記の予備重合に於いて、［Ｉ］、［ＩＩ］、［IV］及び必要に応じて ［III］の各成分の存在下に、先ず、プロピレンを予備重合せしめて第一予備重合触媒を得、次いで該第一予備重合触媒と上記成分［III］の存在下に更に１−ブテンの予備重合が段階的に行なわれる方法が好適に用いられる。
【００８１】
予備重合における成分［III］の使用量は、特に制限されないが、一般には、成分［Ｉ］中の遷移金属原子１モルに対して、１〜５０，０００モルであり、好ましくは５〜１０，０００モルである。さらに好ましくは１０〜５，０００モルである。上記のプロピレンの予備重合により第一予備重合触媒を得た後、通常、未反応のプロピレン及び必要に応じて用いられる成分［III］を洗浄により除去して続く予備重合に供することが望ましい。
【００８２】
各予備重合段階ではプロピレン及び１−ブテンがそれぞれ９５モル％以上、好ましくは９８モル％以上の実質的に単独重合を行なうことが好ましい。
【００８３】
該予備重合で最初に施こされるプロピレンの重合量は、触媒成分［Ｉ］、［ＩＩ］、［IV］から形成される触媒１ｇ当り０．１〜１０００ｇ、好ましくは１〜１０ｇの範囲から選べぱよく、次いで行なわれる１−ブテンの重合量は触媒成分［Ｉ］、［ＩＩ］、［III］から形成される触媒１ｇ当り０．１〜１０００ｇ、好ましくは１〜５００ｇの範囲から選べばよい。プロピレン重合量と１−ブテン重合量の比率は、プロピレン重合量／１−ブテン重合量の重量比で０．００１〜１００、好ましくは０．００５〜１０の範囲であることが好適である。
【００８４】
予備重合は通常スラリー重合を適用させるのが好ましく、溶媒として、ヘキサン，ヘプタン，シクロヘキサン，ベンゼン，トルエンなどの飽和脂肪族炭化水素若しくは芳香族炭化水素を単独で、又はこれらの混合溶媒を用いることができる。各予備重合温度は、−２０〜１００℃、特に０〜６０℃の温度が好ましく、予備重合の各段階はそれぞれ異なる温度の条件下で行ってもよい。予備重合時間は、予備重合温度及び予備重合での重合量に応じ適宜決定すれぱ良く、予備重合における圧力は、限定されるものではないが、スラリー重合の場合は、一般に大気圧〜５ｋｇ／ｃｍ²程度である。
【００８５】
各予備重合は、回分，半回分，連続のいずれの方法で行ってもよい。
【００８６】
各予備重合終了後には，ヘキサン，ヘプタン，シクロヘキサン，ベンゼン，トルエン等の飽和脂肪族炭化水素若しくは芳香族炭化水素を単独で、またはこれらの混合溶媒で洗浄することが好ましく、洗浄回数は通常の場合５〜６回が好ましい。
【００８７】
改質剤Ａは、上記した触媒成分の存在下にポリプロピレン成分の重合とプロピレンとエチレンの共重合体成分の重合が段階的に行われて製造される。重合順序は、特に制限されないが、第一段階でポリプロピレン成分（ａ）を第２段階でプロピレンとエチレンの共重合体成分（ｂ）の製造を行うことが良好な粒子性状で重合体を製造するために好ましい。
【００８８】
重合条件については、効果が認められる限り、特に制限はされないが、一般に次の条件が好ましい。
【００８９】
ポリプロピレン成分（ａ）の重合は、プロピレン単独または、本発明の要件を満足する範囲内でのプロピレンと他のエチレンを含むα-オレフィンの混合物を供給して実施すればよい。プロピレン重合における重合温度は、０〜１００℃、好ましくは、２０〜８０℃の範囲から採用することが好適である。
【００９０】
ポリプロピレン成分（ａ）の重合に際し、分子量調節剤として水素を共存させることもできる。また、重合に用いるモノマー自身を溶媒とするスラリー重合、気相重合、溶液重合等の何れの方法でも良い。プロセスの簡略性および反応速度、また、生成する共重合体の粒子性状を勘案するとプロピレン自身を溶媒とするスラリー重合が好ましい形態である。
【００９１】
重合形式は回分式、半回分式、連続式の何れの方法でも良い。更に重合を水素濃度、重合温度等の条件の異なる２段階以上に分けて行うこともできる。
【００９２】
次にプロピレンとエチレンのランダム共重合が行われる。プロピレンとエチレンのランダム共重合は、プロピレン自身を溶媒とするスラリー重合の場合には前記プロピレン重合に引き続いてエチレンガスを供給することで、また気相重合の場合はプロピレンとエチレンの混合ガスを供給することで実施される。
【００９３】
プロピレンとエチレンのランダム共重合ではプロピレン重合に続いて１段のランダム共重合を行うことが好ましいが、エチレンの供給濃度を多段階に変化させて製造することもできる。プロピレンとエチレンのランダム共重合の重合温度は、０〜１００℃、好ましくは、２０〜８０℃の範囲から採用することが好適である。また、必要に応じて分子量調節剤として水素を用いることもでき、その際の水素濃度を多段階または連続的に変化させて重合を実施することもできる。
【００９４】
プロピレンとエチレンのランダム共重合は回分式、半回分式、連続式のいずれの方法でもよく、重合を多段階に分けて実施することもできる。また、本工程の重合は、スラリー重合、気相重合、溶液重合のいずれの方法を採用してもよい。
【００９５】
本重合の終了後には、重合系からモノマーを蒸発させ本発明の改質剤Ａを得ることができる。この改質剤Ａは、炭素数７以下の炭化水素で公知の洗浄又は向流洗浄を行うことができる。
【００９６】
上記のごとき改質剤Ａを結晶性ポリオレフィン樹脂に混合して本発明のポリオレフィン樹脂組成物を製造する方法は、特に限定されない。例えば、タンブラー、ヘンシェルミキサー等を用いたパウダーブレンド方法またはペレットブレンド法等を用いることができる。
【００９７】
また、重合により、改質剤Ａの有効成分と結晶性ポリオレフィン樹脂とを製造する過程で混合して本発明のポリオレフィン樹脂組成物を製造する場合、例えば異なる立体規則性のポリプロピレン樹脂を重合し得る触媒成分を数種混合してプロピレンを重合する方法を挙げることができる。特に、固体状チタン触媒成分、有機アルミニウム化合物および立体規則性の異なるポリプロピレン樹脂を与える電子供与体を２種以上混合してプロピレンを重合する方法を好適に採用することができる。
【００９８】
この方法において、電子供与体は、プロピレンの重合において一般に知られているものを何等制限なく使用できるが、下記の一般式（Ｖ）および一般式（VI）で示される有機ケイ素化合物を併用すると、本発明の範囲のＴＲＥＦ／ＳＥＣ法による溶出温度が３６〜１０４℃、分子量が１０万〜１００万の範囲の成分を４〜２０重量％含有する組成物を容易に得ることができので特に好ましい。
【００９９】
【化３】

【０１００】
（Ｒ₃）_n−Ｓi−（ＯＣ₂Ｈ₅）_4-n （VI）
（但し、Ｒ₁、Ｒ₂及びＲ₃は同種または異種の炭化水素基であり、ｎは０または１である。）
【０１０１】
前記した固体状チタン触媒成分は、プロピレンの重合に使用されることが公知の化合物をなんら制限なく用いることができる。特に、チタン、マグネシウム及びハロゲンを成分とする触媒活性の高い固体状チタン触媒成分が好適である。このような触媒成分は、ハロゲン化チタン、特に四塩化チタンを種々のマグネシウム化合物、特に塩化マグムシウムに担持させたものとなっている。
【０１０２】
有機アルミニウム化合物は、プロピレンの重合に使用されることが公知の化合物をなんら制限なく採用できる。
【０１０３】
例えば、トリメチルアルミニウム、トリエチルアルミニウム、トリ−ｎ−プロピルアルミニウム、トリ−ｎ−ブチルアルミニウム、トリ−イソブチルアルミニウム、トリ−ｎ−ヘキシルアルミニウム、トリ−ｎ−オクチルアルミニウム、トリ−ｎ−デシルアルミニウム等のトリアルキルアルミニウム類；ジエチルアルミニウムモノクロライド等のジエチルアルミニウムモノハライド類；メチルアルミニウムジクロライド、エチルアルミニウムジクロライド等のアルキルアルミニウムハライド類などが挙げられる。
【０１０４】
他にモノエトキシジエチルアルミニウム、ジエトキシモノエチルアルミニウム等のアルコキシアルミニウム類を用いることができる。なかでもトリエチルアルミニウムが最も好ましい。
【０１０５】
有機アルミニウム化合物の使用量は固体状チタン触媒成分中のチタン原子に対しアルミニウム／チタン（モル比）で１０〜１０００であることが好ましく、さらに５０〜５００であることが好ましい。
【０１０６】
前記一般式（Ｖ）および一般式（VI）で示される有機ケイ素化合物において、Ｒ₁、Ｒ₂およびＲ₃で示される炭化水素基は、鎖状、分枝状、環状の脂肪族炭化水素基、または芳香族炭化水素基を挙げることができ、その炭素数は特に制限されない。
【０１０７】
本発明において好適な炭化水素基を例示すると、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基等の炭素数１〜６のアルキル基；ビニル基、プロペニル基、アリル基等の炭素数２〜６のアルケニル基；エチニル基、プロピニル基等の炭素数２〜６のアルキニル基；シクロペンチル基、シクロヘキシル基、シクロヘプチル基等の炭素数５〜７のシクロアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等の炭素数６〜１２のアリール基等を挙げることができる。このなかで、Ｒ３は直鎖状のアルキル基、アルケニル基、アリール基であることが好ましい。また、ｎは０または１である。
【０１０８】
本発明において好適に用いられる有機ケイ素化合物を例示すると次の通りである。
【０１０９】
一般式（Ｖ）で示される有機ケイ素化合物としては、例えば、ジメチルジメトキシシラン、ジエチルジメトキシシラン、ジプロピルジメトキシシラン、ジビニルジメトキシシラン、ジアリルジメトキシシラン、ジ−１−プロペニルジメトキシシラン、ジエチニルジメトキシシラン、ジフェニルジメトキシシラン、メチルフェニルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、ターシャリーブチルエチルジメトキシシラン、エチルメチルジメトキシシラン、プロピルメチルジメトキシシラン、シクロヘキシルトリメトキシシラン、ジイソプロピルジメトキシシラン、ジシクロペンチルジメトキシシラン、ビニルトリメトキシシラン、フェニルトリメトキシシラン、アリルトリメトキシシラン等を挙げることができる。
【０１１０】
一般式（VI）で示される有機ケイ素化合物としては、例えば、テトラエトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、ビニルトリエトキシシラン、ブチルトリエトキシシラン、ペンチルトリエトキシシラン、イソプロピルトリエトキシシラン、１−プロペニルトリエトキシシラン、イソプロペニルトリエトキシシラン、エチニルトリエトキシシラン、オクチルトリエトキシシラン、ドデシルトリエトキシシラン、フェニルトリエトキシシラン、アリルトリエトキシシラン等を挙げることができる。
【０１１１】
一般式（Ｖ）および一般式（VI）で示される有機ケイ素化合物の使用量は、それぞれ固体状チタン触媒成分のＴｉ原子に対しＳｉ／Ｔｉ（モル比）で０．１〜５００が好ましく、さらには１〜１００であることが好ましい。また、これら二種の有機ケイ素化合物の使用比率はモル比で（Ｖ）：（VI）＝１：５〜１：２５であることが必要であり、１：１０〜１：２０であることが好ましい。、有機ケイ素化合物（Ｖ）と（VI）の使用比率が１：５よりも少ない場合には、得られたポリプロピレン樹脂のＴＲＥＦによる溶出ピーク幅が狭くなるため、すなわち、溶出温度３６〜１０４℃の成分量が低くなるため、製膜時の延伸性が低下し、機械負荷が上昇してフィルムの延伸破れが発生しやすくなる。
【０１１２】
上記した各成分の添加順序は特に限定されず、一般式（Ｖ）および一般式（VI）で示される有機ケイ素化合物を同時に混合供給しても、または別々に供給してもよい。またこれらは、予め有機アルミニウム化合物と接触あるいは混合した後に供給することもできる。
【０１１３】
その他の重合条件は、本発明の効果が認められる限り、特に制限されないが一般には次の条件が好ましい。重合温度は２０〜２００℃、好ましくは５０〜１５０℃であり、分子量調節剤として水素を共存させることもできる。また重合は、スラリー重合、無溶媒重合および気相重合等が適用でき、回分式、半回分式、連続式のいずれの方法でもよく、更に重合を条件の異なる２段階に分けて行うこともできる。また、プロピレンの重合前に、プロピレンや他のモノマーの予備重合を行なってもよい。さらに、上記した重合を多段に行ってもよい。
【０１１４】
本発明においては、上記した方法で得られたポリプロピレン樹脂組成物を単独で使用することができ、また、他のポリプロピレン樹脂とをブレンドして用いることもできる。勿論、上記した方法で得られたポリプロピレン樹脂組成物同士をブレンドすることもできる。
【０１１５】
本発明においては、上記の如くして得られたポリオレフィン樹脂組成物を、そのままで或いは適宜選択することによりＴＲＥＦ／ＳＥＣ法による溶出温度３６〜１０４℃、分子量が１０〜１００万の範囲の成分を４〜２０重量％含有するポリオレフィン樹脂組成物にすることができる。或いは、該樹脂組成物にさらに、改質剤Ａ、または、結晶性ポリオレフィン樹脂を混合して所望の組成の本発明のポリオレフィン樹脂組成物とすることができる。
【０１１６】
なお、ＴＲＥＦ／ＳＥＣ法による溶出温度が１１６℃を超えて、且つ分子量が１万〜１０万の範囲の成分を４〜２０重量％含有する本発明のポリオレフィン樹脂組成物も上記と同様にして得ることが可能である。また、ＴＲＥＦ／ＳＥＣ法による溶出温度が１１６℃を超え、且つ分子量が１万〜１０万の範囲の成分を２０重量％超〜１００重量％含有する改質剤（以下改質剤Ｂという）と改質剤Ａとを、結晶性ポリオレフィン樹脂に混合することによって製造することも可能である。
【０１１７】
上記改質剤Ｂは、高結晶性ポリプロピレン樹脂であることを特徴とする。上記改質剤Ｂのメルトフローレイトは、特に制限されるものではないが、フィルムへの成形性を考えると、５〜１００ｇ／１０分の範囲のものが好ましく、さらに３０〜８０ｇ／１０分の範囲にあることがより好ましい。また、重量平均分子量（Ｍｗ）は、５万〜８０万、好ましくは１０万〜３０万の範囲が好適である。
【０１１８】
上記改質剤Ｂの分子量分布（Ｍｗ／Ｍｎ）は、特に制限されるものではないが、フィルム成形時の容易さや溶融張力を増加させ加工性を向上させることを勘案すると１．５〜４０であることが好ましく、さらに２〜１０であることがより好ましい。
【０１１９】
上記改質剤Ｂの融点は、特に制限されるのもではないが、１５０℃以上であることが好ましく、１５５〜１７０℃の範囲であることがより好ましい。
【０１２０】
上記改質剤ＢのＴＲＥＦ法による溶出曲線のピークトップ温度は、製膜して得られた延伸フィルムの剛性及び耐熱性を勘案すると、１１０以上であることが好ましく、１１５〜１３０℃の範囲であることがより好ましい。
【０１２１】
上記改質剤ＢのＴＲＥＦ／ＳＥＣ法における０℃以下の溶出成分は、特に制限されるものではないが、製膜されたポリオレフィンフィルムの耐ブロッキング性、耐スクラッチ性、滑り性等のフィルム表面物性を勘案すると５重量％以下であることが好ましく、３重量％以下であることがより好ましい。
【０１２２】
また、上記改質剤Ｂが、プロピレン単独重合体及びプロピレン−αオレフィン共重合体であってプロピレン以外のα−オレフィンの含有量が１ｍｏｌ％未満の場合、その結晶性を示す¹³Ｃ−ＮＭＲによるアイソタクチックペンタッド分率は特に制限されるものではないが、０．８０〜１であることが好ましく、０．９３〜０．９９であることがより好ましい。
【０１２３】
さらに、改質剤Ａと改質剤Ｂとをあらかじめ２０〜８０または８０〜２０の割合で混合した改質剤（改質剤Ａ・Ｂという）を得て、これを結晶性ポリオレフィン樹脂に混合することも可能である。
【０１２４】
結晶性ポリオレフィン樹脂に混合される改質剤Ａと改質剤Ｂの各有効成分の重量比（Ｂ／Ａ）は、好ましくは０．５〜２の範囲、より好ましくは０．８〜１．５の範囲である。この範囲とすることによって、製膜における延伸性の改良効果、すなわち、延伸における製膜可能温度の幅の拡大、機械負荷の低減、フィルム破れの低減、厚薄精度の向上を図ることができる。
【０１２５】
本発明に用いられるポリオレフィン樹脂組成物には、必要に応じて、酸化防止剤、塩素捕捉剤、耐熱安定剤、帯電防止剤、防曇剤、紫外線吸収剤、滑剤、造核剤、ブロッキング防止剤、顔料、他の樹脂やフィラー等の添加剤が効果の阻害されない範囲で配合されていてもよい。
【０１２６】
本発明のポリオレフィン樹脂組成物はあらゆる成形体の製造に使用することができ、優れた押し出し特性、延伸性を発揮するが、特に、延伸フィルムを得るための延伸加工により製膜した場合に顕著な効果を発揮する。
【０１２７】
本発明のポリオレフィン延伸フィルムとしては二軸延伸フィルムおよび一軸延伸フィルムのいずれであってもよい。延伸フィルムの厚さは特に制限されないが、二軸延伸フィルムの場合３〜１５０μｍ、一軸延伸フィルムの場合１０〜２５４μｍの範囲であることが好ましい。本発明のポリオレフィン延伸フィルムは、少なくとも一軸方向に延伸されている。もちろん二軸方向に延伸されていてもよい。延伸倍率は特に制限されないが、一軸方向に４〜１０倍であることが一般的であり、二軸延伸の場合はそれと直角な方向に更に４〜１５倍の範囲で延伸されていることが一般的である。
【０１２８】
本発明のポリオレフィン延伸フィルムの片面あるいは両面には、必要に応じてコロナ放電処理等の表面処理が施されてもよい。さらに、ヒートシール性等の機能を付与する目的で片面あるいは両面に本発明で使用されるポリオレフィン樹脂よりも融点の低い他の樹脂よりなる層が積層されてもよい。他の樹脂の積層方法は特に制限されないが、共押し出し法、ラミネート法等が好適である。
【０１２９】
本発明のポリオレフィン延伸フィルムの製造方法は、公知の方法を何等制限なく採用することができる。例えば、テンター法による逐次二軸延伸法によって延伸フィルムを製造する方法としては、上記のポリプロピレン組成物をＴダイ法、インフレーション法等でシートあるいはフィルムに成形した後、縦延伸装置に供給し、加熱ロール温度１２０〜１７０℃で３〜１０倍縦延伸し、つづいてテンターを用いてテンター温度１３０〜１８０℃で４〜１５倍横延伸する方法が好適である。
【０１３０】
上記の成形条件は特に制限されないが、厚薄精度や溶断シール性等の良好な延伸フィルムを得るためには、縦延伸において１４５〜１７０℃で３〜５倍、横延伸において１５５〜１８０℃で４〜１２倍延伸することが好ましい。さらに、必要に応じて横方向に０〜２５％の緩和を許しながら８０〜１８０℃で熱処理する方法を挙げることができる。もちろん、これらの延伸の後に再び延伸してもよく、また縦延伸において多段延伸、圧延等の延伸法を組み合わせることができる。
また、一軸のみの延伸によっても延伸フィルムとすることができる。
【０１３１】
【発明の効果】
本発明のポリオレフィン樹脂組成物は、延伸フィルムの製膜に際して、従来公知のポリオレフィン樹脂に比べて製膜可能な温度調整範囲が広く、延伸時の機械負荷が小さく、製膜されたフィルムの厚薄精度が優れ、延伸性が良好で延伸破れが発生しにくい。従って、長時間高速で、安定に連続運転の可能な延伸フィルムの製造に適したポリオレフィン樹脂である。さらに、製膜された延伸フィルムの熱収縮率等の耐熱性が良好である。このような効果は、本発明のポリオレフィン樹脂組成物が延伸フィルム用ポリオレフィン樹脂組成物として優れており、その工業的な価値の極めて高いことを示している。
【０１３２】
【実施例】
本発明を更に具体的に説明するため以下に実施例及び比較例を挙げて説明するが、本発明はこれらの実施例に限定されるものではない。
【０１３３】
（１）ＴＲＥＦ／ＳＥＣ
ＴＲＥＦ／ＳＥＣによる溶出温度範囲の分子量分布曲線及び重量平均分子量及び溶出量は、ユニフローズ社製マルチパーパスリキッドクロマトグラフ装置を用い、次の条件でＴＲＥＦ／ＳＥＣモードにて測定した。
【０１３４】
溶媒：オルトジクロルベンゼン
ＴＲＥＦカラム：４．６ｍｍφ×１５０ｍｍ
充填剤：クロモソルブＰ
流速：１．０ｍｌ／ｍｉｎ
結晶化条件：１４０℃ 〜 ０℃ （降温速度：２．０℃／時間）
昇温条件:４℃ステップ 計３６フラクション（０，４，８，１２，１６，２０，２４，２８，３２，３６，４０，４４，４８，５２，５６，６０，６４，６８，７２，７６，８０，８４，８８，９２，９６，１００，１０４，１０８，１１２，１１６，１２０，１２４，１２８，１３２，１３６，１４０）
ＳＥＣカラム：ＳＨＯＤＥＸ ＵＴ ８０７＋８０６M×２本
ＳＥＣ恒温槽：１４５℃
検出器：高温液クロ用赤外検出器
測定波数：３．４１μｍ
試料濃度：０．４ｗｔ％
注入量：５００μｌ
【０１３５】
この場合、ＴＲＥＦカラム内に試料溶液を１４０℃で導入した後、送液を止め、１４０℃から０℃まで２℃／時間で降温し、試料ポリマーを充填剤表面に結晶化させる。０℃で３０分間保持させた後、０℃で溶解している成分を１．０ｍｌ／ｍｉｎでＳＥＣカラムへ導入し、ＳＥＣ測定を行う。その間にＴＲＥＦ恒温槽では、次の測定温度（４℃）まで急速昇温し、ＳＥＣ測定が終了するまで保持しておく。同様にして、４℃で溶解している成分をＳＥＣカラムに導入してＳＥＣ測定を行う。以下設定温度まで繰り返しＳＥＣ測定を行う。
【０１３６】
（２）ＴＲＥＦ
ＴＲＥＦによる溶出温度量は、ユニフローズ社製マルチパーパスリキッドクロマトグラフ装置を用い、下記条件のＴＲＥＦモードで測定した。
【０１３７】
溶媒：オルトジクロルベンゼン
ＴＲＥＦカラム：４．６ｍｍφ×１５０ｍｍ
充填剤：クロモソルブＰ
流速：１．０ｍｌ／ｍｉｎ
結晶化条件：１４０℃ 〜 ０℃ （降温速度：２．０℃／時間）
昇温条件 ： 連続昇温 ４０℃／ｈｒ （温度範囲 ０℃〜１４０℃）
検出器：高温液クロ用赤外検出器
測定波数：３．４１μｍ
試料濃度：０．４ｗｔ％
注入量：５００μｌ
【０１３８】
ＴＲＥＦ／ＳＥＣ測定と同様に、試料を結晶化させた後、０℃で３０分間保持し、０℃で溶解した成分の濃度を検出する。その後、所定の速度で直線的にＴＲＥＦカラム温度を上昇させながら、溶媒を流して濃度を検出器し、溶出温度に対する溶出量を得る。
【０１３９】
（３）メルトフローレイト（ＭＦＲ）
ＪＩＳ Ｋ ７２１０に準じて測定した。
【０１４０】
（４）分子量分布
センシュー科学社製の高温ＧＰＣ装置ＳＳＣ−７１００を用い、次の条件で測定した溶出プロファイルから算出した重量平均分子量及び数平均分子量の値を用いて求めた。
【０１４１】
溶媒 ：オルトジクロルベンゼン
流速 ：１．０ｍｌ／分
カラム温度：１４５℃
検出機 ：高温示差屈折検出器
カラム ：ＳＨＯＤＥＸ ＵＴ807(1本)、806M(2本)、802.5(1本)
試料濃度 ：０．１重量％
注入量 ：０．５０ｍｌ
【０１４２】
（５）ペンタッド分率
日本電子社製のＪＮＭ−ＧＳＸ−２７０（¹³Ｃ−核共鳴周波数６７．８ＭＨｚ）を用い、次の条件で測定した。
【０１４３】
測定モード： １Ｈ−完全デカップリング
パルス幅 ： ７．０マイクロ秒（Ｃ４５度）
パルス繰り返し時間： ３秒
積算回数 ： ５００００回
溶媒 ： オルトジクロルベンゼン／重ベンゼンの混合溶媒
（９０／１０容量％）
試料濃度 ： １２０ｍｇ／２．５ｍｌ溶媒
測定温度 ： １２０℃
【０１４４】
この場合、ペンタッド分率は１３Ｃ−ＮＭＲスペクトルのメチル基領域における分裂ピークの測定により求めた。また、メチル基領域のピークの帰属はＡ．Ｚａｍｂｅｌｌｉ ｅｔ ａｌ［Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ １３， ２６７（１９８０）］によった。
【０１４５】
（６）ＤＳＣ測定
セイコーインスツルメンツ社製ＤＳＣ６２００Ｒ装置を用いて、下記の条件で融点の測定を行った。
【０１４６】
昇温速度 ： １０℃／ｍｉｎ （温度範囲 ２３０〜―３０℃）
降温速度 ： １０℃／ｍｉｎ （温度範囲 −３０〜２３０℃）
【０１４７】
参考例１
（固体チタン触媒の調製）
固体チタン触媒の調製法は、特開昭５８−８３００６号公報の実施例１に記載の方法に準じて行なった。すなわち、無水塩化マグネシウム９．５ｇ（１００ｍｍｏｌ）、デカン１００ｍｌ及び２−エチルヘキシルアルコール４７ｍｌ（３００ｍｍｏｌ）を１２５℃で２時間加熱攪拌した後、この溶媒中に無水フタル酸５．５ｇ（３７．５ｍｍｏｌ）を添加し、１２５℃にてさらに１時間攪拌混合を行ない、均一溶液とした。
【０１４８】
室温まで冷却した後、−２０℃に保持された四塩化チタン４００ｍｌ（３．６ｍｍｏｌ）中に１時間にわたって全量滴下装入した。その後、この混合液の温度を２時間かけて１１０℃に昇温し、１１０℃に達したところでジイソブチルフタレート５．４ｍｌ（２５ｍｍｏｌ）を添加し、これより２時間、１１０℃にて攪拌下に保持した。２時間の反応終了後、熱時濾過にて固体部を採取し、この固体部を２０００ｍｌの四塩化チタンにて再懸濁させた後、再び１１０℃で２時間、加熱反応を行なった。反応終了後、再び熱濾過にて固体部を採取し、デカン及びヘキサンにて、洗液中に遊離のチタン化合物が検出されなくなるまで、充分洗浄した。
【０１４９】
以上の製造方法にて調整された固体チタン触媒は、ヘプタンスラリーとして保存した。固体チタン触媒の組成はチタン２．１重量％、塩素５７．０重量％、マグネシウム１８．０重量％及びジイソブチルフタレート２１．９重量％であった。
【０１５０】
（予備重合）
窒素置換を施した１０Ｌ重合器中に精製ｎ−ヘキサン２０００ｍｌ、トリエチルアルミニウム５００ｍｍｏｌ、シクロヘキシルメチルジメトキシシラン２５ｍｍｏｌ、および接触処理の施された固体チタン化合物成分をチタン原子換算で５０ｍｍｏｌ装入した後、プロピレンを固体チタン触媒成分１ｇに対し２ｇとなるように１時間連続的に重合器に導入した。尚、この間の温度は１５℃に保持した。
【０１５１】
１時間後に反応を停止し、反応器内を窒素で充分に置換した。得られたスラリーの固体部分を精製ｎ−ヘキサンで５回洗浄し、予備重合触媒（チタン含有ポリプロピレン）を得た。分析の結果、固体チタン触媒１ｇに対し１．７ｇのプロピレンが重合されていた。
【０１５２】
（本重合）
窒素置換を施した内容量２０００Ｌの重合器に、プロピレン５００ｋｇを装入し、トリエチルアルミニウム１７５２ｍｍｏｌ、有機ケイ素化合物としてシクロヘキシルメチルジメトキシシラン１７．５ｍｍｏｌとテトラエトキシシラン３５０ｍｍｏｌ、さらに水素１０Ｌを装入した後、重合器の内温を６５℃に昇温した。上記予備重合で得られた予備重合触媒をチタン原子で４．３８ｍｍｏｌ装入し、続いて重合器の内温を７０℃まで昇温し、２時間のプロピレンとエチレンの共重合を行なった。
【０１５３】
重合終了後、未反応のプロピレンをパージし、得られた白色顆粒状の重合体は、７０℃で１時間の減圧乾燥を行なった。得られたポリオレフィン樹脂ａの構造特性を表１及び表２に示した。
【０１５４】
（造粒）
上記（本重合）で得たポリオレフィン樹脂ａパウダー１００重量部に、酸化防止剤として２，６−ジ−ｔ−ブチルヒドロキシトルエンを０．１重量部、塩素補足剤としてステアリン酸カルシウムを０．１重量部、帯電防止剤としてステアリルジエタノールアミド０．２重量部、ブロッキング防止剤として平均粒径１．５μｍの球状ポリメチルメタクリレート粒子を０．１重量部添加し、ヘンシェルミキサーで５分間混合した後、スクリュー径６５ｍｍφの押出造粒機を用いて２３０℃で押し出し、ペレットを造粒し原料ペレットを得た。
【０１５５】
（二軸延伸フィルムの製膜）
得られた原料ペレットを用いて以下の方法で二軸延伸フィルムの製膜実験を行なった。原料ペレットを、スクリュー径９０ｍｍφのＴダイシート押出機を用い、２８０℃で押し出し、３０℃の冷却ロールで厚さ１ｍｍのシートを成形した。次いで、この原反シートをテンター方式の逐次二軸延伸装置を用いて、縦方向（ＭＤ）に５．６倍ロール間延伸し、引き続いて１６５℃のテンター内で横方向（ＴＤ）に機械倍率で１０倍延伸した後、４％緩和させて熱処理を行い、厚さ２０μｍの二軸延伸ポリオレフィンフィルムを５０ｍ／分の速度で製膜した。
【０１５６】
製膜の際、縦延伸のロール予熱温度を変化させ、製膜可能な温度範囲（下限温度〜上限温度）を評価した。なお、ロール予熱温度を下げていき、フィルムの白化、厚薄ムラ、フィルム破れ等が起こらずに１０分間の安定製膜が可能な下限の温度を製膜可能下限温度とした。
【０１５７】
また、ロール予熱温度を上げていき、縦延伸したシート表面の溶融によるフィルムの白化、厚薄ムラ等が起こらずに１０分間の安定製膜が可能な上限の温度を製膜可能上限温度とした。製膜可能上限温度と製膜可能下限温度との差を製膜可能な温度幅とした。
【０１５８】
また、該温度幅の中心温度における縦延伸及び横延伸にかかる機械負荷（電流値、単位アンペア）により製膜性（延伸性）を評価した。また、延伸ムラの厚薄精度への影響は、テンターと巻取り機の間に設置した横河電機社製の赤外線厚み測定機ＷＥＢ ＧＡＧＥを用いて測定したフィルムの厚みパターンにより下記の基準で評価した。
【０１５９】
◎： ±０．５μｍ未満
○： ±０．５μｍ以上１．０μ未満
△： ±１．０μｍ以上１．５μ未満
×： ±１．５μｍ以上
【０１６０】
さらに、５時間連続運転を行ない、テンターでのフィルム延伸破れの回数を評価した。また、成形されたフィルムの片面には常法に従い３０Ｗ 分／ｍ²のコロナ放電処理を施し、巻取った。得られた延伸フィルムは４０℃で３日間エージングした後、熱収縮率（耐熱性）の測定を以下の方法で行なった。
【０１６１】
フィルムのＭＤおよびＴＤを長さ方向として、長さ６００ｍｍ、幅１５ｍｍのテープ状に試料を切り出し、５００ｍｍの長さ（両端から５０ｍｍ）の位置に印を付け、１２０℃の雰囲気で１５分間放置した後、フィルム試料を取り出し室温で１５分間冷却し、印の間の長さを測定し、下記式により熱収縮率を測定した。
熱収縮率（％）＝｛（Ｌ_O−Ｌ_S）／Ｌ_O｝×100
但し、Ｌ_O：熱収縮前の印間の長さ（５００ｍｍ）
Ｌ_S：熱収縮後の印間の長さ（ｍｍ）
製膜可能な温度範囲、縦および横延伸における機械負荷、５時間連続運転におけるフィルム延伸破れの回数、厚薄精度、延伸フィルムのＭＤ及びＴＤの熱収縮率結果を表３に示した。
【０１６２】
参考例２
本重合において、有機ケイ素化合物としてシクロヘキシルメチルジメトキシシラン２７ｍｍｏｌとエチルトリエトキシシラン２８５ｍｍｏｌを用いて、プロピレンの単独重合を行ない、表１に示すポリオレフィン樹脂ｂを得たこと以外は参考例１と同様に行なった。その結果を表１、２、３に示した。
【０１６３】
比較例１
本重合において、有機ケイ素化合物としてシクロヘキシルメチルジメトキシシラン１６４ｍｍｏｌを単独で用いて、プロピレンの単独重合を行ない、表１に示すポリプロピレン（ポリオレフィン樹脂ｃ）を得たこと以外は参考例１と同様に行った。その結果を表１、２、３に示した。
【０１６４】
比較例２，３
本重合において、エチレンとの共重合を行なったこと以外は比較例１と同様に行いポリオレフィン樹脂ｄ，ｅを得た。その結果を表１、２、３に示した。
【０１６５】
比較例４
本重合において、有機ケイ素化合物としてｔ−ブチルエチルジメトキシシランを用いてプロピレンの単独重合を行った。それ以外は比較例1と同様に行いポリオレフィン樹脂ｆを得た。その結果を表１、２、３に示した。
【０１６６】
参考例３
本重合において、エチレンとの共重合を行った。それ以外は、比較例1と同様に行い表1に示すポリオレフィン樹脂ｇを得た。
【０１６７】
上述のポリオレフィン樹脂ｇと、比較例１で得たポリオレフィン樹脂ｃを用い、表２に示す配合量とした。それ以外は参考例１と同様に行った。その結果を表２、３に示した。
【０１６８】
実施例１，２
表２に示す配合量としたこと以外は参考例３と同様に行った。その結果を表２，３に示した。
【０１６９】
実施例３
表１に示すプロピレン−エチレン共重合体（三洋化成ビスコール６６０（ポリオレフィン樹脂ｈ））と、比較例２で得たポリオレフィン樹脂ｄを用い、表２に示す配合量としたこと以外は参考例１と同様に行った。その結果を表２、３に示した。
【０１７０】
実施例４
ポリオレフィン樹脂ｉの製造方法
（担持メタロセン触媒の調製）
シリカゲル担持メチルアルミノキサン（ＭＡＯ ｏｎ ＳｉＯ_２、ウイットコ社製、２５ｗｔ％−Ａｌ品）１０ｇにｒａｃ−ジメチルシリレンビス−１−（２−メチルベンズインデニル）ジルコニウムジクロリドのトルエン溶液１００ｍｌ（０．００５ｍｍｏｌ／ｍｌトルエン溶液）を加え、室温で３０分間撹拌した。次にその反応混合物をろ過し、得られた固体をトルエン５０ｍｌで２回洗浄後、減圧下乾燥させることによりシリカゲルに担持されたメタロセン触媒を得た。触媒１ｇ当たり０．０４５ｍｍｏｌのメタロセンが担持されていた。
【０１７１】
（重合）
内容積２ｍ³の重合槽にプロピレンを６００ｋｇ挿入し、トリイソブチルアルミニウム６１２ｍｍｏｌを導入した。その後、重合槽の内温を５５℃に昇温した。次いで、気相濃度でエチレンガスを６．０モル％となるように供給した後、前記のシリカゲルに担持されたメタロセン触媒１０ｇを装入した。続いてオートクレーブの内温を６０℃まで昇温し、エチレン気相濃度が一定になるようにエチレンガスを供給しながら２時間重合を行った。
【０１７２】
重合終了後、未反応のプロピレンをパージし、５０℃で１時間乾燥を行うことにより白色顆粒状の重合体１７５ｋｇを得た。得られたプロピレン−エチレン共重合体（ポリオレフィン樹脂ｉ）の構造特性を表１に示した。
【０１７３】
上述のポリオレフィン樹脂ｉと、比較例２で得たポリオレフィン樹脂ｄを用い、表２に示す配合量としたこと以外は参考例１と同様に行った。その結果を表２，３に示した。
【０１７４】
実施例５
ポリオレフィン樹脂ｊの製造方法
（重合）
（前段、プロピレンの重合）
内容積２ｍ^３の重合槽にプロピレンを６００ｋｇ挿入し、トリイソブチルアルミニウム６１２ｍｍｏｌを導入した。その後、重合槽の内温を５５℃に昇温した。次いで、実施例４［担持メタロセン触媒の調製］と同様にして得られたシリカゲルに担持されたメタロセン触媒５ｇを装入した。続いてオートクレーブの内温を６０℃まで昇温し、７０分重合を行った。
【０１７５】
（後段、プロピレンとエチレンの共重合）
前段の重合を行った後に、気相濃度でエチレンガスを１０．１ｍｏｌ％濃度まで供給し、更にエチレンの気相濃度を一定に保つように供給しながら７０分間共重合を行った。重合終了後、未反応のプロピレンをパージし、５０℃で１時間乾燥を行うことにより白色顆粒状の重合体１３５ｋｇを得た。得られたポリオレフィン樹脂ｊの構造特性を表１に示した。
【０１７６】
上述のポリオレフィン樹脂ｊと、比較例２で得たポリオレフィン樹脂ｄを用い、表２に示す配合量としたこと以外は参考例１と同様に行った。その結果を表２、３に示した。
【０１７７】
実施例６
実施例５において後段重合における気相エチレン濃度を１７．２ｍｏｌ％とした以外は実施例５と同様に行い白色顆粒状の重合体１７５ｋｇを得た。得られたポリオレフィン樹脂ｋの構造特性を表１に示した。
【０１７８】
ポリオレフィン樹脂ｋと比較例２で得たポリオレフィン樹脂ｄを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１７９】
実施例７、参考例４，５
表１に示す市販のプロピレン−ブテン共重合体（ポリオレフィン樹脂ｌ）と、比較例２で得たポリオレフィン樹脂ｄを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２、３に示した。
【０１８０】
比較例５
実施例７で用いたオレフィン樹脂ｌと、比較例１で得たポリオレフィン樹脂ｃを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１８１】
参考例６、実施例８
実施例７で用いたオレフィン樹脂ｌと、比較例１で得たポリオレフィン樹脂ｃを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１８２】
比較例６
実施例７で用いたオレフィン樹脂ｌと、比較例１で得たポリオレフィン樹脂ｃを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１８３】
参考例７、実施例９、参考例８
実施例５で得たポリオレフィン樹脂ｊと、比較例１で得たポリオレフィン樹脂ｃを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１８４】
実施例１０
実施例６で得たポリオレフィン樹脂ｋと、比較例１で得たポリオレフィン樹脂ｃを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１８５】
実施例１１，１２
実施例６で得たポリオレフィン樹脂ｋと、比較例４で得たポリオレフィン樹脂ｆを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１８６】
比較例７
表１に示す市販エラストマー（ポリオレフィン樹脂ｍ）と、比較例４で得たポリオレフィン樹脂ｆを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１８７】
参考例９、実施例１３
（固体チタン触媒の調製）
固体チタン触媒の調製法は、特開昭５８−８３００６号公報の実施例１の方法に準じて行なった。
【０１８８】
すなわち、無水塩化マグネシウム０．９５ｇ（１０ｍｍｏｌ）、デカン１０ｍｌ及び２−エチルヘキシルアルコール４．７ｍｌ（３０ｍｍｏｌ）を１２５℃で２時間加熱撹拌した後、この溶媒中に無水フタル酸０．５５ｇ（６．７５ｍｍｏｌ）を添加し、１２５℃にてさらに１時間撹拌混合を行ない、均一溶液とした。室温まで冷却した後、−２０℃に保持された四塩化チタン４０ｍｌ（０．３６ｍｍｏｌ）中に１時間にわたって全量滴下装入した。
【０１８９】
その後、この混合液の温度を２時間かけて１１０℃に昇温し、１１０℃に達したところでジイソブチルフタレート０．５４ｍｌ（２．５ｍｍｏｌ）を添加し、これより２時間、１１０℃にて撹拌下に保持した。２時間の反応終了後、熱時濾過にて固体部を採取し、この固体部を２００ｍｌの四塩化チタンにて再懸濁させた後、再び１１０℃で２時間、加熱反応を行なった。
【０１９０】
反応終了後、再び熱濾過にて固体部を採取し、デカン及びヘキサンにて、洗液中に遊離のチタン化合物が検出されなくなるまで、充分洗浄した。以上の製造方法にて調整された固体チタン触媒は、ヘプタンスラリーとして保存した。固体チタン触媒の組成はチタン２．１重量％、塩素５７．０重量％、マグネシウム１８．０重量％及びジイソブチルフタレート２１．９重量％であった。
【０１９１】
（予備重合）
窒素置換を施した１Ｌ重合器中に精製ｎ−ヘキサン２００ｍｌ、トリエチルアルミニウム５０ｍｍｏｌ、ジジクロペ１０ｍｍｏｌ、および接触処理の施された固体チタン化合物成分をチタン原子換算で５ｍｍｏｌ装入した後、プロピレンを固体チタン触媒成分１ｇに対し２ｇとなるように３０分間連続的に重合器に導入した。尚、この間の温度は１０℃に保持した。３０分間後に反応を停止し、反応器内を窒素で充分に置換した。得られたスラリーの固体部分を精製ｎ−ヘキサンで５回洗浄し、予備重合触媒（チタン含有ポリプロピレン）を得た。分析の結果、固体チタン触媒１ｇに対し１．７ｇのプロピレンが重合されていた。
【０１９２】
（本重合）
窒素置換を施した内容量４００Ｌの重合器に、プロピレン１００ｋｇを装入し、トリエチルアルミニウム７５ｍｍｏｌ、有機ケイ素化合物としてジジクロペンチルジメトキシシラン３７．５ｍｍｏｌ、さらに水素ガスを装入した後、重合器の内温を６５℃に昇温した。上記予備重合で得られた予備重合触媒をチタン原子として０．２５ｍｍｏｌ装入し、続いて重合器の内温を７０℃まで昇温し、６時間の重合を行なった。
【０１９３】
重合終了後、重合停止剤としてメタノール５０ｍｌを加え反応を停止させ、次いで、重合槽中に液体プロピレンを３０Ｋｇ追加し、１時間攪拌した後、静置し重合体粒子を沈降させ、液体プロピレン部分を重合槽上部より取り付けられた抜き出しノズルで抜き取った。重合槽中の重合体スラリーはフラッシュタンクへ送り、未反応のプロピレンと分離させ、白色顆粒状の重合体を得た。得られたポリオレフィン樹脂ｎの構造特性を表１に示した。
【０１９４】
実施例７で用いたポリオレフィン樹脂ｌ及び上記のポリオレフィン樹脂ｎと、比較例２で得たポリオレフィン樹脂ｄを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１９５】
実施例１４
表１に示す実施例６で得たポリオレフィン樹脂ｋ及び参考例９で得たポリオレフィン樹脂ｎと、比較例１で得たポリオレフィン樹脂ｃを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０１９６】
実施例１５、参考例１０、実施例１６
（固体チタン触媒の調製）
固体チタン触媒の調製法は、特開平７−２９２０２９号公報の実施例１の方法に準じて行なった。
【０１９７】
すなわち、窒素ガスで十分に置換され、攪拌機を具備した容量２００ｍｌの丸底フラスコにジエトキシマグネシウム１０ｇおよびトルエン８０ｍｌを装入し、懸濁状態とした。次いで該懸濁溶液に四塩化チタン２０ｍｌを加えて、昇温し、８０℃に達した時点で、フタル酸ジ−ｎ−ブチル２．７ｍｌを加え、さらに昇温して１１０℃とした。その後１１０℃の温度を保持した状態で、２時間攪拌しながら反応させた。反応終了後、９０℃のトルエン１００ｍｌで２回洗浄し、新たにじ四塩化チタン２０ｍｌおよびトルエン８０ｍｌを加え、１００℃に昇温し、２時間攪拌しながら反応させた。
【０１９８】
反応終了後、４０℃のｎ−ヘプタン１００ｍｌで１０回洗浄して、固体チタン触媒を得た。尚、この固体チタン触媒中の固液を分離して、固体中のチタン含有率を測定したところ２．９１重量％であった。
【０１９９】
次いで、参考例９と同様にして予備重合および本重合を行ない、白色顆粒状の重合体を得た。得られたポリオレフィン樹脂ｏの構造特性を表１に示した。
【０２００】
表１に示す実施例６で得たポリオレフィン樹脂ｋ及び上記のポリオレフィン樹脂ｏと、比較例２で得たポリオレフィン樹脂ｄを用い、表２に示す配合量としたこと以外は、参考例１と同様に行った。その結果を表２，３に示した。
【０２０１】
【表１】

【０２０２】
【表２】

【０２０３】
【表３】

[0001]
BACKGROUND OF THE INVENTION
The present invention is a polyolefin resin modifier, particularly a crystalline polyolefin resin used in a stretched film, such as a polypropylene resin, for example, a modification effective for improving heat resistance such as film forming property, stretchability and low heat shrinkability. The present invention relates to an agent, a modified polyolefin resin composition, and a stretched film comprising the resin composition.
[0002]
[Prior art]
Stretched polyolefin films, especially biaxially stretched polyolefin films, are widely used for packaging materials and the like due to their excellent mechanical and optical properties. As the production method, a biaxial stretching method by a tenter method is generally used.
[0003]
In recent years, production facilities for biaxially stretched polyolefin films have been increased in size and speeded up. With conventional conventional polyolefin resins, the mechanical load of the stretching apparatus during film formation has increased, the thickness accuracy of the film has decreased, and the film Problems such as occurrence of stretching tears have occurred. Therefore, various methods for improving the stretch processability have been proposed. For example, Japanese Patent Application Laid-Open No. 9-324014 proposes a technique characterized by containing a specific indefinite amount and widening the stereoregularity distribution. However, there remains room for improvement as a stretched polyolefin film having good film forming properties even during high-speed film formation and excellent mechanical properties and heat resistance.
[0004]
[Problems to be solved by the invention]
Therefore, it has been desired to develop a polyolefin resin with good stretchability that can cope with an increase in the size and speed of production facilities for stretched polyolefin films. Therefore, the object of the present invention is to provide a wide temperature adjustment range capable of film formation during stretching, a small mechanical load, excellent thickness accuracy of the formed film, good stretchability, and no stretching breakage. The object is to obtain a polyolefin resin composition suitable for a uniaxially or biaxially stretched film that can be stably produced and has good heat resistance such as a film heat shrinkage rate, and a stretched film comprising the polyolefin resin composition. Another object of the present invention is to provide means for solving the problem of how to achieve the object.
[0005]
[Means for Solving the Problems]
The present inventors have intensively studied to solve the above objects and problems. As a result, when the crystalline polyolefin resin contains a specific amount of polyolefin present at a specific elution temperature and in a specific molecular weight range when measured by a temperature rising fractional correlation molecular weight measurement method, a film of an extensible film is formed. At that time, the temperature adjustment range of the film formation is wide, the mechanical load in stretching is reduced, the film is hardly stretched, the thickness accuracy of the formed stretched film is excellent, and the heat resistance such as the heat shrinkage rate is good. As a result, the present invention was completed.
[0006]
That is, the present invention is (1) Modification of a polyolefin resin containing a polyolefin having an elution temperature of 36 to 104 ° C. and a molecular weight in the range of 100,000 to 1,000,000 as an active ingredient, as measured by a temperature rising fractional correlation molecular weight measurement method. And (2) a crystalline polyolefin resin composition containing 4 to 20% by weight of an active ingredient for modifying the polyolefin resin.
[0007]
Furthermore, the present invention is (3) In addition to the above-mentioned polyolefin resin modifier, the elution temperature exceeds 116 ° C. and the molecular weight ranges from 10,000 to 100,000 when measured by a temperature rising fractional correlation molecular weight measurement method. By providing a crystalline polyolefin resin composition containing 4 to 20% by weight of the polyolefin as described above, a polyolefin resin composition having even better film processing characteristics is provided.
[0008]
Furthermore, the stretched film which consists of polyolefin resin composition shown to said (2) and (3) is also provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the temperature rising fractionation correlation molecular weight measurement method is an analytical method in which the temperature rising fractionation method (Temperature Rising Elution Fractionation: TREF method) and the molecular weight distribution measurement (Size Exclusion Chromatography: SEC method) are linked online. Also simply abbreviated as TREF / SEC method. In the TREF / SEC method, a polyolefin (polypropylene resin, etc.) crystallized in a solution is dissolved in a solvent at different temperatures, and the molecular weight distribution measurement and the elution amount (concentration) of the polyolefin at each dissolution temperature are continuously measured. This is a method for evaluating the composition distribution of the polyolefin.
[0010]
That is, an inert carrier such as diatomaceous earth or silica beads is used as a filler, and a sample solution having an arbitrary concentration obtained by dissolving a sample polyolefin in a solvent composed of orthodichlorobenzene is injected into the TREF column. After the sample temperature is lowered and the sample is attached to the packing material surface, the column temperature is raised stepwise to an arbitrary temperature, and a solvent made of orthodichlorobenzene is passed through and further eluted at the temperature. The polyolefin component is continuously introduced into a high-temperature SEC column, and the elution amount (% by weight) and the molecular weight distribution of the polyolefin are measured.
[0011]
By this operation, the composition distribution of the polyolefin can be seen in a graph drawn by the elution temperature and the molecular weight distribution (the crystallinity-molecular weight correlation diagram is shown by a contour line or a bird's eye view).
[0012]
The projected figure for the elution temperature shows the crystallinity distribution, and the elution temperature increases as the elution component becomes more easily crystallized. Therefore, by calculating the relationship between the elution temperature and the elution amount (% by weight) of the polymer, It is possible to know the distribution of crystallinity.
[0013]
In the above method, the temperature decrease rate of the TREF column needs to be adjusted to a rate necessary for crystallization of the crystalline part contained in the sample polyolefin at a predetermined temperature, and the temperature decrease rate of such a TREF column. May be determined in advance by experiments. Usually, the rate of temperature drop of the column is determined in the range of 5 ° C./min or less.
[0014]
In the present invention, the crystalline polyolefin resin composition contains 4 to 20% by weight, preferably 5 to 5% by weight of components having an elution temperature of 36 to 104 ° C. and a molecular weight of 100,000 to 1,000,000 by TREF / SEC method. It is an important point that it is present as an active ingredient at 18% by weight, more preferably 6-15% by weight. If the amount of the above-mentioned active ingredient in the crystalline polyolefin is less than 4% by weight, the stretchability at the time of stretching in the film formation is reduced, the temperature range in which the film can be formed is narrowed, the mechanical load is increased, and the film is broken. And the film thickness accuracy also deteriorates. On the other hand, if it exceeds 20% by weight, the heat shrinkage of the stretched film increases and the heat resistance decreases.
[0015]
Furthermore, with respect to the above active ingredient, a preferred embodiment is that the molecular weight of the elution component is in the range of 40 to 88 ° C., more preferably in the temperature range of 44 to 68 ° C. by the TREF / SEC method. Is preferred.
[0016]
In short, it is important that these active ingredients are present in the crystalline polyolefin resin composition of the present invention in an amount of 4 to 20% by weight, and the means is not particularly limited. For example, a polyolefin containing more than 20% by weight to 100% by weight of the active ingredient is produced as a crystalline polyolefin resin modifier (hereinafter referred to as modifier A), which is mechanically combined with the crystalline polyolefin resin. A method of mixing, or a method of obtaining a crystalline polyolefin resin and the active ingredient at the time of polymerization by appropriately selecting a catalyst to be used for polymerization when a crystalline polyolefin resin is obtained by polymerization is used. It is done. That is, the former is preferable for easily obtaining the crystalline polyolefin resin composition of the present invention, but the latter method is effective for obtaining uniform mixing of the modifier of the present invention and the crystalline polyolefin resin. There are many cases.
[0017]
In the present specification, regardless of the mixing method of the modifier active ingredient and the crystalline polyolefin resin, a material in which both are substantially uniformly integrated is referred to as a polyolefin resin composition of the present invention.
[0018]
In the present invention, the crystalline polyolefin resin that is modified by mixing a modifier is a propylene homopolymer or a propylene-α-olefin copolymer containing an α-olefin other than propylene as a copolymer component. Examples thereof include a combination and a mixture thereof.
[0019]
The propylene-α-olefin copolymer is a propylene-α-olefin having a content of monomer units based on one or more α-olefins other than propylene of 10 mol% or less, and further 5 mol% or less. It is preferably a copolymer or a mixture thereof. As the α-olefin, ethylene, butene-1, pentene-1, 3-methyl-1-butene, hexene-1, 3-methyl-1-pentene, 4-methyl-1-pentene, heptene-1, octene- Examples thereof include α-olefins having 2 to 20 carbon atoms such as 1, nonene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecene-1, and eicosene-1. The propylene-α-olefin copolymer may be either a random copolymer or a block copolymer, and among them, a random copolymer is preferable.
[0020]
When the crystalline polyolefin resin is a propylene homopolymer and a propylene-α-olefin copolymer and the content of α-olefin other than propylene is less than 1 mol%, the isotactic by 13C-NMR showing the crystallinity is shown. The tic pentad fraction is not particularly limited, but is preferably 0.80 to 0.99, more preferably 0.85 to 0.98, and further 0.88 to 0.97. It is more preferable that The isotactic pentad fraction referred to here is a. Macromolecules by A. Zambelli et al.,13267, (1980) is a fraction in which five propylene units quantified based on the assignment of the peak of the 13C-NMR spectrum published in (1980) continuously take the same configuration.
[0021]
Of course, the crystalline polyolefin resin used in the present invention is not limited to the above-described polypropylene resin, but is an olefin polymer or copolymer other than the polypropylene resin, and the amount of crystal part by X-ray diffraction. Is a polyolefin resin in which is present at 30% or more, preferably 40% or more.
[0022]
The physical properties of the polyolefin resin composition of the present invention are not particularly limited, but the melt flow rate (MFR) is usually in the range of 0.1 to 20 g / 10 min in view of moldability to a film. Is more preferable, and more preferably in the range of 1 to 10 g / 10 min. The weight average molecular weight (Mw) is 200,000 to 800,000, preferably 250,000 to 450,000. The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 2 considering the ease of film formation and the melt tension to improve workability. A range of 20 is preferable, and a range of 4 to 10 is more preferable.
[0023]
The molecular weight distribution was obtained from the weight average and number average molecular weight values calculated from the general-purpose calibration curve of polypropylene under the measurement conditions, as an elution profile measured by SEC at 145 ° C. using orthodichlorobenzene as a solvent. . Moreover, it is preferable that melting | fusing point is 130 degreeC or more, It is more preferable that it is the range of 135-170 degreeC, Furthermore, it is preferable that it is the range of 140-160 degreeC. The melting point of the polyolefin resin referred to here is the peak temperature of the crystal melting curve at the time of temperature rise measured by a differential scanning calorimeter (hereinafter simply referred to as DSC).
[0024]
The peak temperature of the elution curve by the TREF method of the polyolefin resin composition is preferably in the range of 100 to 130 ° C, considering the rigidity and heat resistance of the stretched film obtained by film formation, and in the range of 110 to 125 ° C. More preferably, it is in the range of 115 to 120 ° C. In addition, TREF said here melt | dissolves the polyolefin (polypropylene resin etc.) crystallized in the solution in a solvent at different temperature, measures the elution amount (concentration) of polyolefin in each melt temperature continuously, This is a method for evaluating the crystalline distribution of polyolefin.
[0025]
That is, an inert carrier such as diatomaceous earth or silica beads is used as a filler, and a sample solution having an arbitrary concentration obtained by dissolving a sample polyolefin in a solvent composed of orthodichlorobenzene is injected into the TREF column. The column temperature is increased linearly to an arbitrary temperature, a solvent made of orthodichlorobenzene is passed through, and the sample is further eluted at the temperature. The elution amount (% by weight) of the polyolefin component is measured. By this operation, the crystalline distribution of the polyolefin with respect to the elution temperature can be observed.
[0026]
In this method, the rate of temperature decrease of the TREF column needs to be adjusted to a rate necessary for crystallization at a predetermined temperature of the crystalline part contained in the polyolefin of the sample, and the rate of temperature decrease of such a TREF column. May be determined in advance by experiments. Usually, the rate of temperature drop of the column is determined in the range of 5 ° C./min or less.
[0027]
The elution component at 0 ° C. or less in the TREF / SEC method of the polyolefin resin composition is not particularly limited, but film surface physical properties such as blocking resistance, scratch resistance and slipping property of the formed polyolefin film. Is preferably 10% by weight or less, more preferably 7% by weight or less, and particularly preferably 5% by weight or less.
[0028]
Furthermore, the molecular weight of the elution component at 0 ° C. in the TREF / SEC method of the polyolefin resin composition is not particularly limited, but taking into consideration the occurrence of bleeding out on the film surface, the occurrence of fish eyes, etc., the SEC measurement The molecular weight at the peak top position of the obtained molecular weight distribution curve of the eluted component at 0 ° C. is preferably 10,000 to 400,000, more preferably 150,000 to 300,000.
[0029]
The polyolefin resin composition of the present invention has excellent thickness accuracy as long as the elution temperature by TREF / SEC method is 36 to 104 ° C. and the component having a molecular weight in the range of 100,000 to 1,000,000 is in the range of 4 to 20% by weight. Although stretchability is obtained, in order to further improve the heat resistance such as the heat shrinkage rate of the stretched film formed, the elution temperature by the TREF / SEC method exceeds 116 ° C., and the molecular weight is 10,000 to 100,000. It is preferable to contain 4 to 20% by weight of the polyolefin component in the range, more preferably 5 to 15% by weight, and even more preferably 6 to 10% by weight. Such a polyolefin component is also a polymer or copolymer made of olefins similar to the modifier.
[0030]
The present invention is described in further detail below.
[0031]
First, the modifier A of the present invention contains a component having an elution temperature of 36 to 104 ° C. and a molecular weight in the range of 101 to 1,000,000 by the TREF / SEC method, that is, containing more than 20% by weight to 100% by weight as an active ingredient. Further, it is preferably 40 to 100% by weight, and more preferably 50 to 100% by weight. Furthermore, it is more preferable that the elution temperature according to the TREF / SEC method is 50 to 100% by weight in the range of 40 to 88 ° C. and a molecular weight of 100 to 1,000,000, and the elution temperature is 44 to 68 ° C. and the molecular weight is 10 to 10%. Most preferably, the component in the range of 1 million is contained in an amount of 50 to 100% by weight.
[0032]
As long as the modifier A contains more than 20% by weight to 100% by weight of the active ingredient, a crystalline polyolefin resin generally having lower crystallinity than the crystalline polyolefin resin can be used without any limitation. . Examples of the modifier A include an α-olefin homopolymer, a copolymer of two or more α-olefins, a mixture of these polymers, and the like. The α-olefin copolymer may be either a random copolymer or a block copolymer, and among them, a random copolymer is preferable.
[0033]
Examples of the α-olefin include ethylene, propylene, butene-1, pentene-1, 3-methyl-1-butene, hexene-1, 3-methyl-1-pentene, 4-methyl-1-pentene, and heptene-1. Octene-1, nonene-1 and the like.
[0034]
Among these modifiers A, in particular, propylene homopolymer, ethylene-propylene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene A -1-hexene copolymer, a propylene-ethylene-1-butene copolymer, and a mixture thereof are preferably used.
[0035]
The melt flow rate of the modifier A is not particularly limited, but is preferably 1 to 20 g / 10 minutes. The weight average molecular weight (Mw) is preferably in the range of 100,000 to 400,000. Furthermore, the range of 1.5-15 is suitable for molecular weight distribution (Mw / Mn).
[0036]
Furthermore, the melting point of the modifier A is not particularly limited, but it is preferable that at least one melting peak exists in the range of 60 to 150 ° C.
[0037]
In addition, the elution component of the modifying agent A at 0 ° C. or less in the TREF / SEC method is not particularly limited, but the film such as blocking resistance, scratch resistance, and slipping property of the formed polyolefin film is not limited. Considering the surface properties, it is preferably 5% by weight or less, more preferably 4% by weight or less, and further preferably 3% by weight or less.
[0038]
The modifier A may be obtained by any method. For example, a method of individually polymerizing each elution component constituting the modifier A and mixing them, a state in which a polypropylene component and a propylene-ethylene random copolymer component are arranged in a single molecular chain, and / or There is a method of obtaining a so-called block copolymer that can achieve a state in which molecular chains composed of each of a polypropylene component and a propylene ethylene random copolymer component are mixed microscopically to a degree that cannot be achieved by mechanical mixing. The modifier A obtained as a block copolymer has an excellent stretchability improving effect and is preferable for obtaining a more transparent stretched film.
[0039]
Although the manufacturing method for obtaining the modifier A as a block copolymer is not specifically limited as long as the requirements of the present invention are satisfied, for example, it can be suitably manufactured by the following method.
[0040]
That is, a polypropylene component (a), propylene and ethylene in the presence of a catalyst comprising a metallocene compound (hereinafter abbreviated as component [I]) and an aluminoxane compound or a non-coordinating ionized compound (hereinafter abbreviated as component [II]). And a method of producing the copolymer component (b) in a stepwise manner.
[0041]
As the component [I], a compound known to be used for olefin polymerization can be used without any limitation. Among them, the following general formula (1) can be used.
Q (C_FiveH_4-mR_1m) (C_FiveH_4-nR_2nMX₁X₂    (1)
(In the formula, M represents a transition metal atom of Group IVb of the periodic table. (C_FiveH_4-mR_1m), (C_FiveH_4-nR_2n) Represents a substituted cyclopentadienyl group, m and n are integers of 1 to 3, and R₁And R₂May be the same or different from each other, and are substituted with a hydrocarbon bonded to two carbon atoms on a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, or a cyclopentadienyl ring. It is the hydrocarbon group which forms the 1 or more hydrocarbon ring which may be made.
[0042]
Q is (C_FiveH_4-mR_1m) And (C_FiveH_4-nR_2nAnd a divalent hydrocarbon group, unsubstituted silylene group or hydrocarbon-substituted silylene group. X₁And X₂May be the same or different and each represents a hydrogen, halogen or hydrocarbon group. ) Can be preferably used.
[0043]
More preferably, in the formula (1), M is a zirconium or hafnium atom, and R₁, R₂Are the same or different hydrocarbon groups having 1 to 20 carbon atoms, X₁And X₂Are the same or different halogen atoms or chiral metallocene compounds in which the hydrocarbon group Q is a hydrocarbon-substituted silylene group.
[0044]
Specific components [I] are exemplified by rac-dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene (2,4- Dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dimethyl, rac-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′trimethylcyclo Pentadienyl) zirconium dichloride, rac-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4′5 ′, 5′-trimethylcyclopentadienyl) zirconium dimethyl, rac-dimethylsilylenebis (2-Methyl-indenyl) zirconium dichloride rac-diphenylsilylenebis (2-methyl-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-indenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-indenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-Methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, ac-dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, rac-diphenylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dimethyl Rac-diphenylsilylenebis (2,4-dimethyl-indenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-isopropyl) Indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl) -4-Isopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium Dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis ( 2-Methyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-t-butylindenyl) zirconium dichloride, rac-dimethylsilyl Bis (2-methyl-4-t-butylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4-t-butylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4- Phenylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-Methyl-4-phenylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4- Phthylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2 -Methyl-benzindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-benzindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-benzindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-benzindenyl) Zirconium dimethyl etc. are mentioned.
[0045]
A compound in which zirconium in the above compound is replaced with hafnium is also preferably used. Moreover, the above metallocene compounds can be used in combination.
[0046]
As the component [II], known compounds can be used without any limitation, and among them, the following can be preferably used. The aluminoxane compound is preferably an aluminum compound represented by the general formula (2) or (3).
[0047]
[Chemical 1]

[0048]
[Chemical 2]

[0049]
In the general formula (2) or (3), R is an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. Among these, a methyl group is particularly preferable, and a part of the alkyl group having 2 to 6 carbon atoms may be included. m is an integer of 4 to 100, preferably 6 to 80, particularly preferably 10 to 60.
[0050]
The production method of the above aluminoxane compound may be any of various known methods, for example, a method of reacting trialkylaluminum directly with water in a hydrocarbon solvent, copper sulfate hydrate having crystal water, aluminum sulfate Examples thereof include a method of reacting moisture adsorbed in a hydrocarbon solvent with trialkylaluminum using hydrate, water-containing silica gel or the like.
[0051]
As the non-coordinating ionizable compound, any known non-coordinating ionizable compound other than the aluminoxane compound can be used without particular limitation. In particular, an ionized compound containing a boron atom can be suitably used.
[0052]
Specific examples of ionized compounds containing boron atoms include Lewis acids containing boron atoms and ionic compounds containing boron atoms.
[0053]
Examples of the Lewis acid containing a boron atom include a compound represented by the general formula (4).
[0054]
BR_Three             (4)
In the above general formula, R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group, trifluoromethyl group or the like.
[0055]
Specific examples of the compound represented by the general formula (4) include trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, and tris (4-fluoro). Examples thereof include methylphenyl) borane, tris (pentafluorophenyl) borane, tris (p-tolyl) borane, tris (o-tolyl) borane, and tris (3,5-dimethylphenyl) borane. Among these, tris (pentafluoro) borane is preferably used.
[0056]
Examples of ionic compounds containing boron include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
[0057]
Specifically, the trialkyl-substituted ammonium salt includes triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributyl Examples include ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, and the like, and N, N-dialkylanilinium salts. N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron, etc. Examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Examples of the triarylphosphonium salt include triphenylphosphonium salt. Examples thereof include nium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.
[0058]
Among the above-mentioned Lewis acids containing boron atoms or ionic compounds containing boron atoms, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium Mention may also be made of tetra (pentafluorophenyl) borate. Of these, triphenylcarbonium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferably used.
[0059]
The amount of component [I] and component [II] used is arbitrary, but the amount of component [II] used when an aluminoxane compound is used for component [II] (the molar amount of Al atoms in component [II]) ) Is preferably 0.1 to 100,000 mol, more preferably 1 to 50,000 mol, and still more preferably 10 to 30,000 mol with respect to 1 mol of the transition metal in component [I]. is there. In addition, when the non-coordinating ionized compound is used as the component [II], the amount of the component [II] used (the molar amount of the group 3B atom in the component [II]) is the transition metal in the component [I]. 0.01-10,000 mol is preferable with respect to 1 mol, More preferably, it is 0.1-5,000 mol, More preferably, 1-3000 mol is suitable.
[0060]
In the method of producing a polypropylene component (a) and a copolymer component (b) of propylene and ethylene stepwise in the presence of a catalyst comprising the components [I] and [II], an organoaluminum compound (hereinafter referred to as “aluminum compound”) Component (III)) may be used in combination. Component [III] is a compound represented by general formula (5).
[0061]
AlR_mX_3-m  (5)
(In the formula, R represents a hydrocarbon group such as an alkyl group having 1 to 10 carbon atoms, an aryl group, or an alkoxy group. X represents a halogen atom. M is an Al valence of 1 to 3. is there.)
[0062]
Specific examples of the compound represented by the general formula (5) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and trin. -Trialkylaluminums such as octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, diethylaluminum monobromide, dialkylaluminum monohalides such as diethylaluminum monofluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethyl Alkyl aluminum halides such as aluminum dichloride, diethyl aluminum monoethoxide, ethyl acetate Alkoxy aluminum such as mini um di ethoxide. Among these, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum are preferably used.
[0063]
The amount of component [III] to be used is not particularly limited, but in general, it is preferably 1 to 50,000 mol, more preferably 5 to 10, with respect to 1 mol of the transition metal atom in component [I]. 000 mol. Especially preferably, it is 10-5,000 mol.
[0064]
Component [I] and / or component [II] can be used by being supported on a particulate carrier (hereinafter abbreviated as component [IV]). When the catalyst component is supported on the support, the particle properties of the polymer obtained are improved, and process compatibility in resin production, such as prevention of polymerization scale in the reactor, can be greatly improved.
[0065]
As the fine particle carrier, those having a function as a carrier are used without limitation, and inorganic oxides are particularly preferable.
[0066]
Specifically, SiO₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Etc. or mixtures thereof such as SiO₂-Al₂O_Three, SiO₂-MgO, SiO₂-TiO₂, SiO₂-V₂O_Five, SiO₂-Cr₂O_Three, SiO₂-TiO₂-MgO etc. can be used conveniently. Among these, especially SiO₂And Al₂O_ThreeA carrier containing at least one component selected from the group consisting of as a main component is more preferable.
[0067]
The carrier has different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, more preferably 20 to 200 μm, and a specific surface area of preferably 50 to 1000 m.^Three/ G, more preferably 100 to 700 m^Three/ G, pore volume is preferably 0.3 to 3.0 cm^Three/ G, more preferably 0.5 to 2.5 cm^Three/ G.
[0068]
The inorganic fine particle carrier is usually used after being fired at 150 to 1000 ° C, preferably 200 to 800 ° C.
[0069]
The particle size of these carriers is generally 0.1 to 500 μm, preferably 1 to 200 μm, more preferably 10 to 100 μm. When the particle size is small, the produced particles become a finely divided polymer, and when the particle size is too large, the particles become coarse and difficult to handle the powder.
[0070]
The pore volume of these carriers is usually 0.1 to 5 cm.^Three/ G, preferably 0.3-3 cm^Three/ G. The pore volume can be measured by a BET method or a mercury intrusion method.
[0071]
The amount of the metallocene compound [I] used per 1 g of the fine particle carrier [IV] is 0.005 to 1 mmol, preferably 0.05 to 0.5 mmol in terms of transition metal atoms. When an aluminoxane compound is used as component [II], the amount of the aluminoxane compound used relative to the metallocene compound [I] is 1 mol of transition metal atoms in component [I] in terms of the molar amount of Al atoms. The amount is preferably 1 to 200 mol, more preferably 15 to 150 mol.
[0072]
When the non-coordinating ionized compound is used, the amount of the non-coordinating ionized compound used relative to the metallocene compound [I] is converted into the molar amount of the Group 5A atom in the non-coordinating ionized compound. Preferably it is 0.1-20 mol with respect to 1 mol of transition metal atoms in [I], More preferably, it is 1-15 mol.
[0073]
In order to obtain the obtained polymer with more excellent particle properties, the following method can also be employed. That is, olefin prepolymerization is first performed in the presence of the component [I], the component [II], the component [IV] and, if necessary, the component [III]. The amount of the component [III] used in the prepolymerization is not particularly limited, but is preferably 1 to 50,000 mol, more preferably 5 to 10, with respect to 1 mol of the transition metal atom in the component [I]. 000 mol. Especially preferably, it is 10-5,000 mol.
[0074]
Each of the above components used in the prepolymerization may be added sequentially one by one, or a mixture may be added all at once. Preferably, a method of bringing the components [I] and [IV] into contact with the catalyst component [IV] in advance is employed. More preferably, after the component [II] is supported on the catalyst component [IV], the method of supporting the component [I] is effective for obtaining a random copolymer with a better bulk specific gravity.
[0075]
Examples of the olefin used in the preparation of the prepolymerization catalyst component include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 4,4-dimethyl. -1-pentene, 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and other α-olefins; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1 , 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like. It is.
[0076]
Furthermore, styrene, dimethylstyrenes, allyl norbornane, allylbenzene, allylnaphthalene, allyltoluenes, vinylcyclopentane, vinylcyclohexane, vinylcyclopeptane, diene, and the like can be used.
[0077]
Preferably, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-heptene, 4 -Methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene, 1-octene, 1-decene, cyclopentene, vinylcyclohexane, particularly preferred Are ethylene, propylene, 1-butene, 1-heptene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene.
[0078]
The prepolymerization is preferably carried out by substantially homopolymerization of 95 mol% or more of olefin.
[0079]
The polymerization amount of the olefin initially applied in the prepolymerization of the present invention is preferably 0.1 to 1000 g, more preferably 1 per 1 g of the catalyst formed from the catalyst components [I], [II] and [IV]. Select from a range of ~ 50g.
[0080]
In addition, as a particularly preferred embodiment of the prepolymerization, in the above prepolymerization, first, in the presence of each component of [I], [II], [IV] and optionally [III], propylene A method in which 1-butene is further preliminarily polymerized stepwise in the presence of the first prepolymerization catalyst and the component [III] is preferably used.
[0081]
The amount of component [III] used in the prepolymerization is not particularly limited, but is generally 1 to 50,000 mol, preferably 5 to 10, mol per 1 mol of transition metal atom in component [I]. 000 mol. More preferably, it is 10-5,000 mol. After obtaining the first prepolymerization catalyst by the above-mentioned prepolymerization of propylene, it is usually desirable to remove unreacted propylene and the component [III] used as necessary by washing, and then subject to the subsequent prepolymerization.
[0082]
In each preliminary polymerization stage, it is preferable to carry out substantially homopolymerization of propylene and 1-butene at 95 mol% or more, preferably 98 mol% or more.
[0083]
The polymerization amount of propylene initially applied in the preliminary polymerization is from 0.1 to 1000 g, preferably from 1 to 10 g, per 1 g of the catalyst formed from the catalyst components [I], [II] and [IV]. The polymerization amount of 1-butene to be performed next is selected in the range of 0.1 to 1000 g, preferably 1 to 500 g, per 1 g of the catalyst formed from the catalyst components [I], [II] and [III]. Good. The ratio of the propylene polymerization amount to the 1-butene polymerization amount is preferably in the range of 0.001 to 100, preferably 0.005 to 10 in terms of the weight ratio of propylene polymerization amount / 1-butene polymerization amount.
[0084]
For the prepolymerization, it is usually preferable to apply slurry polymerization, and as the solvent, saturated aliphatic hydrocarbons or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene may be used alone, or a mixed solvent thereof may be used. it can. Each prepolymerization temperature is preferably −20 to 100 ° C., particularly preferably 0 to 60 ° C., and each stage of the prepolymerization may be performed under different temperature conditions. The prepolymerization time may be appropriately determined according to the prepolymerization temperature and the amount of polymerization in the prepolymerization, and the pressure in the prepolymerization is not limited, but in the case of slurry polymerization, generally from atmospheric pressure to 5 kg / cm.²Degree.
[0085]
Each preliminary polymerization may be carried out by any of batch, semi-batch and continuous methods.
[0086]
After completion of each prepolymerization, it is preferable to wash saturated aliphatic hydrocarbons or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene alone or with a mixed solvent thereof. 5-6 times are preferable.
[0087]
The modifier A is produced by stepwise polymerization of a polypropylene component and a copolymer component of propylene and ethylene in the presence of the catalyst component described above. The order of polymerization is not particularly limited, but the production of the polypropylene component (a) in the first stage and the production of the copolymer component (b) of propylene and ethylene in the second stage produces a polymer with good particle properties. Therefore, it is preferable.
[0088]
The polymerization conditions are not particularly limited as long as the effect is recognized, but the following conditions are generally preferred.
[0089]
The polymerization of the polypropylene component (a) may be carried out by supplying propylene alone or a mixture of propylene and another α-olefin containing ethylene within the range satisfying the requirements of the present invention. The polymerization temperature in the propylene polymerization is 0 to 100 ° C, preferably 20 to 80 ° C.
[0090]
In the polymerization of the polypropylene component (a), hydrogen can be allowed to coexist as a molecular weight regulator. In addition, any method such as slurry polymerization, gas phase polymerization, solution polymerization or the like using the monomer itself used for polymerization as a solvent may be used. Considering the simplicity of the process and the reaction rate, and the particle properties of the copolymer to be produced, slurry polymerization using propylene itself as a solvent is a preferred form.
[0091]
The polymerization method may be any of batch, semi-batch and continuous methods. Furthermore, the polymerization can be carried out in two or more stages with different conditions such as hydrogen concentration and polymerization temperature.
[0092]
Next, random copolymerization of propylene and ethylene is performed. In the random copolymerization of propylene and ethylene, in the case of slurry polymerization using propylene itself as a solvent, ethylene gas is supplied following the propylene polymerization, and in the case of gas phase polymerization, a mixed gas of propylene and ethylene is supplied. It is carried out by doing.
[0093]
In the random copolymerization of propylene and ethylene, it is preferable to perform one-stage random copolymerization following propylene polymerization, but it can also be produced by changing the ethylene supply concentration in multiple stages. The polymerization temperature for the random copolymerization of propylene and ethylene is 0 to 100 ° C, preferably 20 to 80 ° C. Further, if necessary, hydrogen can be used as a molecular weight regulator, and the polymerization can be carried out by changing the hydrogen concentration at that time in multiple steps or continuously.
[0094]
The random copolymerization of propylene and ethylene may be any of batch, semi-batch and continuous methods, and the polymerization can be carried out in multiple stages. Further, the polymerization in this step may employ any method of slurry polymerization, gas phase polymerization, and solution polymerization.
[0095]
After the completion of the main polymerization, the monomer can be evaporated from the polymerization system to obtain the modifier A of the present invention. This modifier A can be subjected to known washing or countercurrent washing with a hydrocarbon having 7 or less carbon atoms.
[0096]
The method for producing the polyolefin resin composition of the present invention by mixing the modifier A with the crystalline polyolefin resin as described above is not particularly limited. For example, a powder blend method or a pellet blend method using a tumbler, a Henschel mixer, or the like can be used.
[0097]
Also, when the polyolefin resin composition of the present invention is produced by mixing in the process of producing the active ingredient of the modifier A and the crystalline polyolefin resin by polymerization, for example, different stereoregular polypropylene resins can be polymerized. A method of polymerizing propylene by mixing several kinds of catalyst components can be mentioned. In particular, a method in which propylene is polymerized by mixing two or more kinds of electron donors that give polypropylene resins having different solid titanium catalyst components, organoaluminum compounds, and stereoregularity can be suitably employed.
[0098]
In this method, as the electron donor, those generally known in the polymerization of propylene can be used without any limitation. However, when an organosilicon compound represented by the following general formula (V) and general formula (VI) is used in combination, A composition containing 4 to 20% by weight of a component having an elution temperature of 36 to 104 ° C. and a molecular weight of 100,000 to 1,000,000 in the range of the present invention is particularly preferable.
[0099]
[Chemical Formula 3]

[0100]
(R_Three)_n-Si- (OC₂H_Five)_4-n         (VI)
(However, R₁, R₂And R_ThreeAre the same or different hydrocarbon groups, and n is 0 or 1. )
[0101]
As the solid titanium catalyst component, any compound known to be used for propylene polymerization can be used without any limitation. In particular, a solid titanium catalyst component having high catalytic activity containing titanium, magnesium and halogen as components is suitable. Such a catalyst component is obtained by supporting titanium halide, particularly titanium tetrachloride, on various magnesium compounds, particularly, magnesium chloride.
[0102]
As the organoaluminum compound, a compound known to be used for polymerization of propylene can be used without any limitation.
[0103]
For example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, etc. Examples include alkylaluminums; diethylaluminum monohalides such as diethylaluminum monochloride; alkylaluminum halides such as methylaluminum dichloride and ethylaluminum dichloride.
[0104]
In addition, alkoxyaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can be used. Of these, triethylaluminum is most preferable.
[0105]
The amount of the organoaluminum compound used is preferably 10 to 1000, more preferably 50 to 500, in terms of aluminum / titanium (molar ratio) with respect to titanium atoms in the solid titanium catalyst component.
[0106]
In the organosilicon compounds represented by the general formula (V) and the general formula (VI), R₁, R₂And R_ThreeThe hydrocarbon group represented by can include a chain, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and the number of carbon atoms is not particularly limited.
[0107]
Examples of suitable hydrocarbon groups in the present invention include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group. An alkyl group having 1 to 6 carbon atoms such as hexyl group; an alkenyl group having 2 to 6 carbon atoms such as vinyl group, propenyl group and allyl group; an alkynyl group having 2 to 6 carbon atoms such as ethynyl group and propynyl group; cyclopentyl A cycloalkyl group having 5 to 7 carbon atoms such as a group, a cyclohexyl group and a cycloheptyl group; an aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group. Among these, R3 is preferably a linear alkyl group, alkenyl group, or aryl group. N is 0 or 1.
[0108]
Examples of the organosilicon compound suitably used in the present invention are as follows.
[0109]
Examples of the organosilicon compound represented by the general formula (V) include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, divinyldimethoxysilane, diallyldimethoxysilane, di-1-propenyldimethoxysilane, diethynyldimethoxysilane, Diphenyldimethoxysilane, methylphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, tertiary butylethyldimethoxysilane, ethylmethyldimethoxysilane, propylmethyldimethoxysilane, cyclohexyltrimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, vinyltrimethoxysilane, Examples thereof include phenyltrimethoxysilane and allyltrimethoxysilane.
[0110]
Examples of the organosilicon compound represented by the general formula (VI) include tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, isopropyltriethoxysilane, Examples thereof include 1-propenyltriethoxysilane, isopropenyltriethoxysilane, ethynyltriethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane, and allyltriethoxysilane.
[0111]
The amount of the organosilicon compound represented by the general formula (V) and the general formula (VI) is preferably 0.1 to 500 in terms of Si / Ti (molar ratio) with respect to Ti atoms of the solid titanium catalyst component, respectively. Is preferably 1 to 100. Further, the use ratio of these two kinds of organosilicon compounds is required to be (V) :( VI) = 1: 5 to 1:25 in molar ratio, and 1:10 to 1:20. preferable. When the use ratio of the organosilicon compounds (V) and (VI) is less than 1: 5, the elution peak width by TREF of the obtained polypropylene resin becomes narrow, that is, the elution temperature is 36 to 104 ° C. Since the component amount is low, the stretchability at the time of film formation is lowered, the mechanical load is increased, and the film is easily stretched and broken.
[0112]
The order of addition of the above components is not particularly limited, and the organosilicon compounds represented by the general formula (V) and the general formula (VI) may be mixed and supplied at the same time or may be supplied separately. They can also be supplied after previously contacting or mixing with the organoaluminum compound.
[0113]
Other polymerization conditions are not particularly limited as long as the effects of the present invention are recognized, but the following conditions are generally preferred. The polymerization temperature is 20 to 200 ° C., preferably 50 to 150 ° C., and hydrogen can coexist as a molecular weight regulator. The polymerization can be performed by slurry polymerization, solventless polymerization, gas phase polymerization, and the like, and may be any of batch, semi-batch, and continuous methods, and the polymerization can be performed in two stages with different conditions. . In addition, prepolymerization of propylene and other monomers may be performed before the polymerization of propylene. Furthermore, the above polymerization may be performed in multiple stages.
[0114]
In the present invention, the polypropylene resin composition obtained by the above-described method can be used alone, or can be blended with other polypropylene resins. Of course, the polypropylene resin compositions obtained by the above-described method can also be blended.
[0115]
In the present invention, the polyolefin resin composition obtained as described above is used as it is or appropriately, so that components having an elution temperature of 36 to 104 ° C. and a molecular weight of 101 to 1,000,000 by TREF / SEC method are obtained. A polyolefin resin composition containing 4 to 20% by weight can be obtained. Or the modifier A or crystalline polyolefin resin can be further mixed with this resin composition, and it can be set as the polyolefin resin composition of this invention of a desired composition.
[0116]
The polyolefin resin composition of the present invention containing 4 to 20% by weight of a component having an elution temperature by TREF / SEC method exceeding 116 ° C. and a molecular weight in the range of 10,000 to 100,000 is obtained in the same manner as described above. It is possible. Further, a modifying agent (hereinafter referred to as modifying agent B) having an elution temperature by TREF / SEC method exceeding 116 ° C. and containing a component having a molecular weight in the range of 10,000 to 100,000 in excess of 20% by weight to 100% by weight; It is also possible to produce the modifier A by mixing it with a crystalline polyolefin resin.
[0117]
The modifier B is a highly crystalline polypropylene resin. The melt flow rate of the modifying agent B is not particularly limited, but considering the moldability to a film, the range of 5 to 100 g / 10 min is preferable, and further 30 to 80 g / 10 min. More preferably, it is in the range. The weight average molecular weight (Mw) is preferably in the range of 50,000 to 800,000, preferably 100,000 to 300,000.
[0118]
The molecular weight distribution (Mw / Mn) of the modifier B is not particularly limited, but is 1.5 to 40 in consideration of the ease of film formation and the improvement of workability by increasing the melt tension. It is preferable that it is, and it is more preferable that it is 2-10.
[0119]
The melting point of the modifier B is not particularly limited, but is preferably 150 ° C. or higher, and more preferably in the range of 155 to 170 ° C.
[0120]
The peak top temperature of the elution curve by the TREF method of the modifier B is preferably 110 or more in consideration of the rigidity and heat resistance of the stretched film obtained by film formation, and is in the range of 115 to 130 ° C. More preferably.
[0121]
The elution component at 0 ° C. or lower in the TREF / SEC method of the modifier B is not particularly limited, but film surface physical properties such as blocking resistance, scratch resistance and slipping property of the formed polyolefin film. Is preferably 5% by weight or less, and more preferably 3% by weight or less.
[0122]
In addition, when the modifier B is a propylene homopolymer and a propylene-α olefin copolymer and the content of α-olefin other than propylene is less than 1 mol%, it shows its crystallinity.¹³Although the isotactic pentad fraction by C-NMR is not particularly limited, it is preferably 0.80 to 1, and more preferably 0.93 to 0.99.
[0123]
Furthermore, a modifier (referred to as modifiers A and B) in which modifier A and modifier B are mixed in advance in a ratio of 20 to 80 or 80 to 20 is obtained and mixed with the crystalline polyolefin resin. It is also possible to do.
[0124]
The weight ratio (B / A) of each active ingredient of the modifier A and the modifier B mixed with the crystalline polyolefin resin is preferably in the range of 0.5 to 2, more preferably 0.8 to 1. The range is 5. By setting it within this range, it is possible to improve the stretchability in film formation, that is, to increase the range of temperature at which the film can be formed in stretching, reduce the mechanical load, reduce film breakage, and improve the thickness accuracy.
[0125]
The polyolefin resin composition used in the present invention includes an antioxidant, a chlorine scavenger, a heat stabilizer, an antistatic agent, an antifogging agent, an ultraviolet absorber, a lubricant, a nucleating agent, and an antiblocking agent as necessary. Further, additives such as pigments, other resins and fillers may be blended within a range where the effects are not hindered.
[0126]
The polyolefin resin composition of the present invention can be used for the production of any molded body, and exhibits excellent extrusion characteristics and stretchability, but is particularly prominent when it is formed by stretching to obtain a stretched film. Demonstrate the effect.
[0127]
The polyolefin stretched film of the present invention may be a biaxially stretched film or a uniaxially stretched film. The thickness of the stretched film is not particularly limited, but is preferably in the range of 3 to 150 μm for a biaxially stretched film and 10 to 254 μm for a uniaxially stretched film. The stretched polyolefin film of the present invention is stretched in at least a uniaxial direction. Of course, it may be extended in a biaxial direction. Although the stretching ratio is not particularly limited, it is generally 4 to 10 times in the uniaxial direction, and in the case of biaxial stretching, it is generally stretched in the range of 4 to 15 times in the direction perpendicular thereto. Is.
[0128]
One side or both sides of the stretched polyolefin film of the present invention may be subjected to surface treatment such as corona discharge treatment, if necessary. Furthermore, a layer made of another resin having a lower melting point than the polyolefin resin used in the present invention may be laminated on one side or both sides for the purpose of imparting a function such as heat sealability. The method for laminating other resins is not particularly limited, but a coextrusion method, a laminating method and the like are preferable.
[0129]
As a method for producing the stretched polyolefin film of the present invention, a known method can be adopted without any limitation. For example, as a method for producing a stretched film by a sequential biaxial stretching method using a tenter method, the above polypropylene composition is formed into a sheet or film by a T-die method, an inflation method, etc., and then supplied to a longitudinal stretching apparatus and heated. A method in which the film is longitudinally stretched 3 to 10 times at a roll temperature of 120 to 170 ° C., and then stretched 4 to 15 times in a tenter temperature of 130 to 180 ° C. using a tenter is preferable.
[0130]
The molding conditions are not particularly limited, but in order to obtain a stretched film having good thickness accuracy and fusing sealability, it is 3 to 5 times at 145 to 170 ° C in longitudinal stretching and 4 to 155 to 180 ° C in transverse stretching. It is preferable to stretch ~ 12 times. Furthermore, the method of heat-processing at 80-180 degreeC can be mentioned, allowing the relaxation of 0-25% to a horizontal direction as needed. Of course, you may extend | stretch again after these extending | stretching and can extend | stretch drawing methods, such as multistage extending | stretching and rolling, in longitudinal stretch.
Moreover, it can be set as a stretched film also by uniaxial stretching.
[0131]
【The invention's effect】
The polyolefin resin composition of the present invention has a wide temperature adjustment range in which a stretched film can be formed as compared to a conventionally known polyolefin resin, a small mechanical load during stretching, and a thickness accuracy of the formed film. Is excellent, stretchability is good, and stretch breakage hardly occurs. Therefore, it is a polyolefin resin suitable for production of a stretched film capable of continuous operation stably at high speed for a long time. Furthermore, the heat resistance such as the heat shrinkage rate of the formed stretched film is good. Such an effect indicates that the polyolefin resin composition of the present invention is excellent as a polyolefin resin composition for stretched film and has an extremely high industrial value.
[0132]
【Example】
In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples.
[0133]
(1) TREF / SEC
The molecular weight distribution curve, weight average molecular weight and elution amount in the elution temperature range by TREF / SEC were measured in the TREF / SEC mode under the following conditions using a uniflows multi-purpose liquid chromatograph apparatus.
[0134]
Solvent: orthodichlorobenzene
TREF column: 4.6 mmφ × 150 mm
Filler: Chromosolve P
Flow rate: 1.0 ml / min
Crystallization conditions: 140 ° C. to 0 ° C. (Cooling rate: 2.0 ° C./hour)
Temperature rising condition: 4 ° C. step Total 36 fractions (0, 4, 8, 12, 16, 20, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 76 80, 84, 88, 92, 96, 100, 104, 108, 112, 116, 120, 124, 128, 132, 136, 140)
SEC column: SHODEX UT 807 + 806M x 2
SEC temperature chamber: 145 ° C
Detector: Infrared detector for high-temperature liquid chromatography
Measurement wave number: 3.41 μm
Sample concentration: 0.4 wt%
Injection volume: 500 μl
[0135]
In this case, after introducing the sample solution into the TREF column at 140 ° C., the liquid feeding is stopped and the temperature is decreased from 140 ° C. to 0 ° C. at 2 ° C./hour to crystallize the sample polymer on the surface of the filler. After holding at 0 ° C. for 30 minutes, the components dissolved at 0 ° C. are introduced into the SEC column at 1.0 ml / min, and SEC measurement is performed. In the meantime, in the TREF thermostat, the temperature is rapidly raised to the next measurement temperature (4 ° C.) and held until the SEC measurement is completed. Similarly, a component dissolved at 4 ° C. is introduced into the SEC column, and SEC measurement is performed. Thereafter, the SEC measurement is repeated until the set temperature.
[0136]
(2) TREF
The amount of elution temperature by TREF was measured in a TREF mode under the following conditions using a multi-purpose liquid chromatograph manufactured by Uniflows.
[0137]
Solvent: orthodichlorobenzene
TREF column: 4.6 mmφ × 150 mm
Filler: Chromosolve P
Flow rate: 1.0 ml / min
Crystallization conditions: 140 ° C. to 0 ° C. (Cooling rate: 2.0 ° C./hour)
Temperature rise conditions: Continuous temperature rise 40 ° C / hr (temperature range 0 ° C to 140 ° C)
Detector: Infrared detector for high-temperature liquid chromatography
Measurement wave number: 3.41 μm
Sample concentration: 0.4 wt%
Injection volume: 500 μl
[0138]
Similar to the TREF / SEC measurement, after crystallization of the sample, the sample is held at 0 ° C. for 30 minutes, and the concentration of the component dissolved at 0 ° C. is detected. Thereafter, while increasing the TREF column temperature linearly at a predetermined rate, the solvent is passed to detect the concentration, and the elution amount with respect to the elution temperature is obtained.
[0139]
(3) Melt flow rate (MFR)
It measured according to JISK7210.
[0140]
(4) Molecular weight distribution
It calculated | required using the value of the weight average molecular weight and the number average molecular weight computed from the elution profile measured on the following conditions using the high temperature GPC apparatus SSC-7100 made by Senshu Scientific.
[0141]
Solvent: Orthodichlorobenzene
Flow rate: 1.0 ml / min
Column temperature: 145 ° C
Detector: High-temperature differential refraction detector
Column: SHODEX UT807 (1), 806M (2), 802.5 (1)
Sample concentration: 0.1% by weight
Injection volume: 0.50 ml
[0142]
(5) Pentad fraction
JNM-GSX-270 (manufactured by JEOL Ltd.)¹³C-nuclear resonance frequency (67.8 MHz) was measured under the following conditions.
[0143]
Measurement mode: 1H-complete decoupling
Pulse width: 7.0 microseconds (C45 degrees)
Pulse repetition time: 3 seconds
Integration count: 50000 times
Solvent: Mixed solvent of ortho dichlorobenzene / heavy benzene
(90/10% by volume)
Sample concentration: 120 mg / 2.5 ml solvent
Measurement temperature: 120 ° C
[0144]
In this case, the pentad fraction was determined by measuring the splitting peak in the methyl group region of the 13C-NMR spectrum. Moreover, the assignment of the peak in the methyl group region is A. According to Zambelli et al [Macromolecules 13, 267 (1980)].
[0145]
(6) DSC measurement
Using a Seiko Instruments DSC6200R apparatus, the melting point was measured under the following conditions.
[0146]
Temperature increase rate: 10 ° C / min (temperature range 230 to -30 ° C)
Temperature drop rate: 10 ° C / min (Temperature range -30 to 230 ° C)
[0147]
Reference example1
(Solid titanium catalystPreparation)
  Solid titanium catalystPreparationThe method was performed according to the method described in Example 1 of JP-A-58-83006. That is, 9.5 g (100 mmol) of anhydrous magnesium chloride, 100 ml of decane and 47 ml (300 mmol) of 2-ethylhexyl alcohol were heated and stirred at 125 ° C. for 2 hours, and then 5.5 g (37.5 mmol) of phthalic anhydride was added to this solvent. The mixture was added and further stirred and mixed at 125 ° C. for 1 hour to obtain a uniform solution.
[0148]
After cooling to room temperature, the whole amount was dropped into 400 ml (3.6 mmol) of titanium tetrachloride maintained at −20 ° C. over 1 hour. Thereafter, the temperature of the mixed solution was raised to 110 ° C. over 2 hours, and when it reached 110 ° C., 5.4 ml (25 mmol) of diisobutyl phthalate was added, and then kept at 110 ° C. with stirring for 2 hours. did. After the completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 2000 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration, and washed sufficiently with decane and hexane until no free titanium compound was detected in the washing solution.
[0149]
The solid titanium catalyst prepared by the above production method was stored as a heptane slurry. The composition of the solid titanium catalyst was 2.1 wt% titanium, 57.0 wt% chlorine, 18.0 wt% magnesium and 21.9 wt% diisobutyl phthalate.
[0150]
(Preliminary polymerization)
Purified n-hexane 2000 ml, triethylaluminum 500 mmol, cyclohexylmethyldimethoxysilane 25 mmol, and a solid titanium compound component subjected to contact treatment were charged 50 mmol in terms of titanium atom into a 10-liter polymerization vessel subjected to nitrogen substitution. It was continuously introduced into the polymerization vessel for 1 hour so as to be 2 g per 1 g of the solid titanium catalyst component. The temperature during this period was kept at 15 ° C.
[0151]
The reaction was stopped after 1 hour, and the inside of the reactor was sufficiently replaced with nitrogen. The solid part of the obtained slurry was washed 5 times with purified n-hexane to obtain a prepolymerized catalyst (titanium-containing polypropylene). As a result of analysis, 1.7 g of propylene was polymerized per 1 g of the solid titanium catalyst.
[0152]
(Main polymerization)
After charging 500 kg of propylene into a 2000 L internal volume polymerized nitrogen-substituted polymer, 1752 mmol of triethylaluminum, 17.5 mmol of cyclohexylmethyldimethoxysilane and 350 mmol of tetraethoxysilane as an organosilicon compound, and 10 L of hydrogen were further charged. The internal temperature of the polymerization vessel was raised to 65 ° C. The prepolymerized catalyst obtained by the above prepolymerization was charged with 4.38 mmol of titanium atoms, and then the internal temperature of the polymerization vessel was raised to 70 ° C. to carry out copolymerization of propylene and ethylene for 2 hours.
[0153]
After completion of the polymerization, unreacted propylene was purged, and the resulting white granular polymer was dried under reduced pressure at 70 ° C. for 1 hour. The structural characteristics of the obtained polyolefin resin a are shown in Tables 1 and 2.
[0154]
(Granulation)
100 parts by weight of the polyolefin resin a powder obtained in the above (main polymerization), 0.1 part by weight of 2,6-di-t-butylhydroxytoluene as an antioxidant and 0.1 part by weight of calcium stearate as a chlorine scavenger After adding 0.2 parts by weight of stearyl diethanolamide as an antistatic agent and 0.1 parts by weight of spherical polymethyl methacrylate particles having an average particle diameter of 1.5 μm as an antiblocking agent, the mixture was mixed with a Henschel mixer for 5 minutes, and then screwed. Extrusion was performed at 230 ° C. using an extrusion granulator having a diameter of 65 mmφ, and pellets were granulated to obtain raw material pellets.
[0155]
(Biaxially stretched film production)
Using the obtained raw material pellets, a biaxially stretched film was formed by the following method. The raw material pellets were extruded at 280 ° C. using a T-die sheet extruder with a screw diameter of 90 mmφ, and a 1 mm thick sheet was formed with a 30 ° C. cooling roll. Next, this raw sheet is stretched 5.6 times between rolls in the machine direction (MD) by using a tenter type sequential biaxial stretching apparatus, and subsequently in the transverse direction (TD) in a 165 ° C. tenter. The film was stretched 10 times and then heat-treated by relaxing 4%, and a biaxially stretched polyolefin film having a thickness of 20 μm was formed at a speed of 50 m / min.
[0156]
During film formation, the roll preheating temperature for longitudinal stretching was changed, and the temperature range (lower limit temperature to upper limit temperature) at which film formation was possible was evaluated. In addition, the roll preheating temperature was lowered, and the lower limit temperature at which stable film formation for 10 minutes was possible without causing film whitening, thickness unevenness, film breakage, etc. was defined as the film forming minimum temperature.
[0157]
Further, the roll preheating temperature was raised, and the upper limit temperature at which stable film formation for 10 minutes was possible without causing whitening of the film due to melting of the longitudinally stretched sheet surface, uneven thickness, etc. was taken as the upper limit temperature for film formation. The difference between the upper limit temperature for film formation and the lower limit temperature for film formation was defined as the temperature range for film formation.
[0158]
Further, the film forming property (stretchability) was evaluated by the mechanical load (current value, unit ampere) required for longitudinal stretching and lateral stretching at the center temperature of the temperature range. In addition, the influence of stretching unevenness on the thickness accuracy was evaluated according to the following criteria based on the film thickness pattern measured using an infrared thickness measuring machine WEB GAGE manufactured by Yokogawa Electric Co., Ltd. installed between the tenter and the winder. .
[0159]
: Less than ± 0.5μm
○: ± 0.5μm or more and less than 1.0μ
Δ: ± 1.0 μm or more and less than 1.5 μm
×: ± 1.5 μm or more
[0160]
Further, continuous operation was performed for 5 hours, and the number of film stretching breaks in the tenter was evaluated. In addition, one side of the formed film is 30 W min / m according to a conventional method.²Were subjected to corona discharge treatment and wound up. The obtained stretched film was aged at 40 ° C. for 3 days, and then the thermal shrinkage rate (heat resistance) was measured by the following method.
[0161]
A sample was cut out in a tape shape having a length of 600 mm and a width of 15 mm with the MD and TD of the film as the length direction, marked at a position of 500 mm in length (50 mm from both ends), and left at 120 ° C. for 15 minutes. Thereafter, the film sample was taken out and cooled at room temperature for 15 minutes, the length between the marks was measured, and the thermal shrinkage was measured by the following formula.
Thermal contraction rate (%) = {(L_O-L_S) / L_O} × 100
However, L_O: Length between marks before heat shrinkage (500mm)
L_S: Length between marks after heat shrinkage (mm)
Table 3 shows the temperature range in which the film can be formed, the mechanical load in the longitudinal and transverse stretching, the number of film stretching breaks in 5 hours continuous operation, the thickness accuracy, the MD and TD thermal shrinkage results of the stretched film.
[0162]
Reference example2
  In this polymerization, propylene homopolymerization was carried out using 27 mmol of cyclohexylmethyldimethoxysilane and 285 mmol of ethyltriethoxysilane as the organosilicon compound, and the polyolefin resin b shown in Table 1 was obtained.Reference example1 was performed. The results are shown in Tables 1, 2, and 3.
[0163]
Comparative Example 1
  In this polymerization, except that 164 mmol of cyclohexylmethyldimethoxysilane was used alone as an organosilicon compound, propylene was homopolymerized to obtain polypropylene (polyolefin resin c) shown in Table 1.Reference example1 was performed. The results are shown in Tables 1, 2, and 3.
[0164]
Comparative Examples 2 and 3
In this polymerization, polyolefin resins d and e were obtained in the same manner as in Comparative Example 1 except that copolymerization with ethylene was performed. The results are shown in Tables 1, 2, and 3.
[0165]
Comparative Example 4
In the main polymerization, propylene homopolymerization was performed using t-butylethyldimethoxysilane as the organosilicon compound. Otherwise in the same manner as in Comparative Example 1, a polyolefin resin f was obtained. The results are shown in Tables 1, 2, and 3.
[0166]
Reference example3
  In the main polymerization, copolymerization with ethylene was performed. Otherwise in the same manner as in Comparative Example 1, a polyolefin resin g shown in Table 1 was obtained.
[0167]
  Using the above-mentioned polyolefin resin g and the polyolefin resin c obtained in Comparative Example 1, the blending amounts shown in Table 2 were obtained. Other than thatReference example1 was performed. The results are shown in Tables 2 and 3.
[0168]
Example1, 2
  Except for the amount shown in Table 2,Reference exampleSame as 3. The results are shown in Tables 2 and 3.
[0169]
Example3
  Except for using the propylene-ethylene copolymer (Sanyo Kasei Biscol 660 (polyolefin resin h)) shown in Table 1 and the polyolefin resin d obtained in Comparative Example 2, with the blending amounts shown in Table 2.Reference example1 was performed. The results are shown in Tables 2 and 3.
[0170]
Example4
  Method for producing polyolefin resin i
(Preparation of supported metallocene catalyst)
  Silica gel supported methylaluminoxane (MAO on SiO₂100 g of toluene solution of rac-dimethylsilylenebis-1- (2-methylbenzindenyl) zirconium dichloride (0.005 mmol / ml toluene solution) is added to 10 g of 10 wt. Stir for minutes. Next, the reaction mixture was filtered, and the resulting solid was washed twice with 50 ml of toluene and dried under reduced pressure to obtain a metallocene catalyst supported on silica gel. 0.045 mmol of metallocene was supported per gram of catalyst.
[0171]
(polymerization)
Internal volume 2m^ThreeInto this polymerization tank, 600 kg of propylene was inserted, and 612 mmol of triisobutylaluminum was introduced. Thereafter, the internal temperature of the polymerization tank was raised to 55 ° C. Next, after supplying ethylene gas at a gas phase concentration of 6.0 mol%, 10 g of the metallocene catalyst supported on the silica gel was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was carried out for 2 hours while supplying ethylene gas so that the ethylene gas phase concentration was constant.
[0172]
After the completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 175 kg of a white granular polymer. The structural properties of the resulting propylene-ethylene copolymer (polyolefin resin i) are shown in Table 1.
[0173]
  Except for using the above-mentioned polyolefin resin i and the polyolefin resin d obtained in Comparative Example 2, the compounding amounts shown in Table 2 were used.Reference example1 was performed. The results are shown in Tables 2 and 3.
[0174]
Example5
Method for producing polyolefin resin j
(polymerization)
(First stage, polymerization of propylene)
  Internal volume 2m³Into this polymerization tank, 600 kg of propylene was inserted, and 612 mmol of triisobutylaluminum was introduced. Thereafter, the internal temperature of the polymerization tank was raised to 55 ° C. Then examples45 g of a metallocene catalyst supported on silica gel obtained in the same manner as in [Preparation of supported metallocene catalyst] was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was performed for 70 minutes.
[0175]
(Later, copolymerization of propylene and ethylene)
After the previous polymerization, ethylene gas was supplied at a gas phase concentration to 10.1 mol%, and further copolymerization was performed for 70 minutes while supplying the ethylene gas phase so as to keep the gas concentration constant. After the polymerization was completed, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 135 kg of a white granular polymer. The structural characteristics of the resulting polyolefin resin j are shown in Table 1.
[0176]
  Except for using the above-described polyolefin resin j and the polyolefin resin d obtained in Comparative Example 2, the blending amounts shown in Table 2 were used.Reference example1 was performed. The results are shown in Tables 2 and 3.
[0177]
Example6
  Example5In Example, except that the gas phase ethylene concentration in the latter stage polymerization was 17.2 mol%5And 175 kg of white granular polymer was obtained. The structural characteristics of the resulting polyolefin resin k are shown in Table 1.
[0178]
  Except for using the polyolefin resin k and the polyolefin resin d obtained in Comparative Example 2 and using the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0179]
Example7, Reference Examples 4 and 5
  Except for using the commercially available propylene-butene copolymer (polyolefin resin 1) shown in Table 1 and the polyolefin resin d obtained in Comparative Example 2 and using the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0180]
Comparative Example 5
  Example7Except for using the olefin resin l used in Example 1 and the polyolefin resin c obtained in Comparative Example 1 and setting the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0181]
Reference Example 6, Example 8
  Example7Except for using the olefin resin l used in Example 1 and the polyolefin resin c obtained in Comparative Example 1 and setting the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0182]
Comparative Example 6
  Example7Except for using the olefin resin l used in Example 1 and the polyolefin resin c obtained in Comparative Example 1 and setting the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0183]
Reference Example 7, Example 9, Reference Example 8
  Example5Except for using the polyolefin resin j obtained in the above and the polyolefin resin c obtained in Comparative Example 1 and using the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0184]
Example10
  Example6Using the polyolefin resin k obtained in 1 and the polyolefin resin c obtained in Comparative Example 1, except that the blending amounts shown in Table 2 were used.Reference example1 was performed. The results are shown in Tables 2 and 3.
[0185]
Example11, 12
  Example6Except for using the polyolefin resin k obtained in the above and the polyolefin resin f obtained in Comparative Example 4 and using the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0186]
Comparative Example 7
  Except for using the commercially available elastomer (polyolefin resin m) shown in Table 1 and the polyolefin resin f obtained in Comparative Example 4 and using the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0187]
Reference Example 9, Example 13
(Solid titanium catalystPreparation)
  Solid titanium catalystPreparationThe method was carried out in accordance with the method of Example 1 of JP-A-58-83006.
[0188]
That is, 0.95 g (10 mmol) of anhydrous magnesium chloride, 10 ml of decane and 4.7 ml (30 mmol) of 2-ethylhexyl alcohol were heated and stirred at 125 ° C. for 2 hours, and then 0.55 g (6.75 mmol) of phthalic anhydride was added to this solvent. ) And stirred and mixed at 125 ° C. for another hour to obtain a uniform solution. After cooling to room temperature, the whole amount was charged dropwise into 40 ml (0.36 mmol) of titanium tetrachloride maintained at −20 ° C. over 1 hour.
[0189]
Thereafter, the temperature of the mixture was raised to 110 ° C. over 2 hours, and when it reached 110 ° C., 0.54 ml (2.5 mmol) of diisobutyl phthalate was added, and the mixture was stirred at 110 ° C. for 2 hours. Held on. After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 200 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.
[0190]
After completion of the reaction, the solid part was collected again by hot filtration, and washed sufficiently with decane and hexane until no free titanium compound was detected in the washing solution. The solid titanium catalyst prepared by the above production method was stored as a heptane slurry. The composition of the solid titanium catalyst was 2.1 wt% titanium, 57.0 wt% chlorine, 18.0 wt% magnesium and 21.9 wt% diisobutyl phthalate.
[0191]
(Preliminary polymerization)
Purified n-hexane 200 ml, triethylaluminum 50 mmol, didiclope 10 mmol, and 5 mmol of contacted solid titanium compound component in terms of titanium atom were charged into a 1 L polymerization vessel subjected to nitrogen substitution, and then propylene was used as a solid titanium catalyst. The mixture was continuously introduced into the polymerization vessel for 30 minutes so as to be 2 g per 1 g of the component. The temperature during this period was kept at 10 ° C. The reaction was stopped after 30 minutes, and the inside of the reactor was sufficiently replaced with nitrogen. The solid part of the obtained slurry was washed 5 times with purified n-hexane to obtain a prepolymerized catalyst (titanium-containing polypropylene). As a result of analysis, 1.7 g of propylene was polymerized per 1 g of the solid titanium catalyst.
[0192]
(Main polymerization)
A polymerization vessel having an internal volume of 400 L subjected to nitrogen substitution was charged with 100 kg of propylene, 75 mmol of triethylaluminum, 37.5 mmol of didiclopentyldimethoxysilane as an organosilicon compound, and hydrogen gas were further charged. The temperature was raised to 65 ° C. 0.25 mmol of the prepolymerized catalyst obtained by the above prepolymerization was charged as titanium atoms, and then the internal temperature of the polymerization vessel was raised to 70 ° C. to carry out polymerization for 6 hours.
[0193]
After completion of the polymerization, 50 ml of methanol was added as a polymerization terminator to stop the reaction. Then, 30 kg of liquid propylene was added to the polymerization tank, stirred for 1 hour, and then allowed to stand to allow the polymer particles to settle. It extracted with the extraction nozzle attached from the polymerization tank upper part. The polymer slurry in the polymerization tank was sent to a flash tank and separated from unreacted propylene to obtain a white granular polymer. The structural characteristics of the resulting polyolefin resin n are shown in Table 1.
[0194]
  Example7Except for using the polyolefin resin 1 and the polyolefin resin n used in the above and the polyolefin resin d obtained in Comparative Example 2 and using the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0195]
Example14
  Examples shown in Table 16Polyolefin resin k obtained inReference Example 9Except for using the polyolefin resin n obtained in the above and the polyolefin resin c obtained in Comparative Example 1 and using the blending amounts shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0196]
Example 15, Reference Example 10, Example 16
(Solid titanium catalystPreparation)
  Solid titanium catalystPreparationThe method was carried out according to the method of Example 1 of JP-A-7-292029.
[0197]
That is, 10 g of diethoxymagnesium and 80 ml of toluene were charged into a 200-ml round bottom flask sufficiently substituted with nitrogen gas and equipped with a stirrer, and suspended. Next, 20 ml of titanium tetrachloride was added to the suspension solution, and the temperature was raised. When the temperature reached 80 ° C., 2.7 ml of di-n-butyl phthalate was added, and the temperature was further raised to 110 ° C. Thereafter, the reaction was carried out with stirring for 2 hours while maintaining a temperature of 110 ° C. After completion of the reaction, it was washed twice with 100 ml of toluene at 90 ° C., 20 ml of titanium tetrachloride and 80 ml of toluene were newly added, the temperature was raised to 100 ° C., and the mixture was reacted for 2 hours with stirring.
[0198]
After completion of the reaction, it was washed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid titanium catalyst. In addition, when the solid-liquid in this solid titanium catalyst was isolate | separated and the titanium content rate in solid was measured, it was 2.91 weight%.
[0199]
  ThenReference Example 9In the same manner as above, prepolymerization and main polymerization were carried out to obtain a white granular polymer. The structural characteristics of the obtained polyolefin resin o are shown in Table 1.
[0200]
  Examples shown in Table 16The polyolefin resin k and the polyolefin resin o obtained in the above and the polyolefin resin d obtained in Comparative Example 2 were used, except for the amount shown in Table 2,Reference example1 was performed. The results are shown in Tables 2 and 3.
[0201]
[Table 1]

[0202]
[Table 2]

[0203]
[Table 3]

Claims (2)

When measured by a temperature rising fractional correlation molecular weight measurement method, when measured by a temperature rising fractional correlation molecular weight measurement method, the elution temperature is 36 to 104 ° C. and the molecular weight is 6 to 15% by weight of a polypropylene resin having a molecular weight of 100,000 to 1,000,000. A melt flow rate which contains 4 to 20% by weight of a polypropylene resin having an elution temperature exceeding 116 ° C. and a molecular weight of 10,000 to 100,000, with the balance being made of a crystalline polypropylene resin other than these polypropylene resins. Is a polypropylene-based resin composition having 0.1 to 20 g / 10 min. A stretched film comprising the polypropylene resin composition according to claim 1.