JP4688247B2 - Propylene resin composition, production method and use thereof - Google Patents

Description

【００４３】
【化２】

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。
【００４４】
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。
【００４５】
非配位性イオン化化合物としては、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。
【００４６】
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。
【００４７】
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。
【００４８】
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。
【００４９】
かかる一般式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（ペンタフルオロフェニル）ボランが好適に用いられる。
【００５０】
ホウ素を含有するイオン性化合物は、カチオン性化合物とホウ素を含有するアニオン性化合物の塩であり、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ることができる。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テトラ（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。
【００５１】
また、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。
【００５２】
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。
【００５３】
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］中のホウ素原子のモル量）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。
【００５４】
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とプロピレンとエチレンの共重合体成分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。
【００５５】
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。）
上記、一般式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。
【００５６】
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。
【００５７】
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。
【００５８】
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。
【００５９】
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。
【００６０】
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。
【００６１】
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。
【００６２】
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。
【００６３】
また、これら担体の比表面積は通常５０〜１０００ｍ²／ｇ、好ましくは１００〜７００ｍ²／ｇである。
【００６４】
上記成分 [IV]１ｇに対する成分 [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、成分［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１〜２００モルであり、好ましくは１５〜１５０モルである。
【００６５】
非配位性イオン化化合物を用いる場合には、成分［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ホウ素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０．１〜２０モルであり、好ましくは１〜１５モルである。
【００６６】
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。
【００６７】
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、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。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［II］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ブロック共重合体を得るために有効である。
【００６８】
予備重合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。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。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。
【００６９】
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。
【００７０】
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０．１〜１０００ｇ、好ましくは１〜５０ｇの範囲から選べばよい。
【００７１】
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、第一予備重合としてプロピレンを予備重合せしめて第一予備重合触媒を得、次いで第二予備重合として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。
【００７２】
各予備重合段階における成分［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第二予備重合に供することが望ましい。
【００７３】
各予備重合段階ではプロピレン及び１−ブテンが夫々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。
【００７４】
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の範囲から選べばよく、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。
【００７５】
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。第一及び第二予備重合の温度は、−２０〜１００℃、特に０〜６０℃の温度が好ましく、予備重合の各段階は夫々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ば良く、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。
【００７６】
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。
【００７７】
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。
【００７８】
本発明のプロピレン系樹脂組成物を重合によりプロピレン／プロピレン−エチレン系ブロック共重合体として得る方法においては、上記した触媒成分の存在下にポリプロピレン成分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を第２段階でプロピレンとエチレンの共重合体成分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。
【００７９】
重合条件については、本発明の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。
【００８０】
ポリプロピレン成分の重合は、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α−オレフィンおよび／またはエチレンの混合物を供給して実施すればよい。ポリプロピレン成分の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。
【００８１】
上記重合において、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。
【００８２】
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。
【００８３】
上記ポリプロピレン成分を得るための重合に続いて、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。
【００８４】
本発明の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。
【００８５】
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。
【００８６】
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プロピレン系樹脂組成物を得ることができる。このプロピレン系樹脂組成物は、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。
【００８７】
本発明のプロピレン系樹脂組成物には、酸化防止剤、熱安定剤、塩素補捉剤等の市販の添加剤を添加してもよい。この場合、これらの添加剤は樹脂組成物に混合した後、押出機でペレットにして用いてもよい。また、上記添加剤に加えて有機過酸化物も添加して熱分解を行い、本発明の要件を満足する範囲で分子量の調節を行ってもよい。
【００８８】
本発明のプロピレン系樹脂組成物は、従来にない優れた透明性、柔軟性と共に、ベタツキ感の顕著な低減効果を示すために、耐ブロッキング性、ヒートシール性に優れ、かつ、透明性が良好なためフィルム、特に軟質フィルムとして好適である。フィルムの用途は特に制限されず、食品、衣料、文具、雑貨等の包装用途に用いられるが、それら用途の中で、経時後の透明性の悪化が発生しないため特に食品用途に対して好適に用いることができる。
【００８９】
上記プロピレン系樹脂組成物をフィルムに成形する方法は、公知のフィルム成形法が特に制限されることなく採用できる。その際の成形温度は、メルトフラクチャーの発生やフィルムの成形性、樹脂の熱劣化等を勘案すると、通常、２００〜３００℃、好ましくは２２０〜２７０℃であるのが好適である。フィルムの成形方法としては、Ｔダイによる無延伸フィルム、一軸延伸フィルム、二軸延伸フィルム、あるいはカレンダー成形やインフレーション成形等のあらゆる成形方法が使用できる。
【００９０】
なお、本発明においてフィルムとは、特に厚みに関して厳密な意味を有するものではなく、シートを含めて総称するものであり、通常１０〜１０００μｍ程度が好適に使用される。
【００９１】
また、本発明により得られるプロピレン系樹脂組成物からなる軟質フィルムは、透明性が高く、ヒートシール性が良好であるので、該フィルムを他の熱可塑性フィルム、例えばポリプロピレンフィルム、ポリエチレンフィルム、ポリエチレンテレフタレートフィルム、ポリアミド系フィルム、ポリ塩化ビニルフィルム、エチレン酢酸ビニル共重合体フィルムなどの表層に積層することによって、該熱可塑性樹脂フィルムの物性を損なうことなく、ヒートシール性を向上させることができる。
【００９２】
特にプロピレン単独重合体、及びプロピレンとプロピレン以外のα−オレフィンおよび／またはエチレン、例えばエチレン、１−ブテンなどを５モル％以下共重合したポリプロピレン系樹脂フィルムとはなじみがよく、本発明のフィルムを積層することにより優れた透明性と易ヒートシール性を有するフィルムをあたえる。
【００９３】
また、低密度ポリエチレン、直鎖状低密度ポリエチレン、プロピレンと他のα−オレフィンとの共重合体であって、比較的低結晶性樹脂、エチレン−酢酸ビニルなど軟質樹脂のフィルムに積層することにより、軟質樹脂フィルムのヒートシール性を向上させることができる。
【００９４】
本発明のプロピレン系樹脂組成物からなる軟質フィルムを表層に採用した場合の積層フィルムの層構成は、本発明のプロピレン系樹脂組成物からなる軟質フィルムが表層であれば特に制限されず、本発明のプロピレン系樹脂組成物からなる軟質フィルム層（Ａ）と上記熱可塑性樹脂フィルム層（Ｂ）は、二層構造に限らず、層（Ａ）、層（Ｂ）、層（Ａ）の様な三層構造でも良く、フィルムの剛性、柔軟性等の物性を勘案して適宜に構成すれば良い。さらに、他の層（Ｃ）を積層しても良い。
【００９５】
他の層（Ｃ）の原料も特に制限されず、目的に応じて種々の樹脂を採用することもできる。
【００９６】
上記、積層フィルムは、全体の厚みが、１０ないし１００μｍが好ましく、特に、２０ないし６０μｍの範囲であることがより好ましい。
【００９７】
また、積層された各層の厚みは、層（Ａ）の厚みが、０．５ないし３０μｍであることが好ましく、１ないし１０μｍであることがより好ましい。
【００９８】
また、層（Ｂ）の厚みが、５ないし７０μｍであることが好ましく、１０ないし５０μｍであることがより好ましい。
【００９９】
他の層（Ｃ）の厚みは特に制限されないが、２ないし３０μｍであることが好ましい。
【０１００】
積層フィルムの各層の原料には、必要に応じて、酸化防止剤、滑剤、アンチブロッキング剤、帯電防止剤、防曇剤等の添加剤を、本発明の効果を阻害しない範囲内で添加することもできる。
【０１０１】
積層フィルムは、単に、押出成形した無延伸フィルムでも、一軸または二軸延伸した延伸フィルムでもよい。
【０１０２】
積層フィルムの製造方法は、特に制限されないが、共押出Ｔダイ法、共押出インフレーション法、押出ラミネーション法、ドライラミネーション法、サンドラミネーション法が使用され、その中でも共押出Ｔダイ法が特に好適に使用される。
【０１０３】
上記した共押出Ｔダイ法で製造する場合、例えば層（Ｂ）に結晶性ポリオレフィンフィルムを、層（Ａ）に本発明のプロピレン系樹脂組成物からなる軟質フィルムを、さらに必要に応じて、層（Ｃ）に結晶性ポリオレフィンフィルムを用いた場合、層（Ａ）／層（Ｂ）／層（Ｃ）となるように、複数の押出機を用いて、溶融押出し、ダイス前後またはダイス内部で積層する共押出積層方法にて製造することができる。
【０１０４】
積層フィルムの成形条件は、特に制限されないが、一般的には樹脂温度１９０〜３００℃、エアーギャップ６０から２００ｍｍ、冷却ロール温度１０〜７０℃、製膜速度５０〜５００ｍ／分で行われるのが好適である。
【０１０５】
積層フィルムは、そのまま用いても良いが、印刷インキとの接着性を改良するために、コロナ放電処理を行うことが好ましい。
【０１０６】
コロナ放電処理の条件は、特に制限されないが、得られた積層フィルムの印刷インキとの接着性、あるいは、コロナ放電処理の損傷による異臭の発生防止等の点から、フィルム表面の濡れ張力が３１ないし４３ダイン／ｃｍ、好ましくは、３３ないし３８ダイン／ｃｍとなるように行うことが好ましい。
【０１０７】
本発明のプロピレン系樹脂組成物層が積層された積層フィルムの用途は特に制限されず、食品、衣料、文具、雑貨等の包装用途に用いられるが、それら用途の中で、経時後の透明性の悪化が発生しないため特に食品用途に対して好適に用いることができる。
【０１０８】
また、本発明のプロピレン系樹脂組成物は、ヒートシール性改良剤として、公知のポリプロピレン系樹脂に混合することにより、ヒートシール性の良好なフィルムを得ることができる。用いるポリプロピレン系樹脂は、プロピレン単独重合体、プロピレン単位を５０モル以上含むプロピレンと、他のα−オレフィンおよび／またはエチレンとのランダム或いはブロック共重合体及びそれらの混合物或いはそれらのポリプロピレン系樹脂に他の熱可塑性樹脂を混合したものなどであるが、オレフィン類のランダム共重合体、例えば、プロピレン−エチレン共重合体、プロピレン−エチレン−ブテン−１共重合体、プロピレン−α−オレフィン共重合体等の融点の低い共重合体に対して特に優れた改良効果を発現する。
【０１０９】
混合割合は、該ポリプロピレン系樹脂１００重量部に対して通常１ないし１００重量部、好ましくは２ないし６０重量部の範囲である。
【０１１０】
本発明のプロピレン系樹脂組成物からなるヒートシール性改良剤と公知のポリプロピレン系樹脂の混合法についても何ら制限されないが、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法またはペレットブレンド法を挙げることができる。得られるヒートシール性を改良されたポリプロピレン系樹脂組成物の混合物には、必要に応じて酸化防止剤、塩酸吸収剤、凝集防止剤、耐熱安定剤、紫外線吸収剤、滑剤、耐候安定剤、帯電防止剤、核剤、顔料、充填剤など各種添加剤を配合することもできる。その配合割合は適宜であり、調製法は、従来知られている方法が何ら制限されることなく用いることができる。
【０１１１】
上記プロピレン系樹脂組成物の混合物を製品であるフィルムに成形する方法は、公知のフィルム成形法が特に制限されることなく採用できる。その際の成形温度は、メルトフラクチャーの発生やフィルムの成形性、樹脂の熱劣化等を勘案すると、通常、２００〜３００℃、好ましくは２２０〜２７０℃であるのが好適である。フィルムの成形方法としては、Ｔダイによる無延伸フィルム、一軸延伸フィルム、二軸延伸フィルム、あるいはカレンダー成形やインフレーション成形等のあらゆる成形方法が使用できる。また、上記ポリプロピレン系樹脂組成物の混合物は、単層フィルムとして用いても良く、また、多層フィルムのヒートシール層として用いることも可能である。また、フィルム表面をコロナ処理を施すこともできる。
【０１１２】
さらに、本発明により得られたプロピレン系樹脂組成物は、柔軟性、透明性、引張伸度、耐熱性に優れ、ベタツキ感がないため、従来の熱可塑性エラストマーが用いられている種々の分野に好適に用いることができる。例えば射出成形分野では自動車部品におけるバンパー、マットガード、ランプパッキン類、また、家電分野においては、各種パッキン類、およびスキーシューズ、グリップ、ローラースケート類が挙げられる。一方、押出成形分野では、各種自動車内装材、家電・電線材として各種絶縁シート、コード類の被覆材料および土木建材分野における防水シート、止水材、目地材、包装用ストレッチフィルム等を挙げることができる。
【０１１３】
成形法も特に制限されず、押出成形、射出成形、プレス成形、真空成形など任意の成形方法による各種用途に好適に用いることができる。
【０１１４】
成形する際に各種安定剤、酸化防止剤、紫外線吸収剤、帯電防止剤、凝集防止剤、滑剤、可塑剤、顔料、無機または有機の充填剤を配合することもできる。これら添加剤を例示すると、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、テトラキス［メチレン−３−（３，５−ジ−t−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン、４，４’−ブチリデンビス（６−ｔ−ブチル−ｍ−クレゾール）、トコフェノール類、アスコルビン酸、ジラウリルチオジプロピオネート、リン酸系安定剤、脂肪酸モノグリセライド、Ｎ，Ｎ−（ビス−２−ヒドロキシエチル）アルキルアミン、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロルベンゾトリアゾール、ステアリン酸カルシウム、酸化マグネシウム、水酸化マグネシウム、アルミナ、水酸化アルミニウム、シリカ、ハイドロタルサイト、タルク、クレイ、石膏、ガラス繊維、チタニア、炭酸カルシウム、カーボンブラック、石油樹脂、ポリブテン、ワックス、合成または天然ゴムを挙げることができる。
【０１１５】
【発明の効果】
以上の説明から理解されるように、ＴＲＥＦ法で測定される結晶性分布が特定の様式をなすポリプロピレン系樹脂組成物は、柔軟性、透明性に優れ、かつ、ベタツキ感がないため、透明軟質フィルムとしておよび透明性を悪化させることがないポリプロピレン系樹脂のヒートシール性改良剤として好適に用いることができる。
【０１１６】
また、従来の熱可塑性エラストマーが用いられている種々の分野に好適に用いられる。
【０１１７】
【実施例】
本発明を更に具体的に説明するために以下実施例および比較例を掲げて説明するが、本発明はこれらの実施例に限定されるものではない。
【０１１８】
尚、以下の実施例および比較例において得られた重合体の諸物性の測定方法は次の通りである。
【０１１９】
（１）メルトフローレート（ＭＦＲと略す）
ＡＳＴＭ Ｄ１２３８に準拠した。
【０１２０】
（２）嵩密度
ＡＳＴＭ Ｄ１８９５に準拠した。
【０１２１】
（３）融点
セイコー電子社製ＤＳＣ−６２００Ｒを用いて、試料約５ｍｇをアルミパンに詰め１０℃／分で２００℃まで昇温し、２００℃で５分間保持したのち２０℃／分で室温まで降温し、次いで１０℃／分で昇温する際の吸熱曲線より求めた。
【０１２２】
（４）エチレン含有量
ＪＥＯＬ ＧＳＸ−２７０を用いて¹³Ｃ−ＮＭＲスペクトルを測定した。
【０１２３】
（５）分子量分布
ウォーターズ社製１５０Ｃ型ゲルパーミェーションクロマトグラフィー（ＧＰＣ）を用い、カラムＧＭＨ６ＨＴ（東ソー社製）にて展開した。得られた重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比から分子量分布（Ｍｗ／Ｍｎ）を求めた。
【０１２４】
（６）ＴＲＥＦ（温度上昇溶離分別）溶出曲線
センシュウ科学社製の自動ＴＲＥＦ装置（ＳＳＣ−７３００、ＡＴＲＥＦ）を用いて以下の条件で測定した。
【０１２５】
溶媒 ：オルトジクロロベンゼン
流速 ：１５０ｍｌ／時間
昇温速度：４℃／時間
検出器 ：赤外検出器
測定波数：３．４１μｍ
カラム ：センシュウ科学社製「パックドカラム３０Φ」、３０ｍｍΦ×３００ｍｍ
濃度 ：１ｇ／１２０ｍｌ
注入量 ：１００ｍｌ
この場合、カラム内に試料溶液を１４５℃で導入した後、２℃／時間の速度で−１０℃まで徐冷して試料ポリマーを充填剤表面に吸着させた後、カラム温度を上記条件で昇温すると同時に溶媒を流し始めることにより各温度で溶出してきたポリマー濃度を、赤外検出器で測定して、溶出温度−溶出量の曲線を得た。
【０１２６】
（７）透明性（ヘイズ値）
ＪＩＳ Ｋ６７１４に準拠した。
【０１２７】
（８）曲げ弾性率
ＡＳＴＭ Ｄ−７９０に準拠した。
【０１２８】
（９）ビカット軟化温度
ＪＩＳ Ｋ７２０６に準じて荷重２５０ｇの条件で測定した。
【０１２９】
（１０）引張応力
ＪＩＳ Ｋ６２５１に準拠した。
【０１３０】
（１１）ブロッキング性
［厚み１５０μｍフィルムおよび積層フィルム（３０μｍ）の場合］
２枚のフィルム（２×７ｃｍ）を長さ２ｃｍにわたって重ね合わせ、５００ｇ／ｃｍ²の荷重をかけて温度５０℃で２４時間放置後、引張り試験機（速度：１００ｍｍ／分）で剥離強度を測定した。尚、厚み１５０μｍフィルムの場合は、キャスティングロール接触面同士、積層フィルムの場合は、本発明のプロピレン系樹脂組成物または、比較に用いた樹脂を積層した表層同士を重ねあわせて測定した。
【０１３１】
［厚み３０μｍフィルム（積層フィルム除く）の場合］
２枚のフィルム（１２×１２ｃｍ）を重ね合わせ、１０ｋｇの荷重をかけて温度４０℃で２４時間放置後、４×４ｃｍにサンプルを切り出し、引張り試験機（速度：１００ｍｍ／分）で剥離強度を測定した。尚、フィルムのキャスティングロール接触面同士を重ねあわせて測定した。
【０１３２】
（１２）−２０℃衝撃強度
−２０℃にて、東洋精機（株）製、フィルムインパクトテスターを用いて直径１センチの衝撃ヘッドを使用し、容量３０ｋｇ−ｃｍの条件下で得られたエネルギー値を厚みで除することにより算出した。
【０１３３】
（１３）ヒートシール開始温度
２枚のフィルムをヒートシーラーを用いて所定の温度で１ｋｇ／ｃｍ²の荷重をかけ、２秒間圧着して得た幅１５ｍｍの試料を引張り試験機（速度：１００ｍｍ／ｍｉｎ．）で剥離強度を測定し剥離抵抗力が３００ｇ／１５ｍｍの時の温度をヒートシール開始温度とした。尚、単層フィルムの場合は、キャスティングロール接触面同士、積層フィルムの場合は、本発明のプロピレン系樹脂組成物または、比較に用いた樹脂を積層した表層同士を重ねあわせて測定した。
【０１３４】
（１４）ベタツキ感
射出成形により、縦５０ｍｍ×横４０ｍｍ×厚さ１ｍｍの平板を作成し、２枚の平板を重ね合わせて、３ｋｇｆの荷重下に、４０℃、３日間放置した後、重ね合わせた２枚の平板を、テストスピード３００ｍｍ／分の速度にて接着面に対して垂直方向に引っ張り、剥離した時の最大応力により評価した（図１参照）。
【０１３５】
実施例１
［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 ＳｉＯ₂、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。
【０１３６】
次に、その反応混合物を濾過し、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。
【０１３７】
［重合］
（前段、プロピレンの重合）
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。次いで前記の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分間重合を行った。
【０１３８】
（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１６．１ｍｏｌ％の濃度まで供給し、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１５０ｋｇを得た。
【０１３９】
得られた重合体のＴＲＥＦにより分取した高温溶出成分と中低温溶出成分の分析を行ったところ、高温溶出成分の融点は１４６℃であった。
【０１４０】
更に、中低温溶出成分はエチレン含有量８．６ｗｔ％であり、ＤＳＣによる融点ピークは検出されなかった。
【０１４１】
表１に得られたポリマーのＭＦＲ、分子量分布、嵩密度、ＴＲＥＦ溶出成分量、および高温溶出成分量と融点、中低温溶出成分の成分量とエチレン含有量を示す。
【０１４２】
また、図２に得られた重合体のＴＲＥＦ法の溶出曲線を示す。
【０１４３】
［物性評価］
得られたポリマー１００重量部に、酸化防止剤として２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．１重量部および塩素捕捉剤としてステアリン酸カルシウム０．０５重量部を添加し、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、物性測定に供した。尚、ヘイズ値は、射出成形により得た３ｍｍ厚の透明性評価用試験片の値である。結果を表２に示す。
【０１４４】
実施例２
実施例１の前段での重合時間を３０分、後段重合における気相エチレン濃度を１５．９ｍｏｌ％、重合時間を１１０分とした以外は実施例１と同様に行った。
結果を表１、表２に示す。
【０１４５】
実施例３
実施例１の前段での重合時間を９０分、後段重合における気相エチレン濃度を１５．９ｍｏｌ％、重合時間を５０分とした以外は実施例１と同様に行った。結果を表１、表２に示す。
【０１４６】
実施例４
実施例１の前段での重合時間を１１０分、後段重合における気相エチレン濃度を１６．３ｍｏｌ％、重合時間を３０分とした以外は実施例１と同様に行った。
結果を表１、表２に示す。
【０１４７】
実施例５
実施例１の前段での重合時間を８０分、後段重合における気相エチレン濃度を３０．３ｍｏｌ％、重合時間を６０分とした以外は実施例１と同様に行った。結果を表１、表２に示す。
【０１４８】
実施例６
実施例１の前段での重合時間を１２０分、後段重合における気相エチレン濃度を３２．７ｍｏｌ％、重合時間を２０分とした以外は実施例１と同様に行った。
結果を表１、表２に示す。
【０１４９】
実施例７
［担持触媒メタロセン触媒の調製］
実施例１と同様に行った。
【０１５０】
［予備重合］
Ｎ₂置換を施した１Ｌオートクレーブ中に精製ヘプタン２００ｍｌ、トリイソブチルアルミニウム５０ｍｍｏｌ、及び担持メタロセン触媒成分をＺｒ原子換算で５ｍｍｏｌ装入した後、プロピレンを担持メタロセン触媒成分１ｇに対し５ｇとなるように１時間連続的に反応器に導入し予備重合を施した。なお、この間の温度は１５℃に保持した。
【０１５１】
１時間後プロピレンの導入を停止し、反応器内をＮ₂で充分に置換した。得られたスラリーの固体成分を生成ヘプタンで６回洗浄した。
【０１５２】
［重合］
上記の予備重合触媒を用いて、実施例１の［重合］と同様に行った。結果を表１に示す。
【０１５３】
［物性評価］
実施例１と同様に行った。結果を表２に示す。
【０１５４】
実施例８
［担持触媒メタロセン触媒の調製］
実施例１と同様に行った。
【０１５５】
［予備重合］
Ｎ₂置換を施した１Ｌオートクレーブ中に精製ヘプタン２００ｍｌ、トリイソブチルアルミニウム５０ｍｍｏｌ、及び担持メタロセン触媒成分をＺｒ原子換算で５ｍｍｏｌ装入した後、プロピレンを担持メタロセン触媒成分１ｇに対し５ｇとなるように１時間連続的に反応器に導入し予備重合を施した。
【０１５６】
なお、この間の温度は１５℃に保持した。１時間後プロピレンの導入を停止し、反応器内をＮ₂で充分に置換した。得られたスラリーの固体成分（第一予備重合触媒）を精製ヘプタンで６回洗浄した。
【０１５７】
更に、この第一予備重合触媒をＮ₂置換を施した１Ｌオートクレーブ中に装入し、精製ヘプタン２００ｍｌ、トリイソブチルアルミニウム５０ｍｍｏｌを加えた後、１−ブテンを担持メタロセン触媒成分１ｇに対し２０ｇとなるように１時間、連続的に反応器内に導入し、予備重合を施した。なお、この間の温度は１５℃に保持した。
【０１５８】
得られたスラリーの固体部分を精製ヘプタンで６回洗浄し、メタロセン含有ポリオレフィンよりなる予備重合触媒を得た。
【０１５９】
［重合］
上記の予備重合触媒を用いて実施例１の［重合］と同様に行った。
【０１６０】
結果を表１に示す。
【０１６１】
［物性評価］
実施例１と同様に行った。結果を表２に示す。
【０１６２】
実施例９
［重合］
（前段、プロピレンの重合）
内容積２Ｌのオートクレーブにプロピレンを４５０ｇ装入し、メチルアルミノキサンのトルエン溶液（ＰＭＡＯ−Ｓ、東ソーアクゾ社製、３．１ｍｍｏｌ−Ａｌ／ｍｌ）を１ｍｌ導入した。その後、オートクレーブの内温を５５℃に昇温した。次いで予め室温で１５分間、予備活性化したメチルアルミノキサンのトルエン溶液（ＰＭＡＯ−Ｓ、東ソーアクゾ社製、３．１ｍｍｏｌ−Ａｌ／ｍｌ）０．５ｍｌと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０．１ｍｇの混合溶液全量を装入した。続いてオートクレーブの内温を６０℃まで昇温し、７０分間重合を行った。
【０１６３】
（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１５．５ｍｏｌ％の濃度まで供給し、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塊状の重合体１５０ｇを得た。結果を表１に示す。
【０１６４】
［物性評価］
実施例１と同様に行った。結果を表２に示す。
【０１６５】
参考例１
［重合］
実施例９において使用するメタロセンをジメチルシリレンビス（２−メチル−４−ナフチル−インデニル）ジルコニウムジクロリド０．０１ｍｇ使用した以外は実施例９と同様に行った。白色塊状の重合体１４５ｇを得た。結果を表１、表２に示す。
【０１６６】
参考例２
［ランダム共重合体の製造］
内容積２Ｌの重合槽にプロピレンを４５０ｇ挿入し、トリイソブチルアルミニウム１．２ｍｍｏｌを導入した。その後、重合槽の内温を５５℃に昇温し、エチレンガスを気相濃度で１５．９ｍｏｌ％の濃度まで供給した。次いで実施例１と同様の方法で調製したシリカゲルに担持されたメタロセン触媒５ｍｇ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、エチレンの気相濃度を一定に保つように供給しながら１２０分間重合を行った。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塊状の重合体１５０ｇを得た。嵩密度は、塊状の為測定できなかった。
【０１６７】
［結晶性ポリプロピレンとのブレンド］
結晶性ポリプロピレン（プロピレンホモポリマー、ＭＦＲ＝２．０ｇ／１０分、Ｍｗ／Ｍｎ＝６．２、融点＝１６３℃）２０重量部と上記ランダム共重合体（塊状の重合体を凍結粉砕したもの）８０重量部をブレンドした。得られたブレンド物の結果を表１に示す。
【０１６８】
［物性評価］
実施例１と同様に行った。結果を表２に示す。
【０１６９】
比較例１
[触媒の調製]
触媒の調製法は、特開昭５８−８３００６号公報の実施例１の方法に準じて行った。即ち、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２５℃で２時間加熱撹拌した。
【０１７０】
この溶液中に無水フタル酸０．５５ｇ（６．７５ｍｍｏｌ）を添加し、１２５℃にて更に１時間撹拌混合を行い均一溶液とした。室温まで冷却した後、１２０℃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。
【０１７１】
その後、この混合溶液の温度を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、濾過し固体部を採取し、この固体部を２００ｍｌのＴｉＣｌ₄にて再懸濁させた後、再び１１０℃で２時間の加熱反応を行った。
【０１７２】
反応終了後、再び１１０℃で２時間の加熱反応を行った。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十分洗浄した。固体Ｔｉ触媒の組成はチタン２．１重量％、塩素５７重量％、マグネシウム１８．０％、及びジイソブチルフタレート２１．９重量％であった。
【０１７３】
［予備重合］
Ｎ₂置換を施した内容積１Ｌのオートクレーブに精製ｎ−ヘキサン２００ｍｌ、トリエチルアルミニウム５０ｍｍｏｌ、ジフェニルジメトキシシラン１０ｍｍｏｌ、ヨウ化エチル５０ｍｍｏｌ、及び固体Ｔｉ触媒成分をＴｉ原子換算で５ｍｍｏｌ装入した後、プロピレンを固体触媒成分１ｇに対し３ｇとなるように３０分間連続的にオートクレーブに導入した。なお、この間の温度は１５℃に保持した。
【０１７４】
３０分後に反応を停止し、オートクレーブ内をＮ₂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４回洗浄し、チタン含有ポリプロピレンを得た。分析の結果、固体Ｔｉ触媒成分１ｇに対し２．１ｇのプロピレンが重合されていた。
【０１７５】
[重合]
（前段、プロピレンの重合）
内容積２ｍ³の重合槽にプロピレンを６００ｋｇ装入し、トリエチルアルミニウム６１２ｍｍｏｌ、シクロヘキシルメチルジメトキシシラン３０６ｍｍｏｌ、更に水素ガスを導入した後、を導入した後、重合槽の内温を５５℃に昇温した。
【０１７６】
次いで、チタン含有ポリプロピレンをＴｉ原子として１．４ｍｍｏｌ装入し、重合を開始した。続いてオートクレーブの内温を６０℃まで昇温し、４０分間重合を行った。
【０１７７】
（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５．５ｍｏｌ％の濃度まで供給し、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１００分間共重合を行った。
【０１７８】
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１４５ｋｇを得た。結果を表１に示す。
【０１７９】
［物性評価］
実施例１と同様に行った。結果を表２に示す。
【０１８０】
比較例２
実施例１の[重合]において前段の重合時間を５０分、後段の重合時間を９０分とした以外は実施例１と同様に行った。結果を表１、表２に示す。
【０１８１】
比較例３
実施例１の［重合］において前段の重合時間を９０分、後段の重合時間を５０分、エチレン気相濃度を４７．８ｍｏｌ％とした以外は実施例１と同様に行った。結果を表１、表２に示す。
【０１８２】
比較例４
実施例１の［重合］において前段の重合時間を１０分、後段の重合時間を１３０分、エチレン気相濃度を１６．１ｍｏｌ％とした以外は実施例１と同様に行った。結果を表１、表２に示す。
【０１８３】
比較例５
実施例１の［重合］において前段の重合時間を１２０分、後段の重合時間を２０分、エチレン気相濃度を１５．９ｍｏｌ％とした以外は実施例１と同様に行った。結果を表１、表２に示す。
【０１８４】
比較例６
実施例１の［重合］において、前段の重合時間を６０分、エチレン気相濃度を６．０ｍｏｌ％、後段の重合時間を８０分、エチレン気相濃度を１６．０ｍｏｌ％とした以外は実施例１と同様にして重合を行った。結果を表１，２に示す。
【０１８５】
【表１】

【０１８６】
【表２】

フィルム物性評価
実施例１２
[ペレタイズ]
実施例１で得られた重合体５ｋｇに酸化防止剤として２，６−ジ−ｔ−ブチル−ｐ−クレゾールを０．１重量部、塩素捕捉剤としてステアリン酸カルシウム０．０５重量部、ブロッキング防止剤としてサイロイド５５（平均粒径；２．７３μｍ）０．１５重量部、滑剤としてエルカ酸アミド０．０６重量部を添加し、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単軸押出し機で２３０℃の条件で押出しペレットを造粒し原料ペレットを得た。
【０１８７】
[フィルムの作成]
得られたペレットを２６０℃で加熱された４０ｍｍΦ押出機に供給し、Ｔダイ口金から押出し、表面温度４０℃に調整されたキャスティングロールでキャストし、厚さ１５０μｍの無延伸フィルムを得た。得られたフィルムの物性を表３に示す。
【０１８８】
実施例１３〜２０、参考例３、４
実施例２〜９、参考例１、２で得られた重合体を用いて、実施例１２と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表３に示す。
【０１８９】
比較例７〜１２
比較例１〜６で得られた重合体を用いて、実施例１２と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表３に示す。
【０１９０】
比較例１３
プロピレン−エチレン共重合体（ＭＦＲ；７．０ｇ／１０分、エチレン含有量；３．５重量％、融点；１４５℃）１００重量部に対して軟質樹脂としてエチレン−ブテン−１共重合体（ＭＩ；７．０、１−ブテン含有量；１２モル％）１００重量部を混合した樹脂を用いて実施例１２と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表３に示す。（表３中には、ＰＰ＋ＥＢＲと記載）
比較例１４
低結晶樹脂としてプロピレン−ブテン−１共重合体（ＭＩ；７．０ｇ／１０分、ブテン−１含有量；２３モル％）を用いて実施例１２と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表３に示す。（表３中には、ＰＢ共重合体と記載）
【０１９１】
【表３】

実施例２３
３台の押出し機を用いて、表層原料（Ａ）として実施例１で得られた重合体ペレット、基材層原料（Ｂ）として結晶性プロピレン単独重合体（ＭＩ；８．５ｇ／１０分）、他の表面層原料（Ｃ）として、結晶性のプロピレン−エチレン−ブテン−１共重合体（ＭＩ；７ｇ／１０分、エチレン含有量；３．７モル％、１−ブテン含有量；３．５モル％）を用いて積層比Ａ：Ｂ：Ｃが１：２：１となるように押出し、厚さ３０μｍの積層フィルムを得た。結果を表４に示す。ヘイズの経時変化は、得られたフィルムを４０℃で一週間保存した後のヘイズを測定することにより評価した。
【０１９２】
比較例１５
表層原料（Ａ）を比較例１で得られた重合体ペレットを用いた他は、実施例２３と同様の方法で行った。結果を表４に示す。
【０１９３】
比較例１６
表層原料（Ａ）として比較例１３で用いた樹脂を用いた他は、実施例２３と同様の方法で行った。結果を表４に示す。
【０１９４】
比較例１７
表層原料（Ａ）として比較例１４で用いた樹脂を用いた他は、実施例２３と同様の方法で行った。結果を表４に示す。
【０１９５】
【表４】

ヒートシール性改良剤としての評価
実施例２4
[ペレタイズ]
実施例１で得られた重合体５ｋｇに酸化防止剤として２，６−ジ−ｔ−ブチル−ｐ−クレゾールを０．１重量部、塩素捕捉剤としてステアリン酸カルシウム０．０５重量部、ブロッキング防止剤としてサイロイド５５（平均粒径；２．７３μｍ）０．１５重量部、滑剤としてエルカ酸アミド０．０６重量部を添加し、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単軸押出し機で２３０℃の条件で押出しペレットを造粒し原料ペレットを得た。
【０１９６】
[フィルムの作成]
結晶性のプロピレン−エチレン−１−ブテン共重合体ペレット（ＭＩ；７ｇ/１０分、エチレン含有量；３．７モル％、１−ブテン含有量；３．５モル％）と実施例１で得られた重合体のペレットを重量比８０／２０（プロピレン−エチレン−１−ブテン共重合体／実施例１で得られた共重合体）での混合比でタンブラーミキサーを用いて混合し、スクリュー径４０ｍｍΦのＴダイ製膜機でダイ温度２３０℃で溶融押出しを行い、表面温度３７℃のキャスティングロールで冷却し厚み３０μｍの無延伸フィルムを得た。得られたフィルムは成形後、２４時間後に物性測定を行った。得られたフィルムの物性を表５に示す。
【０１９７】
実施例２５〜３２、参考例５，６
実施例２〜９、参考例１、２で得られた重合体を用いて、実施例２４と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表５に示す。
【０１９８】
実施例３５
プロピレン−エチレン−１−ブテン共重合体とヒートシール改良剤を重量比７０／３０（プロピレン−エチレン−1−ブテン共重合体／ヒートシール改良剤）で用いた他は実施例２４と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表５に示す。
【０１９９】
比較例１８〜２３
比較例１〜６で得られた重合体を用いて、実施例２４と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表５に示す。
【０２００】
比較例２４
ヒートシール改良剤として低結晶性プロピレン−ブテン−１共重合体（ＭＩ；７．０ｇ／１０分、ブテン−１含有量；２３モル％）を用い、実施例１と同じプロピレン−エチレン−１−ブテン共重合体とヒートシール改良剤を重量比８０／２０（プロピレン−エチレン−１−ブテン共重合体／ヒートシール改良剤）で用いた他は実施例２４と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表５に示す。
【０２０１】
比較例２５
プロピレン−エチレン−１−ブテン共重合体とヒートシール改良剤を重量比７０／３０（プロピレン−エチレン−１−ブテン共重合体／ヒートシール改良剤）で用いた他は比較例２４と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表５に示す。
【０２０２】
比較例２６
ヒートシール改良剤としてエチレン−ブテン−１共重合体（ＭＩ；７．０ｇ／１０分、ブテン−１含有量；１２モル％）を用いた他は比較例２４と同様の方法で無延伸フィルムを得た。得られたフィルムの物性を表５に示す。
【０２０３】
比較例２７
実施例２４においてヒートシール改良剤を用いなかった他は、実施例２４と同様に行った。
【０２０４】
【表５】

【図面の簡単な説明】
【図１】 本発明におけるプロピレン系樹脂組成物の粘着性評価方法を示す図である。
【図２】 実施例１のプロピレン系樹脂組成物の昇温溶離分別法の溶出曲線である。
【図３】 本発明の代表的な重合方法を示すフローチャートである。
【図４】 本発明の代表的な重合方法を示すフローチャートである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a propylene-based resin composition that is excellent in flexibility and transparency, and has no stickiness, a method for producing the same, and a use thereof.
[0002]
[Prior art]
Olefin-based thermoplastic elastomers have an excellent balance between economic efficiency and performance, and can be reduced in weight and recycled. Therefore, in the field of various industrial parts, home appliance parts, films, and sheets, including automobile parts such as bumpers. Widely used.
[0003]
Conventionally, for the production of olefin-based thermoplastic elastomers, a machine for kneading an ethylene-propylene rubber (hereinafter referred to as EPR) or ethylene-propylene terpolymer (hereinafter referred to as EPDM) and a thermoplastic resin such as polypropylene with an extruder. A known mixing method and a method (polymerization method) in which both components are produced by a series of polymerizations to obtain a mixture of both components are known. In the production by such a polymerization method, a two-stage polymerization method in which propylene is copolymerized in the first stage and ethylene and propylene are copolymerized in the second stage is generally performed.
[0004]
However, conventional EPR and EPDM have a sticky feeling, and a molded product made of a mixture of these with polypropylene also has a sticky feeling and is white or milky white, and containers, sheets, films, etc. that require transparency It could not be used as a material for moldings.
[0005]
In addition, the thermoplastic elastomer produced by the polymerization method has better transparency than that obtained by mechanical mixing, but the resin obtained by this method also has a sticky feeling and its molding. The product was white or milky white and could not be used in fields where transparency was required.
[0006]
[Problems to be solved by the invention]
Therefore, the development of a material having good properties such as flexibility and the like of the EPR, EPDM, and polypropylene mixture, excellent in transparency, and having no stickiness is an issue.
[0007]
In order to solve the above problems, Japanese Patent No. 2679920 and Japanese Patent Application Laid-Open No. 07-118354 disclose that a propylene-based copolymer having a specific composition exhibits good flexibility and transparency. .
[0008]
However, since the propylene-based polymer obtained by the above method contains a lot of non-crystalline components, which are stickiness and transparency inhibiting factors, in addition to the low crystalline component, There was still room for improvement, and further improvements were desired.
[0009]
Accordingly, an object of the present invention is to provide a propylene-based resin composition having good flexibility and transparency and having no stickiness.
[0010]
[Means for Solving the Problems]
As a result of diligent research to achieve the above object, the present inventors have determined that a propylene-based copolymer comprising a specific amount of a copolymer of propylene and ethylene having low crystallinity with a limited amount of non-crystalline components. The present inventors have succeeded in developing a resin composition and found that such a composition satisfies all of the above objects, thereby completing the present invention.
[0011]
That is, the present invention comprises a polypropylene component and a copolymer component of propylene and ethylene, and (I) a component that elutes at a temperature up to 90 ° C. (hereinafter referred to as “temperature elution fractionation using an o-dichlorobenzene solvent”). The medium-low temperature elution component) is 50 to 99% by weight of the total, the component that elutes at a temperature of 90 ° C. or more (hereinafter referred to as the high temperature elution component) is 50 to 1% by weight of the total, and further, the temperature is up to 0 ° C. Elution component (hereinafter referred to as “low temperature elution component”) is 10% by weight or less of the total, and (II) the content of ethylene unit in the low temperature elution component is 4% by weight or more and less than 20% by weight. The propylene unit content is 97 to 100% by weight, a propylene-based resin composition, its production method, and use.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
[0013]
The propylene resin composition of the present invention is composed of a polypropylene component and a copolymer component of propylene and ethylene.
[0014]
The ratio of the polypropylene component and the copolymer component of propylene and ethylene should be specified by the amount of the eluted component determined from the elution curve by the temperature rising elution fractionation (hereinafter referred to as TREF) method using o-dichlorobenzene as a solvent. Can do.
[0015]
That is, the polypropylene component mainly comprises an elution component of 90 ° C. or higher in the elution curve by the TREF method. The copolymer component of propylene and ethylene is mainly composed of a component that elutes at a temperature up to 90 ° C.
[0016]
Here, the TREF method is a method described in detail in, for example, Journal of Applied Polymer Science; Applied Polymer Symposium 45, 1-24 (1990). That is, a high-temperature polymer solution is introduced into a column packed with a diatomaceous earth filler, and the column temperature is gradually lowered to cause crystallization from a highly crystalline component in order on the filler surface. This is a method of separating the eluted polymer components by gradually elevating the components so as to elute them in order from components having low crystallinity. By this method, the crystalline distribution of the polymer can be measured.
[0017]
In the present invention, the features of the present invention, which are excellent in flexibility and transparency and have no stickiness, are measured by the TREF method which indirectly represents the composition ratio of the polypropylene component and the copolymer component of propylene and ethylene. The ratio of the eluted components (crystallinity distribution) is extremely important.
[0018]
In the propylene-based resin composition of the present invention, the high temperature eluting component has a propylene unit content of 97 to 100% by weight. Specifically, the high temperature elution component is a propylene homopolymer, or a monomer unit composed of α-olefin other than propylene or ethylene, 3 wt% or less, preferably 1.5 wt% or less, more preferably 1 It is a random copolymer of not more than% by weight. In the random copolymer, when the monomer unit other than propylene exceeds 3% by weight, the heat resistance of the product is lowered.
[0019]
As the α-olefin, an α-olefin having 4 to 18 carbon atoms can be used, and an α-olefin having 4 to 8 carbon atoms is preferable, and 1-butene, 1-hexene, and 1-octene are particularly preferable. Can be used.
[0020]
In the propylene-based resin composition of the present invention, the proportion of the high temperature eluting component is 1 to 50% by weight, preferably 3 to 30% by weight, and more preferably 5 to 20% by weight. That is, when the proportion of the high temperature eluting component is lower than 1% by weight, the heat resistance is impaired and the balance between rigidity and flexibility is deteriorated, and when it is 50% by weight or more, the transparency is remarkably deteriorated.
[0021]
In the propylene-based resin composition of the present invention, the medium-low temperature elution component is a component necessary for imparting flexibility to the product, and is 4% by weight or more and less than 20% by weight, preferably 5 to 17% by weight, Preferably, it is composed of a copolymer of low crystalline propylene and ethylene containing 6 to 15% by weight of ethylene units. The copolymer is preferably a copolymer obtained by random copolymerization of propylene and ethylene in order to more effectively impart flexibility to the product.
[0022]
When the ethylene unit content is less than 4% by weight in the above-mentioned medium / low temperature elution component, the flexibility and transparency of the product are low, and when it exceeds 20% by weight, the transparency is lowered and the stickiness is increased. The blocking resistance of the film product is significantly deteriorated.
[0023]
In the propylene-based resin composition of the present invention, the amount of the medium-low temperature elution component is 50 to 99% by weight, preferably 70 to 97% by weight, and more preferably 80 to 95% by weight. When the medium-low temperature elution component is less than 50% by weight, the product has low flexibility and poor transparency. On the other hand, when the amount of the medium-low temperature elution component is more than 99% by weight, the heat resistance is impaired and the balance between rigidity and flexibility is deteriorated.
[0024]
In addition, the propylene-based resin composition of the present invention is also characterized in that the amount of the low temperature elution component is small. That is, it is important that the amount of the low temperature elution component is 10% by weight or less, preferably 8% by weight or less, more preferably 6% by weight or less of the whole (the total amount of the medium and low temperature elution components and the high temperature elution component). When the amount of the eluted component exceeds 10% by weight, the transparency of the product and the heat resistance are deteriorated and the blocking resistance of the film product is remarkably deteriorated, and the object of the present invention cannot be achieved.
[0025]
The propylene-based resin composition of the present invention is not particularly limited as long as it satisfies the above-described configuration. For example, it is measured by a differential scanning calorimeter (hereinafter referred to as DSC) of the high temperature elution component. The melting point is preferably 120 to 170 ° C., more preferably 130 to 155 ° C. in order to improve transparency and heat resistance of the film as a product. Polypropylene having a melting point higher than 170 ° C. is difficult to produce, and a melting point lower than 120 ° C. is not preferable because the heat resistance of the product is lowered.
[0026]
Further, the molecular weight distribution dispersity (Mw / Mn) measured by gel permeation chromatography (GPC) of the propylene-based resin composition of the present invention is 5 or less, preferably 4 or less, more preferably 3 or less. Is preferred.
[0027]
When the molecular weight distribution dispersity is larger than the above range, the low molecular weight component is also increased, the tensile elongation of the product is decreased, the stickiness of the product is increased due to the bleeding of the low molecular weight component, and the blocking resistance of the film product is deteriorated. This is not preferable.
[0028]
Further, the intrinsic viscosity [η] measured using an Ubbelohde viscometer in 135 ° C. tetralin is 0.5 to 5.0 dl / g, preferably 0.5 to 3.0 dl / g, more preferably 0. .8 to 2.0 dl is desirable. When [η] is less than 0.5 dl / g, the sticky feeling increases, and when [η] is 5.0 dl / g or more, the melt fluidity tends to be poor and the moldability tends to deteriorate, which is not preferable.
[0029]
Furthermore, the propylene-based resin composition of the present invention has a melt flow rate of 0.01 to 50 g / 10 minutes, preferably 0.2%, measured under a load of 2.16 kg at 230 ° C. according to ASTM-D1238. What is 1-30 g / 10min, More preferably, it is 0.5-20 g / 10min is suitable. A melt flow rate larger than the above value is not preferable because the melt tension of the product is lowered and the moldability is lowered. Moreover, when smaller than the said value, melt fluidity | liquidity is bad and molding workability deteriorates and it is unpreferable.
[0030]
Furthermore, the calorific value of the endothermic peak measured by DSC is 80 mJ / mg or less, preferably 70 mJ or less, more preferably 50 mJ or less. Outside the above range, the transparency of the product deteriorates, which is not preferable.
[0031]
The propylene-based resin composition of the present invention has, for example, 5 wt% as long as it does not inhibit the effects of the propylene-based resin composition of the present invention in addition to the above-described polypropylene component and propylene-ethylene copolymer component as the resin component. % Α-olefin polymer may be contained as a component in the range of not more than%. Examples of the α-olefin include 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, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-octadecene, 1-eicosene and the like can be exemplified.
[0032]
The propylene-based resin composition used in the present invention may be obtained by any method.
[0033]
For example, a method in which a polypropylene component and a copolymer component of propylene and ethylene are individually polymerized and mixed may be used, but the polypropylene component and the copolymer component of propylene and ethylene are in a single molecular chain. So-called block co-polymerization which can achieve a state of being arranged in a microscopic state and / or a state in which a polypropylene component and a molecular chain composed of propylene and ethylene copolymer components alone are not mixed by mechanical mixing. The method obtained as a coalescence is preferable because a propylene-based resin composition that can be used as a film having better transparency can be obtained.
[0034]
The production method for obtaining the propylene-based resin composition of the present invention as a block copolymer is not particularly limited as long as it satisfies the requirements of the present invention. For example, a polypropylene component and a random copolymer of propylene and ethylene The block copolymer with the coalescing component can be suitably produced by the following method.
[0035]
That is, polypropylene component (A) and propylene in the presence of a catalyst comprising a metallocene compound (hereinafter abbreviated as component [I]) and an aluminoxane compound and / or a non-coordinating ionized compound (hereinafter abbreviated as component [II]). And a method of producing a copolymer component (B) of ethylene in a stepwise manner.
[0036]
As the component [I], compounds 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-mR¹ _m) (C_FiveH_4-nR² _nMX¹X²      (1)
(In the formula, M represents a transition metal atom of Group IVb of the periodic table. (C_FiveH_4-mR¹ _m), (C_FiveH_4-nR² _n) Represents a substituted cyclopentadienyl group, m and n are integers of 1 to 3, and R¹And R²May be the same as or different from each other, and may be bonded to two carbon atoms on a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, or a cyclopentadienyl ring to form a hydrocarbon group. It is a hydrocarbon group forming one or more hydrocarbon rings which may be substituted. Q is (C_FiveH_4-mR¹ _m) And (C_FiveH_4-nR² _nAnd 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. )
The chiral compound represented by these can be used suitably.
[0037]
More preferably, in the above 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 preferably the same or different halogen atoms or hydrocarbon groups, and chiral metallocene compounds in which Q is a hydrocarbon-substituted silylene group.
[0038]
Specific examples of the component [I] include 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, r c-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-na Tilindenyl) 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.
[0039]
Moreover, the compound which replaced said zirconium with hafnium is also used suitably.
[0040]
Further, the above metallocene compounds can be used in combination.
[0041]
As the component [II], known compounds can be used without any limitation. Among them, the following compounds can be preferably used. As the aluminoxane compound, an aluminum compound represented by the general formula (2) or (3) is preferable.
[0042]
[Chemical 1]

[0043]
[Chemical 2]

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.
[0044]
The production method of the aluminoxane compound may be any of various known methods, for example, a method of reacting trialkylaluminum directly with water in a hydrocarbon solvent. Examples thereof include a method of reacting water adsorbed in a hydrocarbon solvent and trialkylaluminum using hydrated copper sulfate hydrate, aluminum sulfate hydrate, water-containing silica gel or the like.
[0045]
As the non-coordinating ionized compound, known compounds are used without particular limitation. In particular, an ionized compound containing a boron atom can be suitably used.
[0046]
Specific examples of ionized compounds containing boron atoms include Lewis acids containing boron atoms and ionic compounds containing boron atoms.
[0047]
Examples of the Lewis acid containing a boron atom include a compound represented by the general formula (4).
[0048]
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.
[0049]
Specific examples of the compound represented by the general formula include trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, and tris (4-fluoromethylphenyl). Examples include borane, tris (pentafluorophenyl) borane, tris (p-tolyl) borane, tris (o-tolyl) borane, and tris (3,5-dimethylphenyl) borane. Of these, tris (pentafluorophenyl) borane is preferably used.
[0050]
The ionic compound containing boron is a salt of a cationic compound and an anionic compound containing boron, and a trialkyl-substituted ammonium salt, N, N-dialkylanilinium salt, dialkylammonium salt, triarylphosphonium salt And so on. Examples of trialkyl-substituted ammonium salts include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium. Tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium 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 and the like. And dialkylammonium salts include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Triarylphosphonium salts include triphenylphosphonium tetra ( Phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, tri (dimethylphenyl) phosphonium tetra (phenyl) boron and the like.
[0051]
Further, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate can also be mentioned.
[0052]
Of these, triphenylcarbonium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferably used.
[0053]
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 a non-coordinating ionized compound is used for component [II], the amount of component [II] used (mol amount of boron atom in component [II]) is 1 mol of transition metal in component [I]. The amount is preferably 0.01 to 10,000 mol, more preferably 0.1 to 5,000 mol, and still more preferably 1 to 3,000 mol.
[0054]
In the method of producing a polypropylene component and a copolymer component of propylene and ethylene stepwise in the presence of a catalyst comprising component [I] and component [II], an organoaluminum compound (hereinafter abbreviated as component [III]) is used as necessary. ) Can be used in combination. Component [III] is a compound represented by general formula (5).
[0055]
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.)
Specific examples of the compound represented by the above general formula include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. , Trialkylaluminums such as tri-n-decylaluminum, diethylaluminum monochloride, diethylaluminum monobromide, dialkylaluminum monohalides such as diethylaluminum monofluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum dichloride Alkyl aluminum halides, diethyl aluminum monoethoxide, ethyl aluminum Alkoxy aluminum such as Mujietokishido like. Among these, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum are preferably used.
[0056]
Although the usage-amount of component [III] is not restrict | limited in particular, Generally, it is 1-50,000 mol with respect to 1 mol of transition metal atoms in component [I], Preferably it is 5-10,000 mol. is there. More preferably, it is 10-5,000 mol.
[0057]
Component [I] and / or component [II] can also be used by being supported on a particulate carrier (hereinafter abbreviated as component [IV]). When the catalyst component is supported on the carrier, the particle properties of the resulting polymer are improved, and process compatibility in resin production, such as prevention of polymerization scale in the reactor, can be greatly improved.
[0058]
As the fine particle carrier, those having a function as a carrier are used without limitation, and inorganic oxides are particularly preferable.
[0059]
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.
[0060]
The inorganic fine particle carrier is usually used after being fired at 150 to 1000 ° C, preferably 200 to 800 ° C.
[0061]
Although the properties of the carrier vary depending on the type and production method, the particle size of the carrier preferably used in the present invention 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.
[0062]
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.
[0063]
The specific surface area of these carriers is usually 50 to 1000 m.²/ G, preferably 100-700m²/ G.
[0064]
Component [I] is used in an amount of 0.005 to 1 mmol, preferably 0.05 to 0.5 mmol in terms of transition metal atoms, relative to 1 g of component [IV]. When an aluminoxane compound is used as component [II], the amount of the aluminoxane compound used relative to component [I] is converted to 1 mol of transition metal atoms in component [I] in terms of the molar amount of Al atoms. It is 1-200 mol with respect to it, Preferably it is 15-150 mol.
[0065]
When a non-coordinating ionized compound is used, the amount of the non-coordinating ionized compound used relative to component [I] is converted to the molar amount of boron atoms in the non-coordinating ionized compound, and the component [I] It is 0.1-20 mol with respect to 1 mol of transition metal atoms in it, Preferably it is 1-15 mol.
[0066]
In order to obtain the obtained polymer with more excellent particle properties, the following method can also be employed.
[0067]
That is, olefin prepolymerization is first carried out in the presence of the component [I], component [II], component [IV] and, if necessary, component [III]. The amount of component [III] used in the prepolymerization is not particularly limited, but is generally 1 to 50,000 moles, preferably 5 to 10, moles per mole of transition metal atoms in component [I]. 000 mol. More preferably, it is 10-5,000 mol. 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 [II] 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 block copolymer with a better bulk specific gravity.
[0068]
Examples of the olefin used in the prepolymerization 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-eicosene 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. Furthermore, styrene, dimethylstyrenes, allyl norbornane, allylbenzene, allylnaphthalene, allyltoluenes, vinylcyclopentane, vinylcyclohexane, vinylcyclopeptane, diene, and the like can be used. 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.
[0069]
The prepolymerization is preferably carried out by substantially homopolymerization of 95 mol% or more of olefin.
[0070]
The polymerization amount of the olefin initially applied in the prepolymerization of the present invention is 0.1 to 1000 g, preferably 1 to 50 g, per 1 g of the catalyst formed from the catalyst components [I], [II] and [IV]. Choose from a range.
[0071]
Further, as a particularly preferred embodiment of the prepolymerization, in the prepolymerization described above, first, in the presence of each component of [I], [II], [IV] and, if necessary, [III] Propylene is preliminarily polymerized as one prepolymerization to obtain a first prepolymerization catalyst, and then prepolymerization of 1-butene is further performed in the presence of the first prepolymerization catalyst and the above component [III] as a second prepolymerization. The method carried out in 1 is preferably used.
[0072]
The amount of component [III] used in each prepolymerization stage is not particularly limited, but is generally 1 to 50,000 mol, preferably 5 to 1 mol per 1 mol of transition metal atom in component [I]. 10,000 moles. 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 second prepolymerization. .
[0073]
In each prepolymerization stage, it is preferable to carry out substantially homopolymerization of propylene and 1-butene of 95 mol% or more, preferably 98 mol% or more.
[0074]
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.
[0075]
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. The temperature of the first and second prepolymerization 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 polymerization amount 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.
[0076]
Each preliminary polymerization may be carried out by any of batch, semi-batch and continuous methods.
[0077]
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.
[0078]
In the method of obtaining the propylene-based resin composition of the present invention as a propylene / propylene-ethylene block copolymer by polymerization, polymerization of the polypropylene component, the copolymer component of propylene and ethylene in the presence of the catalyst component described above is performed. Done. The polymerization order is not particularly limited, but it is preferable to produce a polypropylene component in the first stage and a copolymer component of propylene and ethylene in the second stage in order to produce a polymer with good particle properties.
[0079]
The polymerization conditions are not particularly limited as long as the effect of the present invention is recognized, but the following conditions are generally preferred.
[0080]
Polymerization of the polypropylene component may be carried out by supplying propylene alone or a mixture of propylene and other α-olefin and / or ethylene within the range satisfying the requirements of the present invention. The polymerization temperature in the polymerization of the polypropylene component is 0 to 100 ° C, preferably 20 to 80 ° C.
[0081]
In the polymerization, 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.
[0082]
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.
[0083]
Following the polymerization to obtain the polypropylene component, 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.
[0084]
In the random copolymerization of propylene and ethylene of the present invention, it is preferable to carry out 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.
[0085]
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.
[0086]
After the completion of the main polymerization, the monomer can be evaporated from the polymerization system to obtain the propylene resin composition of the present invention. This propylene-based resin composition can be subjected to known cleaning or countercurrent cleaning with a hydrocarbon having 7 or less carbon atoms.
[0087]
You may add commercially available additives, such as antioxidant, a heat stabilizer, and a chlorine scavenger, to the propylene-type resin composition of this invention. In this case, these additives may be mixed with the resin composition and then pelletized with an extruder. In addition to the above additives, an organic peroxide may also be added for thermal decomposition, and the molecular weight may be adjusted within a range that satisfies the requirements of the present invention.
[0088]
The propylene-based resin composition of the present invention has excellent anti-blocking property and heat-sealing property and excellent transparency in order to show a remarkable reduction effect of stickiness feeling together with excellent transparency and flexibility that have not been achieved in the past. Therefore, it is suitable as a film, particularly as a soft film. The use of the film is not particularly limited, and it is used for packaging applications such as food, clothing, stationery, sundries, etc., but among those uses, transparency deterioration with time does not occur and it is particularly suitable for food applications. Can be used.
[0089]
As a method for forming the propylene-based resin composition into a film, a known film forming method can be adopted without any particular limitation. The molding temperature at that time is preferably 200 to 300 ° C., preferably 220 to 270 ° C., considering the occurrence of melt fracture, film moldability, thermal degradation of the resin, and the like. As a method for forming the film, any forming method such as a non-stretched film using a T-die, a uniaxially stretched film, a biaxially stretched film, or calendar molding or inflation molding can be used.
[0090]
In the present invention, the film does not have a strict meaning particularly regarding the thickness, and is a generic name including a sheet, and usually about 10 to 1000 μm is preferably used.
[0091]
In addition, since the soft film made of the propylene-based resin composition obtained by the present invention has high transparency and good heat sealability, the film is used as another thermoplastic film, for example, polypropylene film, polyethylene film, polyethylene terephthalate. By laminating on a surface layer such as a film, a polyamide-based film, a polyvinyl chloride film, or an ethylene vinyl acetate copolymer film, the heat sealability can be improved without impairing the physical properties of the thermoplastic resin film.
[0092]
In particular, propylene homopolymers and polypropylene resin films copolymerized with 5 mol% or less of α-olefin other than propylene and propylene and / or ethylene such as ethylene, 1-butene, etc. By laminating, a film having excellent transparency and easy heat sealability is provided.
[0093]
Also, it is a low density polyethylene, linear low density polyethylene, a copolymer of propylene and other α-olefin, and is laminated on a soft resin film such as a relatively low crystalline resin or ethylene-vinyl acetate. The heat sealability of the soft resin film can be improved.
[0094]
The layer structure of the laminated film when the soft film composed of the propylene-based resin composition of the present invention is adopted as the surface layer is not particularly limited as long as the soft film composed of the propylene-based resin composition of the present invention is the surface layer. The soft film layer (A) composed of the propylene resin composition and the thermoplastic resin film layer (B) are not limited to a two-layer structure, but are layer (A), layer (B), layer (A) and the like. A three-layer structure may be used, and it may be appropriately configured in consideration of physical properties such as film rigidity and flexibility. Furthermore, you may laminate | stack another layer (C).
[0095]
The raw material of the other layer (C) is not particularly limited, and various resins can be employed depending on the purpose.
[0096]
The total thickness of the laminated film is preferably 10 to 100 μm, more preferably 20 to 60 μm.
[0097]
In addition, the thickness of each laminated layer is preferably 0.5 to 30 μm, more preferably 1 to 10 μm.
[0098]
In addition, the thickness of the layer (B) is preferably 5 to 70 μm, more preferably 10 to 50 μm.
[0099]
The thickness of the other layer (C) is not particularly limited, but is preferably 2 to 30 μm.
[0100]
Additives such as antioxidants, lubricants, anti-blocking agents, antistatic agents, anti-fogging agents, etc., to the raw materials for each layer of the laminated film, as long as they do not impair the effects of the present invention. You can also.
[0101]
The laminated film may simply be an extruded non-stretched film or a uniaxially or biaxially stretched film.
[0102]
The production method of the laminated film is not particularly limited, but the coextrusion T die method, the coextrusion inflation method, the extrusion lamination method, the dry lamination method, and the sand lamination method are used, and among them, the coextrusion T die method is particularly preferably used. Is done.
[0103]
When producing by the above-described coextrusion T-die method, for example, a crystalline polyolefin film is used for the layer (B), a soft film made of the propylene-based resin composition of the present invention is used for the layer (A), When a crystalline polyolefin film is used for (C), melt extrusion is performed using a plurality of extruders so that the layer (A) / layer (B) / layer (C) is formed, and is laminated before or after the die or inside the die. Can be produced by the coextrusion lamination method.
[0104]
The molding conditions of the laminated film are not particularly limited, but generally the resin temperature is 190 to 300 ° C., the air gap is 60 to 200 mm, the cooling roll temperature is 10 to 70 ° C., and the film forming speed is 50 to 500 m / min. Is preferred.
[0105]
The laminated film may be used as it is, but it is preferable to perform a corona discharge treatment in order to improve the adhesion with the printing ink.
[0106]
The conditions of the corona discharge treatment are not particularly limited, but the film surface has a wetting tension of 31 to from the viewpoint of adhesion of the laminated film to the printing ink or prevention of off-flavor due to damage of the corona discharge treatment. It is preferably performed so as to be 43 dynes / cm, preferably 33 to 38 dynes / cm.
[0107]
The use of the laminated film on which the propylene-based resin composition layer of the present invention is laminated is not particularly limited, and is used for packaging applications such as food, clothing, stationery, and miscellaneous goods. In particular, it can be suitably used for food applications.
[0108]
Moreover, the propylene-type resin composition of this invention can obtain a film with favorable heat-sealing property by mixing with a well-known polypropylene-type resin as a heat-sealability improving agent. Polypropylene resins to be used include propylene homopolymers, random or block copolymers of propylene containing 50 mol or more of propylene units with other α-olefins and / or ethylene, mixtures thereof, or polypropylene resins thereof. Random copolymers of olefins such as propylene-ethylene copolymer, propylene-ethylene-butene-1 copolymer, propylene-α-olefin copolymer, etc. It exhibits a particularly excellent improvement effect on a copolymer having a low melting point.
[0109]
The mixing ratio is usually in the range of 1 to 100 parts by weight, preferably 2 to 60 parts by weight with respect to 100 parts by weight of the polypropylene resin.
[0110]
The mixing method of the heat-sealability improving agent comprising the propylene-based resin composition of the present invention and a known polypropylene-based resin is not limited at all, but examples include a powder blend method or a pellet blend method using a tumbler, a Henschel mixer, etc. Can do. The resulting mixture of polypropylene resin compositions with improved heat-sealability includes, as necessary, antioxidants, hydrochloric acid absorbers, anti-aggregation agents, heat stabilizers, UV absorbers, lubricants, weathering stabilizers, electrification Various additives such as an inhibitor, a nucleating agent, a pigment, and a filler can also be blended. The blending ratio is appropriate, and any conventionally known method can be used as the preparation method without any limitation.
[0111]
As a method of forming the mixture of the propylene-based resin composition into a film as a product, a known film forming method can be adopted without any particular limitation. The molding temperature at that time is preferably 200 to 300 ° C., preferably 220 to 270 ° C., considering the occurrence of melt fracture, film moldability, thermal degradation of the resin, and the like. As a method for forming the film, any forming method such as a non-stretched film using a T-die, a uniaxially stretched film, a biaxially stretched film, or calendar molding or inflation molding can be used. Moreover, the mixture of the polypropylene resin composition may be used as a single layer film or as a heat seal layer of a multilayer film. Further, the film surface can be subjected to corona treatment.
[0112]
Furthermore, since the propylene-based resin composition obtained by the present invention is excellent in flexibility, transparency, tensile elongation and heat resistance and has no stickiness, it is used in various fields where conventional thermoplastic elastomers are used. It can be used suitably. For example, bumpers, mat guards, and lamp packings for automobile parts in the injection molding field, and various packings, ski shoes, grips, and roller skates in the household appliance field. On the other hand, in the extrusion molding field, various automotive interior materials, home appliances and electric wire materials, various insulating sheets, cord coating materials, and waterproof sheets, waterproofing materials, joint materials, stretch films for packaging, etc. it can.
[0113]
The molding method is not particularly limited, and can be suitably used for various applications by any molding method such as extrusion molding, injection molding, press molding, and vacuum molding.
[0114]
When molding, various stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, anti-aggregation agents, lubricants, plasticizers, pigments, inorganic or organic fillers can be blended. Illustrative of these additives are 2,6-di-t-butyl-p-cresol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 4,4 '-Butylidenebis (6-t-butyl-m-cresol), tocophenols, ascorbic acid, dilauryl thiodipropionate, phosphate stabilizer, fatty acid monoglyceride, N, N- (bis-2-hydroxyethyl) Alkylamine, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, silica, hydro Talcite, talc, clay, plaster, glass fiber, titania, calcium carbonate, carbon fiber Mention may be made of racks, petroleum resins, polybutenes, waxes, synthetic or natural rubber.
[0115]
【The invention's effect】
As understood from the above description, the polypropylene resin composition in which the crystallinity distribution measured by the TREF method has a specific mode is excellent in flexibility and transparency, and has no stickiness. It can be suitably used as a heat sealability improver for polypropylene resins that do not deteriorate transparency as a film.
[0116]
Further, it is suitably used in various fields where conventional thermoplastic elastomers are used.
[0117]
【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.
[0118]
In addition, the measuring method of the various physical properties of the polymer obtained in the following Examples and Comparative Examples is as follows.
[0119]
(1) Melt flow rate (abbreviated as MFR)
Conforms to ASTM D1238.
[0120]
(2) Bulk density
Conforms to ASTM D1895.
[0121]
(3) Melting point
Using DSC-6200R manufactured by Seiko Electronics Co., Ltd., about 5 mg of a sample was packed in an aluminum pan, heated to 200 ° C. at 10 ° C./minute, held at 200 ° C. for 5 minutes, then cooled to room temperature at 20 ° C./minute, It calculated | required from the endothermic curve at the time of heating up at 10 degree-C / min.
[0122]
(4) Ethylene content
With JEOL GSX-270¹³C-NMR spectrum was measured.
[0123]
(5) Molecular weight distribution
The column was developed on a column GMH6HT (manufactured by Tosoh Corporation) using 150C gel permeation chromatography (GPC) manufactured by Waters. The molecular weight distribution (Mw / Mn) was determined from the ratio of the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).
[0124]
(6) TREF (temperature rise elution fractionation) elution curve
Measurement was performed under the following conditions using an automatic TREF device (SSC-7300, ATREF) manufactured by Senshu Kagaku.
[0125]
Solvent: Orthodichlorobenzene
Flow rate: 150 ml / hour
Temperature increase rate: 4 ° C / hour
Detector: Infrared detector
Measurement wave number: 3.41 μm
Column: “Packed column 30Φ” manufactured by Senshu Scientific Co., Ltd., 30 mmΦ × 300 mm
Concentration: 1g / 120ml
Injection volume: 100ml
In this case, after introducing the sample solution into the column at 145 ° C., the sample solution is gradually cooled to −10 ° C. at a rate of 2 ° C./hour to adsorb the sample polymer to the surface of the packing material, and then the column temperature is increased under the above conditions. The polymer concentration eluted at each temperature by starting to flow the solvent simultaneously with warming was measured with an infrared detector to obtain an elution temperature-elution amount curve.
[0126]
(7) Transparency (haze value)
Conforms to JIS K6714.
[0127]
(8) Flexural modulus
Conforms to ASTM D-790.
[0128]
(9) Vicat softening temperature
The measurement was performed under the condition of a load of 250 g according to JIS K7206.
[0129]
(10) Tensile stress
Conforms to JIS K6251.
[0130]
(11) Blocking property
[In the case of 150 μm thick film and laminated film (30 μm)]
Two films (2 × 7 cm) are overlapped over a length of 2 cm, 500 g / cm²The film was allowed to stand at a temperature of 50 ° C. for 24 hours, and the peel strength was measured with a tensile tester (speed: 100 mm / min). In the case of a 150 μm-thick film, the measurement was performed by overlapping the casting roll contact surfaces, and in the case of a laminated film, the propylene-based resin composition of the present invention or the surface layers on which the resins used for comparison were laminated.
[0131]
[In the case of a 30 μm thick film (excluding laminated film)]
Two films (12 x 12 cm) are overlapped, a 10 kg load is applied and left at a temperature of 40 ° C for 24 hours, then a sample is cut out to 4 x 4 cm, and the peel strength is measured with a tensile tester (speed: 100 mm / min). It was measured. In addition, the casting roll contact surfaces of the film were overlapped and measured.
[0132]
(12) -20 ° C impact strength
Using an impact head with a diameter of 1 cm using a film impact tester manufactured by Toyo Seiki Co., Ltd. at -20 ° C, and dividing the energy value obtained under the capacity of 30 kg-cm by the thickness. did.
[0133]
(13) Heat seal start temperature
1 kg / cm of two films at a predetermined temperature using a heat sealer²A sample with a width of 15 mm obtained by pressure-bonding for 2 seconds was measured with a tensile tester (speed: 100 mm / min.), And the temperature when the peel resistance was 300 g / 15 mm was determined as the heat seal start temperature. It was. In addition, in the case of a single layer film, the casting roll contact surfaces were measured, and in the case of a laminated film, the propylene-based resin composition of the present invention or the surface layers on which the resins used for comparison were laminated were measured.
[0134]
(14) Stickiness
A flat plate of 50 mm length × 40 mm width × 1 mm thickness was prepared by injection molding, and the two flat plates were stacked and left under a load of 3 kgf for 3 days at 40 ° C. Was evaluated by the maximum stress when it was pulled and peeled at a test speed of 300 mm / min in the direction perpendicular to the adhesive surface (see FIG. 1).
[0135]
Example 1
[Preparation of supported metallocene catalyst]
Silica gel supported methylaluminoxane (MAO on SiO₂100 ml (0.005 mmol / ml toluene solution) of rac-dimethylsilylenebis-1- (2-methylindenyl) zirconium dichloride was added to 10 g of a 25 wt% -Al product (manufactured by Witco) and 30 minutes at room temperature. Stir.
[0136]
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.
[0137]
[polymerization]
(First stage, polymerization of propylene)
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, 5 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 performed for 70 minutes.
[0138]
(Later, copolymerization of propylene and ethylene)
After the previous polymerization, ethylene gas was supplied to a concentration of 16.1 mol% at a gas phase concentration, and further, copolymerization was performed for 70 minutes while supplying the gas phase concentration of ethylene to be kept constant. After the completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 150 kg of a white granular polymer.
[0139]
When the high temperature elution component and the medium-low temperature elution component fractionated by TREF of the obtained polymer were analyzed, the melting point of the high temperature elution component was 146 ° C.
[0140]
Further, the medium-low temperature elution component had an ethylene content of 8.6 wt%, and no melting point peak was detected by DSC.
[0141]
Table 1 shows the MFR, molecular weight distribution, bulk density, TREF eluting component amount, high temperature eluting component amount and melting point, and medium and low temperature eluting component amount and ethylene content of the polymers obtained.
[0142]
Moreover, the elution curve of the TREF method of the polymer obtained in FIG. 2 is shown.
[0143]
[Evaluation of the physical properties]
To 100 parts by weight of the obtained polymer, 0.1 part by weight of 2,6-di-t-butyl-p-cresol as an antioxidant and 0.05 part by weight of calcium stearate as a chlorine scavenger are added. After mixing for 5 minutes, extrusion was performed at 230 ° C. using an extrusion granulator having a screw diameter of 65 mmΦ, and pellets were granulated to obtain raw material pellets, which were subjected to physical property measurement. The haze value is a value of a 3 mm thick test piece for transparency evaluation obtained by injection molding. The results are shown in Table 2.
[0144]
Example 2
The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was 30 minutes, the gas phase ethylene concentration in the latter stage polymerization was 15.9 mol%, and the polymerization time was 110 minutes.
The results are shown in Tables 1 and 2.
[0145]
Example 3
The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was 90 minutes, the gas phase ethylene concentration in the latter stage polymerization was 15.9 mol%, and the polymerization time was 50 minutes. The results are shown in Tables 1 and 2.
[0146]
Example 4
The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was 110 minutes, the vapor phase ethylene concentration in the latter stage polymerization was 16.3 mol%, and the polymerization time was 30 minutes.
The results are shown in Tables 1 and 2.
[0147]
Example 5
The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was 80 minutes, the gas phase ethylene concentration in the latter stage polymerization was 30.3 mol%, and the polymerization time was 60 minutes. The results are shown in Tables 1 and 2.
[0148]
Example 6
The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was 120 minutes, the gas phase ethylene concentration in the latter stage polymerization was 32.7 mol%, and the polymerization time was 20 minutes.
The results are shown in Tables 1 and 2.
[0149]
Example 7
[Preparation of supported catalyst metallocene catalyst]
The same operation as in Example 1 was performed.
[0150]
[Preliminary polymerization]
N₂200 mL of purified heptane, 50 mmol of triisobutylaluminum, and 5 mmol of the supported metallocene catalyst component were charged into the substituted 1 L autoclave in terms of Zr atom, and then propylene was continuously added for 1 hour so as to be 5 g per 1 g of the supported metallocene catalyst component. Was introduced into the reactor and prepolymerized. The temperature during this period was maintained at 15 ° C.
[0151]
After 1 hour, the introduction of propylene was stopped and N in the reactor was₂And fully substituted. The solid component of the resulting slurry was washed 6 times with product heptane.
[0152]
[polymerization]
The same procedure as [Polymerization] in Example 1 was performed using the above prepolymerization catalyst. The results are shown in Table 1.
[0153]
[Evaluation of the physical properties]
The same operation as in Example 1 was performed. The results are shown in Table 2.
[0154]
Example 8
[Preparation of supported catalyst metallocene catalyst]
The same operation as in Example 1 was performed.
[0155]
[Preliminary polymerization]
N₂200 mL of purified heptane, 50 mmol of triisobutylaluminum, and 5 mmol of the supported metallocene catalyst component were charged into the substituted 1 L autoclave in terms of Zr atom, and then propylene was continuously added for 1 hour so as to be 5 g per 1 g of the supported metallocene catalyst component. Was introduced into the reactor and prepolymerized.
[0156]
The temperature during this period was maintained at 15 ° C. After 1 hour, the introduction of propylene was stopped and N in the reactor was₂And fully substituted. The solid component (first prepolymerization catalyst) of the obtained slurry was washed 6 times with purified heptane.
[0157]
Further, this first prepolymerization catalyst is converted to N₂After charging in a substituted 1 L autoclave, 200 ml of purified heptane and 50 mmol of triisobutylaluminum were added, and 1-butene was continuously added in the reactor for 1 hour so as to be 20 g with respect to 1 g of the supported metallocene catalyst component. And prepolymerized. The temperature during this period was maintained at 15 ° C.
[0158]
The solid part of the obtained slurry was washed 6 times with purified heptane to obtain a prepolymerized catalyst comprising a metallocene-containing polyolefin.
[0159]
[polymerization]
It carried out similarly to [Polymerization] of Example 1 using the above-mentioned prepolymerization catalyst.
[0160]
The results are shown in Table 1.
[0161]
[Evaluation of the physical properties]
The same operation as in Example 1 was performed. The results are shown in Table 2.
[0162]
Example 9
[polymerization]
(First stage, polymerization of propylene)
450 g of propylene was charged into an autoclave having an internal volume of 2 L, and 1 ml of a toluene solution of methylaluminoxane (PMAO-S, manufactured by Tosoh Akzo Co., Ltd., 3.1 mmol-Al / ml) was introduced. Thereafter, the internal temperature of the autoclave was raised to 55 ° C. Next, 0.5 ml of a pre-activated toluene solution of methylaluminoxane (PMAO-S, manufactured by Tosoh Akzo Co., Ltd., 3.1 mmol-Al / ml) and rac-dimethylsilylenebis-1- (2-methyl) were preliminarily activated at room temperature for 15 minutes. Benzindenyl) zirconium dichloride 0.1 mg mixed solution was charged in total. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was performed for 70 minutes.
[0163]
(Later, copolymerization of propylene and ethylene)
After the previous polymerization, ethylene gas was supplied at a gas phase concentration of 15.5 mol%, and copolymerization was performed for 70 minutes while supplying the ethylene gas phase so as to keep it constant. After completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 150 g of a white block polymer. The results are shown in Table 1.
[0164]
[Evaluation of the physical properties]
The same operation as in Example 1 was performed. The results are shown in Table 2.
[0165]
Reference example 1
[polymerization]
  The same procedure as in Example 9 was performed except that 0.01 mg of dimethylsilylene bis (2-methyl-4-naphthyl-indenyl) zirconium dichloride was used as the metallocene used in Example 9. 145 g of white block polymer was obtained. The results are shown in Tables 1 and 2.
[0166]
Reference example 2
[Production of random copolymer]
  450 g of propylene was inserted into a polymerization tank having an internal volume of 2 L, and 1.2 mmol of triisobutylaluminum was introduced. Thereafter, the internal temperature of the polymerization tank was raised to 55 ° C., and ethylene gas was supplied to a concentration of 15.9 mol% in a gas phase concentration. Next, 5 mg of a metallocene catalyst supported on silica gel prepared in the same manner as in Example 1 was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was carried out for 120 minutes while supplying the vapor phase concentration of ethylene to be kept constant. After completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 150 g of a white block polymer. The bulk density could not be measured due to the bulk.
[0167]
[Blend with crystalline polypropylene]
20 parts by weight of crystalline polypropylene (propylene homopolymer, MFR = 2.0 g / 10 min, Mw / Mn = 6.2, melting point = 163 ° C.) and the above random copolymer (freeze-pulverized bulk polymer) 80 parts by weight were blended. The results of the obtained blend are shown in Table 1.
[0168]
[Evaluation of the physical properties]
The same operation as in Example 1 was performed. The results are shown in Table 2.
[0169]
Comparative Example 1
[Preparation of catalyst]
The catalyst was prepared according to the method of Example 1 of JP-A-58-83006. 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 25 ° C. for 2 hours.
[0170]
To this solution, 0.55 g (6.75 mmol) of phthalic anhydride was added, and further stirred and mixed at 125 ° C. for 1 hour to obtain a uniform solution. After cooling to room temperature, the entire amount was dropped into 40 ml (0.36 mmol) of titanium tetrachloride maintained at 120 ° C. over 1 hour.
[0171]
Thereafter, the temperature of this mixed solution was raised to 110 ° C. over 2 hours, and when it reached 110 ° C., 0.54 ml of diisobutyl phthalate was added, and then kept at 110 ° C. with stirring for 2 hours. After the reaction for 2 hours, the solid part was collected by filtration, and the solid part was added to 200 ml of TiCl_FourThen, the reaction was again heated at 110 ° C. for 2 hours.
[0172]
After completion of the reaction, a heating reaction was performed again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was again collected by hot filtration, and washed sufficiently with decane and hexane until no free titanium compound was detected in the washing solution. The composition of the solid Ti catalyst was 2.1% by weight of titanium, 57% by weight of chlorine, 18.0% of magnesium, and 21.9% by weight of diisobutyl phthalate.
[0173]
[Preliminary polymerization]
N₂Purified n-hexane (200 ml), triethylaluminum (50 mmol), diphenyldimethoxysilane (10 mmol), ethyl iodide (50 mmol), and solid Ti catalyst component (5 mmol in terms of Ti atom) were charged into a substituted 1 L autoclave and then propylene was used as a solid catalyst. The mixture was continuously introduced into the autoclave for 30 minutes so as to be 3 g per 1 g of the component. The temperature during this period was maintained at 15 ° C.
[0174]
The reaction was stopped after 30 minutes, and the inside of the autoclave was N₂And fully substituted. The solid part of the obtained slurry was washed 4 times with purified n-hexane to obtain titanium-containing polypropylene. As a result of analysis, 2.1 g of propylene was polymerized per 1 g of the solid Ti catalyst component.
[0175]
[polymerization]
(First stage, polymerization of propylene)
Internal volume 2m^ThreeInto this polymerization tank, 600 kg of propylene was charged, 612 mmol of triethylaluminum, 306 mmol of cyclohexylmethyldimethoxysilane and hydrogen gas were further introduced, and then the internal temperature of the polymerization tank was raised to 55 ° C.
[0176]
Next, 1.4 mmol of titanium-containing polypropylene as Ti atoms was charged to initiate polymerization. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was carried out for 40 minutes.
[0177]
(Later, copolymerization of propylene and ethylene)
After the previous polymerization, ethylene gas was supplied to a concentration of 5.5 mol% in a gas phase concentration, and further copolymerization was performed for 100 minutes while supplying the gas phase concentration of ethylene to be kept constant.
[0178]
After the completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 145 kg of a white granular polymer. The results are shown in Table 1.
[0179]
[Evaluation of the physical properties]
The same operation as in Example 1 was performed. The results are shown in Table 2.
[0180]
Comparative Example 2
Example 1 [Polymerization] In the same manner as in Example 1, except that the former polymerization time was 50 minutes and the latter polymerization time was 90 minutes. The results are shown in Tables 1 and 2.
[0181]
Comparative Example 3
Example 1 [Polymerization] was carried out in the same manner as in Example 1 except that the former polymerization time was 90 minutes, the latter polymerization time was 50 minutes, and the ethylene gas phase concentration was 47.8 mol%. The results are shown in Tables 1 and 2.
[0182]
Comparative Example 4
In [Polymerization] of Example 1, the same procedure as in Example 1 was carried out except that the former polymerization time was 10 minutes, the latter polymerization time was 130 minutes, and the ethylene gas phase concentration was 16.1 mol%. The results are shown in Tables 1 and 2.
[0183]
Comparative Example 5
Example 1 [Polymerization] was carried out in the same manner as in Example 1 except that the former polymerization time was 120 minutes, the latter polymerization time was 20 minutes, and the ethylene gas phase concentration was 15.9 mol%. The results are shown in Tables 1 and 2.
[0184]
Comparative Example 6
In Example 1 [Polymerization], except that the former polymerization time was 60 minutes, the ethylene gas phase concentration was 6.0 mol%, the latter polymerization time was 80 minutes, and the ethylene gas phase concentration was 16.0 mol%. Polymerization was carried out in the same manner as in 1. The results are shown in Tables 1 and 2.
[0185]
[Table 1]

[0186]
[Table 2]

Film physical property evaluation
Example 12
[Pelletize]
  To 5 kg of the polymer obtained in Example 1, 0.1 part by weight of 2,6-di-t-butyl-p-cresol as an antioxidant, 0.05 part by weight of calcium stearate as a chlorine scavenger, an anti-blocking agent As a syloid 55 (average particle size; 2.73 μm) 0.15 parts by weight and as a lubricant 0.06 parts by weight erucamide is mixed for 5 minutes with a Henschel mixer, and then with a screw diameter 65 mmΦ single screw extruder 230 Extruded pellets were granulated under conditions of ° C. to obtain raw material pellets.
[0187]
[Create film]
The obtained pellets were supplied to a 40 mmΦ extruder heated at 260 ° C., extruded from a T die die, and cast with a casting roll adjusted to a surface temperature of 40 ° C. to obtain an unstretched film having a thickness of 150 μm. Table 3 shows the physical properties of the obtained film.
[0188]
  Example 13-20, Reference Examples 3 and 4
  Examples 2 to 9, Reference Examples 1 and 2An unstretched film was obtained in the same manner as in Example 12 using the polymer obtained in 1. Table 3 shows the physical properties of the obtained film.
[0189]
Comparative Examples 7-12
An unstretched film was obtained in the same manner as in Example 12 using the polymers obtained in Comparative Examples 1-6. Table 3 shows the physical properties of the obtained film.
[0190]
Comparative Example 13
Propylene-ethylene copolymer (MFR; 7.0 g / 10 min, ethylene content: 3.5 wt%, melting point: 145 ° C.) 100 parts by weight of ethylene-butene-1 copolymer (MI 7.0, 1-butene content; 12 mol%) An unstretched film was obtained in the same manner as in Example 12 using a resin mixed with 100 parts by weight. Table 3 shows the physical properties of the obtained film. (In Table 3, described as PP + EBR)
Comparative Example 14
An unstretched film was obtained in the same manner as in Example 12 using a propylene-butene-1 copolymer (MI; 7.0 g / 10 min, butene-1 content: 23 mol%) as the low crystalline resin. Table 3 shows the physical properties of the obtained film. (In Table 3, described as PB copolymer)
[0191]
[Table 3]

Example 23
  Using three extruders, the polymer pellet obtained in Example 1 as the surface layer raw material (A), and the crystalline propylene homopolymer (MI; 8.5 g / 10 min) as the base material raw material (B) As other surface layer raw materials (C), crystalline propylene-ethylene-butene-1 copolymer (MI; 7 g / 10 min, ethylene content; 3.7 mol%, 1-butene content; 5 mol%) and extruded so that the lamination ratio A: B: C was 1: 2: 1 to obtain a laminated film having a thickness of 30 μm. The results are shown in Table 4. The change with time of haze was evaluated by measuring the haze after the obtained film was stored at 40 ° C. for one week.
[0192]
Comparative Example 15
The surface layer material (A) was prepared in the same manner as in Example 23 except that the polymer pellets obtained in Comparative Example 1 were used. The results are shown in Table 4.
[0193]
Comparative Example 16
The same procedure as in Example 23 was performed, except that the resin used in Comparative Example 13 was used as the surface layer material (A). The results are shown in Table 4.
[0194]
Comparative Example 17
The same procedure as in Example 23 was performed, except that the resin used in Comparative Example 14 was used as the surface layer material (A). The results are shown in Table 4.
[0195]
[Table 4]

Evaluation as heat sealability improver
Example 24
[Pelletize]
To 5 kg of the polymer obtained in Example 1, 0.1 part by weight of 2,6-di-t-butyl-p-cresol as an antioxidant, 0.05 part by weight of calcium stearate as a chlorine scavenger, an anti-blocking agent As a syloid 55 (average particle size; 2.73 μm) 0.15 parts by weight and as a lubricant 0.06 parts by weight erucamide is mixed for 5 minutes with a Henschel mixer, and then with a screw diameter 65 mmΦ single screw extruder 230 Extruded pellets were granulated under conditions of ° C. to obtain raw material pellets.
[0196]
[Create film]
Obtained in Example 1 with crystalline propylene-ethylene-1-butene copolymer pellets (MI; 7 g / 10 min, ethylene content; 3.7 mol%, 1-butene content; 3.5 mol%) The obtained polymer pellets were mixed using a tumbler mixer at a weight ratio of 80/20 (propylene-ethylene-1-butene copolymer / copolymer obtained in Example 1), and screw diameter It was melt-extruded at a die temperature of 230 ° C. with a 40 mmφ T-die film forming machine and cooled with a casting roll having a surface temperature of 37 ° C. to obtain an unstretched film having a thickness of 30 μm. The obtained film was measured for physical properties 24 hours after molding. Table 5 shows the physical properties of the obtained film.
[0197]
Example 25-32, Reference Examples 5 and 6
Example 29, Reference Examples 1 and 2An unstretched film was obtained in the same manner as in Example 24 using the polymer obtained in 1. Table 5 shows the physical properties of the obtained film.
[0198]
Example 35
The same method as in Example 24 except that propylene-ethylene-1-butene copolymer and heat seal improver were used in a weight ratio of 70/30 (propylene-ethylene-1-butene copolymer / heat seal improver). An unstretched film was obtained. Table 5 shows the physical properties of the obtained film.
[0199]
Comparative Examples 18-23
An unstretched film was obtained in the same manner as in Example 24 using the polymers obtained in Comparative Examples 1-6. Table 5 shows the physical properties of the obtained film.
[0200]
Comparative Example 24
Low propylene-butene-1 copolymer (MI; 7.0 g / 10 min, butene-1 content; 23 mol%) was used as the heat seal improver, and the same propylene-ethylene-1- An unstretched film was obtained in the same manner as in Example 24 except that the butene copolymer and the heat seal improver were used in a weight ratio of 80/20 (propylene-ethylene-1-butene copolymer / heat seal improver). It was. Table 5 shows the physical properties of the obtained film.
[0201]
Comparative Example 25
The same method as in Comparative Example 24 except that propylene-ethylene-1-butene copolymer and heat seal improver were used in a weight ratio of 70/30 (propylene-ethylene-1-butene copolymer / heat seal improver). An unstretched film was obtained. Table 5 shows the physical properties of the obtained film.
[0202]
Comparative Example 26
An unstretched film was prepared in the same manner as in Comparative Example 24 except that an ethylene-butene-1 copolymer (MI; 7.0 g / 10 min, butene-1 content; 12 mol%) was used as the heat seal improver. Obtained. Table 5 shows the physical properties of the obtained film.
[0203]
Comparative Example 27
The same procedure as in Example 24 was performed except that the heat seal improver was not used in Example 24.
[0204]
[Table 5]

[Brief description of the drawings]
FIG. 1 is a view showing a method for evaluating the tackiness of a propylene-based resin composition in the present invention.
2 is an elution curve of a temperature rising elution fractionation method for the propylene-based resin composition of Example 1. FIG.
FIG. 3 is a flowchart showing a typical polymerization method of the present invention.
FIG. 4 is a flowchart showing a typical polymerization method of the present invention.

Claims (7)

In the presence of a catalyst composed of a metallocene compound containing zirconium and an aluminoxane compound , a polypropylene component, a copolymer component of propylene and ethylene are obtained in stages,
(I) According to the temperature rising temperature elution fractionation method using an o-dichlorobenzene solvent, components that elute at a temperature up to 90 ° C. (hereinafter referred to as “medium / low temperature eluting components”) are 50 to 99% by weight of the total, Ingredients eluting at temperature (hereinafter referred to as high temperature eluting components) are 50 to 1% by weight of the total, and further, components eluting at temperatures up to 0 ° C. (hereinafter referred to as low temperature eluting components) are 8% by weight or less of the total,
(II) The ethylene unit content in the medium-low temperature elution component is 4% by weight or more and less than 20% by weight, and the propylene unit content in the high-temperature elution component is 97 to 100% by weight,
The molecular weight distribution dispersity (Mw / Mn) is 5 or less,
A propylene-based resin composition having a melting point measured by a thermal differential scanning calorimeter of a high-temperature elution component of 130 to 155 ° C.   2. The propylene-based resin composition according to claim 1, wherein a melting point of the high temperature eluting component measured by a thermal differential scanning calorimeter is 130 to 146 ° C. 3. 2. The propylene-based resin according to claim 1, wherein a polypropylene component, a copolymer component of propylene and ethylene are produced in stages in the presence of a catalyst comprising a metallocene compound containing zirconium and an aluminoxane compound. A method for producing the composition.   A flexible film comprising the propylene-based resin composition according to claim 1.   A film in which a thermoplastic resin and the propylene-based resin composition layer according to claim 1 are laminated.   A heat sealability improver for a polypropylene film comprising the propylene-based resin composition according to claim 1.   A film comprising a mixture of 100 parts by weight of a polypropylene-based resin and 1 to 100 parts by weight of the heat sealability improving agent for polypropylene film according to claim 6.

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