JP3618462B2 - Propylene resin molding - Google Patents

Description

【００２５】
ブロック性（ＣＳＤ）はエチレンとプロピレンの反応性比のことであり、この定義は、高分子学会編，「共重合１反応解析，ｐ５〜１３」培風館発行（１９７５）に述べられている。計算方法は、Ｓｏｇａ，Ｋ， Ｐａｒｋ，Ｊ，Ｒ， Ｓｈｉｏｎｏ，Ｔ；Ｐｏｌｙｍｅｒ Ｃｏｍｍｕｎｉｃａｔｉｏｎｓ，Ｖｏｌ．３２，Ｎｏ．１０，ｐ３１０（１９９１）の方法に従った。すなわち、図１の_１３Ｃ−ＮＭＲスペクトルの▲１▼▲２▼▲３▼▲６▼▲７▼▲９▼の強度比を用い以下の式（ＩＶ）で求めた。
（ＣＳＤ）＝［（０．５×▲７▼＋０．２５×▲６▼＋０．５×▲３▼）×▲１▼］／［０．５×（▲２▼＋▲３▼）］^２
…式（ＩＶ）
このようにして求められる、平均のプロピレン含量（ＦＰ）は３０〜６０モル％の範囲であり、好ましくは３５〜５８モル％であり、さらに好ましくは３８〜５５モル％である。プロピレン含量が３０モル％未満であると、製品の外観が著しく低下し好ましくない。一方、６０モル％を超えると、低結晶性重合物の副生成量が増加するので好ましくない。
【００２６】
２サイトモデルによる高プロピレン含量側のプロピレン含量（Ｐ_Ｐ）は６０〜８０モル％である。好ましくは６３〜７８であり、さらに好ましくは６５〜７５モル％である。（Ｐ_Ｐ）が６０モル％未満の場合は、プロピレンブロック共重合体の剛性および耐熱性が低下し、好ましくない。８０モル％を超える場合は、耐衝撃性が損なわれ好ましくない。（Ｐ_Ｐ）がＦＰ中に占める割合については、０．２５〜０．５５の範囲であり、好ましくは０．２７〜０．５３の範囲であり、さらに好ましくは０．２０〜０．５１の範囲である。（Ｐ_Ｐ）がＦＰ中に占める割合が、０．２５未満では、剛性、耐熱性が低下し好ましくない。一方、０．５５を超えると耐衝撃性が損なわれ好ましくない。ブロック性（ＣＳＤ）に関しては、１．４〜２．５の範囲にあるものが良い、好ましくは１．６〜２．３の範囲であり、さらに好ましくは１．７〜２．０の範囲である。（ＣＳＤ）が１．４未満では、剛性、耐熱性が低下し好ましくない。一方、２．５を超えると耐衝撃性のうち特に低温衝撃強度が損なわれ好ましくない。
【００２７】
また、（Ｉ）キシレン不溶分の極限粘度［η］_１とキシレン可溶分の極限粘度［η］_２の比［η］_２／［η］_１およびキシレン不溶分の極限粘度［η］_１との関係が、式（Ｉ）を満たし、および
［η］_２／［η］_１≦０．２１［η］_１＋０．５６ …式（Ｉ）
（ＩＩ）キシレン不溶分が、ゲルパーミエーションクロマトグラフ（ＧＰＣ）による、重量平均分子量（Ｍｗ_１）が、１０万〜７０万の範囲にあり、かつ重量平均分子量（Ｍｗ_１）と数平均分子量（Ｍｎ_１）との比（Ｍｗ_１／Ｍｎ_１）である分子量分布ＭＤ_１が４．０〜１０の範囲にあるもの。
（ＩＩＩ）キシレン可溶分が、ゲルパーミエーションクロマトグラフ（ＧＰＣ）による、重量平均分子量（Ｍｗ_２）が、１０万〜６０万の範囲にあり、かつ重量平均分子量（Ｍｗ_２）と数平均分子量（Ｍｎ_２）との比（Ｍｗ_２／Ｍｎ_２）である分子量分布ＭＤ_２が４．０〜８．０の範囲にあるもの。
（ＩＶ）キシレン可溶分の分子量分布（ＭＤ_２）とキシレン不溶分の分子量分布（ＭＤ_１）の比が、１．０以下であるプロピレン樹脂成形物は、剛性と耐衝撃性のバランスに優れ、透明性に優れるものが得られる。
【００２８】
（Ｉ）キシレン不溶分の極限粘度［η］_１とキシレン可溶分の極限粘度［η］_２の比［η］_２／［η］_１およびキシレン不溶分の極限粘度［η］_１との関係が、好ましくは、［η］_２／［η］_１≦０．２１［η］_１＋０．５２、特に好ましくは、［η］_２／［η］_１≦０．２１［η］_１＋０．４８である。［η］_２／［η］_１が、０．２１［η］_１＋０．５６を超える場合は、透明性、耐衝撃性に劣る。
【００２９】
（ＩＩ）キシレン不溶分が、ゲルパーミエーションクロマトグラフ（ＧＰＣ）による、重量平均分子量（Ｍｗ_１）は、好ましくは１５万〜６５万の範囲であり、特に好ましくは、２０万〜６０万である。キシレン不溶分の重量平均分子量（Ｍｗ_１）と数平均分子量（Ｍｎ_１）との比（Ｍｗ_１／Ｍｎ_１）であるキシレン不溶分の分子量分布（ＭＤ_１）は、好ましくは４．２〜７．０の範囲であり、特に好ましくは、４．５〜６．０である。
キシレン不溶分の重量平均分子量（Ｍｗ_１）が、１０万未満の場合は、機械的強度が劣り好ましくない。また、７０万を超える場合は、成形物のゲル、フィシュ・アイなどが発生しやすく好ましくない。
キシレン不溶分の分子量分布（ＭＤ_１）すなわち（Ｍｗ_１／Ｍｎ_１）が４．０未満の場合は、成形性が劣る。一方、１０を超える場合は、機械的強度、成形物の外観が劣り好ましくない。
【００３０】
（ＩＩＩ）キシレン可溶分が、ゲルパーミエーションクロマトグラフ（ＧＰＣ）による、重量平均分子量（Ｍｗ_２）は、好ましくは１５万〜５０万の範囲であり、特に好ましくは、２０万〜４０万の範囲がよい。また、キシレン可溶分の重量平均分子量（Ｍｗ_２）と数平均分子量（Ｍｎ_２）との比（Ｍｗ_２／Ｍｎ_２）であるキシレン可溶分の分子量分布（ＭＤ_２）は、好ましくは、４．５〜７．５の範囲であり、特に好ましくは、５．０〜７．０の範囲である。
キシレン可溶分の重量平均分子量（Ｍｗ_２）が１０万未満の場合は、耐衝撃性、耐寒性が劣り好ましくない。また、６０万を超える場合は、成形物のゲル、フィシュ・アイなどが発生しやすく好ましくない。
キシレン可溶分の分子量分布（ＭＤ_２）すなわち（Ｍｗ_２／Ｍｎ_２）が４．０未満の場合は、成形性が劣り好ましくない。一方、キシレン可溶分の分子量分布（ＭＤ_２）が８．０を超える場合は、耐熱性、成形物の表面のべたつきが発生しやすく好ましくない。
【００３１】
（ＩＶ）キシレン不溶分の分子量分布（ＭＤ_１）とキシレン可溶分の分子量分布（ＭＤ_２）の比は、好ましくは０．９５以下であり、特に好ましくは０．９以下である。下限値については、特に制限はないが、通常０．５以上である。
キシレン不溶分の分子量分布（ＭＤ_１）とキシレン可溶分の分子量分布（ＭＤ_２）の比が１．０を超える場合は、成形物の透明性、剛性と耐衝撃性のバランスが劣る。
【００３２】
なお、本発明におけるゲルパーミエーションクロマトグラフ（ＧＰＣ）による、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は以下のように定義される。分子量の分かっている一連の単分散標準ポリスチレンのゲルパーミエーションクロマトグラフ（ＧＰＣ）の測定を行い、ポリスチレンの分子量と溶出時間の関係式（以下、較正曲線とする）を作成する。Ｒ．Ｌｅｗ，Ｄ．Ｓｕｗａｎｄａ，Ｓ．Ｔ．Ｂａｌｋｅ；Ｊ．Ａｐｐｌｉ．Ｐｏｌｙｍ．Ｓｃｉ．，Ｖｏｌ．３５，ｐ１０４９−１０６３（１９８８）に記載されているポリスチレンとポリプロピレンの固有粘度と分子量の関係式から、ポリスチレンの分子量からポリプロピレンの分子量への分子量換算式を求める。
ポリプロピレンのゲルパーミエーションクロマトグラフ（ＧＰＣ）測定データから較正曲線を使用して分子量を求め、更に分子量換算式を使用して、ポリプロピレンの重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）を求める。
【００３３】
具体的には、Ｓｈｏｄｅｘ ＨＴ−８０６Ｍカラムを２本直列に接続したＷａｔｅｒｓ社製１５０Ｃ型ＧＰＣ装置を用いて測定できる。キシレン可溶分、キシレン不溶分の各々の測定データから、較正曲線を用いて分子量を求め、更に以下の分子量換算式を使用して、重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）を求めた。
Ｍ_ＰＰ＝０．９３１×Ｍ_ＰＳ ^{０．９７５}
Ｍ_ＰＳ：ある溶出時間でのポリスチレンの分子量
Ｍ_ＰＰ：同一溶出時間でのポリプロピレンの分子量
尚、このような分子量計算法は、武内次夫，森定雄著，「ゲルクロマトグラフィー＜基礎編＞」講談社発行（１９７２）に詳細に述べられている。
【００３４】
本発明のプロピレン樹脂成形物を得るための好ましい例としては、例えばマグネシウム化合物、チタン化合物、ハロゲン含有化合物および電子供与性化合物を必須成分とする固体触媒または、更に、一般式：ＴｉＸ_ａ・Ｙ_ｂ（式中、ＸはＣｌ，Ｂｒ，Ｉのハロゲン原子を、Ｙは電子供与性化合物を、ａは３もしくは４を、ｂは３以下の整数をそれぞれ表す）で示されるチタン化合物で処理後、ハロゲン含有化合物で洗浄し、更に炭化水素で洗浄して得られる重合触媒を用いて重合したものが挙げられる。
このような重合触媒は、マグネシウム化合物、チタン化合物、ハロゲン含有化合物、電子供与性化合物を用いて調製される。
【００３５】
マグネシウム化合物としては、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウムのようなハロゲン化マグネシウム；ジメトキシキマグネシウム、ジエトキシキマグネシウム、ジプロポキシキマグネシウム、ジブトキシキマグネシウム、ジフェノキシマグネシウムのようなアルコキシマグネシウムなどが好適である。また、触媒形成時にハロゲン化マグネシウムを形成するものも使用できる。 これら各種マグネシウム化合物は、単独で使用しても良いし、２種以上併用して使用しても良い。
チタン化合物としては、四塩化チタン、三塩化チタン、四臭化チタン、四ヨウ化チタンのようなハロゲン化チタンなどが好適である。また、これら各種チタン化合物は単独で使用しても良いし、２種以上併用して使用しても良い。
ハロゲン含有化合物は、ハロゲンがフッ素、塩素、臭素、またはヨウ素、好ましくは塩素であり、具体例としては、触媒調製法に依存するが、四塩化チタンなどのハロゲン化チタン、四塩化ケイ素、四臭化ケイ素などのハロゲン化珪素、三塩化リン、五塩化リンのようなハロゲン化リンなどが挙げられる。触媒調製法によっては、ハロゲン化炭化水素、ハロゲン分子、ハロゲン化水素酸を用いても良い。
【００３６】
電子供与性化合物としては、一般に含酸素化合物、含窒素化合物、含リン化合物、含硫黄化合物、含ケイ素化合物等が挙げられる。
具体的には、アルコール類、フェノール類、ケトン類、アルデヒド類、有機酸エステル類、アルコキシエステル類、ケトエステル類、無機酸エステル類、エーテル類、アミド類、有機酸ハライド類、有機酸無水物類、アミン類、ニトリル類、チオエーテル類、硫酸エステル類、スルホン酸類、ケイ素含有化合物類などを挙げることができる。この中で特に好ましいのは有機酸エステル類であり、さらに具体的には、フタル酸エチル、フタル酸ブチル、フタル酸２−エチルヘキシルなどのフタル酸エステル類を例示できる。これらの電子供与性化合物は、１種でもよく、２種類以上を併用して用いても良い。
前記各成分の使用量は、本発明において効果が認められる限り任意のものであるが、一般的に次の範囲が好ましい。チタン化合物の使用量は、使用するマグネシウム化合物の使用量に対してモル比で０．０００１〜１０００の範囲内が良く、好ましくは０．０１〜１００の範囲である。必要に応じてハロゲン化合物を使用する場合は、使用するマグネシウム化合物の使用量に対してモル比で０．０１〜１０００の範囲内が良く、好ましくは０．１〜１００の範囲内である。
電子供与性化合物の使用量は、前記マグネシウム化合物の使用量に対して、モル比で０．００１〜１０の範囲内が良く、好ましくは０．０１〜５の範囲内である。
固体触媒の調製方法としては、マグネシウム化合物、チタン化合物および電子供与性化合物、さらに必要に応じてハロゲン含有化合物等の助剤とを一時的または段階的に接触、反応させて得られる従来公知の固体触媒の調製方法を用いることができる。
【００３７】
公知方法の具体例として、以下の調製方法がある。
（１）ハロゲン化マグネシウムと必要に応じて電子供与性化合物とチタン化合物を接触させる方法。
（２）ハロゲン化マグネシウムとテトラアルコキシチタンおよび特定のポリマーケイ素化合物を接触させて得られる固体成分に、ハロゲン化チタン化合物および／またはケイ素のハロゲン化合物を接触させる方法。
（３）マグネシウム化合物をテトラアルコキシチタンおよび電子供与性化合物で溶解させて、ハロゲン化剤またはハロゲン化チタン化合物で析出させた固体成分に、チタン化合物を接触させる方法。
（４）アルミナまたはマグネシアをハロゲン化リン化合物で処理し、それにハロゲン化マグネシウム、電子供与性化合物、ハロゲン化チタン化合物を接触させる方法。
（５）有機マグネシウム化合物に代表されるグリニャール試薬を、還元剤や、ハロゲン化剤と作用させた後、電子供与性化合物とチタン化合物とを接触させる方法。
（６）アルコキシマグネシウム化合物にハロゲン化剤および／またはチタン化合物を電子供与性化合物の存在下もしくは不存在下で接触させる方法。
（７）マグネシウム化合物をテトラアルコキシチタンで溶解し、ポリマーケイ素化合物で処理した後、ケイ素のハロゲン化合物および有機金属化合物で処理する方法。
（８）球状のマグネシウム化合物／アルコール錯体を電子供与性化合物およびハロゲン化チタン化合物等で処理する方法。
これら調製方法で特に好ましい方法としては（８）の方法が挙げられる。
【００３８】
上記の方法で調製された固体触媒は、一般式ＴｉＸ_ａ・Ｙ_ｂ（式中、ＸはＣｌ、Ｂｒ、Ｉのハロゲン原子、ａは３もしくは４、Ｙは電子供与性化合物、０＜ｂ≦３を表す）で表されるチタン化合物で１回以上、ハロゲン含有化合物で１回以上処理し、炭化水素で洗浄することによって触媒成分が調製される。
一般式ＴｉＸ_ａ・Ｙ_ｂ（式中、ＸはＣｌ、Ｂｒ、Ｉのハロゲン原子、ａは３もしくは４）は、例えば、Ｒ．Ｓ．Ｐ．Ｃｏｕｔｔｓ，Ｐ．Ｃ．Ｗａｉｌｅｓ； Ａｄｏｖａｎ． Ｏｒｇａｎｏｍｅｔａｌ．Ｃｈｅｍ．，Ｖｏｌ．９，Ｐ−１３５（１９７０）、第４版新実験化学講座１７無機錯体・キレート錯体ｐ．３５、日本化学会、丸善（１９９１）、Ｈ．Ｋ．Ｋａｋｋｏｅｎ，Ｊ．Ｐｕｒｓｉａｉｎｅｎ，Ｔ．Ａ．Ｐａｋｋａｎｅｎ，Ｍ．Ａｈｌｇｒｅｎ，Ｅ．Ｉｉｓｋｏｌａ；Ｊ．Ｏｒｇａｎｏｍｅｔ．Ｃｈｅｍ．，Ｖｏｌ．４５３，ｐ１７５（１９９３）などに記載されているように、一般に電子供与性化合物とは容易に錯体を形成することが知られている。
ＴｉＸ_ａ・Ｙ_ｂのＹ（電子供与性化合物）は、固体触媒調製時に使用したものと同様のもの、または異なるものでも良い。ＴｉＸ_ａ・Ｙ_ｂを調製する際、電子供与性化合物は１種でも良く、２種以上併用してもよい。
また、ハロゲン含有化合物は、固体触媒調製時に使用したものと同様もの、あるいは異なるものを用いても良い。ハロゲン含有化合物は１種でも、２種以上併用し用いてもよい。
【００３９】
固体触媒をＴｉＸ_ａ・Ｙ_ｂで処理する温度は、−３０℃〜１５０℃、好ましくは０℃〜１００℃の範囲である。また、固体触媒をハロゲン含有化合物で処理する温度は０℃〜２００℃、好ましくは５０℃〜１５０℃である。
ＴｉＸ_ａ・Ｙ_ｂの使用量は、固体触媒中のチタン原子に対して、モル比で０．００１〜５００の範囲がよく、好ましくは０．１〜１０００の範囲内である。
固体触媒のＴｉＸ_ａ・Ｙ_ｂおよびハロゲン含有化合物による処理は、通常、不活性炭化水素媒体中で行うことができる。この際、用いられる不活性炭化水素媒体としては、ペンタン、ヘキサン、ヘプタン、オクタン、デカンなどの脂肪族炭化水素；ベンゼン、トルエン、キシレンなどの芳香族炭化水素などを例示することができる。
また、これらの不活性炭化水素溶媒は、固体触媒のＴｉＸ_ａ・Ｙ_ｂおよびハロゲン含有化合物による処理後のオレフィン重合用触媒の洗浄溶媒として用いることができる。
【００４０】
このように調製される重合触媒のうち、次の粉体物性を有するものを用いると良い。
（ａ）表面積が１００ｍ^２／ｇ〜３００ｍ^２／ｇであり、好ましくは１２０ｍ^２／ｇ〜２８０ｍ^２／ｇ、特に好ましくは１３０ｍ^２／ｇ〜２６０ｍ^２／ｇである。
表面積が１００ｍ^２／ｇ未満の場合は、ＢＰＰ中の（Ｂ）成分の増量が困難になる。一方、３００ｍ^２／ｇを超える場合は、重合したポリマーが破壊しやすくなり、微粉が発生し、プラントの粉体輸送が困難になったり、反応器の壁に付着しやすくなる。
（ｂ）細孔体積が細孔２ｎｍ〜４０ｎｍの範囲で、０．３０ｃｃ／ｇ〜０．４５ｃｃ／ｇのものを用いるとよい。
細孔２ｎｍ〜４０ｎｍの範囲で、０．３０ｃｃ／ｇ未満の場合は、ＢＰＰ中の（Ｂ）成分の増量が困難になる。一方、０．４５ｃｃ／ｇを超えると重合したポリマーが破壊しやすくなり、微粉が発生し、プラントの粉体輸送が困難になったり、反応器の壁に付着しやすくなる。
【００４１】
（ｃ）また、重量平均粒子径が５０〜１００μｍで、好ましくは５５〜９８μｍ、特に６０〜９６μｍの範囲が好適である。
重量平均粒子径が、５０μｍ未満の場合は、ＢＰＰ中の（Ｂ）成分の増量が困難になる。一方、１００μｍを超えると重合したポリマーが破壊しやすくなり、微粉が発生し、プラントの粉体輸送が困難になったり、反応器の壁に付着しやすくなる。
（ｄ）粒子径１２３μｍ以上のものが１５重量％以下、好ましくは１３重量％以下、特に１０重量％以下が好適である。
粒子径１２３μｍ以上のものが１５重量％を超える場合は、重合したポリマーが破壊しやすくなり、微粉が発生し、プラントの粉体輸送が困難になったり、反応器の壁に付着しやすくなる。
（ｅ）粒子径８７μｍ以下のものが３５重量％以上であり、好ましくは３８重量％以上、特に４０重量％以上のものが好適である。
粒子径８７μｍ以下のものが３５重量％未満の場合は、ＢＰＰ中の（Ｂ）成分の増量が困難になる。
【００４２】
上記のような、表面積、細孔体積を得る方法としては、特開平３−６２８０５号公報に記載されている。この先行文献には、固体触媒の調製時に塩化マグネシウムとアルコール付加物について述べられており、塩化マグネシウム１モル当たり０．２〜２モルのアルコール付加物を調製している。そして、この固体触媒は平均直径１０〜３５０ｎｍ、表面積２０〜２５０ｍ^２／ｇおよび細孔度０．２ｃｃ／ｇ以上であり、高嵩密度、流動性および機械的耐性を有する球状粒子のオレフィン（コ）ポリマーが得られると述べている。
上記特開平３−６２８０５号公報に記載された方法と本発明との相違点は、本発明の重合触媒の表面積、細孔体積および粒度分布は、固体触媒をＴｉＸ_ａ・Ｙ_ｂで処理し、不活性炭化水素溶媒で洗浄した後の改良触媒を表すのに対し、上記先行文献に記載されているものは、固体触媒そのものの表面積および細孔体積を述べており、本発明の改良重合触媒とは異なるものである。
表面積の測定方法に関しては、ＢＥＴ法（Ｓ．Ｂｒｕｎａｕｅｒ，Ｐ．Ｈ．Ｅｍｍｅｔｔ，Ｅ．Ｔｅｌｌｅｒ；Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，Ｖｏｌ．６０，ｐ３０９（１９３８）によって測定されるものである。
【００４３】
一方、細孔体積に関しては、多孔性物質に含まれる細孔の全体積をいう。一般に、細孔は単一径のものではなく、種々の半径の細孔の集合体であるため、細孔分布を求めて細孔体積を求めることができる。ＢＥＴ法については、市販の測定装置であるＣＡＲＬＯ ＥＲＢＡ ＳＴＲＵＭＥＮＴＡＺＩＯＮＥ社製Ｓｏｒｐｔｏｍａｔｉｃ Ｓｅｒｉｅｓ１８００を用い、窒素ガス吸着法により求めることができる。
触媒などの細孔体積の測定方法は水銀圧入法（Ｅ．Ｗ．Ｗａｓｈｂｕｒｎ，Ｐｒｏｃ．Ｎａｔｌ．Ａｃａｄ．Ｓｃｉ．，Ｖｏｌ．７，ｐ−１１５（１９２１））によって求めることができる。この水銀圧入法は、触媒の細孔内に水銀を圧入し、水銀の細孔への浸入量を圧力の関数として求めることができる。この測定については、市販の測定装置であるＭＩＣＲＯＭＥＲＩＴＩＳ社製Ａｕｔｏ Ｐｏｒｅ９２００型を用い測定できる。
【００４４】
本発明でいう粒子径については、粒径分布の計測を回析パターン解析によって得られるものである。すなわち、ビームエックスパンダで広げられたレーザビームを気相または液相中に分散した粒子に当て、この粒子によって発生する回析パターンをレンズによって集光し、検出器に投影し、この検出器に投影されるフランホーファ回析パターンの強度分布から求められる。
このような解析方法に関しては、Ｍｉｃｈａｅｌ Ｈｅｕｅｒ，Ｋｕｒｔ Ｌｅｓｃｈｏｎｓｋｉ：Ｒｅｓｕｌｔｓ Ｏｂｔａｉｎｅｄ ｗｉｔｈ ａ Ｎｅｗ Ｉｎｓｔｒｕｍｅｎｔ ｆｏｒ ｔｈｅ Ｍｅａｓｕｒｍｅｎｔ ｏｆ Ｐａｒｔｉｃｌｅ Ｓｉｚｅ Ｄｉｓｔｒｉｂｕｔｉｏｎｓ ｆｒｏｍ Ｄｉｆｆｒａｃｔｉｏｎ Ｐａｔｔｅｒｎｓ． Ｐａｒｔ ２ （１９８５） ｐ７−１３およびＪ．Ｆｒａｕｎｈｏｆｅｒ：Ｂｒｅｈｕｎｇｓ ｕｎｄ Ｆｒａｒｂｚｅｒｓｔｒｅｕｕｎｇｓｖｅｒｍ ｇｅｎｓ ｖｅｒｓｃｈｉｅｄｅｎｅｒ Ｇｌａｓａｒｔｅｎ．ＧｉｌｂｅｒｔｓＡｎｎａｌｅｎ ｄｅｒ Ｐｈｙｓｉｋ ５６（１９８７），ｐ１９３−２２６等に詳細に述べられている。
より具体的には、市販の日本電子（株）製レーザ回析式粒度分布測定装置ＨＥＬＯＳ＆ＲＯＤＯＳを使用し、測定することができる。
【００４５】
また、上記粉体特性以外に、以下の力学特性を有するものがよい。すなわち、市販の粉体圧縮・引張り強度計測装置である、ホソカワミクロン（株）「アグロボット」装置を用い測定される圧縮破壊強度が、１．０×１０^６ Ｎ／ｍ^２以上であり、引張り応力が５０ｇ以上の重合触媒を用いるとよい。
装置の概要については、辻本広行、井上善之、横山豊和；粉砕Ｎｏ．３８、ｐｐ７４−８０（１９９４）に述べられている。
圧縮破壊強度は、好ましくは１．１×１０^６ Ｎ／ｍ^２以上であり、特に好ましくは、１．２×１０^６ Ｎ／ｍ^２以上である。一方、引張り応力については、好ましくは６０ｇ以上であり、特に好ましくは７０ｇ以上のものがよい。
装置を用い測定される圧縮破壊強度が、１．０×１０^６ Ｎ／ｍ^２未満および引張り応力が５０ｇ未満の場合は、本発明のプロピレン樹脂成形物を得るのが困難である。またプロピレンやその他のα−オレフィンを予備重合したものの上記分体特性に関しては、圧縮破壊強度が１．０×１０^６Ｎ／ｍ^２以上および引張強度が４ｇ以上であるものが好ましい。
上記のような重合触媒は、後述する有機アルミニウム化合物、立体規則性改良剤との組み合わせにより、本発明のＢＰＰの製造に使用される。
【００４６】
有機アルミニウム化合物の代表的なものとしては、トリメチルアルミニウム、トリエチルアルミニウム、トリプロピルアルミニウム、トリブチルアルミニウム、トリヘキシルアルミニウム、トリオクチルアルミニウムのようなトリアルキルアルミニウム、メチルアルミノキサン、エチルアルミノキサン、プロピルアルミノキサンのようなアルミノキサンが挙げられる。このような有機アルミニウム化合物は、１種でもよく、２種以上併用し用いてもよい。
立体規則性改良剤としては、フェニルトリエトキシシラン、ジフェニルジメトキシシラン、ジ−ｎ−プロピルジメトキシシラン、ジ−ｉ−プロピルジメトキシシラン、ジ−ｔ−ブチルジメトキシシラン、ジシクロヘキシルジメトキシシラン、ジシクロペンチルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、テキシルトリメトキシシラン、ｔ−ブチルトリメトキシシラン、シクロヘキシルトリメトキシシラン、テトラメトキシシラン、テトラエトキシシランのようなＳｉ−Ｏ−Ｃ結合を有するケイ素化合物を挙げることができる。これら立体規則性改良剤は、１種でもよく、２種以上併用し用いてもよい。
【００４７】
重合方法については、特に限定されず公知の方法を用いることができる。連続式、回分式の方法いずれの方法でも得ることができ、重合反応器の形態に特に制限はない。上記ＢＰＰはヘキサン、ヘプタン、燈油等の不活性炭化水素またはプロピレンのような液化α−オレフィン溶媒存在下でのスラリー法や無溶媒下の気相重合法で、重合温度が室温〜１３０℃の範囲で行われる。好ましくは、５０〜９０℃の範囲で行われる。重合圧力は２〜５０ｋｇ／ｃｍ^２の範囲で行われる。重合工程における反応器は、当該技術分野で一般に用いられるものが適宜使用できる。例えば、攪拌槽型反応器、流動床型反応器、循環式反応器を用いて、重合操作を連続式、半回分式、回分式のいずれかの方法で行うことができる。
得られたＢＰＰスラリーまたは粉末は、必要に応じ、アルコールや水等で不活性化または残触媒の除去を行った後、乾燥し、添加剤と溶融混合し供される。
このＢＰＰは、さらに造核剤を配合すると剛性、耐熱性、衝撃強度に優れるものが得られる。
【００４８】
また、本発明における造核剤は、合成樹脂分野において結晶性樹脂に添加して核となって結晶を成長させる効果の物質をいい、各種の物質がある。
例えば、カルボン酸の金属塩、ジベンジリデンソルビトール誘導体、フォスフェート金属塩、タルクや炭酸カルシウムなどの無機フィラーなどが挙げられる。具体例としては、安息香酸ナトリウム、アジピン酸アルミニウム、ｐ−ｔ−ブチル安息香酸アルミニウム塩、チォフェネカルボン酸ナトリウム、１，３，２，４−ジベンジリデンソルビトール、１，３，２，４，−ジ−（ｐ−メチルベンジリデン）ソルビトール、１，３，−ｐ−クロルベンジリデン−２，４−ｐ−メチルベンジリデンソルビトール、ナトリウム−ビス−（４−ｔ−ブチルフェニル）フオスフェート、カリウム−ビス−（４−ｔ−ブチルフェニル）フォスフェート、ナトリウム−２，２’−エチリデン−ビス（４，６−ジ−ｔ−ブチルフェニル）フォスフェート、タルク、炭酸カルシウム等の無機化合物などが挙げられる。これらの造核剤は１種でもよく２種以上を併用することもできる。
これら造核剤の添加量は、ポリオレフィン系樹脂成形物に少なくとも造核剤を０．０５〜０．５重量％の範囲で配合すると、本発明の効果が著しい。
好ましくは、０．０８〜０．４重量％、特に好ましくは、０．１〜０．３５重量％添加するのが望ましい。但し、タルク等の無機化合物は、上記に例示した造核剤よりも、核剤効果が小さいので、５〜３０重量％添加すると良い。好ましくは、７〜２８重量％、特に好ましくは、９〜２５重量％である。
【００４９】
本発明のポリオレフィン系樹脂成形物に対しては、熱可塑性樹脂に慣用の他の添加剤（例えば、酸化防止剤、耐候性安定剤、帯電防止剤、滑剤、ブロックキング防止剤、防曇剤、染料、顔料、オイル、ワックス等）を本発明の目的を損なわない範囲で適宜量配合できる。
例えば、このような添加剤の例としては、酸化防止剤として２，５−ジ−ｔ−ブチルハイドロキノン、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、４，４’−チオビス−（６−ｔ−ブチルフェノール）、２，２−メチレン−ビス（４−メチル−６−ｔ−ブチルフェノール）、オクタデシル−３−（３’，５’−ジ−ｔ−ブチル−１’−ヒドロキシフェニル）プロピオネート、４，４’−チオビス−（６−ブチルフェノール）、紫外線吸収剤としてはエチル−２−シアノ−３、３−ジフェニルアクリレート、２−（２’−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、２−ヒドロキシ−４−オクトキシベンゾフェノン、可塑剤としてフタル酸ジメチル、フタル酸ジエチル、ワックス、流動パラフィン、りん酸エステル、帯電防止剤としてはペンタエリスリットモノステアレート、ソルビタンモノパルミテート、硫酸化オレイン酸、ポリエチレンオキシド、カーボンワックス、滑剤としてエチレンビスステアロアミド、ブチルステアレート等、着色剤としてカーボンブラック、フタロシアニン、キナクリドン、インドリン、アゾ系顔料、酸化チタン、ベンガラ等、充填剤としてグラスファイバー、アスベスト、マイカ、バラストナイト、ケイ酸カルシウム、ケイ酸アルミニウム、炭酸カルシウム等である。又、他の多くの高分子化合物も本発明の作用効果が阻害されない程度にブレンドすることもできる。
【００５０】
本発明のプロピレン樹脂成形物の製造方法としては、ポリプロピレンに造核剤をその他の添加剤とともに溶融混練する方法がある。具体的には、従来公知の混合方法、例えば、リボンブレンダー、ヘンシェルなどを用いて各成分を混合し、さらに、ニーダー、ミキシングロール、バンバリミキサー、押出機などを用いて溶融混合する方法が挙げられる。溶融混練温度については、１７０〜２８０℃の範囲が良い。好ましくは、１９０〜２６０℃の範囲が良い。特に、好ましくは、２００〜２５０℃の範囲である。一方、各成分を直接成形機に供給し成形加工しても良い。
【００５１】
上記樹脂の溶融指数（ＭＦＲ，ＪＩＳ−Ｋ７２１０により荷重２．１６ｋｇ，温度２３０℃）は特に制限されるものではなく、成形法によって選ばれるが、押出成形によっては０．１〜２５０（ｇ／１０分）の範囲が適当である。
本発明の樹脂成形物を得るためには、溶融した樹脂が一定の方向に押し出され、成形される成形方法を用いることが好ましい。
本発明の樹脂成形物は、公知の溶融成形法及び圧縮成形法によって得られた射出成形体、フィルム、シート、チューブ、ボトルなどでよく、単体での使用することもできるし、他の材料を積層しても使用できる。
例えばこの様な製品の積層方法としてはポリウレタン系、ポリエステル系ポリアクリル系等のドライラミネート接着剤を用い、本発明の樹脂成形物の単層品にその他の熱可塑性樹脂層を積層するいわゆるドライラミネート成形法やサンドウィッチラミネーション法、によって行なわれるか、又は共押出ラミ、共押出法（フィードブロック方式、マルチマニホールド方式）、共射出成形法、共押出パイプ成形法である。
このようにして得られた多層積層体は次に真空成形機、圧空成形機、延伸ブロー成形機等を用い、再加熱し延伸操作を加える方法あるいは前述の多層積層体又は樹脂成形物の単層成形物を一軸、或は二軸延伸機を用いて加熱延伸操作を施すことができる。
以下、実施例をあげ本発明を更に詳しく説明する。
【００５２】
【実施例】
以下の条件で重合を行い、種々のＢＰＰを作製した（実施例１〜８、比較例１〜３）。
［重合］
（実施例１の重合）
▲１▼固体触媒の調製
無水塩化マグネシウム５６．８ｇを、無水エタノール１００ｇ、出光興産（株）製のワセリンオイルＣＰ１５Ｎ５００ｍｌおよび信越シリコーン（株）製のシリコーン油ＫＦ９６ ５００ｍｌ中、窒素雰囲気下、１２０℃で完全に溶解させた。この混合物を、特殊機化工業（株）製のＴＫホモミキサーを用いて１２０℃、５０００回転／分で２分間攪拌した。攪拌を保持しながら、２リットルの無水ヘプタン中に０℃を越えないように移送した。得られた白色固体は無水ヘプタンで十分に洗浄し室温下で真空乾燥し、さらに窒素気流下で部分的に脱エタノール化した。
得られたＭｇＣｌ_２・１．２Ｃ_２Ｈ_５ＯＨの球状固体３０ｇを無水ヘプタン２００ｍｌ中に懸濁させた。０℃で攪拌しながら、四塩化チタン５００ｍｌを１時間かけて滴下した。次に、加熱を始めて４０℃になったところで、フタル酸ジイソブチル４．９６ｇを加えて、１００℃まで約１時間で昇温させた。１００℃で２時間反応させた後、熱時ろ過にて固体部分を採取した。その後、この反応物に四塩化チタン５００ｍｌを加え攪拌させた後、１２０℃で１時間反応させた。反応終了後、再度、熱時ろ過にて固体部分を採取し、６０℃のヘキサン１．０リットルで７回、室温のヘキサン１．０リットルで３回洗浄した。得られた固体触媒成分中のチタン含有率を測定したところ、２．３６重量％であった。
【００５３】
▲２▼ＴｉＣｌ_４［Ｃ_６Ｈ_４（ＣＯＯｉＣ_４Ｈ_９）_２］の調製
四塩化チタン１９ｇを含むヘキサン１．０リットルの溶液に、フタル酸ジイソブチル：Ｃ_６Ｈ_４（ＣＯＯｉＣ_４Ｈ_９）_２２７．８ｇを、温度０℃を維持しながら約３０分で滴下した。滴下終了後、４０℃に昇温し３０分間反応させた。反応終了後、固体部分を採取しヘキサン５００ｍｌで５回洗浄し目的物を得た。
【００５４】
▲３▼重合触媒の調製
上記▲１▼で得られた固体触媒２０ｇをトルエン３００ｍｌに懸濁させ、温度２５℃で、上記▲２▼で得られたＴｉＣｌ_４［Ｃ_６Ｈ_４（ＣＯＯｉＣ_４Ｈ_９）_２］で１時間攪拌洗浄し、熱時ろ過にて固体部分を採取し、その後、この反応物を９０℃のトルエン５００ｍｌで３回、室温のヘキサン５００ｍｌで３回洗浄した。得られた固体触媒成分中のチタン含有率は、１．７８重量％で、さらにこの重合触媒の表面積および細孔体積を測定したところ、以下の通りであった。
表面積 ：１９６ｍ^２／ｇ
細孔体積 ：細孔２〜４０ｎｍの範囲で０．３７ｃｃ／ｇ
重量平均粒子径（μｍ） ：８７．９
粒子径１２３μｍ以上の割合：５．８重量％
粒子径８７μｍ以下の割合 ：４９．０重量％
圧縮破壊強度：１．６×１０^６Ｎ／ｍ^２
引張り応力：１０９ｇ
【００５５】
▲４▼予備重合
窒素雰囲気下のもと内容量３リットルのオートクレーブ中に、ｎ−ヘプタン５００ｍｌ、トリエチルアルミニウム６．０ｇ、ジシクロペンチルジメトキシシラン３．９８ｇ、および、上記▲３▼で得られた重合触媒１０ｇを投入し、０〜５℃の温度範囲で５分間攪拌した。次に、重合触媒１ｇあたり１０ｇのプロピレンが重合するようにプロピレンをオートクレーブ中に供給し、０〜５℃の温度範囲で１時間予備重合した。得られた予備重合固体触媒は、ｎ−ヘプタン５００ｍｌで３回洗浄を行い、以下のＢＰＰの製造に使用した。
【００５６】
▲５▼本重合
第一段目：ホモポリプロピレンの重合
窒素雰囲気下、内容積６０リットルの攪拌機付きオートクレーブに上記の方法で調製された予備重合固体触媒２．０ｇ、トリエチルアルミニウム１１．４ｇ、ジシクロペンチルジメトキシシラン６．８４ｇを入れ、次いでプロピレン１８Ｋｇ、プロピレンに対して１．４ｍｏｌ％になるように水素を装入し、７０℃まで昇温させ１時間の重合を行った。１時間後、未反応のプロピレンを除去し、重合を終結させた。
第二段目：プロピレン−エチレン共重合体の重合
上記の如く第一段目の重合が終結した後、液体プロピレンを除去し、温度７５℃でエチレン／プロピレン＝４０／６０（モル比）の混合ガス２．２Ｎｍ^３／時間、水素２０ＮＬ／時間の供給速度で、４０分間共重合した。４０分後、未反応ガスを除去し、重合を終結させた。その結果、７．２Ｋｇのプロピレンブロック共重合体が得られた。
【００５７】
（実施例２〜７の重合）
実施例１に準じ、重合時の水素の装入量、第二段目の重合時間、エチレン量を調整し重合を行って、実施例２〜７のＢＰＰを得た。
（実施例８の重合）
第一段目にプロピレン以外にエチレンを供給し、以下実施例１と同様に重合したところ、第一段目がエチレン含有量２．５重量％のＢＰＰが得られた。なお、このエチレン含有量は、第一段目の重合が終了した時点でエチレン含有量測定用サンプルをサンプリングし測定を行った。
【００５８】
（比較例１の重合）
重合時に、実施例１の▲１▼で調製された固体触媒を用いた他は、実施例１と同様に行い、比較例１のＢＰＰを得た。尚、重合に用いた粉体物性は以下の通りであった。
表面積 ：２４７ｍ^２／ｇ
細孔体積 ：細孔２〜４０ｎｍの範囲で０．４２ｃｃ／ｇ
重量平均粒子径（μｍ） ：９５．４
粒子径１２３μｍ以上の割合：１５．８重量％
粒子径８７μｍ以下の割合 ：３２．２重量％
圧縮破壊強度：９．０×１０^５Ｎ／ｍ^２
引張り応力：３２ｇ
【００５９】
（比較例２の重合）
窒素雰囲気下、内容積６０リットルの攪拌機付きオートクレーブに東ソー・アクゾ（株）製のＡＡ型三塩化チタン６．０ｇ、ジエチルアルミニウムクロライド２３．５ｇを入れ、次いでプロピレン１８Ｋｇ，プロピレンに対して０．４ｍｏｌ％になるように水素を装入し、７０℃まで昇温させ、以下実施例１と同様に行って、比較例２のＢＰＰを得た。
表面積 ：４９ｍ^２／ｇ
細孔体積 ：細孔２〜４０ｎｍの範囲で０．２７ｃｃ／ｇ
重量平均粒子径（μｍ） ：６．１
粒子径１２３μｍ以上の割合：０．６重量％
粒子径８７μｍ以下の割合 ：９２．０重量％
圧縮破壊強度：０．７×１０^５Ｎ／ｍ^２
引張り応力：２７ｇ
【００６０】
（比較例３の重合）
▲１▼固体触媒の調製
特開平８−１０００３７号公報の実施例１に記載された方法により固体触媒を調製した。すなわち下記のように調製した。
無水塩化マグネシウム９５．３ｇ、乾燥エタノール３５２ｍｌを窒素置換したステンレス製のオートクレーブに入れ、この混合物を１０５℃で攪拌加熱溶解した。１時間攪拌後、１０５℃の加圧窒素（１．１ＭＰａ）で二流体ノズルスプレーに送入した。スプレー塔中には液体窒素を入れ、塔内温度を−１５℃に保持した。塔内底部の冷却ヘキサン中に２５２ｇの担体を得た。篩いを行い５０〜２００μｍの球形の担体１９７ｇを得た。これを窒素フロー乾燥により、ＭｇＣｌ_２・１．７ＥｔＯＨの組成の担体を得た。
上記で得られた担体２０ｇ、四塩化チタン１６０ｍｌ、１，２−ジクロロエタン２４０ｍｌを窒素置換したガラスフラスコに入れ、攪拌しながら１００℃まで加熱した。フタル酸ジイソブチル６．８ｍｌを加え、１００℃で２時間加熱後、熱時ろ過にて固体部分を採取した。その後、再び四塩化チタン１６０ｍｌ、１，２−ジクロロエタン３２０ｍｌを加えて、１００℃で１時間加熱攪拌した。反応終了後、再度、熱時ろ過にて固体部分を採取し精製ヘキサンで洗浄した。得られた固体触媒成分中のチタン含有率は１．７２重量％で、さらに固体触媒成分の表面積、細孔体積およびその他特性を測定したところ、以下のとおりであった。
表面積 ：１７５ｍ^２／ｇ
細孔体積 ：細孔２〜４０ｎｍの範囲で０．３０ｃｃ／ｇ
重量平均粒子径（μｍ） ：１０８
粒子径１２３μｍ以上の割合：４１．３重量％
粒子径８７μｍ以下の割合 ：１７．７重量％
圧縮破壊強度：７．５×１０^５Ｎ／ｍ^２
引張り応力：４６ｇ
【００６１】
▲２▼予備重合
窒素雰囲気下のもと内容積３リットルのオートクレーブ中にｎ−ヘプタン５００ｍｌ、トリエチルアルミニウム６．０ｇ、イソプロピルジメトキシシラン２．９ｇおよび上記▲１▼で得られた固体触媒１０ｇを投入し、０〜５℃の温度範囲で５分間攪拌した。次に固体触媒１ｇあたり１０ｇのプロピレンが重合するようにプロピレンをオートクレーブ中に供給し、０〜５℃の温度範囲で１時間予備重合した。得られた予備重合固体触媒は、さらにｎ−ヘプタン５００ｍｌで３回洗浄を行い、最終の予備重合触媒を得た。
【００６２】
▲３▼本重合
第一段目：ホモポリプロピレンの重合
窒素雰囲気下、内容積６０リットルの攪拌機付きのオートクレーブに上記予備重合触媒２．０ｇ、トリエチルアルミニウム１１．４ｇ、ジイソプロピルジメトキシシラン５．１６ｇを入れ、次いでプロピレン１８ｋｇ、プロピレンに対して１．２６ｍｏｌ％になるように水素を装入し、７０℃まで昇温させ１時間の重合を行った。１時間後、未反応のプロピレンを除去し、重合を終結させた。
第二段目：プロピレン−エチレン共重合体の重合
第一段目の重合が終結した後、液体プロピレンを除去し、温度７５℃でエチレン／プロピレン＝４０／６０（モル比）の混合ガス２．２Ｎｍ^３／時間、水素２０ＮＬ／時間の供給速度で、４０分間共重合した。４０分後、未反応ガスを除去し重合を終結させた。その後、６．５ｋｇのプロピレンブロック共重合体が得られた。
【００６３】
上述の方法で得られた実施例１〜８および比較例１〜３のＢＰＰについて後述の方法および装置を用いて、プロピレン−ブロック共重合体の諸物性および２サイトモデルの解析結果を調べた。その詳細は後述する（表２〜表４）。
【００６４】
［成形］
さらに上述の方法で得られたＢＰＰを用いて以下の通り成形を行った。
（添加剤の混合）
以上のようにして得られたプロピレンブロック共重合体に、ジ−ｔ−ブチル−ｐ−クレゾールを０．０５重量％、ペンタエリスリチル−テトラキス［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］を０．１０重量％およびカルシウムステアレートを０．１０重量％、（株）川田製作所製スーパーミキサー（ＳＭＶ２０型）を用いて混合し、ナカタニ機械社製二軸押出機（ＡＳ３０型）を用いてペレット化した。得られたペレットを用い、下記射出成形、フィルム成形、中空成形を行った。
【００６５】
（フィルム成形）
実施例１〜８、比較例１〜３のＢＰＰを用い、吉井鉄工（株）製４０ｍｍφＴダイ成形機で、成形温度２３０℃、冷却ロール温度４０℃で、厚み６０μｍのフィルムを作製した。
【００６６】
（射出成形）
上記実施例４〜実施例６、比較例１、比較例３を用い、東芝機械（株）製ＩＳ−１７０ＦＩＩ（理論射出量２５０ｃｍ^３）で、成形温度２２０℃、金型冷却温度５０℃で、試験片を作製した。
【００６７】
（中空成形）
上記実施例１〜実施例２、実施例７、比較例２〜比較例３を用い、日本製鋼所製ＪＢ１０５型の中空成形機で、外径５５ｍｍ、内容量３００ｃｃの円筒容器（厚さ１ｍｍ）を成型した。
【００６８】
［各ＢＰＰの物性］
上記実施例１〜８、比較例１〜３で得られたＢＰＰについて、以下に示す方法および装置を用いて、プロピレン−ブロック共重合体の諸物性および２サイトモデルの解析結果を調べた（表２〜表４）。
（１）エチレン含有量の測定
Ｃ．Ｊ． Ｃａｒｍａｎらによって報告されている^１３Ｃ−ＮＭＲ法による方法（Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，１０，５３７（１９７７）をもとに行った。その結果を表２に示す。
（２）ＭＦＲの測定
ＪＩＳ Ｋ７２１０ 表１条件１４に準拠して行った。装置はタカラ（株）製のメルトインデクサーを用いた。その結果を表２に併せて示す。
（３）キシレン不溶分（Ｘ_ＩＳ）、キシレン可溶分（Ｘ_ｓ）の測定
プロピレン−ブロック共重合体を１３５℃のオルトキシレンにいったん溶解した後、２５℃に冷却してポリマーを析出させた。そのとき析出した成分をキシレン不溶分（Ｘ_ＩＳ）とし、溶解している成分をキシレン可溶分（Ｘ_ｓ）とした。キシレン可溶分は、エタノールで再沈させ回収した。２５℃におけるキシレン可溶分Ｘ_ｓを重量％として表した結果を表２に併せて示す。
【００６９】
【表２】

【００７０】
（４）極限粘度［η］の測定
Ｕｂｂｅｌｏｈｄｅ毛細管粘度計を用い、デカリンを溶媒として、１３５℃の温度条件下で、キシレン不溶分の極限粘度［η］_１、キシレン可溶分の極限粘度［η］_２を求めた。その結果を表３に示す。また［η］_２／［η］_１の算出値を表４に示す。
（５）分子量、分子量分布の測定
測定装置：Ｗａｔｅｒｓ社製１５０Ｃ型ＧＰＣ装置
カラム：Ｓｈｏｄｅｘ ＨＴ−８０６Ｍカラムを２本直列に接続して使用
溶媒：１，２，４−トリクロロベンゼン（ＢＨＴを０．１％含有）
溶媒に試料を溶解後、０．５μｍの燒結金属フィルターでろ過し、１４０℃で測定した。測定データは、較正曲線を用いて分子量を求め、更に分子量換算式を使用して、キシレン不溶分のＭｎ_１、Ｍｗ_１、キシレン可溶分のＭｎ_２、Ｍｗ_２を算出した。その結果を表３に併せて示す。
またこれらの値から算出したキシレン不溶分、キシレン可溶分の分子量分布（ＭＤ_１）、（ＭＤ_２）を表３に、またＭＤ_２／ＭＤ_１の値を表４に併せて示す。
【００７１】
（６）平均のプロピレン含量および２サイトモデルによる解析
プロピレンブロック共重合体を１，２，４，−トリクロロベンゼン／重ベンゼンの混合溶媒にポリマー濃度が１０重量％となるように１３０℃に加温して溶解する。続いて、以下の装置および条件で^１３Ｃ−ＮＭＲスペクトルの測定を行い、それぞれのシグナルは、Ａ．ＺａｍｂｅｌｌｉらのＭａｃｒｏｍｏｌｅｃｕｌｅｓ，１３，２６７（１９８０）で帰属した。
次に、平均のプロピレン含量（ＦＰ）および２サイトモデルの解析を行い、高プロピレン含量側のプロピレン含量（Ｐ_Ｐ）、かつ（Ｐ_Ｐ）が（ＦＰ）に占める割合（Ｐ_ｆ１）、ブロック性（ＣＳＤ）を求めた。その結果を表３に併せて示す。

【００７２】
【表３】

【００７３】
【表４】

【００７４】
表３で示したように、２サイトモデルによる高プロピレン含量（Ｐ_Ｐ）がキシレン可溶分の平均のプロピレン含量（ＦＰ）中に占める割合（Ｐ_ｆ１）が、実施例１〜８のＢＰＰでは０．２５〜０．５５の範囲にあるのに対し、比較例１〜３のＢＰＰではいずれも０．５５を越えていた。
表３及び表４に示した結果より、実施例１〜４、実施例８、比較例３で得られたＢＰＰは、（Ｉ）キシレン不溶分の極限粘度［η］_１と、キシレン不溶分の極限粘度［η］_１とキシレン可溶分の極限粘度［η］_２の比 ［η］_２／［η］_１が、下記式（Ｉ） ［η］_２／［η］_１≦０．２１［η］_１＋０．５６ …式（Ｉ）
を満たしていることがわかった。
【００７５】
［フィルム成形体の物性］
実施例１〜実施例８、比較例１〜比較例３のＢＰＰを用いて得たフィルム成形体について、以下の通り平均アスペクト比、平均粒子間距離、ｂ軸配向度の測定を行った。その結果を表４に併せて示す。
（８）ｂ軸配向度の測定
測定装置：理学電気製Ｘ線発生装置（ＲＡＤ２−Ｃ：Ｎｉフィルター単色化）
Ｘ線源：ＣｕＫα
電圧、電流値：５０Ｋｖ、４０ｍＡ
散乱角度（２θ）：１０〜３０度
得られた広角Ｘ線回折スペクトル図よりｂ軸配向度（Ｋｂ）を求めた。その結果を表４に併せて示す。
【００７６】
（９）平均アスペクト比および平均粒子間距離
フィルムより縦１ｃｍ×横５ｍｍ×高さ６０μｍの試験片を切り出し、エポキシ樹脂で包埋する。そのブロックをウルトラミクロトーム（Ｒｅｉｃｈｅｒｔ社製ＵＬＴＲＡＣＵＴ ＵＮ、ダイヤモンドナイフ使用）により、ＭＤに垂直な面の面だしをした後、ＲｕＯ_４を用い気相染色を行った。次にウルトラミクロトームにより染色したブロックから厚さ６０ｎｍ設定で超薄切片を切削し、銅メッシュ上に回収した。
ＴＥＭ観察は以下の装置を用い実施した。
装置：株式会社日立製作所Ｈ−８００型透過電子顕微鏡（加速電圧
１００ｋＶ）
上記ＴＥＭ観察で得られた写真をもとに、以下の装置を用い、画像解析処理を行った。
装置：（株）東芝製画像処理装置 ＴＯＳＰＩＸ−Ｕ２
画面サイズ：縦１０２４×横１０２４×奥行き８（画素／枚）
濃淡階調：２５６階調
平均アスペクト比は、各々の粒子でアスペクト比を求めたのち、全体の粒子の平均を求めた。平均粒子間距離は、各粒子の間の任意の２点間の距離を求めたのち、平均を求めた。その結果を表４に併せて示す。
（１０）重合触媒の力学特性の測定
以下の装置を用い、重合触媒の圧縮破壊強度、引っ張り強度を求めた。
装置：ホソカワミクロン（株）粉体圧縮・引張り強度計測装置 アグロボット
【００７７】
表４に示した結果より、実施例１〜８のＢＰＰから得たフィルム成形体は、比較例１〜３のＢＰＰから得たフィルム成形体に比べて、Ｋｂ値が著しく低く、平均アスペクト値が高く、平均粒子間距離が小さいことがわかる。
図７は、ＴＥＭ観察に用いた実施例２のＢＰＰから得たフィルム成形体の流動方向に垂直な面（エンド面）のＴＥＭ写真であり、図８は比較例２のＢＰＰから得たフィルム成形体のエンド面のＴＥＭ写真である。これらのＴＥＭ写真では、共重合体ブロック成分が黒く、マトリックスのポリプロピレン成分ブロックが白く撮影されており、実施例２のＢＰＰから得たフィルム成形体では、その表面付近に限らず全領域において、共重合体ブロック成分が層状分散していることがわかる。
【００７８】
また、実施例２〜実施例４、実施例８、比較例２〜比較例３のＢＰＰを用いて得たフィルム成形体を用いて、以下の通り透明性（Ｈａｚｅ）、光沢（Ｇｒｏｓｓ）、ゲル、フィッシュアイ、フィルム引張試験（降伏強度、破断強度、破断伸び）の測定を行った。これらの結果を表５に示す。
（１１）透明性（Ｈａｚｅ）
ＪＩＳ Ｋ７１０５に準拠し、全Ｈａｚｅを測定した。
（１２）光沢（Ｇｒｏｓｓ）
フィルムの表面光沢（グロス）をＪＩＳ Ｚ８７４１に準拠し、日本電色工業社製ＶＧ−１Ｄ型グロスメーターを用いて測定した。
（１３）フィッシュアイの測定
フィルムを１フィート四方の大きさにサンプリングし、ルーペを用い、下記の基準でフィッシュアイの大きさおよび数を測定した。
大．．．．直径が０．５ｍｍ以上のもの
中．．．．直径が０．２ｍｍ以上０．５ｍｍ未満のもの
小．．．．直径が０．１ｍｍ以上０．２ｍｍ未満のもの
（１４）ゲルの測定
フィルムを３２ｃｍ×１ｍの大きさに各々１０枚サンプリングし、１０枚のフィルムについて目視により下記の基準でゲルナンバーを測定した。
１．．．．全くゲルなし、または１枚のみ長さ５ｃｍ以下のゲル発生
２．．．．２枚以下に５ｃｍ以下のゲル発生
３．．．．５枚以下に５ｃｍ以下のゲル発生
４．．．．５枚以下に５ｃｍ以上のゲル発生
５．．．．５枚以上に５ｃｍ以上のゲル発生、または１枚以上の全面にゲル発生
（１５）引張試験
ＪＩＳ Ｋ７１２７に準拠し、成形時の樹脂の流動方向（ＭＤ）および横方向（ＴＤ）について、引張速度５００ｍｍ／分の条件で降伏強度、破断強度および破断伸びを測定した。
【００７９】
【表５】

【００８０】
また以下の示す方法で、実施例２および比較例２のＢＰＰから得たフィルム成形体について、フィルムインパクト、引張弾性率を測定した。その結果を表６に示す。
（１６）フィルムインパクト測定方法
フィルムを１０ｃｍ×１ｍの大きさにサンプリングし、（株）東洋精機製作所製フィルムインパクトテスターに半径１／２インチの半球状の撃芯を取り付け、ひとつのサンプルにつき１０回試験を行い衝撃エネルギーを測定した。これらの衝撃エネルギーの値をフィルムの厚みで割って、その１０点の平均値をフィルムインパクトとした。
（１７）引張弾性率（ヤング率）測定方法
ＪＩＳ−Ｋ７１２７の方法で、サンプルの幅２０ｍｍ、チャック間２５０ｍｍ，引張速度５ｍｍ／分の条件で、成形時の樹脂の流動方向（ＭＤ）および横方向（ＴＤ）について、引張弾性率を測定した。
【００８１】
【表６】

【００８２】
表５に示した結果より、実施例のＢＰＰから作製されたフィルム成形体は、比較例のＢＰＰから作製されたフィルム成形体に比べて、降伏強度、破断強度、破断伸び、透明性、光沢に優れ、ゲル、フィッシュアイの発生が少ないことがわかった。また表６に示した結果より、実施例のＢＰＰから作製されたフィルム成形体は、比較例のＢＰＰから作製されたフィルム成形体に比べて、特に低温における耐衝撃性に優れていることがわかった。
【００８３】
さらに、実施例２のＢＰＰから作製したＴダイフィルムと、比較例２のＢＰＰから作製したＴダイフィルムについて、ＭＤ方向またはＴＤ方向に延伸した場合の広角Ｘ線回折プロフィルによって、その変形の様子を調べた（図４）。図４において、無延伸とはＴダイフィルムそのものを測定した場合をいい、各々の延伸倍率は延伸終了後のフィルムの長さと延伸する前のフィルムの長さの比から求めたものである。実施例２のＢＰＰから作製したＴダイフィルムは、比較例２のＢＰＰから作製したＴダイフィルムと比較して、広角Ｘ線回折スペクトルの結晶面（０４０）の散乱に対応するピークの半減値幅（Ｂ）の変化が小さいことがわかる。
【００８４】
［射出成形体の物性］
上記実施例４〜実施例６、比較例１、比較例３を用いて得られた射出成形体を、湿度５０％、温度２３℃の恒温室に二昼夜放置後、以下の通り、アイゾット衝撃試験、曲げ弾性率試験、落錘衝撃強度（厚み２ｍｍ×１５ｃｍ×１１ｃｍ平板）、ヒートサイクル性、フローマークの評価を行った。また上述の方法に準じて、透明性（Ｈａｚｅ、厚み２ｍｍ）、光沢（Ｇｒｏｓｓ）の評価を行った。これらの結果を表７に示す。
（１８）アイゾット衝撃強度（ノッチ付き）
ＪＩＳ Ｋ７１１０に準拠して行った。装置は上島製作所（株）製のＵ−Ｆインパクトテスターを用いた。
（１９）曲げ弾性率
ＪＩＳ Ｋ７２０３に準拠して行った。
（２０）落錘衝撃強度
ＡＳＴＭ Ｄ３０２９−７８に準拠し、鋼球直径１／２インチ、重錘の荷重１ｋｇ、高さ７５センチメートルから重錘を落下させ、温度２０℃からドライアイスメタノールで冷却し、各温度下での破壊状況を測定し、５０％が破壊するときの温度を求めた。
（２１）ヒートサイクル性の測定
温度１００℃のギアオーブン中に８時間暴露した後、−３０℃の冷凍庫に３時間保存し、次いで温度２３℃の恒温室に３時間放置した後、目視観察により試料のツイスト状態を次の３段階で評価した。その結果を表７に示す。
○．．．．全くツイスト状態が見られない
△．．．．多少ツイスト状態があるものの使用に耐えうる。
×．．．．ツイストが著しく使用に耐えない。
（２２）フローマークの測定
フローマークの発生状況を目視により次の３段階で評価した。その結果を表７に示す。
○．．．．まったく見られない
△．．．．多少見られる
×．．．．著しい
【００８５】
【表７】

【００８６】
表７に示した結果より、実施例のＢＰＰから作製された射出成形体は、比較例のＢＰＰから作製された射出成形体に比べて、耐衝撃性、透明性、光沢に優れ、フローマークの発生がなく、特に温度変化による変形が少なく、低温における耐衝撃性に優れていることがわかった。
【００８７】
［中空成形体の物性］
実施例１〜実施例２、実施例７、比較例２〜比較例３のＢＰＰを用いて得た中空成形体について、以下の通り、落下繰り返しテスト、ピンチオフ強度の測定を行った。また上述の方法に準じて、透明性（Ｈａｚｅ、厚み２ｍｍ）、光沢（Ｇｒｏｓｓ）の評価を行った。これらの結果を表８に示す。
（２３）落下繰り返しテスト
外径５５ｍｍ、内容量３００ｃｃの円筒容器（厚さ１ｍｍ）に水２９０ｍｌを充填し、温度５℃の条件下で１．２ｍの高さから１本の容器を繰り返し落下させ、何回目で破損するかを試験した。試験は容器の縦方向の落下、横方向の落下をそれぞれ５本づつ行い、平均を求めた。
（２４）ピンチオフ強度
ピンチオフ部分とは、中空成形した容器の底部にある、樹脂の融着した部分を言う。
外径５５ｍｍ、内容量３００ｃｃの円筒容器（厚さ１ｍｍ）の底部から、ピンチオフ部分が試料の長さ方向に垂直かつ中心にくるように、長さ５０ｍｍ、幅４ｍｍのダンベル型に試料を打ち抜き、平均の厚みを測定した後、チャック間１０ｍｍ、引張速度５０ｍｍ／分で引張試験を行い、ピンチオフ部分が破断するまでの伸びおよびその時の荷重を測定し、５点の平均を求めた。その結果を表８に示す。
【００８８】
【表８】

【００８９】
表８に示した結果より、実施例のＢＰＰから作製された中空成形体は、比較例のＢＰＰから作製された中空成形体に比べて、透明性、光沢、ピンチオフ強度に優れていることがわかった。
【００９０】
【発明の効果】
本発明のプロピレン樹脂成形物は、（Ａ）プロピレンとエチレン及び／又は炭素数４〜１２のα−オレフィン共重合体であって該エチレン及び／又は炭素数４〜１２のα−オレフィンに由来する単位が５重量％以下である共重合体、あるいはホモポリプロピレンからなるポリプロピレン成分ブロック３０〜９０重量％と、（Ｂ）プロピレンとエチレン及び／又は炭素数４〜１２のα−オレフィンとの共重合体からなる共重合体成分ブロック１０〜７０重量％からなり、広角Ｘ線回折法によるｂ軸配向を有するものである。本発明の樹脂成形物は従来のポリオレフィン系樹脂成形物に比べ、衝撃強度（特に低温における耐衝撃性）、剛性、透明性、光沢に優れるので、自動車、家電分野等の工業用材料、工業用包装材料、食品包装材料、医療器具材料、医薬品包装材料、化粧品包装材料として有効である。
【００９１】
上記共重合体成分ブロック中の、エチレン及び／又は炭素数４〜１２のα−オレフィンに由来する単位を、３０〜８０モル％とすることにより、低結晶性重合物の副生成量を減少させ、プロピレン樹脂成形物の外観を向上させることができる。
上記共重合体成分ブロックもしくは上記ポリプロピレン成分ブロックが他方の成分ブロックに対して層状分散し、この層状分散した成分ブロックの平均アスペクト比が２．０以上で、平均粒子間距離が０．５μｍ以下であるものは、ｂ軸配向の程度が高く（上記Ｋｂ値が低く）、その成形物は透明性、光沢等の光学特性、耐衝撃性、引張り強度などの機械的強度および耐熱性に優れている。
また、（ａ）キシレン可溶分の平均のプロピレン含量（ＦＰ）が３０〜６０モル％であると、製品の外観が向上しかつ低結晶性重合物の副生成量が減少し、（ｂ）キシレン可溶分の２サイトモデルによる高プロピレン含量側のプロピレン含量（Ｐ_Ｐ）が６０〜８０モル％、かつＰ_ＰがＦＰ中に占める割合（Ｐ_ｆ１）が０．２５〜０．５５であると、プロピレンブロック共重合体の剛性、耐熱性、および耐衝撃性が高く、（ｃ）ブロック性（ＣＳＤ）が１．４〜２．５であると、剛性、耐熱性が高く、耐衝撃性のうち特に低温衝撃強度が高い。
また、（Ｉ）キシレン不溶分の極限粘度［η］_１と、キシレン不溶分の極限粘度［η］_１とキシレン可溶分の極限粘度［η］_２の比 ［η］_２／［η］_１が、下記式（Ｉ）
［η］_２／［η］_１≦０．２１［η］_１＋０．５６ …式（Ｉ）
を満たす場合は、透明性、耐衝撃性に優れたものとなる。（ＩＩ）ゲルパーミエーションクロマトグラフによるキシレン不溶分の重量平均分子量（Ｍｗ_１）が１０万〜７０万の範囲にあり、かつキシレン不溶分の重量平均分子量（Ｍｗ_１）とキシレン不溶分の数平均分子量（Ｍｎ_１）との比（Ｍｗ_１／Ｍｎ_１）であるキシレン不溶分の分子量分布（ＭＤ_１）が４．０〜１０の範囲にあると、機械的強度、成形性、成形物の外観に優れ、成形物のゲル、フィシュ・アイなどが発生しにくい。（ＩＩＩ）ゲルパーミエーションクロマトグラフによるキシレン可溶分の重量平均分子量（Ｍｗ_２）が１０万〜６０万の範囲にあり、かつキシレン可溶分の重量平均分子量（Ｍｗ_２）とキシレン可溶分の数平均分子量（Ｍｎ_２）との比（Ｍｗ_２／Ｍｎ_２）であるキシレン可溶分の分子量分布（ＭＤ_２）が４．０〜８．０の範囲にあると、耐衝撃性、耐寒性、耐熱性、成形性に優れ、成形物のゲル、フィシュ・アイ、表面のべたつきなどが発生しにくい。（ＩＶ）キシレン可溶分の分子量分布（ＭＤ_２）とキシレン不溶分の分子量分布（ＭＤ_１）の比（ＭＤ_２／ＭＤ_１）が、１．０以下であると、成形物の透明性、剛性と耐衝撃性のバランスに優れたものとなる。
【図面の簡単な説明】
【図１】本発明において、ｂ軸配向の程度を示すＫｂ値の求め方を示すＸ線回折スペクトル図である。
【図２】本発明のプロピレン樹脂成形物の観察方向を示す斜視図である。
【図３】本発明のプロピレン樹脂成形物の分散状態の例を示すモデル図であって、流動方向に平行な厚み方向から観察した断面図である。
【図４】フィルム面に対しての反射法で測定した広角Ｘ線回折プロファイルの変化の例を示す図であって、（ａ）は本発明の実施例のＢＰＰから作製したＴダイフィルムをＭＤ方向に延伸した場合、（ｂ）は本発明の実施例のＢＰＰから作製したＴダイフィルムをＴＤ方向に延伸した場合、（ｃ）は比較例のＢＰＰから作製したＴダイフィルムをＭＤ方向に延伸した場合、（ｄ）は比較例のＢＰＰから作製したＴダイフィルムをＴＤ方向に延伸した場合の変化を示した図である。
【図５】プロピレン−エチレン共重合体の核磁気共鳴スペクトルの例を示す図である。
【図６】プロピレン−エチレン共重合体の連鎖分布由来の各炭素の名称を示す図である。
【図７】本発明のプロピレン樹脂成形物の一例のＴＥＭ写真である。
【図８】従来のプロピレン樹脂成形物の一例のＴＥＭ写真である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a propylene resin composition, and is particularly suitable for mechanical parts, electrical / electronic parts, packaging material fields, engineering plastic substitutes, etc., and has an excellent balance of rigidity and impact resistance, and has a tensile elastic modulus and the like. The present invention relates to a propylene resin molded article having excellent mechanical strength and transparency and having a b-axis orientation by a wide-angle X-ray diffraction method in a direction perpendicular to the surface of the molded article.
[0002]
[Prior art]
Propylene resins are widely used in the fields of automobiles, home appliances, and packaging materials because they are excellent in properties such as rigidity and chemical resistance. However, a propylene-α-olefin random copolymer into which an α-olefin component typified by homopolypropylene and ethylene is usually introduced has a drawback of being inferior in impact resistance.
Accordingly, a propylene-block copolymer (hereinafter also referred to as BPP) in which a copolymer elastomer component of propylene and α-olefin is introduced, or a copolymer elastomer of propylene and α-olefin in polypropylene, hydrogenated styrene-butadiene. A resin molded product in which a thermoplastic elastomer such as an elastomer is blended and mixed by a kneader is well known.
[0003]
The propylene-block copolymer is usually produced by copolymerization of propylene in the first stage using a multistage polymerization method and then copolymerization of propylene and α-olefin in the second stage and thereafter. Ethylene is widely used.
Usually, the propylene-block copolymer is a homopolypropylene or a propylene-α-olefin random copolymer polymerized in a first-stage reactor, and propylene and ethylene and / or carbon number 4 in a second-stage reactor or later. A method of polymerizing a copolymer elastomer component with ˜12 α-olefin is used, and an ethylene-propylene elastomer is generally used as the copolymer elastomer component.
[0004]
Such conventional resin moldings of polypropylene and thermoplastic elastomers and propylene-block copolymer moldings usually have a structure in which polypropylene is the sea phase and the thermoplastic elastomer component is spherically dispersed as the island phase. It is what you are doing.
Generally, in the above-mentioned sea-island structure, the molecular weight of the thermoplastic elastomer component in the island phase is set higher than that of the polypropylene in the sea phase in order to impart impact resistance. The thermoplastic elastomer component of a resin molded product of polypropylene and a thermoplastic elastomer has particles having a size of 0.8 to 3 μm larger than the light wavelength of 0.4 to 0.65 μm. Refraction and reflection were caused, the internal haze was lowered, and the transparency was remarkably inferior. As a method of improving the transparency of the propylene-block copolymer, a method of reducing the molecular weight of the copolymer rubber component and reducing the particle diameter can be considered. However, in this method, if the molecular weight of the copolymer rubber component is reduced, the resistance is improved. There was a problem that the impact property was lowered.
[0005]
In addition, the b-axis orientation in the vertical direction with respect to the surface of the molded product is oriented in the skin layer of the injection molded product containing glass fiber, chalk and talc (CHEN Z, FINET MC, LIDDELL K, THOMSON D P, WHITE JR; J Appl Poly Sci, Vol. (FUJIYAMA M; Int Polym Process, Vol. 7, No. 1, P84-96 (1992) and the same work; J Appl Poly Sci, Vol. 42. No. 1, P9-20 (1991) )), Polypropylene and rubber components and talc A polypropylene molded product having a size of 5 to 20 nm in the c-axis direction, 5 to 20 nm in the a-axis direction, and 5 nm or more in the b-axis direction (Japanese Patent Laid-Open No. 7-70383), A polyolefin resin molding comprising an ethylene-propylene copolymer and talc, wherein the polypropylene phase is formed from a crystalline lamella and an amorphous region, and the crystalline lamella has a rectangular column shape having a square cross section of 100 to 155 angstroms on one side A polyolefin resin molded product (Japanese Patent Laid-Open No. 7-70334) or the like that is oriented in a substantially vertical direction with respect to the surface of the molded product is well known.
However, since these all contain an inorganic filler such as talc, there is a problem that transparency is inferior.
[0006]
JP-A-5-331327 discloses a polymer molded product in which the intrinsic viscosity of the copolymer phase and the homopolymer phase is limited to 0.7 / 1 to 1.3 / 1. However, there is no description about what sufficiently satisfies transparency.
On the other hand, in JP-A-8-27238 and JP-A-8-100037, a copolymer of a homopolymer component and ethylene-propylene is formed.
(1) The product of the ratio of the intrinsic viscosity of the copolymer component to the intrinsic viscosity of the homopolymer component and the weight ratio of the homopolymer component to the copolymer component is in the range of 0.2 to 2.0,
(2) The ratio of the MFR of the homopolymer component to the MFR of the copolymer component is in the range of 0.3 to 4.0,
(3) The intrinsic viscosity of the copolymer component is 6.5 or less
A propylene-based block copolymer excellent in gas phase polymerization excellent in transparency, impact whitening resistance, molding shrinkage ratio and bending whitening resistance is disclosed.
However, in the method disclosed in the publication, the MFR of the homopolypropylene component of the matrix is low, as can be seen from the examples of the publication, resulting in insufficient fluidity during molding. There were problems such as a lot of fish eyes in the shot phenomenon and the generation of flow marks and film forming. Moreover, the thing which is fully satisfied with transparency was not obtained.
[0007]
[Problems to be solved by the invention]
The object of the present invention is to reduce mechanical properties such as impact resistance and rigidity, whitening resistance, heat resistance, transparency, gloss and flow mark, gel, fish eye, etc. without impairing the inherent properties of polypropylene. An object of the present invention is to provide a propylene resin molded article that is suitable for automobiles, home appliances, and packaging materials that have less appearance and excellent appearance.
[0008]
[Means for Solving the Problems]
The propylene resin molded product of the present invention is (A) a propylene and ethylene and / or α-olefin copolymer having 4 to 12 carbon atoms, and is derived from the ethylene and / or α-olefin having 4 to 12 carbon atoms. Copolymer having a unit of 5% by weight or less, or 30 to 90% by weight of a polypropylene component block made of homopolypropylene, and (B) a copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms It is characterized by having a b-axis orientation by wide-angle X-ray diffraction method.
The unit derived from ethylene and / or an α-olefin having 4 to 12 carbon atoms in the copolymer component block may be 30 to 80 mol%.
The copolymer component block or the polypropylene component block is layer-dispersed with respect to the other component block, the average aspect ratio of the layer-dispersed component block is 2.0 or more, and the average interparticle distance is 0.5 μm or less. It may be.
Further, the xylene-soluble component may have the following characteristics (a) to (c).
(A) The average propylene content (FP) is 30 to 60 mol%.
(B) Propylene content on the high propylene content side (P_P) Is 60-80 mol% and P_POf FP in the FP (P_f1) Is 0.25 to 0.55.
(C) Block property (CSD) is 1.4 to 2.5.
Moreover, you may have the physical property of following (I)-(IV).
(I) Intrinsic viscosity of xylene insoluble matter [η]₁And intrinsic viscosity of xylene insoluble matter [η]₁And xylene solubles intrinsic viscosity [η]₂Ratio [η]₂/ [Η]₁Satisfies the formula (I).
[Η]₂/ [Η]₁≦ 0.21 [η]₁+0.56 Formula (I)
(II) Weight average molecular weight of xylene insoluble matter by gel permeation chromatography (Mw₁) In the range of 100,000 to 700,000, and the weight average molecular weight (Mw) of the xylene-insoluble matter₁) And xylene insoluble matter number average molecular weight (Mn₁) Ratio (Mw)₁/ Mn₁) Molecular weight distribution (MD) of xylene insolubles₁) Is in the range of 4.0-10.
(III) Weight average molecular weight of xylene solubles by gel permeation chromatography (Mw₂) Is in the range of 100,000 to 600,000, and the weight average molecular weight (Mw) of the xylene solubles₂) And xylene solubles number average molecular weight (Mn₂) Ratio (Mw)₂/ Mn₂) Molecular weight distribution of xylene solubles (MD)₂) Is in the range of 4.0 to 8.0.
(IV) Molecular weight distribution of the xylene solubles (MD₂) And xylene insoluble matter molecular weight distribution (MD₁) Ratio (MD₂/ MD₁) Is 1.0 or less.
Moreover, the b-axis orientation degree by a wide angle X-ray diffraction method may be 0.75 or less.
Further, it may be a propylene resin molded product formed by film molding, injection molding, or hollow molding.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The above-mentioned propylene resin molded product of the present invention is obtained by a method in which the component (A) and the component (B) are melt-mixed using an extruder or the like to satisfy the limiting conditions of the present invention, or propylene by a known multistage polymerization method Although there is a method obtained as a block copolymer, a method using a multistage polymerization method is preferred. When the component (A) and the component (B) are melt-mixed using an extruder or the like to obtain a propylene resin molded product, the MFR of the component (A) = 0.1 to 100 g / 10 minutes, the MFR of the component (B) = 0.1 to 100 g / 10 min is suitable.
The polypropylene component block of component (A) referred to in the present invention is homopolypropylene or propylene and ethylene and / or an α-olefin copolymer having 4 to 12 carbon atoms (ethylene and / or 4 to 4 carbon atoms described herein). The unit derived from 12 α-olefins is 5% by weight or less).
On the other hand, the copolymer component block of the component (B) is composed of a copolymer block of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms, and ethylene and / or carbon number 4 of the copolymer block. Content of the unit derived from? 12? -Olefin is 30 to 80 mol%.
[0010]
Examples of the unit derived from the α-olefin having 4 to 12 carbon atoms of the component (A) and the component (B) include 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4- Examples include methyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclopentane, and vinylcyclohexane.
These α-olefins may be used alone or in combination of two or more.
The component (A) of the present invention is homopolymerization of propylene or copolymerization of propylene with ethylene and / or an α-olefin having 4 to 12 carbon atoms performed in the presence of a catalyst component. The unit derived from ethylene and / or an α-olefin having 4 to 12 carbon atoms in the copolymer (A) is 5% by weight or less, preferably 4.5% by weight or less, particularly preferably 4.0% by weight. It is as follows.
When the unit derived from ethylene and / or α-olefin having 4 to 12 carbon atoms in the copolymer exceeds 5% by weight, the rigidity and heat resistance are hindered, and the low crystalline component is increased. It is not preferable because the powder particles adhere to each other and block the polymerization vessel.
[0011]
The component (B) is a copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms.
(B) Content of the unit derived from the said ethylene and / or C4-C12 alpha olefin of a copolymer component is 30-80 mol%. Preferably, it is 32-78 mol%, Most preferably, it is 35-75 mol%.
In addition, when obtaining the propylene resin molded product of the present invention by the multistage polymerization method, the content of units derived from ethylene and / or α-olefin having 4 to 12 carbon atoms in the copolymer obtained in the second and subsequent stages. Is less than 30 mol%, the amount of by-product of the low crystalline polymer increases, which is not preferable. On the other hand, if it exceeds 80 mol%, the appearance of the propylene resin molded product is remarkably deteriorated, which is not preferable.
Regarding the proportion of the component (A) and the component (B), the proportion of the component (A) is 90 to 30% by weight and the proportion of the component (B) is 10 to 70% by weight, preferably (B The proportion of component) is 12 to 68% by weight, more preferably the proportion of component (B) is 15 to 65% by weight. When the proportion of the component (B) is less than 10% by weight, the impact strength is lowered, which is not preferable. On the other hand, when it exceeds 70% by weight, rigidity, heat resistance and hygiene are hindered.
[0012]
On the other hand, the b-axis orientation by the wide-angle X-ray diffraction method referred to in the present invention is defined as follows.
Since the atoms in the crystal of the crystalline polymer are arranged repeatedly with a three-dimensional periodicity, considering the periodicity, the crystal is a three-dimensional stack of parallelepipeds with a certain structure it is conceivable that. Such a parallelepiped is called a unit cell. The three sides of the unit cell are called a-axis, b-axis, and c-axis, respectively.
In the unit lattice of α-crystal polypropylene crystal, the molecular chain direction is referred to as the c-axis, and the short axis of the two sides of the other crystal axes is referred to as the a-axis and the long axis is referred to as the b-axis. In the polypropylene resin molded product, of the three crystal axes of the α crystal, the b axis is directed to a specific direction of the molded product, generally referred to as b-axis orientation. The b-axis tends to be perpendicular to the surface.
In the case of polypropylene, the degree of b-axis orientation defined as described above is generally obtained by obtaining a wide-angle X-ray diffraction spectrum diagram and calculating the ratio of the scattering intensities of the crystal plane (110) and the crystal plane (040). be able to. As an example of obtaining the degree of b-axis orientation by this method, M.M. FUJIYAMA, T.A. WAKINO; Journal of Applied Polymer Science, Vol. 42, pp. The method described in 9-20 (1991) etc. are mentioned. Hereinafter, a specific measurement method will be described.
[0013]
The degree of b-axis orientation can be measured using an X-ray generator (RAD2-C: Ni filter monochromat) manufactured by Rigaku Denki, which is a commercially available X-ray diffraction device.
Specifically, using CuKα as an X-ray source, using a T-die molding machine under conditions of 50 Kv and 40 mA, a die temperature of 280 ° C. or lower, a cooling temperature of 60 ° C. or lower, and a take-off speed of 200 m / min or lower are obtained. A wide-angle X-ray diffraction spectrum is obtained in the range of scattering angle (2θ) = 10 to 30 degrees by irradiating X-rays perpendicularly to the plane of the T-die film and detecting the transmitted X-rays. Next, the scattering intensity of the crystal plane (110) and the crystal plane (040) is obtained from the obtained wide-angle X-ray spectrum diagram. A point giving 2θ = 12.5 on the wide-angle X-ray diffraction spectrum, a point giving the minimum intensity between two peaks corresponding to the scattering of the crystal plane (110) and the crystal plane (040), and the crystal The points giving the minimum value between the two peaks corresponding to the scattering of the plane (130) and the crystal plane (111) are connected by a smooth curve, and the crystal plane (110) and the crystal plane (040) of the crystal plane (040) are used as a reference. The intensity of the peak corresponding to the scattering is obtained and set as the scattering intensity of the crystal plane (110) and the crystal plane (040), respectively.
If the scattering intensity (h) of the crystal plane (110) and crystal plane (040) is h (110) and h (040), respectively, the degree of b-axis orientation is Kb = h (040) / h (110). Is required. Details are shown in FIG.
[0014]
In addition, the Kb value in the non-oriented state of polypropylene is usually determined by the crystal structure of polypropylene (for example, G. NATTA, P. CORRADINI; SUPPLEMENTO AL VOLUMXV, SERIE X DEL NUVOVO CEMENTO, p40-p95 (1960)), 0.79. It becomes. When it has b-axis orientation, the Kb value is less than 0.79. The Kb value thus obtained is preferably in the range of 0.75 or less. The range is preferably 0.65 or less, and particularly preferably 0.60 or less. The lower the Kb value, the higher the b-axis orientation.
When the Kb value exceeds 0.75, the degree of b-axis orientation is low, and mechanical strength such as rigidity and impact resistance and transparency tend to be inferior, which tends to be undesirable. Although there is no restriction | limiting in particular about the lower limit of Kb value, Usually, it is 0.01 or more. The Kb value of the propylene resin molded product of the present invention is obtained by irradiating X-rays perpendicularly to the plane of the T-die film and detecting the transmitted X-rays.
[0015]
Further, in the propylene resin molded product of the present invention, the copolymer component block (B) or the polypropylene component block (A) is dispersed in a layered manner with respect to the other component block, and the average aspect ratio of the layered dispersed component block is 2 More than 0.0 and the average interparticle distance is 0.5 μm or less, the degree of b-axis orientation is high (the Kb value is low), and the molded product has transparency, gloss and other optical properties, and impact resistance. It is particularly preferable because of excellent mechanical strength such as tensile strength and heat resistance.
In the present invention, those having a structure in which the b-axis is oriented perpendicularly to the surface of the molded product, particularly to the surface of the film, are preferable because of excellent optical characteristics and mechanical strength.
[0016]
In the present invention, the layer dispersion is a dispersion in which the copolymer component block (B) or the polypropylene component block (A) is dispersed in a layer (plate shape) with respect to the other component block. The length of the layered dispersion when observed from the thickness direction (see FIG. 2) parallel to the flow direction (MD) of the film is at least 5 μm and the layered dispersion when observed from a plane perpendicular to the MD. The average thickness is 0.06 μm or less.
An example of the layered dispersion inside the propylene resin molded product of the present invention is shown in FIG. FIG. 3 is a view observed from the thickness direction parallel to the flow direction, and shows a state in which layers of polypropylene component blocks and layers of copolymer component blocks are alternately formed.
[0017]
The average aspect ratio and the average interparticle distance are obtained by image analysis of a transmission electron microscope (hereinafter abbreviated as “TEM”), in which electrons emitted from a microelectronic probe are thin films. This is a device that forms an image using the transmitted electrons as a signal and observes the sample, and the TEM observation image is obtained by cutting out a TEM sample from a test piece, staining it with RuO4, and then cutting the sample using a cutting machine. It is obtained by TEM observation of a thin section.
In the TEM photograph thus obtained, the copolymer block component is generally black and the polypropylene component block of the matrix is photographed white.
[0018]
Next, a method for obtaining the average aspect ratio and average interparticle distance of the copolymer block component using an image processing apparatus will be described.
Specifically, using a T-die molding machine, a TEM photograph of a surface perpendicular to the MD of a T-die film obtained under conditions of a die temperature of 280 ° C. or less, a cooling temperature of 60 ° C. or less, and a take-off speed of 200 m / min or less is used. It can be measured using a commercially available image processing apparatus, TOSPIX-U type high-accuracy monitor particle analysis package manufactured by Toshiba Corporation.
In the present invention, the lamellar dispersion structure may be in the vicinity of the surface of the molded product or in the entire region of the molded product, but in particular in the entire region, the above-mentioned optical characteristics, mechanical strength, etc. are more excellent.
[0019]
For the average aspect ratio, a gray image of a TEM photograph is read into an analysis device, and the copolymer block component is converted to a binary image of white and the polypropylene block component of the matrix is converted to a binary image of black. For each particle, the absolute maximum length (L) is the maximum distance between any two points on the outer periphery of the white part, and the maximum width in the direction perpendicular to the absolute maximum length is the width (BD). The ratio of length to width is defined as the aspect ratio (L / BD), the average of all measured particles is obtained, and this value is referred to as the average aspect ratio.
[0020]
On the other hand, the average interparticle distance is a distance between any two points between the particles parallel to the thickness direction of the particle molding, and the average value is referred to as the average interparticle distance.
When stretching the propylene resin molded product layer-dispersed T-die film of the present invention and the conventional sea-island T-die film in the resin flow direction (MD direction) and transverse direction (TD direction) during molding, The layer-dispersed T-die film is characterized in that the change in the half-value width (B) of the peak corresponding to the scattering of the crystal plane (040) of the wide-angle X-ray diffraction spectrum is smaller than that of the sea-island T-die film. Have. An example of the change in the wide-angle X-ray diffraction profile is shown in FIG. 4 (described later). The wide-angle X-ray diffraction profile is measured by a reflection method with respect to the film surface. Referring to the supervision of Isamu Nita and X-ray crystallography (issued July 30, 1957), the half-value width (B) is approximately expressed by the following formula (II).
B = (k · λ) / (D · cos θ) Formula (II)
At this time, D is the crystal size, k is a constant, λ is the X-ray wavelength, and θ is the Bragg angle.
A small change in half-value width means that the change in crystal size is small because k, λ, and θ are constants. The small change in the half-value width of the peak corresponding to the scattering of the crystal plane (040) means that the crystal size in the b-axis direction is hardly changed by stretching, that is, the crystal in the b-axis direction is not easily destroyed. Means that.
[0021]
In the present invention, the average propylene content (FP) of xylene solubles is 30 to 60 mol%, and the high propylene content (P_P) Is 60-80 mol% and P_POf FP in the FP (P_f1) Is more preferably 0.25 to 0.55, and a block property (CSD) of 1.4 to 2.5 is more preferably used. The xylene-soluble component means a product in which a propylene resin molded product is once dissolved in ortho-xylene at a temperature of 130 ° C. and then cooled to 25 ° C. to precipitate a polymer.
[0022]
The average propylene content (FP) of this xylene-soluble matter, and the propylene content (P_P), P_POf FP in the FP (P_f1), Block conditions (CSD), etc.¹³It can be obtained by statistical analysis of the C-NMR spectrum. This technique will be described below by taking as an example the case where the component (B) is a propylene-ethylene copolymer. FIG. 5 shows a typical propylene-ethylene copolymer.¹³It is a C-NMR spectrum, and the spectrum gives 10 different peaks due to the difference in chain distribution (how ethylene and propylene are arranged).
The name of this chain is Carman, C, J, Horrington, R, A, Wilkes, C, E; Macromolecules, Vol. 10, p536-544 (1977), and are named as shown in FIG. Since such a chain can be represented as a reaction probability (P) assuming a copolymerization reaction mechanism, the relative intensity of each of the peaks (1) to (10) when the overall peak intensity is set to 1 is It can be expressed as a stochastic equation by Bernoulli statistics with (Pa) as a parameter. (1) In the case of Sαα, if the propylene unit is the symbol P and the ethylene unit is the symbol E, there are three possible chains of [PPPP], [PPEE], and [EPPE], and these are the reaction probabilities, respectively. And add together. For the remaining peaks (2) to (10), formulas are obtained in the same manner, and the parameters (Pa) are optimized so that these ten formulas and the actually measured peak intensity are closest. be able to.
[0023]
For the two-site model, see H.C. N. CHENG; Journal of Applied Polymer Science, Vol. 35 p1639-1650 (1988). That is, the active site (P_P) And an active site (P ') for preferential polymerization of ethylene_PAssuming two reaction probabilities, the active point (P_P) Ratio (P_f1) As parameters, using the probability equation in Table 1,¹³It is obtained by optimizing the above three parameters so that the relative intensity of the C-NMR spectrum and this probability equation coincide. In this way, it was determined (P_P), (P ’_P), (P_f1) And the average propylene content (FP) is determined by the following formula (III).
FP = P_P× P_f1+ P ’_P× (1-P_f1] Formula (III)
[0024]
[Table 1]

[0025]
Block property (CSD) is the reactivity ratio of ethylene and propylene, and this definition is described in the Journal of Polymer Science, “Copolymerization 1 Reaction Analysis, p5-13” published by Baifukan (1975). The calculation method is described in Soka, K, Park, J, R, Shiono, T; Polymer Communications, Vol. 32, no. 10, p310 (1991). That is, in FIG.₁₃Using the intensity ratio of (1), (2), (3), (6), (7), and (9) of the C-NMR spectrum, the following formula (IV) was used.
(CSD) = [(0.5 × (7) + 0.25 × (6) + 0.5 × (3)) × (1 ▼) / [0.5 × ((2) + (3))]²
... Formula (IV)
The average propylene content (FP) determined in this manner is in the range of 30 to 60 mol%, preferably 35 to 58 mol%, more preferably 38 to 55 mol%. When the propylene content is less than 30 mol%, the appearance of the product is remarkably deteriorated. On the other hand, when it exceeds 60 mol%, the amount of by-product of the low crystalline polymer increases, which is not preferable.
[0026]
Propylene content on the high propylene content side (P_P) Is 60 to 80 mol%. Preferably it is 63-78, More preferably, it is 65-75 mol%. (P_P) Is less than 60 mol%, the rigidity and heat resistance of the propylene block copolymer are lowered, which is not preferable. When it exceeds 80 mol%, impact resistance is impaired, which is not preferable. (P_P) In the FP is in the range of 0.25 to 0.55, preferably in the range of 0.27 to 0.53, and more preferably in the range of 0.20 to 0.51. . (P_P) In the FP is less than 0.25, the rigidity and heat resistance are lowered, which is not preferable. On the other hand, if it exceeds 0.55, impact resistance is impaired, which is not preferable. Regarding the block property (CSD), one in the range of 1.4 to 2.5 is preferable, preferably in the range of 1.6 to 2.3, and more preferably in the range of 1.7 to 2.0. is there. If (CSD) is less than 1.4, rigidity and heat resistance are lowered, which is not preferable. On the other hand, if it exceeds 2.5, the low temperature impact strength is particularly impaired among the impact resistance, which is not preferable.
[0027]
(I) Intrinsic viscosity of xylene insoluble matter [η]₁And xylene solubles intrinsic viscosity [η]₂Ratio [η]₂/ [Η]₁And xylene insoluble matter intrinsic viscosity [η]₁Satisfies the formula (I), and
[Η]₂/ [Η]₁≦ 0.21 [η]₁+0.56 Formula (I)
(II) The xylene insoluble matter is a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC).₁) In the range of 100,000 to 700,000, and the weight average molecular weight (Mw)₁) And number average molecular weight (Mn₁) Ratio (Mw)₁/ Mn₁) Molecular weight distribution MD₁Is in the range of 4.0-10.
(III) The xylene-soluble matter is a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC).₂) In the range of 100,000 to 600,000, and the weight average molecular weight (Mw)₂) And number average molecular weight (Mn₂) Ratio (Mw)₂/ Mn₂) Molecular weight distribution MD₂Is in the range of 4.0 to 8.0.
(IV) Molecular weight distribution of xylene solubles (MD₂) And xylene insoluble matter molecular weight distribution (MD₁) Ratio is 1.0 or less, a molded product of propylene resin having an excellent balance between rigidity and impact resistance and excellent transparency can be obtained.
[0028]
(I) Intrinsic viscosity of xylene insoluble matter [η]₁And xylene solubles intrinsic viscosity [η]₂Ratio [η]₂/ [Η]₁And xylene insoluble matter intrinsic viscosity [η]₁Preferably, [η]₂/ [Η]₁≦ 0.21 [η]₁+0.52, particularly preferably [η]₂/ [Η]₁≦ 0.21 [η]₁+0.48. [Η]₂/ [Η]₁Is 0.21 [η]₁When it exceeds +0.56, it is inferior to transparency and impact resistance.
[0029]
(II) The xylene insoluble matter is a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC).₁) Is preferably in the range of 150,000 to 650,000, particularly preferably 200,000 to 600,000. Weight average molecular weight of xylene insoluble matter (Mw₁) And number average molecular weight (Mn₁) Ratio (Mw)₁/ Mn₁) Molecular weight distribution (MD) of xylene insolubles₁) Is preferably in the range of 4.2 to 7.0, particularly preferably 4.5 to 6.0.
Weight average molecular weight of xylene insoluble matter (Mw₁) Is less than 100,000, the mechanical strength is inferior. On the other hand, if it exceeds 700,000, gels and fish eyes of the molded product are likely to be generated, which is not preferable.
Molecular weight distribution of xylene insolubles (MD₁) Ie (Mw₁/ Mn₁) Is less than 4.0, the moldability is inferior. On the other hand, when it exceeds 10, the mechanical strength and the appearance of the molded product are inferior.
[0030]
(III) The xylene-soluble matter is a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC).₂) Is preferably in the range of 150,000 to 500,000, particularly preferably in the range of 200,000 to 400,000. Moreover, the weight average molecular weight (Mw) of the xylene solubles₂) And number average molecular weight (Mn₂) Ratio (Mw)₂/ Mn₂) Molecular weight distribution of xylene solubles (MD)₂) Is preferably in the range of 4.5 to 7.5, particularly preferably in the range of 5.0 to 7.0.
Weight average molecular weight of xylene solubles (Mw₂) Is less than 100,000, the impact resistance and cold resistance are inferior. On the other hand, if it exceeds 600,000, gels and fish eyes of the molded product are likely to be generated, which is not preferable.
Molecular weight distribution of xylene solubles (MD₂) Ie (Mw₂/ Mn₂) Is less than 4.0, the moldability is inferior. On the other hand, molecular weight distribution of xylene solubles (MD₂) Exceeding 8.0 is not preferable because it tends to cause heat resistance and stickiness of the surface of the molded product.
[0031]
(IV) Molecular weight distribution of xylene insoluble matter (MD₁) And xylene solubles molecular weight distribution (MD₂) Ratio is preferably 0.95 or less, particularly preferably 0.9 or less. Although there is no restriction | limiting in particular about a lower limit, Usually, it is 0.5 or more.
Molecular weight distribution of xylene insolubles (MD₁) And xylene solubles molecular weight distribution (MD₂) Ratio exceeding 1.0, the balance of the transparency, rigidity and impact resistance of the molded product is poor.
[0032]
In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) by the gel permeation chromatograph (GPC) in this invention are defined as follows. A series of monodisperse standard polystyrene gel permeation chromatographs (GPC) with known molecular weights are measured, and a relational expression between polystyrene molecular weight and elution time (hereinafter referred to as a calibration curve) is prepared. R. Lew, D.D. Suwanda, S .; T. T. et al. Balke; Appl. Polym. Sci. , Vol. 35, p1049-1063 (1988), a molecular weight conversion formula from the molecular weight of polystyrene to the molecular weight of polypropylene is determined from the relational expression of the intrinsic viscosity and molecular weight of polystyrene and polypropylene.
A molecular weight is calculated | required using a calibration curve from the gel permeation chromatograph (GPC) measurement data of a polypropylene, and also the weight average molecular weight (Mw) and number average molecular weight (Mn) of a polypropylene are calculated | required using a molecular weight conversion formula.
[0033]
Specifically, the measurement can be performed using a Waters 150C GPC apparatus in which two Shodex HT-806M columns are connected in series. From the measured data of xylene solubles and xylene insolubles, the molecular weight is obtained using a calibration curve, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) are obtained using the following molecular weight conversion formula. It was.
M_PP= 0.931 x M_PS ^0.975
M_PS: Molecular weight of polystyrene at a certain elution time
M_PP: Molecular weight of polypropylene at the same elution time
Such a molecular weight calculation method is described in detail in Tsutsuo Takeuchi and Sadao Mori, “Gel Chromatography <Basics>” Kodansha (1972).
[0034]
Preferable examples for obtaining the propylene resin molded product of the present invention include, for example, a solid catalyst containing a magnesium compound, a titanium compound, a halogen-containing compound and an electron donating compound as essential components, or a general formula: TiX_a・ Y_b(Wherein X represents a Cl, Br, or I halogen atom, Y represents an electron donating compound, a represents 3 or 4, and b represents an integer of 3 or less), What was polymerized using the polymerization catalyst obtained by wash | cleaning with a halogen-containing compound and also wash | cleaning with a hydrocarbon is mentioned.
Such a polymerization catalyst is prepared using a magnesium compound, a titanium compound, a halogen-containing compound, and an electron donating compound.
[0035]
Magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide and magnesium iodide; alkoxymagnesium such as dimethoxyxymagnesium, diethoxyxymagnesium, dipropoxymagnesium, dibutoxymagnesium and diphenoxymagnesium. Is preferred. Moreover, what forms a magnesium halide at the time of catalyst formation can also be used. These various magnesium compounds may be used alone or in combination of two or more.
As the titanium compound, titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium halides such as titanium tetraiodide, and the like are suitable. These various titanium compounds may be used alone or in combination of two or more.
In the halogen-containing compound, the halogen is fluorine, chlorine, bromine, or iodine, preferably chlorine. Specific examples depend on the catalyst preparation method, but titanium halide such as titanium tetrachloride, silicon tetrachloride, tetraodor And silicon halides such as silicon halide, and phosphorus halides such as phosphorus trichloride and phosphorus pentachloride. Depending on the catalyst preparation method, a halogenated hydrocarbon, a halogen molecule, or a hydrohalic acid may be used.
[0036]
Examples of the electron donating compound generally include oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds, and silicon-containing compounds.
Specifically, alcohols, phenols, ketones, aldehydes, organic acid esters, alkoxy esters, keto esters, inorganic acid esters, ethers, amides, organic acid halides, organic acid anhydrides And amines, nitriles, thioethers, sulfate esters, sulfonic acids, silicon-containing compounds, and the like. Of these, organic acid esters are particularly preferable, and more specific examples include phthalic acid esters such as ethyl phthalate, butyl phthalate, and 2-ethylhexyl phthalate. These electron donating compounds may be used alone or in combination of two or more.
The amount of each component used is arbitrary as long as the effect is recognized in the present invention, but the following ranges are generally preferred. The amount of the titanium compound used is preferably in the range of 0.0001 to 1000, preferably in the range of 0.01 to 100 in terms of molar ratio with respect to the amount of magnesium compound used. When a halogen compound is used as necessary, the molar ratio is preferably in the range of 0.01 to 1000, preferably in the range of 0.1 to 100, based on the amount of the magnesium compound used.
The amount of the electron-donating compound used is preferably in the range of 0.001 to 10 and preferably in the range of 0.01 to 5 in terms of molar ratio with respect to the amount of the magnesium compound used.
As a method for preparing a solid catalyst, a conventionally known solid obtained by contacting or reacting with an auxiliary such as a magnesium compound, a titanium compound, an electron donating compound, and, if necessary, a halogen-containing compound as needed. Catalyst preparation methods can be used.
[0037]
Specific examples of known methods include the following preparation methods.
(1) A method of contacting a magnesium halide with an electron-donating compound and a titanium compound as necessary.
(2) A method in which a halogenated titanium compound and / or a halogen compound of silicon are brought into contact with a solid component obtained by contacting magnesium halide with tetraalkoxytitanium and a specific polymer silicon compound.
(3) A method in which a magnesium compound is dissolved with a tetraalkoxytitanium and an electron donating compound, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a halogenated titanium compound.
(4) A method in which alumina or magnesia is treated with a halogenated phosphorus compound, and magnesium halide, an electron-donating compound or a titanium halide compound is brought into contact therewith.
(5) A method in which a Grignard reagent typified by an organic magnesium compound is allowed to act on a reducing agent or a halogenating agent, and then an electron donating compound and a titanium compound are brought into contact with each other.
(6) A method of contacting an alkoxymagnesium compound with a halogenating agent and / or a titanium compound in the presence or absence of an electron donating compound.
(7) A method in which a magnesium compound is dissolved with tetraalkoxytitanium, treated with a polymer silicon compound, and then treated with a silicon halogen compound and an organometallic compound.
(8) A method of treating a spherical magnesium compound / alcohol complex with an electron donating compound and a halogenated titanium compound.
Among these preparation methods, the method (8) is particularly preferred.
[0038]
The solid catalyst prepared by the above method has the general formula TiX._a・ Y_b(Wherein X is a halogen atom of Cl, Br, or I, a is 3 or 4, Y is an electron-donating compound, and 0 <b ≦ 3) The catalyst component is prepared by treating at least once with and washing with hydrocarbons.
General formula TiX_a・ Y_b(Wherein X is a halogen atom of Cl, Br, and I, a is 3 or 4) S. P. Coutts, P.M. C. Weiles; Adovan. Organometal. Chem. , Vol. 9, P-135 (1970), 4th edition, New Experimental Chemistry Course 17, Inorganic Complexes / Chelate Complexes p. 35, Chemical Society of Japan, Maruzen (1991), H.C. K. Kakkoen, J. et al. Pursiainen, T .; A. Pakkanen, M .; Ahlgren, E .; Iiscola; Organomet. Chem. , Vol. 453, p175 (1993) and the like, and generally known to form a complex easily with an electron donating compound.
TiX_a・ Y_bY (electron-donating compound) may be the same as or different from that used in the preparation of the solid catalyst. TiX_a・ Y_bIn preparing the compound, one kind of electron donating compound may be used, or two or more kinds may be used in combination.
In addition, the halogen-containing compound may be the same as or different from that used when preparing the solid catalyst. One or more halogen-containing compounds may be used in combination.
[0039]
TiX solid catalyst_a・ Y_bThe temperature to be treated with -30 ° C to 150 ° C, preferably 0 ° C to 100 ° C. Moreover, the temperature which processes a solid catalyst with a halogen containing compound is 0 to 200 degreeC, Preferably it is 50 to 150 degreeC.
TiX_a・ Y_bThe amount used is preferably in the range of 0.001 to 500, preferably in the range of 0.1 to 1000, in terms of molar ratio to the titanium atom in the solid catalyst.
Solid catalyst TiX_a・ Y_bThe treatment with the halogen-containing compound can usually be carried out in an inert hydrocarbon medium. In this case, examples of the inert hydrocarbon medium to be used include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; aromatic hydrocarbons such as benzene, toluene and xylene.
In addition, these inert hydrocarbon solvents are TiX of solid catalyst._a・ Y_bAnd a washing solvent for the olefin polymerization catalyst after the treatment with the halogen-containing compound.
[0040]
Among the polymerization catalysts prepared in this way, those having the following powder physical properties may be used.
(A) Surface area is 100m²/ G-300m²/ G, preferably 120 m²/ G-280m²/ G, particularly preferably 130 m²/ G-260m²/ G.
100m surface area²When it is less than / g, it is difficult to increase the amount of component (B) in BPP. Meanwhile, 300m²When the amount exceeds / g, the polymerized polymer tends to break down, and fine powder is generated, making it difficult to transport the powder in the plant or to adhere to the reactor wall.
(B) A pore volume in the range of 2 nm to 40 nm and 0.30 cc / g to 0.45 cc / g may be used.
When the pore is in the range of 2 nm to 40 nm and less than 0.30 cc / g, it is difficult to increase the amount of the component (B) in the BPP. On the other hand, when it exceeds 0.45 cc / g, the polymerized polymer is liable to be destroyed, fine powder is generated, and it becomes difficult to transport the powder in the plant or to adhere to the wall of the reactor.
[0041]
(C) The weight average particle diameter is 50 to 100 μm, preferably 55 to 98 μm, particularly preferably 60 to 96 μm.
When the weight average particle diameter is less than 50 μm, it is difficult to increase the amount of the component (B) in the BPP. On the other hand, when it exceeds 100 μm, the polymerized polymer is liable to be destroyed and fine powder is generated, making it difficult to transport the powder in the plant or to adhere to the reactor wall.
(D) Particles having a particle size of 123 μm or more are 15% by weight or less, preferably 13% by weight or less, and particularly preferably 10% by weight or less.
When the particle size is 123 μm or more, the polymerized polymer is liable to break down, and fine powder is generated, making it difficult to transport the powder in the plant or to adhere to the reactor wall.
(E) Those having a particle diameter of 87 μm or less are 35% by weight or more, preferably 38% by weight or more, and particularly preferably 40% by weight or more.
When the particle size is 87 μm or less and less than 35% by weight, it is difficult to increase the amount of component (B) in BPP.
[0042]
The method for obtaining the surface area and pore volume as described above is described in JP-A-3-62805. This prior art document describes magnesium chloride and alcohol adducts during the preparation of the solid catalyst, and 0.2 to 2 moles of alcohol adduct is prepared per mole of magnesium chloride. This solid catalyst has an average diameter of 10 to 350 nm and a surface area of 20 to 250 m.²/ G and a porosity of 0.2 cc / g or more, it states that spherical olefin (co) polymers having high bulk density, fluidity and mechanical resistance can be obtained.
The difference between the method described in JP-A-3-62805 and the present invention is that the surface area, the pore volume and the particle size distribution of the polymerization catalyst of the present invention are different from that of the solid catalyst TiX._a・ Y_bRepresents the improved catalyst after being treated with and washed with an inert hydrocarbon solvent, whereas those described in the above prior art describe the surface area and pore volume of the solid catalyst itself, It is different from the improved polymerization catalyst.
The surface area is measured by the BET method (S. Brunauer, PH Emmett, E. Teller; J. Am. Chem. Soc., Vol. 60, p309 (1938)).
[0043]
On the other hand, the pore volume refers to the total volume of pores contained in the porous material. In general, since the pores are not a single diameter but an aggregate of pores having various radii, the pore volume can be obtained by obtaining the pore distribution. The BET method can be determined by a nitrogen gas adsorption method using a commercially available measuring device, CARTO ERBA STRUMENTAZION, manufactured by Sorptomatic Series 1800.
A method for measuring the pore volume of a catalyst or the like can be determined by a mercury intrusion method (EW Washburn, Proc. Natl. Acad. Sci., Vol. 7, p-115 (1921)). In this mercury intrusion method, mercury is injected into the pores of the catalyst, and the amount of mercury entering the pores can be determined as a function of pressure. About this measurement, it can measure using the Auto Pore 9200 type | mold made from MICROMERITIS which is a commercially available measuring apparatus.
[0044]
Regarding the particle size referred to in the present invention, measurement of the particle size distribution is obtained by diffraction pattern analysis. That is, a laser beam spread by a beam expander is applied to particles dispersed in a gas phase or a liquid phase, and a diffraction pattern generated by the particles is collected by a lens, projected onto a detector, and applied to the detector. It is obtained from the intensity distribution of the projected Franhofer diffraction pattern.
For such an analysis method, Michael Heuer, Kurt Leschonski: Results Obtained with a New Instrument for the Measurement of Particle Size Converters. Part 2 (1985) p7-13 and J. Org. Fraunhofer: Brehungs und Frarbzerstrüngsverm gens verschiedener Glasarten. It is described in detail in Gilberts Analder der Physik 56 (1987), p193-226 and the like.
More specifically, the measurement can be performed using a commercially available laser diffraction particle size distribution measuring device HELOS & RODOS manufactured by JEOL Ltd.
[0045]
In addition to the above powder characteristics, those having the following mechanical characteristics are preferable. That is, the compressive fracture strength measured by using a commercially available powder compression / tensile strength measuring device, Hosokawa Micron Co., Ltd. “Ag Robot” device, is 1.0 × 10.⁶  N / m²The polymerization catalyst having a tensile stress of 50 g or more may be used.
For the outline of the apparatus, see Hiroyuki Enomoto, Yoshiyuki Inoue, Toyokazu Yokoyama; 38, pp 74-80 (1994).
The compressive fracture strength is preferably 1.1 × 10⁶  N / m²Or more, particularly preferably 1.2 × 10⁶  N / m²That's it. On the other hand, the tensile stress is preferably 60 g or more, particularly preferably 70 g or more.
Compressive fracture strength measured using an apparatus is 1.0 × 10⁶  N / m²And the tensile stress is less than 50 g, it is difficult to obtain the propylene resin molded product of the present invention. In addition, regarding the above-mentioned fractionation characteristics of propylene and other α-olefins prepolymerized, the compression fracture strength is 1.0 × 10.⁶N / m²Those having a tensile strength of 4 g or more are preferred.
The polymerization catalyst as described above is used in the production of the BPP of the present invention in combination with an organoaluminum compound and a stereoregularity improver described later.
[0046]
Typical organoaluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, aluminoxane such as methylaluminoxane, ethylaluminoxane, propylaluminoxane. Is mentioned. Such organoaluminum compounds may be used alone or in combination of two or more.
Examples of the stereoregularity improver include phenyltriethoxysilane, diphenyldimethoxysilane, di-n-propyldimethoxysilane, di-i-propyldimethoxysilane, di-t-butyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, Examples thereof include silicon compounds having Si—O—C bonds such as cyclohexylmethyldimethoxysilane, texyltrimethoxysilane, t-butyltrimethoxysilane, cyclohexyltrimethoxysilane, tetramethoxysilane, and tetraethoxysilane. These stereoregularity improvers may be used alone or in combination of two or more.
[0047]
The polymerization method is not particularly limited, and a known method can be used. It can be obtained by either a continuous type or a batch type method, and the form of the polymerization reactor is not particularly limited. The above BPP is a slurry method in the presence of a liquefied α-olefin solvent such as hexane, heptane, coconut oil, or a liquefied α-olefin solvent such as propylene, and a gas phase polymerization method in the absence of a solvent. Done in Preferably, it is carried out in the range of 50 to 90 ° C. The polymerization pressure is 2-50 kg / cm²It is done in the range. As the reactor in the polymerization step, those generally used in the technical field can be appropriately used. For example, using a stirred tank reactor, a fluidized bed reactor, or a circulation reactor, the polymerization operation can be performed by any one of a continuous method, a semi-batch method, and a batch method.
The obtained BPP slurry or powder is inactivated with alcohol, water or the like, or after removing the residual catalyst, if necessary, dried, melted and mixed with additives.
When this BPP is further blended with a nucleating agent, a product excellent in rigidity, heat resistance and impact strength can be obtained.
[0048]
Further, the nucleating agent in the present invention refers to a substance having an effect of growing a crystal as a nucleus when added to a crystalline resin in the synthetic resin field, and there are various substances.
Examples thereof include metal salts of carboxylic acids, dibenzylidene sorbitol derivatives, phosphate metal salts, inorganic fillers such as talc and calcium carbonate. Specific examples include sodium benzoate, aluminum adipate, aluminum pt-butylbenzoate, sodium thiophenecarboxylate, 1,3,2,4-dibenzylidenesorbitol, 1,3,2,4,- Di- (p-methylbenzylidene) sorbitol, 1,3, -p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, sodium-bis- (4-t-butylphenyl) phosphate, potassium-bis- (4 -T-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, inorganic compounds such as talc and calcium carbonate. These nucleating agents may be used alone or in combination of two or more.
The effect of the present invention is remarkable when the nucleating agent is added in an amount of at least 0.05 to 0.5% by weight of the nucleating agent in the polyolefin resin molded product.
Preferably, 0.08 to 0.4% by weight, particularly preferably 0.1 to 0.35% by weight is added. However, an inorganic compound such as talc has a smaller nucleating agent effect than the nucleating agent exemplified above, so it is preferable to add 5 to 30% by weight. Preferably, it is 7 to 28% by weight, particularly preferably 9 to 25% by weight.
[0049]
For the polyolefin resin molded product of the present invention, other additives commonly used for thermoplastic resins (for example, antioxidants, weathering stabilizers, antistatic agents, lubricants, antiblocking agents, antifogging agents, Dyes, pigments, oils, waxes, etc.) can be mixed in an appropriate amount within a range not impairing the object of the present invention.
For example, examples of such additives include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis- (6 -T-butylphenol), 2,2-methylene-bis (4-methyl-6-t-butylphenol), octadecyl-3- (3 ', 5'-di-t-butyl-1'-hydroxyphenyl) propionate, 4,4'-thiobis- (6-butylphenol), UV absorbers include ethyl-2-cyano-3, 3-diphenyl acrylate, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxy -4-octoxybenzophenone, dimethyl phthalate, diethyl phthalate, wax, liquid paraffin, phosphate ester, antistatic agent as plasticizer Pentaerythritol monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide, carbon wax, ethylene bisstearamide, butyl stearate as a lubricant, carbon black, phthalocyanine, quinacridone, indoline as a colorant Examples of fillers include glass fiber, asbestos, mica, ballastite, calcium silicate, aluminum silicate, and calcium carbonate. Also, many other polymer compounds can be blended to such an extent that the effects of the present invention are not inhibited.
[0050]
As a method for producing the propylene resin molded product of the present invention, there is a method in which a nucleating agent is melt-kneaded with polypropylene together with other additives. Specifically, a conventionally known mixing method, for example, a method of mixing each component using a ribbon blender, Henschel, etc., and further melt mixing using a kneader, mixing roll, Banbury mixer, extruder, etc. . About melt kneading temperature, the range of 170-280 degreeC is good. Preferably, the range of 190-260 degreeC is good. In particular, the range is preferably 200 to 250 ° C. On the other hand, each component may be directly supplied to the molding machine and molded.
[0051]
The melt index of the resin (load: 2.16 kg, temperature: 230 ° C. according to MFR, JIS-K7210) is not particularly limited and is selected depending on the molding method, but is 0.1 to 250 (g / 10) depending on the extrusion molding. The range of minutes) is appropriate.
In order to obtain the resin molded product of the present invention, it is preferable to use a molding method in which a molten resin is extruded and molded in a certain direction.
The resin molded product of the present invention may be an injection-molded product, a film, a sheet, a tube, a bottle or the like obtained by a known melt molding method and compression molding method, and can be used alone or other materials may be used. It can be used even when laminated.
For example, as a method of laminating such products, a dry laminate adhesive such as polyurethane or polyester polyacrylic is used, and the other thermoplastic resin layer is laminated on the single layer product of the resin molded product of the present invention. It is carried out by a molding method or a sandwich lamination method, or is a coextrusion lamination, a coextrusion method (feed block method, multi-manifold method), a co-injection molding method, or a co-extrusion pipe molding method.
The multilayer laminate thus obtained is then subjected to a reheating and stretching operation using a vacuum molding machine, a pressure molding machine, a stretch blow molding machine or the like, or a single layer of the aforementioned multilayer laminate or resin molding The molded product can be subjected to a heat stretching operation using a uniaxial or biaxial stretching machine.
Hereinafter, the present invention will be described in more detail with reference to examples.
[0052]
【Example】
Polymerization was carried out under the following conditions to produce various BPPs (Examples 1 to 8, Comparative Examples 1 to 3).
[polymerization]
(Polymerization of Example 1)
(1) Preparation of solid catalyst
Anhydrous magnesium chloride (56.8 g) was completely dissolved at 120 ° C. in 100 g of absolute ethanol, 500 ml of petroleum oil CP15N manufactured by Idemitsu Kosan Co., Ltd. and 500 ml of silicone oil KF96 manufactured by Shin-Etsu Silicone Co., Ltd. under a nitrogen atmosphere. This mixture was stirred for 2 minutes at 120 ° C. and 5000 rpm using a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. While maintaining stirring, the mixture was transferred into 2 liters of anhydrous heptane so as not to exceed 0 ° C. The obtained white solid was thoroughly washed with anhydrous heptane, vacuum-dried at room temperature, and partially deethanolated under a nitrogen stream.
Obtained MgCl₂・ 1.2C₂H₅30 g of OH spherical solid was suspended in 200 ml of anhydrous heptane. While stirring at 0 ° C., 500 ml of titanium tetrachloride was added dropwise over 1 hour. Next, when heating was started and the temperature reached 40 ° C., 4.96 g of diisobutyl phthalate was added, and the temperature was raised to 100 ° C. in about 1 hour. After reacting at 100 ° C. for 2 hours, the solid portion was collected by hot filtration. Thereafter, 500 ml of titanium tetrachloride was added to the reaction product and stirred, and then reacted at 120 ° C. for 1 hour. After completion of the reaction, the solid part was again collected by hot filtration and washed 7 times with 1.0 liter of hexane at 60 ° C. and 3 times with 1.0 liter of hexane at room temperature. The titanium content in the obtained solid catalyst component was measured and found to be 2.36% by weight.
[0053]
(2) TiCl₄[C₆H₄(COOiC₄H₉)₂Preparation of
To a solution of 1.0 liter of hexane containing 19 g of titanium tetrachloride, diisobutyl phthalate: C₆H₄(COOiC₄H₉)₂27.8 g was added dropwise in about 30 minutes while maintaining the temperature at 0 ° C. After completion of dropping, the temperature was raised to 40 ° C. and reacted for 30 minutes. After completion of the reaction, the solid part was collected and washed 5 times with 500 ml of hexane to obtain the desired product.
[0054]
(3) Preparation of polymerization catalyst
20 g of the solid catalyst obtained in (1) above was suspended in 300 ml of toluene, and TiCl obtained in (2) above was suspended at a temperature of 25 ° C.₄[C₆H₄(COOiC₄H₉)₂] And washed with stirring for 1 hour, and the solid part was collected by hot filtration. The reaction product was then washed 3 times with 500 ml of 90 ° C. toluene and 3 times with 500 ml of hexane at room temperature. The titanium content in the obtained solid catalyst component was 1.78% by weight, and the surface area and pore volume of the polymerization catalyst were further measured.
Surface area: 196m²/ G
Pore volume: 0.37 cc / g in the range of 2 to 40 nm of pores
Weight average particle diameter (μm): 87.9
Ratio of particle size of 123 μm or more: 5.8% by weight
Ratio of particle diameter of 87 μm or less: 49.0% by weight
Compressive fracture strength: 1.6 × 10⁶N / m²
Tensile stress: 109g
[0055]
(4) Prepolymerization
In an autoclave with an internal volume of 3 liters under a nitrogen atmosphere, 500 ml of n-heptane, 6.0 g of triethylaluminum, 3.98 g of dicyclopentyldimethoxysilane, and 10 g of the polymerization catalyst obtained in the above (3) are charged. The mixture was stirred for 5 minutes in a temperature range of 0 to 5 ° C. Next, propylene was supplied into the autoclave so that 10 g of propylene per 1 g of the polymerization catalyst was polymerized, and prepolymerized at a temperature range of 0 to 5 ° C. for 1 hour. The obtained prepolymerized solid catalyst was washed with 500 ml of n-heptane three times and used for the production of the following BPP.
[0056]
(5) Main polymerization
First stage: Polymerization of homopolypropylene
In a nitrogen atmosphere, put 2.0 g of the prepolymerized solid catalyst prepared in the above manner, 11.4 g of triethylaluminum, 6.84 g of dicyclopentyldimethoxysilane in an autoclave with an internal volume of 60 liters, and then add 18 kg of propylene to propylene. On the other hand, hydrogen was charged so as to be 1.4 mol%, and the temperature was raised to 70 ° C. to conduct polymerization for 1 hour. After 1 hour, unreacted propylene was removed and the polymerization was terminated.
Second stage: Polymerization of propylene-ethylene copolymer
After the first stage polymerization was completed as described above, the liquid propylene was removed, and the mixed gas of ethylene / propylene = 40/60 (molar ratio) at a temperature of 75 ° C. 2.2 Nm³Copolymerization was carried out for 40 minutes at a feeding rate of 20 NL / hour of hydrogen / hour. After 40 minutes, unreacted gas was removed and the polymerization was terminated. As a result, 7.2 kg of propylene block copolymer was obtained.
[0057]
(Polymerization of Examples 2-7)
In accordance with Example 1, the amount of hydrogen charged during polymerization, the second stage polymerization time, and the amount of ethylene were adjusted to perform polymerization, and BPPs of Examples 2 to 7 were obtained.
(Polymerization of Example 8)
When ethylene was supplied to the first stage in addition to propylene and polymerized in the same manner as in Example 1, BPP having an ethylene content of 2.5% by weight was obtained in the first stage. The ethylene content was measured by sampling an ethylene content measurement sample when the first stage polymerization was completed.
[0058]
(Polymerization of Comparative Example 1)
A BPP of Comparative Example 1 was obtained in the same manner as in Example 1 except that the solid catalyst prepared in (1) of Example 1 was used during the polymerization. The powder physical properties used for the polymerization were as follows.
Surface area: 247m²/ G
Pore volume: 0.42 cc / g in the range of 2 to 40 nm of pores
Weight average particle diameter (μm): 95.4
Ratio of particle diameter of 123 μm or more: 15.8% by weight
Ratio of particle diameter of 87 μm or less: 32.2% by weight
Compressive fracture strength: 9.0 × 10⁵N / m²
Tensile stress: 32g
[0059]
(Polymerization of Comparative Example 2)
Under a nitrogen atmosphere, 6.0 g of AA-type titanium trichloride manufactured by Tosoh Akzo Co., Ltd. and 23.5 g of diethylaluminum chloride are placed in an autoclave with a stirrer having an internal volume of 60 liters, and then 18 kg of propylene and 0.4 mol of propylene. % Was charged with hydrogen, the temperature was raised to 70 ° C., and the same procedure as in Example 1 was followed to obtain BPP of Comparative Example 2.
Surface area: 49m²/ G
Pore volume: 0.27 cc / g in the range of 2 to 40 nm of pores
Weight average particle diameter (μm): 6.1
Ratio of particle size of 123 μm or more: 0.6% by weight
Ratio of particle diameter of 87 μm or less: 92.0% by weight
Compressive fracture strength: 0.7 × 10⁵N / m²
Tensile stress: 27g
[0060]
(Polymerization of Comparative Example 3)
(1) Preparation of solid catalyst
A solid catalyst was prepared by the method described in Example 1 of JP-A-8-100037. That is, it was prepared as follows.
An anhydrous magnesium chloride 95.3 g and dry ethanol 352 ml were placed in a stainless steel autoclave purged with nitrogen, and the mixture was stirred and dissolved at 105 ° C. After stirring for 1 hour, the mixture was fed into a two-fluid nozzle spray with pressurized nitrogen (1.1 MPa) at 105 ° C. Liquid nitrogen was put in the spray tower, and the temperature in the tower was kept at -15 ° C. 252 g of support was obtained in cooled hexane at the bottom of the column. Sieve was performed to obtain 197 g of a spherical carrier having a diameter of 50 to 200 μm. This was dried by nitrogen flow, and MgCl₂A carrier having a composition of 1.7 EtOH was obtained.
20 g of the carrier obtained above, 160 ml of titanium tetrachloride and 240 ml of 1,2-dichloroethane were placed in a glass flask purged with nitrogen, and heated to 100 ° C. with stirring. After adding 6.8 ml of diisobutyl phthalate and heating at 100 ° C. for 2 hours, the solid portion was collected by hot filtration. Thereafter, 160 ml of titanium tetrachloride and 320 ml of 1,2-dichloroethane were added again, and the mixture was stirred with heating at 100 ° C. for 1 hour. After completion of the reaction, the solid portion was again collected by hot filtration and washed with purified hexane. The titanium content in the obtained solid catalyst component was 1.72% by weight, and the surface area, pore volume and other characteristics of the solid catalyst component were measured.
Surface area: 175m²/ G
Pore volume: 0.30 cc / g in the range of 2 to 40 nm of pores
Weight average particle diameter (μm): 108
Ratio of particle size of 123 μm or more: 41.3% by weight
Ratio of particle diameter of 87 μm or less: 17.7% by weight
Compressive fracture strength: 7.5 × 10⁵N / m²
Tensile stress: 46g
[0061]
(2) Prepolymerization
In an autoclave having an internal volume of 3 liters under a nitrogen atmosphere, 500 ml of n-heptane, 6.0 g of triethylaluminum, 2.9 g of isopropyldimethoxysilane and 10 g of the solid catalyst obtained in the above (1) were charged. The mixture was stirred for 5 minutes in the temperature range of ° C. Next, propylene was fed into the autoclave so that 10 g of propylene was polymerized per 1 g of the solid catalyst, and prepolymerized at a temperature range of 0 to 5 ° C. for 1 hour. The obtained prepolymerized solid catalyst was further washed with 500 ml of n-heptane three times to obtain a final prepolymerized catalyst.
[0062]
(3) Main polymerization
First stage: Polymerization of homopolypropylene
In a nitrogen atmosphere, 2.0 g of the prepolymerized catalyst, 11.4 g of triethylaluminum, and 5.16 g of diisopropyldimethoxysilane were placed in an autoclave with a stirrer having an internal volume of 60 liters. Hydrogen was charged so that the temperature was raised to 70 ° C. and polymerization was performed for 1 hour. After 1 hour, unreacted propylene was removed and the polymerization was terminated.
Second stage: Polymerization of propylene-ethylene copolymer
After the completion of the first stage polymerization, the liquid propylene is removed, and a mixed gas of ethylene / propylene = 40/60 (molar ratio) at a temperature of 75 ° C. is 2.2 Nm.³Copolymerization was carried out for 40 minutes at a feeding rate of 20 NL / hour of hydrogen / hour. After 40 minutes, the unreacted gas was removed to terminate the polymerization. Thereafter, 6.5 kg of a propylene block copolymer was obtained.
[0063]
With respect to the BPPs of Examples 1 to 8 and Comparative Examples 1 to 3 obtained by the above-described method, the physical properties of the propylene-block copolymer and the analysis results of the two-site model were examined using the method and apparatus described later. Details thereof will be described later (Tables 2 to 4).
[0064]
[Molding]
Furthermore, it shape | molded as follows using BPP obtained by the above-mentioned method.
(Mixing of additives)
The propylene block copolymer thus obtained was mixed with 0.05% by weight of di-t-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl- 4-hydroxyphenylpropionate] and 0.10% by weight of calcium stearate were mixed using a super mixer (SMV20 type) manufactured by Kawada Manufacturing Co., Ltd., and a twin screw extruder manufactured by Nakatani Machinery Co., Ltd. (AS30 type) Pelletized using the obtained pellets, the following injection molding, film molding, and hollow molding were performed.
[0065]
(Film forming)
Using the BPPs of Examples 1 to 8 and Comparative Examples 1 to 3, films having a thickness of 60 μm were produced at a molding temperature of 230 ° C. and a cooling roll temperature of 40 ° C. using a 40 mmφT die molding machine manufactured by Yoshii Iron Works.
[0066]
(injection molding)
Using Examples 4 to 6, Comparative Example 1 and Comparative Example 3 above, Toshiba Machine Co., Ltd. IS-170FII (theoretical injection amount 250 cm)³), A test piece was produced at a molding temperature of 220 ° C. and a mold cooling temperature of 50 ° C.
[0067]
(Hollow molding)
A cylindrical container (thickness: 1 mm) having an outer diameter of 55 mm and an inner capacity of 300 cc using a JB105 type hollow molding machine manufactured by Nippon Steel Works, using Examples 1 to 2 and 7 and Comparative Examples 2 to 3. Was molded.
[0068]
[Physical properties of each BPP]
For the BPPs obtained in Examples 1 to 8 and Comparative Examples 1 to 3, the physical properties of the propylene-block copolymer and the analysis results of the two-site model were examined using the following method and apparatus (Table). 2 to 4).
(1) Measurement of ethylene content
C. J. et al. Reported by Carman et al.¹³This was carried out based on the method by C-NMR method (Macromolecules, 10, 537 (1977).
(2) MFR measurement
This was performed according to JIS K7210 Table 1 Condition 14. The apparatus used was a melt indexer manufactured by Takara Corporation. The results are also shown in Table 2.
(3) Xylene insoluble matter (X_IS), Xylene solubles (X_s) Measurement
The propylene-block copolymer was once dissolved in ortho-xylene at 135 ° C. and then cooled to 25 ° C. to precipitate a polymer. The components deposited at that time were dissolved in xylene insolubles (X_IS) And the dissolved components are xylene solubles (X_s). The xylene solubles were recovered by reprecipitation with ethanol. Xylene solubles X at 25 ° C_sTable 2 also shows the results expressed as% by weight.
[0069]
[Table 2]

[0070]
(4) Measurement of intrinsic viscosity [η]
Using an Ubbelohde capillary viscometer, the intrinsic viscosity of xylene insoluble matter [η] under the temperature condition of 135 ° C. using decalin as a solvent₁, Intrinsic viscosity of xylene solubles [η]₂Asked. The results are shown in Table 3. [Η]₂/ [Η]₁Table 4 shows the calculated values.
(5) Measurement of molecular weight and molecular weight distribution
Measuring device: Waters 150C GPC
Column: Two Shodex HT-806M columns connected in series
Solvent: 1,2,4-trichlorobenzene (containing 0.1% BHT)
The sample was dissolved in a solvent, filtered through a 0.5 μm sintered metal filter, and measured at 140 ° C. The measurement data is obtained by calculating the molecular weight using a calibration curve, and further using the molecular weight conversion formula,₁, Mw₁Mn soluble in xylene₂, Mw₂Was calculated. The results are also shown in Table 3.
In addition, the molecular weight distribution of xylene insolubles and xylene solubles calculated from these values (MD₁), (MD₂) In Table 3 and MD₂/ MD₁The values of are also shown in Table 4.
[0071]
(6) Analysis of average propylene content and two-site model
The propylene block copolymer is dissolved in a mixed solvent of 1,2,4, -trichlorobenzene / heavy benzene by heating to 130 ° C. so that the polymer concentration becomes 10% by weight. Then, with the following equipment and conditions¹³The C-NMR spectrum was measured and each signal was A. Zambelli et al., Macromolecules, 13, 267 (1980).
Next, the average propylene content (FP) and the two-site model are analyzed, and the propylene content (P_P) And (P_P) Ratio of (FP) to (FP)_f1) And block property (CSD) was determined. The results are also shown in Table 3.

[0072]
[Table 3]

[0073]
[Table 4]

[0074]
As shown in Table 3, high propylene content (P_P) In the average propylene content (FP) of xylene solubles (P_f1) Was in the range of 0.25 to 0.55 for the BPPs of Examples 1 to 8, but all of the BPPs of Comparative Examples 1 to 3 exceeded 0.55.
From the results shown in Tables 3 and 4, the BPPs obtained in Examples 1 to 4, Example 8, and Comparative Example 3 are (I) the intrinsic viscosity [η] of the xylene-insoluble matter.₁And intrinsic viscosity of xylene insoluble matter [η]₁And xylene solubles intrinsic viscosity [η]₂Ratio [η]₂/ [Η]₁Is represented by the following formula (I) [η]₂/ [Η]₁≦ 0.21 [η]₁+0.56 Formula (I)
It was found that
[0075]
[Physical properties of molded film]
About the film molding obtained using BPP of Examples 1 to 8 and Comparative Examples 1 to 3, the average aspect ratio, the average interparticle distance, and the b-axis orientation were measured as follows. The results are also shown in Table 4.
(8) Measurement of b-axis orientation
Measuring device: Rigaku Denki X-ray generator (RAD2-C: Ni filter monochromatic)
X-ray source: CuKα
Voltage, current value: 50Kv, 40mA
Scattering angle (2θ): 10 to 30 degrees
The b-axis orientation degree (Kb) was determined from the obtained wide-angle X-ray diffraction spectrum diagram. The results are also shown in Table 4.
[0076]
(9) Average aspect ratio and average interparticle distance
A test piece having a length of 1 cm, a width of 5 mm, and a height of 60 μm is cut out from the film and embedded in an epoxy resin. The block was subjected to a surface perpendicular to the MD with an ultramicrotome (Retracet ULTRACUT UN, using a diamond knife), and then RuO.₄Was used for gas phase dyeing. Next, ultrathin sections were cut from a block stained with an ultramicrotome at a thickness of 60 nm and collected on a copper mesh.
TEM observation was performed using the following apparatus.
Apparatus: Hitachi, Ltd. H-800 transmission electron microscope (acceleration voltage
100kV)
Based on the photograph obtained by the TEM observation, image analysis processing was performed using the following apparatus.
Equipment: Toshiba Corporation image processing equipment TOSPIX-U2
Screen size: Vertical 1024 x Horizontal 1024 x Depth 8 (pixels / sheet)
Light / dark gradation: 256 gradations
The average aspect ratio was determined by determining the aspect ratio of each particle and then calculating the average of all the particles. The average interparticle distance was determined by calculating the average after determining the distance between any two points between each particle. The results are also shown in Table 4.
(10) Measurement of mechanical properties of polymerization catalyst
Using the following apparatus, the compression fracture strength and tensile strength of the polymerization catalyst were determined.
Equipment: Hosokawa Micron Co., Ltd. Powder Compression / Tensile Strength Measuring Equipment Ag Robot
[0077]
From the results shown in Table 4, the film molded bodies obtained from the BPPs of Examples 1 to 8 have significantly lower Kb values and average aspect values than the film molded bodies obtained from the BPPs of Comparative Examples 1 to 3. It is high and the average interparticle distance is small.
FIG. 7 is a TEM photograph of a surface (end surface) perpendicular to the flow direction of the film molded body obtained from the BPP of Example 2 used for the TEM observation, and FIG. 8 is a film molding obtained from the BPP of Comparative Example 2. It is a TEM photograph of the end surface of the body. In these TEM photographs, the copolymer block component was photographed black and the polypropylene component block of the matrix was photographed white, and the film molded body obtained from the BPP of Example 2 was not limited to the vicinity of the surface but in all areas. It can be seen that the polymer block component is dispersed in layers.
[0078]
Moreover, transparency (Haze), glossiness (Gross), gel as follows using the film molding obtained using BPP of Example 2-Example 4, Example 8, Comparative Example 2-Comparative Example 3 The fish eye and film tensile tests (yield strength, breaking strength, breaking elongation) were measured. These results are shown in Table 5.
(11) Transparency (Haze)
Total haze was measured according to JIS K7105.
(12) Gloss
The surface gloss (gloss) of the film was measured according to JIS Z8741 using a VG-1D type gloss meter manufactured by Nippon Denshoku Industries Co., Ltd.
(13) Fisheye measurement
The film was sampled to a size of 1 foot square, and the size and number of fish eyes were measured using a loupe according to the following criteria.
Big. . . . The diameter is 0.5mm or more
During. . . . A diameter of 0.2 mm or more and less than 0.5 mm
small. . . . The diameter is 0.1mm or more and less than 0.2mm
(14) Measurement of gel
Ten films each having a size of 32 cm × 1 m were sampled, and the gel numbers of the 10 films were visually measured according to the following criteria.
1. . . . No gel, or only one sheet has a length of 5 cm or less
2. . . . Gel generation of 5 cm or less on 2 sheets or less
3. . . . Gel generation of 5 cm or less in 5 sheets or less
4). . . . Gel generation of 5cm or more in 5 sheets or less
5. . . . Gel generation of 5 cm or more on 5 or more sheets, or gel generation on the entire surface of 1 or more sheets
(15) Tensile test
According to JIS K7127, the yield strength, breaking strength, and breaking elongation were measured under conditions of a tensile speed of 500 mm / min in the flow direction (MD) and transverse direction (TD) of the resin during molding.
[0079]
[Table 5]

[0080]
Moreover, the film impact and the tensile elasticity modulus were measured about the film molded object obtained from BPP of Example 2 and Comparative Example 2 with the method shown below. The results are shown in Table 6.
(16) Film impact measurement method
The film was sampled to a size of 10cm x 1m, and a hemispherical impact core with a radius of 1/2 inch was attached to a film impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd., and the impact energy was measured by performing 10 tests per sample. did. The value of these impact energies was divided by the thickness of the film, and the average value of the 10 points was taken as the film impact.
(17) Tensile modulus (Young's modulus) measurement method
Tensile elastic modulus was measured in the flow direction (MD) and transverse direction (TD) of the resin during molding by the method of JIS-K7127 under the conditions of a sample width of 20 mm, a chuck interval of 250 mm, and a tensile speed of 5 mm / min.
[0081]
[Table 6]

[0082]
From the results shown in Table 5, the film moldings produced from the BPPs of the examples have yield strength, breaking strength, breaking elongation, transparency, and gloss as compared with the film moldings produced from the comparative BPPs. It was found that the gel was excellent and the generation of gel and fish eyes was small. Further, from the results shown in Table 6, it is found that the film molded bodies produced from the BPPs of the examples are superior in impact resistance particularly at low temperatures as compared with the film molded bodies produced from the BPPs of the comparative examples. It was.
[0083]
Furthermore, with respect to the T-die film made from the BPP of Example 2 and the T-die film made from the BPP of Comparative Example 2, the state of deformation was shown by the wide-angle X-ray diffraction profile when stretched in the MD direction or the TD direction. We examined (Figure 4). In FIG. 4, non-stretching refers to the case where the T-die film itself is measured, and each stretching ratio is determined from the ratio of the length of the film after completion of stretching and the length of the film before stretching. The T-die film produced from the BPP of Example 2 was compared with the T-die film produced from the BPP of Comparative Example 2 in the half-value width of the peak corresponding to the scattering of the crystal plane (040) of the wide-angle X-ray diffraction spectrum ( It can be seen that the change in B) is small.
[0084]
[Physical properties of injection molded products]
The injection molded articles obtained using Examples 4 to 6, Comparative Example 1 and Comparative Example 3 were left in a temperature-controlled room with a humidity of 50% and a temperature of 23 ° C. for two days and nights. , Bending elastic modulus test, falling weight impact strength (thickness 2 mm × 15 cm × 11 cm flat plate), heat cycle property, and flow mark were evaluated. Moreover, according to the above-mentioned method, evaluation of transparency (Haze, thickness 2mm) and gloss (Gross) was performed. These results are shown in Table 7.
(18) Izod impact strength (notched)
This was performed in accordance with JIS K7110. A U-F impact tester manufactured by Ueshima Seisakusho was used as the apparatus.
(19) Flexural modulus
This was performed according to JIS K7203.
(20) Drop weight impact strength
In accordance with ASTM D3029-78, the weight is dropped from a steel ball diameter of 1/2 inch, weight load of 1 kg, height of 75 centimeters, and cooled with dry ice methanol from a temperature of 20 ° C. The fracture condition was measured, and the temperature at which 50% was destroyed was determined.
(21) Measurement of heat cycle property
After being exposed in a gear oven at a temperature of 100 ° C. for 8 hours, stored in a freezer at −30 ° C. for 3 hours, and then left in a temperature-controlled room at a temperature of 23 ° C. for 3 hours. Rated by stage. The results are shown in Table 7.
○. . . . There is no twist at all
Δ. . . . Can withstand the use of some twisted state.
×. . . . Twist is extremely difficult to use.
(22) Flow mark measurement
The occurrence of flow marks was visually evaluated in the following three stages. The results are shown in Table 7.
○. . . . Not seen at all
Δ. . . . Somewhat seen
×. . . . Remarkable
[0085]
[Table 7]

[0086]
From the results shown in Table 7, the injection molded articles produced from the BPPs of the examples are superior in impact resistance, transparency, and gloss compared to the injection molded articles produced from the BPPs of the comparative examples. It was found that there was no occurrence, particularly little deformation due to temperature change, and excellent impact resistance at low temperatures.
[0087]
[Physical properties of hollow molded body]
About the hollow molded object obtained using BPP of Example 1- Example 2, Example 7, Comparative Example 2- Comparative Example 3, the fall repetition test and the measurement of pinch-off strength were performed as follows. Moreover, according to the above-mentioned method, evaluation of transparency (Haze, thickness 2mm) and gloss (Gross) was performed. These results are shown in Table 8.
(23) Drop repetition test
A cylindrical container (thickness 1 mm) with an outer diameter of 55 mm and an inner capacity of 300 cc is filled with 290 ml of water, and one container is repeatedly dropped from a height of 1.2 m under the condition of a temperature of 5 ° C. Was tested. In the test, the container was dropped five times in the vertical direction and the horizontal direction, and the average was obtained.
(24) Pinch-off strength
The pinch-off portion refers to a portion where resin is fused at the bottom of a hollow molded container.
From the bottom of a cylindrical container (thickness: 1 mm) having an outer diameter of 55 mm and an internal capacity of 300 cc, the sample is punched into a dumbbell shape having a length of 50 mm and a width of 4 mm so that the pinch-off portion is perpendicular and centered in the length direction of the sample. After measuring the average thickness, a tensile test was performed at a chuck distance of 10 mm and a tensile speed of 50 mm / min, and the elongation until the pinch-off portion broke and the load at that time were measured to obtain an average of five points. The results are shown in Table 8.
[0088]
[Table 8]

[0089]
From the results shown in Table 8, it can be seen that the hollow molded body made from the BPP of the example is superior in transparency, gloss, and pinch-off strength to the hollow molded body made from the BPP of the comparative example. It was.
[0090]
【The invention's effect】
The propylene resin molded product of the present invention is (A) propylene and ethylene and / or an α-olefin copolymer having 4 to 12 carbon atoms, and is derived from the ethylene and / or an α-olefin having 4 to 12 carbon atoms. Copolymer having a unit of 5% by weight or less, or 30 to 90% by weight of a polypropylene component block made of homopolypropylene, and (B) a copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms The copolymer component block is composed of 10 to 70% by weight and has a b-axis orientation by wide-angle X-ray diffraction. The resin molded product of the present invention is superior in impact strength (especially low temperature impact resistance), rigidity, transparency, and gloss compared to conventional polyolefin resin molded products. It is effective as a packaging material, food packaging material, medical device material, pharmaceutical packaging material, and cosmetic packaging material.
[0091]
By making the unit derived from ethylene and / or an α-olefin having 4 to 12 carbon atoms in the copolymer component block 30 to 80 mol%, the amount of by-products of the low crystalline polymer is reduced. The appearance of the propylene resin molded product can be improved.
The copolymer component block or the polypropylene component block is layer-dispersed with respect to the other component block, the average aspect ratio of the layer-dispersed component block is 2.0 or more, and the average interparticle distance is 0.5 μm or less. Some have a high degree of b-axis orientation (the Kb value is low), and the molded product is excellent in transparency, optical properties such as gloss, mechanical strength such as impact resistance and tensile strength, and heat resistance. .
When the average propylene content (FP) of xylene solubles is 30 to 60 mol%, the appearance of the product is improved and the amount of by-product of the low crystalline polymer is reduced, (b) Propylene content on the side of high propylene content (P_P) Is 60-80 mol% and P_POf FP in the FP (P_f1) Is 0.25 to 0.55, the propylene block copolymer has high rigidity, heat resistance and impact resistance, and (c) block property (CSD) is 1.4 to 2.5. It has high rigidity and heat resistance, and the low temperature impact strength is particularly high among the impact resistance.
(I) Intrinsic viscosity of xylene insoluble matter [η]₁And intrinsic viscosity of xylene insoluble matter [η]₁And xylene solubles intrinsic viscosity [η]₂Ratio [η]₂/ [Η]₁Is represented by the following formula (I)
[Η]₂/ [Η]₁≦ 0.21 [η]₁+0.56 Formula (I)
When satisfying, it is excellent in transparency and impact resistance. (II) Weight average molecular weight of xylene insoluble matter by gel permeation chromatography (Mw₁) In the range of 100,000 to 700,000, and the weight average molecular weight (Mw) of the xylene-insoluble matter₁) And xylene insoluble matter number average molecular weight (Mn₁) Ratio (Mw)₁/ Mn₁) Molecular weight distribution (MD) of xylene insolubles₁) In the range of 4.0 to 10 is excellent in mechanical strength, moldability, and appearance of the molded product, and hardly causes gel and fish eyes of the molded product. (III) Weight average molecular weight of xylene solubles by gel permeation chromatography (Mw₂) Is in the range of 100,000 to 600,000, and the weight average molecular weight (Mw) of the xylene solubles₂) And xylene solubles number average molecular weight (Mn₂) Ratio (Mw)₂/ Mn₂) Molecular weight distribution of xylene solubles (MD)₂) Is in the range of 4.0 to 8.0, it is excellent in impact resistance, cold resistance, heat resistance and moldability, and gels, fish eyes, and stickiness of the molded product are less likely to occur. (IV) Molecular weight distribution of xylene solubles (MD₂) And xylene insoluble matter molecular weight distribution (MD₁) Ratio (MD₂/ MD₁) Is 1.0 or less, the molded article has an excellent balance of transparency, rigidity and impact resistance.
[Brief description of the drawings]
FIG. 1 is an X-ray diffraction spectrum diagram showing how to obtain a Kb value indicating the degree of b-axis orientation in the present invention.
FIG. 2 is a perspective view showing the observation direction of the propylene resin molded product of the present invention.
FIG. 3 is a model diagram showing an example of a dispersed state of the propylene resin molded product of the present invention, and is a cross-sectional view observed from the thickness direction parallel to the flow direction.
4A and 4B are diagrams showing examples of changes in a wide-angle X-ray diffraction profile measured by a reflection method with respect to a film surface, in which FIG. 4A shows a T-die film made from BPP of an embodiment of the present invention as an MD. When stretched in the direction, (b) stretched in the TD direction a T-die film made from the BPP of the example of the present invention, and (c) stretched the T-die film made from the BPP in the comparative example in the MD direction. (D) is the figure which showed the change at the time of extending | stretching the T-die film produced from BPP of the comparative example to the TD direction.
FIG. 5 is a diagram showing an example of a nuclear magnetic resonance spectrum of a propylene-ethylene copolymer.
FIG. 6 is a diagram showing names of carbons derived from a chain distribution of a propylene-ethylene copolymer.
FIG. 7 is a TEM photograph of an example of a propylene resin molded product of the present invention.
FIG. 8 is a TEM photograph of an example of a conventional propylene resin molded product.

Claims (8)

(A) Propylene and ethylene and / or an α-olefin copolymer having 4 to 12 carbon atoms, wherein the unit derived from the ethylene and / or the α-olefin having 4 to 12 carbon atoms is 5% by weight or less. 30 to 90% by weight of a polypropylene component block made of a polymer or homopolypropylene,
(B) 10 to 70% by weight of a copolymer component block made of a copolymer of propylene and ethylene and / or an α-olefin having 4 to 12 carbon atoms.
Consists of
The blockiness (CSD) of xylene solubles is 1.4 to 2.5,
Kb values indicating the b-axis orientation degree by wide angle X-ray diffraction method, a propylene resin molded product, characterized in der Rukoto 0.75. 2. The propylene resin molded product according to claim 1, wherein a unit derived from ethylene and / or an α-olefin having 4 to 12 carbon atoms in the copolymer component block is 30 to 80 mol%. The copolymer component block or the polypropylene component block is layer-dispersed with respect to the other component block, the average aspect ratio of the layer-dispersed component block is 2.0 or more, and the average interparticle distance is 0.5 μm or less. The propylene resin molded product according to claim 1, wherein the molded product is propylene resin. The propylene resin molded product according to any one of claims 1 to 3, wherein the xylene-soluble component has the following properties (a) to (b) .
(A) The average propylene content (FP) is 30 to 60 mol%.
(B) The propylene content (P _P ) on the high propylene content side according to the two-site model is 60 to 80 mol%, and the proportion of P _P in the FP (P _f1 ) is 0.25 to 0.55. The propylene resin molded product according to any one of claims 1 to 4, which has the following physical properties (I) to (IV).
The intrinsic viscosity [eta] ₁ of (I) Xylene insolubles, the intrinsic viscosity [eta] ₁ and xylene-intrinsic viscosity [eta] ₂ ratio of matter of the xylene-insoluble portion _{[η] 2 / [η]} 1 is, Formula (I) is satisfied.
[η] ₂ / [η] ₁ ≦ 0.21 [η] ₁ +0.56 Formula (I)
(II) The weight average molecular weight (Mw ₁ ) of xylene-insoluble matter in the range of 100,000 to 700,000 by gel permeation chromatography, and the weight average molecular weight (Mw ₁ ) of xylene-insoluble matter and the number average of xylene-insoluble matter molecular weight (Mn ₁₎ and the ratio (Mw ₁ / Mn ₁₎ the molecular weight distribution of the xylene-insoluble portion is (MD ₁₎ is in the range of 4.0 to 10.
(III) The weight average molecular weight (Mw ₂ ) of xylene solubles by gel permeation chromatography is in the range of 100,000 to 600,000, and the weight average molecular weight (Mw ₂ ) of xylene solubles and xylene solubles The molecular weight distribution (MD ₂ ) of the xylene solubles, which is the ratio (Mw ₂ / Mn ₂ ) to the number average molecular weight (Mn ₂ ), is in the range of 4.0 to 8.0.
(IV) The ratio (MD ₂ / MD ₁ ) between the molecular weight distribution (MD ₂ ) of the xylene solubles and the molecular weight distribution (MD ₁ ) of the xylene insolubles is 1.0 or less. Propylene resin molded product according to any one of claims 1-5, characterized in that the film forming. The propylene resin molded product according to any one of claims 1 to 5 , wherein the molded product is injection molded. The propylene resin molded product according to any one of claims 1 to 5 , wherein the molded product is hollow molded.

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