JP4249326B2 - Crystalline polypropylene resin composition and molded product obtained by molding the same - Google Patents

Description

【００３１】
（式中、Ｒ⁷ 〜Ｒ⁹ は水素原子または炭化水素基を示し、それらは互いに同一でも異なってもよく、隣接する基と互いに結合して環を形成していてもよい。Ｒ¹⁰及びＲ¹¹は炭化水素基を示し、それらは互いに同一でも異なってもよく、隣接する基と互いに結合して環を形成していてもよい。Ｒ¹²及びＲ¹³は炭素数が１〜２０のアルキル基を示し、それらは互いに同一でも異なってもよい。ｍは２以上の整数であり、ｎは２以上の整数である。）
で表されるケイ素化合物を用いることができる。
【００３２】
上記の一般式（IV）において、具体的には、Ｒ⁷ 〜Ｒ⁹ としては、水素原子，メチル基，エチル基，ｎ−プロピル基等の直鎖状炭化水素基、イソプロピル基，イソブチル基，ｔ−ブチル基，テキシル基等の分岐状炭化水素基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の飽和環状炭化水素基、フェニル基、ペンタメチルフェニル基等の不飽和環状炭化水素基を挙げることができる。これらのうち、好ましくは水素、炭素数１〜６の直鎖状炭化水素基であり、特に好ましくは水素、メチル基、エチル基である。
【００３３】
上記の一般式（IV）において、Ｒ¹⁰およびＲ¹¹としては、メチル基，エチル基、ｎ−プロピル基等の直鎖状炭化水素基、イソプロピル基，イソブチル基，ｔ−ブチル基，テキシル基等の分岐状炭化水素基、シクロブチル基，シクロペンチル基，シクロヘキシル基等の飽和環状炭化水素基、フェニル基，ペンタメチルフェニル基等の不飽和環状炭化水素基を挙げることができる。また、これらは同じでも良く、異なっていても良い。これらのうち、好ましくは炭素数１〜６の直鎖状炭化水素基であり、特に好ましくはメチル基、エチル基である。
【００３４】
また、上記の一般式（IV）において、Ｒ¹²およびＲ¹³としては、メチル基，エチル基，ｎ−プロピル基，イソプロピル基，ｎ−ブチル基，イソブチル基，ｓｅｃ−ブチル基，ｔ−ブチル基，ｎ−ペンチル基，ｎ−ヘキシル基，ｎ−オクチル基等の直鎖状もしくは分岐状のアルキル基を挙げることができる。また、これらは同じでもよく、異なっていても良い。これらのうち、好ましくは炭素数１〜６の直鎖状炭化水素基であり、特に好ましくはメチル基である。
【００３５】
上記の一般式（IV）で示されるケイ素化合物の好ましい化合物としては具体的に、ネオペンチルｎ−プロピルジメトキシシラン，ネオペンチルｎ−ブチルジメトキシシラン，ネオペンチルｎ−ペンチルジメトキシシラン，ネオペンチルｎ−ヘキシルジメトキシシラン，ネオペンチルｎ−ヘプチルジメトキシシラン，イソブチルｎ−プロピルジメトキシシラン，イソブチルｎ−ブチルジメトキシシラン、イソブチルｎ−ペンチルジメトキシシラン，イソブチルｎ−ヘキシルジメトキシシラン，イソブチルｎ−ヘプチルジメトキシシラン，２−シクロヘキシルプロピルｎ−プロピルジメトキシシラン，２−シクロヘキシルブチルｎ−プロピルジメトキシシラン，２−シクロヘキシルペンチルｎ−プロピルジメトキシシラン，２−シクロヘキシルヘキシルｎ−プロピルジメトキシシラン，２−シクロヘキシルヘプチルｎ−プロピルジメトキシシラン，２−シクロペンチルプロピルｎ−プロピルジメトキシシラン，２−シクロペンチルブチルｎ−プロピルジメトキシシラン，２−シクロペンチルペンチルｎ−プロピルジメトキシシラン，２−シクロペンチルヘキシルｎ−プロピルジメトキシシラン，２−シクロペンチルヘプチルｎ−プロピルジメトキシシラン，イソペンチルｎ−プロピルジメトキシシラン，イソペンチルｎ−ブチルジメトキシシラン，イソペンチルｎ−ペンチルジメトキシシラン，イソペンチルｎ−ヘキシルジメトキシシラン，イソペンチルｎ−ヘプチルジメトキシシラン，イソペンチルイソブチルジメトキシシラン，イソペンチルネオペンチルジメトキシシラン，ジイソペンチルジメトキシシラン，ジイソヘプチルジメトキシシラン，ジイソヘキシルジメトキシシランなどを挙げることができる。
【００３６】
特に好ましい化合物の具体例としては、ネオペンチルｎ−プロピルジメトキシシラン，ネオペンチルｎ−ペンチルジメトキシシラン，イソペンチルネオペンチルジメトキシシラン，ジイソペンチルジメトキシシラン，ジイソヘプチルジメトキシシラン，ジイソヘキシルジメトキシシランを挙げることができ、さらに好ましい化合物の具体例としては、ネオペンチルｎ−ペンチルジメトキシシラン，ジイソペンチルジメトキシシランを挙げることができる。
前記の一般式（IV）で示されるケイ素化合物は、任意の方法によって合成することができる。代表的な合成経路は、下記のとおりである。
【００３７】
【化２】

【００３８】
この合成経路において、原料化合物〔１〕は市販されているか、または公知のアルキル化、ハロゲン化等により得ることができる。化合物〔１〕に対して、公知のグリニャール反応により、一般式（IV）で表される有機ケイ素化合物を得ることができる。
上記の有機ケイ素化合物はそれぞれ単独で用いてもよいし、二種以上を組み合わせて用いてもよい。
【００３９】
窒素含有化合物の具体例としては、２，６−ジイソプロピルピペリジン、２，６−ジイソプロピル−４−メチルピペリジン、Ｎ−メチル２，２，６，６−テトラメチルピペリジン等の２，６−置換ピペリジン類；２，５−ジイソプロピルアゾリジン、Ｎ−メチル２，２，５，５−テトラメチルアゾリジン等の２，５−置換アゾリジン類；Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルメチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラエチルメチレンジアミン等の置換メチレンジアミン類；１，３−ジベンジルイミダゾリジン、１，３−ジベンジル−２−フェニルイミダゾリジン等の置換イミダゾリジン類などを挙げることができる。
【００４０】
リン含有化合物の具体例としては、トリエチルホスファイト，トリｎ−プロピルホスファイト，トリイソプロピルホスファイト，トリｎ−ブチルホスファイト，トリイソブチルホスファイト，ジエチルｎ−ブチルホスファイト，ジエチルフェニルホスファイトなどの亜リン酸エステル類などである。
酸素含有化合物の具体例としては、２，２，６，６−テトラメチルテトラヒドロフラン、２，２，６，６−テトラエチルテトラヒドロフラン等の２，６−置換テトラヒドロフラン類；１，１−ジメトキシ−２，３，４，５−テトラクロロシクロペンタジエン、９，９−ジメトキシフルオレン、ジフェニルジメトキシメタン等のジメトキシメタン誘導体などを挙げることができる。
【００４１】
固体触媒成分の調製
前記（Ａ）の固体触媒成分の調製方法としては、上記の（ａ）マグネシウム化合物、（ｂ）チタン化合物、（ｃ）電子供与体、および必要に応じて（ｄ）ケイ素化合物を、温度を除き通常の方法で接触させればよく、接触手順については特に問わない。例えば、各成分を炭化水素などの不活性溶媒の存在下で接触させてもよいし、予め炭化水素などの不活性溶媒で各成分を希釈して接触させてもよい。この不活性溶媒としては、例えば、オクタン，デカン，エチルシクロヘキサン等の脂肪族炭化水素、脂環式炭化水素またはこれらの混合物を挙げることができる。
【００４２】
ここで、チタン化合物は、上記のマグネシウム化合物のマグネシウム１モルに対して、通常、０．５〜１００モル、好ましくは、１〜５０モル使用する。このモル比が前記範囲を逸脱すると触媒活性が不十分となることがある。また、上記の電子供与体は、上記のマグネシウム化合物のマグネシウム１モルに対して、通常、０．０１〜１０モル、好ましくは、０．０５〜１．０モル使用する。このモル比が前記範囲を逸脱すると触媒活性や立体規則性が不十分となることがある。さらに、ケイ素化合物を用いるときは、上記のマグネシウム化合物のマグネシウム１モルに対して、通常、０．００１〜１００モル、好ましくは、０．００５〜５．０モル使用する。このモル比が前記範囲を逸脱すると触媒活性や立体規則性の向上効果が十分に発揮されず、かつ生成ポリマー中の微粉量が多くなることがある。
【００４３】
上記の（ａ）〜（ｄ）成分の接触は、全成分を加えた後、１２０〜１５０℃、好ましくは１２５〜１４０℃の温度範囲にて行う。この接触温度が前記範囲外では、触媒活性や立体規則性の向上効果が十分に発揮されない。また、接触は、通常、１分〜２４時間、好ましくは、１０分〜６時間行われる。このときの圧力は、溶媒を使用する場合はその種類、接触温度などにより、その範囲は変化するが、通常、０〜５０ｋｇ／ｃｍ² Ｇ、好ましくは０〜１０ｋｇ／ｃｍ² Ｇの範囲にて行う。また、接触操作中は、接触の均一性および接触効率の面から攪拌を行うことが好ましい。
【００４４】
さらに、チタン化合物の接触を２回以上行い、触媒担体としての役割をするマグネシウム化合物に十分担持させることが好ましい。
接触操作において溶媒を使用するときは、チタン化合物１モルに対して、通常、５，０００ミリリットル以下、好ましくは、１０〜１，０００ミリリットルの溶媒を使用する。この比が前記範囲を逸脱すると接触の均一性や接触効率が悪化することがある。
【００４５】
以上の接触で得られた固体触媒成分は、１００〜１５０℃、好ましくは１２０〜１４０℃の温度にて不活性溶媒で洗浄する。この洗浄温度が上記範囲外では、触媒活性や立体規則性の向上効果が十分に発揮されないことがある。この不活性溶媒としては、例えば、オクタン，デカン等の脂肪族炭化水素、メチルシクロヘキサン，エチルシクロヘキサン等の脂環式炭化水素、トルエン，キシレン等の芳香族炭化水素、テトラクロロエタン，クロロフルオロ炭素類等のハロゲン化炭化水素またはこれらの混合物を挙げることができる。これらのなかでは、脂肪族炭化水素が好ましく使用される。
【００４６】
洗浄方法としては、特に制限はないが、デカンテーション、濾過などの方式が好ましい。不活性溶媒の使用量、洗浄時間、洗浄回数についても特に制限はないが、マグネシウム化合物１モルに対して、通常、１００〜１００，０００ミリリットル、好ましくは、１，０００〜５０，０００ミリリットルの溶媒を使用し、通常、１分〜２４時間、好ましくは、１０分〜６時間行われる。この比が前記範囲を逸脱すると洗浄が不完全になることがある。
【００４７】
このときの圧力は、溶媒の種類、洗浄温度などにより、その範囲は変化するが、通常、０〜５０ｋｇ／ｃｍ² Ｇ、好ましくは、０〜１０ｋｇ／ｃｍ² Ｇの範囲にて行う。また、洗浄操作中は、洗浄の均一性および洗浄効率の面から攪拌を行うことが好ましい。
なお、得られた固体触媒成分は、乾燥状態または炭化水素などの不活性溶媒中で保存することもできる。
【００４８】
重合方法
本発明の結晶性ポリプロピレンを製造する際の触媒成分の使用量については、特に制限はないが、前記（Ａ）成分の固体触媒成分は、チタン原子に換算して、反応容積１リットル当たり、通常０．００００５〜１ミリモルの範囲になるような量が用いられ、（Ｂ）成分の有機アルミニウム化合物は、アルミニウム／チタン原子比が通常１〜１，０００、好ましくは１０〜５００の範囲になるような量が用いられる。この原子比が前記範囲を逸脱すると触媒活性が不十分となることがある。また、（Ｃ）第３成分として有機ケイ素化合物等の電子供与性化合物を用いるときは、（Ｃ）電子供与性化合物／（Ｂ）有機アルミニウム化合物モル比が、通常０．００１〜５．０、好ましくは０．０１〜２．０、より好ましくは０．０５〜１．０の範囲になるような量が用いられる。このモル比が前記範囲を逸脱すると十分な触媒活性および立体規則性が得られないことがある。ただし、予備重合を行う場合は、さらに低減することができる。
【００４９】
本発明の結晶性プロピレンの重合においては、重合活性、立体規則性および重合体パウダー形態の面から、所望に応じ、先ずオレフィンの予備重合を行ったのち、本重合を行ってもよい。この場合、前記（Ａ）固体触媒成分、（Ｂ）有機アルミニウム化合物および必要に応じて（Ｃ）電子供与性化合物を、それぞれ所定の割合で混合してなる触媒の存在下に、オレフィンを通常１〜１００℃の範囲の温度において、常圧ないし５０ｋｇ／ｃｍ² Ｇ程度の圧力で予備重合させ、次いで触媒と予備重合生成物との存在下に、プロピレンを本重合させる。
【００５０】
予備重合に用いられるオレフィンとしては、一般式（Ｖ）
Ｒ¹⁴−ＣＨ＝ＣＨ₂ ・・・（Ｖ）
で表されるα−オレフィンが好ましい。
上記の一般式（Ｖ）において、Ｒ¹⁴は水素原子または炭化水素基であって、炭化水素基は飽和基や不飽和基であってもよい。具体的にはエチレン，プロピレン，１−ブテン，１−ペンテン，１−ヘキセン，１−ヘプテン，１−オクテン，１−デセン，３−メチル−１−ペンテン，４−メチル−１−ペンテン，ビニルシクロヘキサン，ブタジエン，イソプレン，ピペリレン等を挙げることができる。これらのオレフィンは一種用いてもよいし、二種以上組み合わせて用いてもよい。前記オレフィンの中で、特にエチレン、プロピレンが好適である。
【００５１】
この本重合における重合形式については特に制限はなく、溶液重合、スラリー重合、気相重合、バルク重合等のいずれにも適用可能であり、さらに、回分式重合や連続重合のどちらにも適用可能であり、異なる条件での２段階重合や多段重合にも適用可能である。
さらに、反応条件については、その重合圧は、特に制限はなく、重合活性の面から、通常、大気圧〜８０ｋｇ／ｃｍ² Ｇ、好ましくは２〜５０ｋｇ／ｃｍ² Ｇ、重合温度は、通常、０〜２００℃、好ましくは、２０〜９０℃、さらに好ましくは、４０〜９０℃の範囲で適宜選ばれる。重合時間は原料のプロピレンの重合温度によって左右され一概に定めることができないが、通常、５分〜２０時間、好ましくは、１０分〜１０時間程度である。
【００５２】
分子量は、連鎖移動剤の添加、好ましくは水素の添加を行うことで調節することができる。また、窒素等の不活性ガスを存在させてもよい。
異なる重合条件で、２段階以上にわたって重合することもできる。
また、本発明の（ｉ）成分の結晶性ポリプロピレンの製造のための重合においては、前記触媒成分については、（Ａ）成分と（Ｂ）成分と（Ｃ）成分とを所定の割合で混合し、接触させたのち、直ちにプロピレンを導入して重合を行ってもよいし、接触後、０．２〜３時間程度熟成させたのち、プロピレンを導入して重合を行ってもよい。さらに、この触媒成分は不活性溶媒やプロピレンなどに懸濁して供給することができる。
【００５３】
本発明の（ｉ）成分の結晶性ポリプロピレンを製造する重合においては、重合後の後処理は常法により行うことができる。すなわち、気相重合法においては、重合後、重合器から導出されるポリマー粉体に、その中に含まれるオレフィンなどを除くために、窒素気流などを通過させてもよいし、また、所望に応じて押出機によりペレット化してもよく、その際、触媒を完全に失活させるために、少量の水、アルコールなどを添加することもできる。また、バルク重合法においては、重合後、重合器から導出されるポリマーから完全にモノマーを分離したのち、ペレット化することができる。
【００５４】
なお、プロピレンの本重合においては、生成した結晶性ポリプロピレンが前記式（１）の関係を満たす範囲で、プロピレンの他に、若干のエチレン，１−ブテン，１−ペンテン，１−ヘキセン，１−ヘプテン，１−オクテン，１−デセン，３−メチル−１−ペンテン，４−メチル−１−ペンテンのようなα−オレフィンと共重合をさせてもよい。
【００５５】
次に、（ｉ）成分の結晶性ポリプロピレンに配合される（ｉｉ）成分の添加剤と、必要に応じて配合される（ｉｉｉ）成分、（ｉｖ）成分の添加剤について説明する。
（ｉｉ）成分
（ｉｉ）成分のうち、酸化防止剤については、特に限定されないが、フェノール系、リン系、イオウ系、ビタミン系、ラクトン系の酸化防止剤から好適に選択することができる。
【００５６】
フェノール系酸化防止剤としては、従来から酸化防止剤として使用されているフェノール系の酸化防止剤を使用できる。
具体的には、２，６−ジ−ｔ−ブチル−４−メチルフェノール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，６−ジシクロヘキシル−４−メチルフェノール、２，６−ジ−ｔ−アミル−４−メチルフェノール、２，６−ジ−ｔ−オクチル−４−ｎ−プロピルフェノール、２，６−ジシクロヘキシル−４−ｎ−オクチルフェノール、２−イソプロピル−４−メチル−６−ｔ−ブチルフェノール、２−ｔ−ブチル−２−エチル−６−ｔ−オクチルフェノール、２−イソブチル−４−エチル−６−ｔ−ヘキシルフェノール、２−シクロヘキシル−４−ｎ−ブチル−６−イソプロピルフェノール、ｄｌ−α−トコフェロール、ｔ−ブチルヒドロキノン、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔ−ブチルフェノール）、２，２−チオビス（４−メチル−６−ｔ−ブチルフェノール）、４，４’−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）、２，２’−メチレンビス［６−（１−メチルシクロヘキシル）−ｐ−クレゾール］、２，２’−エチリデンビス（４，６−ジ−ｔ−ブチルフェノール）、２，２’−ブチリデンビス（２−ｔ−ブチル−４−メチルフェノール）、２−ｔ−ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート、２−［１−（２−ヒドロキシ−３，５−ジ−ｔ−ペンチルフェニル）エチル］−４，６−ジ−ｔ−ペンチルフェニルアクリレート、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオール−ビス［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］、２，２−チオジエチレンビス［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］、Ｎ，Ｎ’−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナミド）、３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルホスホネート−ジエチルエステル、トリス（２，６−ジメチル−３−ヒドロキシ−４−ｔ−ブチルベンジル）イソシアヌレート、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、トリス［（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシエチル］イソシアヌレート、トリス（４−ｔ−ブチル−２，６−ジメチル−３−ヒドロキシベンジル）イソシアヌレート、２，４−ビス（ｎ−オクチルチオ）−６−（４−ヒドロキシ−３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジン、テトラキス［メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）テレフタレート、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、３，９−ビス［１，１−ジメチル−２−（β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝エチル］−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、２，２−ビス［４−（２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロシンナモイルオキシ））エトキシフェニル］プロパン、β−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオン酸ステアリルエステルなどを挙げることができる。
【００５７】
これらの中では、β−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオン酸ステアリルエステル、テトラキス［メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、ｄｌ−α−トコフェロール、トリス（２，６−ジメチル−３−ヒドロキシ−４−ｔ−ブチルべンジル）イソシアヌレート、トリス［（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシエチル］イソシアヌレート、３，９−ビス［１，１−ジメチル−２−｛β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝エチル］−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカンが好ましい。
【００５８】
また、フェノール系酸化防止剤としては市販品を使用することもでき、例えばイルガノクス１０１０（Ｉｒｇａｎｏｘ１０１０、チバ・スペシャリティ・ケミカルズ社、商標）、イルガノクス１０７６（Ｉｒｇａｎｏｘ１０７６、チバ・スペシャリティ・ケミカルズ社、商標）、イルガノクス１３３０（Ｉｒｇａｎｏｘ１３３０、チバ・スペシャリティ・ケミカルズ社、商標）、イルガノクス３１１４（Ｉｒｇａｎｏｘ３１１４、チバ・スペシャリティ・ケミカルズ社、商標）、イルガノクス３１２５（Ｉｒｇａｎｏｘ３１２５、チバ・スペシャリティ・ケミカルズ社、商標）、ＢＨＴ（武田薬品工業社、商標）、シアノクス１７９０（Ｃｙａｎｏｘ１７９０、サイアナミド社、商標）、スミライザーＧＡ−８０（ＳｕｍｉｌｉｚｅｒＧＡ−８０、住友化学社、商標）などを挙げることができる。
【００５９】
リン系酸化防止剤としては、従来から酸化防止剤として使用されているリン系の酸化防止剤を使用できる。
具体的には、トリオクチルホスファイト、トリラウリルホスファイト、トリデシルホスファイト、オクチル−ジフェニルホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、トリフェニルホスファイト、トリス（ブトキシエチル）ホスファイト、トリス（ノニルフェニル）ホスファイト、ジステアリルペンタエリスリトールジホスファイト、テトラ（トリデシル）−１，１，３−トリス（２−メチル−５−ｔ−ブチル−４−ヒドロキシフエニル）ブタンジホスファイト、テトラ（Ｃ₁₂〜Ｃ₁₅混合アルキル）−４，４’−イソプロピリデンジフェニルジホスファィト、テトラ（トリデシル）−４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）ジホスファイト、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）ホスファイト、トリス（モノ・ジ混合ノニルフェニル）ホスフアイト、水素化−４，４’−イソプロピリデンジフェノールポリホスファイト、ビス（オクチルフェニル）・ビス［４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）］・１，６−ヘキサンジオールジホスファイト、フェニル・４，４’−イソプロピリデンジフェノール・ペンタエリスリトールジホスファイト、トリス［４，４’−イソプロピリデンビス（２−ｔ−ブチルフェノール）］ホスファイト、フェニル・ジイソデシルホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、トリス（１，３−ジ−ステアロイルオキシイソプロピル）ホスファイト、４，４’−イソプロピリデンビス（２−ｔ−ブチルフェノール）・ジ（ノニルフェニル）ホスファイト、９，１０−ジ−ヒドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド、ビス（２，４−ジ−ｔ−ブチル−６−メチルフェニル）・エチルホスファイト、２−［｛２，４，８，１０−テトラキス（１，１−ジメチルエチル）ジベンゾ（Ｄ，Ｆ）（１，３，２）−ジオキサホスフェフィン−６−イル｝オキシ］−Ｎ，Ｎ−ビス〔［｛２，４，８，１０−テトラキス（１，１−ジメチルエチル）ジベンゾ（Ｄ，Ｆ）（１，３，２）−ジオキサホスフェフィン−６−イル｝オキシ］エチル〕エタンアミンなどを挙げることができる。
また、ビス（ジアルキルフェニル）ペンタエリスリトールジホスファイトエステルは下記一般式（VI）
【００６０】
【化３】

【００６１】
で示されるスピロ型や下記一般式（VII)
【００６２】
【化４】

【００６３】
で示されるケージ型ものも使用できる。通常はこのようなホスファイトエステルを製造する方法から生じる経済的理由のために両異性体の混合物を最も多く使用できる。
ここで、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷は、水素または炭素原子数１〜９のアルキル基、特に分枝のあるアルキル基、なかでもｔ−ブチル基が好ましく、またフェニル基におけるその置換位置は２，４，６位が最も好ましい。好適なホスファイトエステルは、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェエル）ベンタエリスリトールジホスファイト等であり、また炭素とリンとが直接結合した構造を持つホスフォナイト、例えばテトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレンジホスフォナイトなどの化合物も挙げることができる。
【００６４】
リン系酸化防止剤としては市販品を使用することもでき、例えばイルガフォス１６８（Ｉｒｇａｆｏｓ１６８、チバ・スペシャリティ・ケミカルズ社、商標）、イルガフォス１２（Ｉｒｇａｆｏｓ１２、チバ・スペシャリティ・ケミカルズ社、商標）、イルガフォス３８（Ｉｒｇａｆｏｓ３８、チバ・スペシャリティ・ケミカルズ社、商標）、アデカスタブ３２９Ｋ（ＡＤＫＳＴＡＢ３２９Ｋ、旭電化社、商標）、アデカスタブＰＥＰ３６（ＡＤＫＳＴＡＢ ＰＥＰ３６、旭電化社、商標）、アデカスタブＰＥＰ−８（ＡＤＫＳＴＡＢ ＰＥＰ−８、旭電化社、商標）、Ｓａｒｄｓｔａｂ Ｐ−ＥＰＱ（クラリアント社、商標）、ウエストン６１８（Ｗｅｓｔｏｎ ６１８、ＧＥ社、商標）、ウエストン６１９Ｇ（Ｗｅｓｔｏｎ ６１９Ｇ、ＧＥ社、商標）、ウエストン−６２４（Ｗｅｓｔｏｎ−６２４、ＧＥ社、商標）などを挙げることができる。
【００６５】
その他に、リン系酸化防止剤として、特開平１０−５３５９５号公報，特開平１０−１０１６８７号公報，特開平１０−１１４７８４号公報，特開平１０−１２０６９１号公報，特開平１０−１２０６９３号公報，特開平１０−１２０６９４号公報，特開平１０−１５２４９４号公報，特開平１０−１５２４９６号公報，特開平１０−１５８２８３号公報，特開平１０−１５８２８５号公報，特開平１０−１８２６７５号公報，特開平１０−２５９１９０号公報，特開平１０−２５９１９３号公報，特開平１０−２７３４９３号公報，特開平１０−２７３４９４号公報，特開平１０−２９８３４８号公報に記載のものも好適に使用することができる。
【００６６】
イオウ系酸化防止剤としては、従来から酸化防止剤として使用されているイオウ系の酸化防止剤を使用できる。
具体的には、ジラウリルチオジプロピオネート，ジミリスチルチオジプロピオネート，ジステアリルチオジプロピオネート等のジアルキルチオジプロピオネート、ブチルチオプロピオン酸、オクチルチオプロピオン酸、ラウリルチオプロピオン酸、ステアリルチオプロピオン酸等のアルキルチオプロピオン酸の多価アルコール（例えばグリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、トリスヒドロキシエチルイソシアヌレート）のエステル（例えばペンタエリスリトールテトララウリルチオプロピオネート）などを挙げることができる。
【００６７】
イオウ系酸化防止剤としては市販品を使用することもでき、例えばＤＳＴＰ（ヨシトミ）（吉富社、商標）、ＤＬＴＰ（ヨシトミ）（吉富社、商標）、ＤＬＴＯＩＢ（吉富社、商標）、ＤＭＴＰ（ヨシトミ）（吉富社、商標）、Ｓｅｅｎｏｘ ４１２Ｓ（シプロ化成社、商標）、Ｃｙａｎｏｘ １２１２（サイアナミド社、商標）などを挙げることができる。
【００６８】
ビタミン系酸化防止剤としては、従来から酸化防止剤として使用されているビタミン系の酸化防止剤を使用できる。
具体的には、酢酸ｄ−α−トコフェロール，コハク酸ｄ−α−トコフェロール，ｄ−α−トコフェロール，ｄ−β−トコフェロール，ｄ−γ−トコフェロール，ｄ−δ−トコフェロール，ｄ−α−トコトリエノール，ｄ−β−トコフェトリエノール，ｄ−γ−トコフェトリエノール，ｄ−δ−トコフェトリエノール等の天然品、ｄｌ−α−トコフェロール，酢酸ｄｌ−α−トコフェロール，コハク酸ｄｌ−α−トコフェロールカルシウム，ニコチン酸ｄｌ−α−トコフェロール等の合成品を挙げることができる。
【００６９】
ビタミン系酸化防止剤としては市販品を使用することもでき、例えばトコフェロール（エーザイ社製），イルガノクスＥ２０１（ＩｒｇａｎｏｘＥ２０１、チバ・スペシャリティ・ケミカルズ社、商標、化合物名；２，５，７，８−テトラメチル−２（４’，８’，１２’−トリメチルトリデシル）クマロン−６−オール）などを挙げることができる。
【００７０】
ラクトン系酸化防止剤としては、従来から酸化防止剤として使用されているラクトン系の酸化防止剤を使用できる。例えば、特開平７−２３３１６０号公報、特開平７−２４７２７８号公報に記載されているものを使用できる。また、ＨＰ−１３６（チバ・スペシャリティ・ケミカルズ社、商標、化合物名；５，７−ジ−ｔ−ブチル−３−（３，４−ジメチルフェニル）−３Ｈ−ベンゾフラン−２−オン）などの市販品も使用できる。
【００７１】
（ｉｉ）成分のうち、発錆防止剤については、特に限定されないが、高級脂肪酸金属塩、複化合物、アルカリ金属化合物、アルカリ土類金属化合物、アルキル乳酸金属塩、乳酸金属塩の化合物から好適に選択することができる。
高級脂肪酸金属塩として、炭素数８〜２３の脂肪酸のアルカリ金属塩またはアルカリ土類金属塩を挙げることができる。脂肪酸として、ラウリル酸，ミリスチン酸，パルミチン酸，ステアリン酸，オレイン酸，リノール酸，リノレイン酸を挙げることができ、これらの脂肪酸と塩をつくる金属として、カリウム，ナトリウム，カルシウム，バリウム，マグネシウム，アルミニウムを挙げることができる。
【００７２】
複化合物は、下記一般式（VIII）
Ｍ_x Ａｌ_y （ＯＨ）_2x+3y-2z（Ａ）_z ・ａＨ₂ Ｏ ・・・（VIII）
（ＭはＭｇ、ＣａまたはＺｎを示し、ＡはＣＯ₃ 又はＨＰＯ₄ を示し、ｘ、ｙ、ｚは正数、ａは０又は正数を示す。）
で表される化合物である。具体的には、Ｍｇ₆ Ａｌ₂ （ＯＨ）₁₆ＣＯ₃ ・４Ｈ₂ Ｏ，Ｍｇ₈ Ａｌ₂ （ＯＨ）₂₀ＣＯ₃ ・５Ｈ₂ Ｏ，Ｍｇ₅ Ａｌ₂ （ＯＨ）₁₄ＣＯ₃ ・４Ｈ₂ Ｏ，Ｍｇ₁₀Ａｌ₂ （ＯＨ）₂₂（ＣＯ₃ ）₂ ・４Ｈ₂ Ｏ，Ｍｇ₆ Ａｌ₂ （ＯＨ）₁₆ＨＰＯ₄ ・４Ｈ₂ Ｏ，Ｃａ₆ Ａｌ₂ ＣＯ₃ ・４Ｈ₂ Ｏ，Ｚｎ₆ Ａｌ₆ （ＯＨ）₁₆ＣＯ₃ ・４Ｈ₂ Ｏなどを挙げることができる。また、特開平７−３１６３５４号公報（Ｍｇ，Ｚｎ，Ａｌ含有化合物），特公平７−２８５８号公報（Ａｌ，Ｌｉ含有化合物）に記載された化合物も使用できる。
【００７３】
アルカリ金属化合物として、酸化ナトリウム，酸化カリウム，水酸化ナトリウム，水酸化カリウム，アルミン酸ソーダ，ケイ酸ソーダ，炭酸ナトリウム，炭酸カリウムなどを挙げることができる。
アルカリ土類化合物として、酸化カルシウム，酸化マグネシウム，水酸化カルシウム，水酸化マグネシウム，炭素カルシウムなどを挙げることができる。
【００７４】
アルキル乳酸金属塩は、重合度２の乳酸（２−ラクチル乳酸）とステアリン酸エステル化反応物（ステアリル乳酸）のカルシウム塩を主成分とし、これと少量の関連酸類との塩との混合物であるステアリル酸カルシウムが主に使用できる。乳酸金属塩としては、乳酸カルシウムが一般的であるが、乳酸バリウム，乳酸亜鉛，乳酸マグネシウム等も使用できる。
【００７５】
上記（ｉｉ）成分の配合量は、（ｉ）成分の結晶性ポリプロピレン１００重量部に対して、好ましくは０．００５〜２重量部、さらに好ましくは０．０１〜１重量部、特に好ましくは０．０２〜０．５重量部である。量が少なすぎると、加工安定性，耐熱老化性，耐腐食性等の安定性の向上効果が十分にでない場合があり、量が多すぎると、量に見合った安定性の向上効果がでない場合があり、また引張強度などが低下する場合がある。
【００７６】
（ｉｉｉ）成分
本発明の組成物においては、必要により重金属不活性化剤を併用することによって、耐重金属性（耐金属老化性）を改善することができる。
重金属不活性化剤として、具体的には、ベンゾトリアゾール、２，４，６−トリアミノ−１，３，５−トリアジン、３，９−ビス［２−（３，５−ジアミノ−２，４，６−トリアザフェニル）エチル］−２，４，８，１０−テトラオキサスピロ［５．５］ウンデカン、エチレンジアミン−テトラアセチックアシッド、エチレンジアミン−テトラアセチックアシッドのアルカリ金属塩（Ｌｉ，Ｎａ，Ｋ）塩、Ｎ，Ｎ’−ジサリシリデン−エチレンジアミン、Ｎ，Ｎ’−ジサリシリデン−１，２−プロピレンジアミン、Ｎ，Ｎ”−ジサリシリデン−Ｎ’−メチル−ジプロピレントリアミン、３−サリシロイルアミノ−１，２，４−トリアゾール、デカメチレンジカルボキシリックアシッド−ビス（Ｎ’−サリシロイルヒドラジド）、ニッケル−ビス（１−フェニル−３−メチル−４−デカノイル−５−ピラゾレート）、２−エトキシ−２’−エチルオキサニリド、Ｎ，Ｎ−ジエチル−Ｎ’，Ｎ’−ジフェニルオキサミド、Ｎ，Ｎ’−ジエチル−Ｎ，Ｎ’−ジフェニルオキサミド、オキサリックアシッド−ビス（ベンジリデンヒドラジド）、チオジプロピオニックアシッド−ビス（ベンジリデンヒドラジド）、イソフタリックアシッド−ビス（２−フェノキシプロピオニルヒドラシド）、ビス（サリシロイルヒドラジン）、Ｎ−サリシリデン−Ｎ’−サリシロイルヒドラゾン、Ｎ，Ｎ’−ビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニル］ヒドラジン、トリス［２−ｔ−ブチル−４−チオ（２’−メチル−４’−ヒドロキシ−５’−ｔ−ブチルフェニル）−５−メチルフェニル］ホスファイト、ビス［２−ｔ−ブチル−４−チオ（２’−メチル−４’−ヒドロキシ−５’−ｔ−ブチルフェニル）−５−メチルフェニル］ペンタエリスリトール−ジホスファイト、テトラキス［２−ｔ−ブチル−４−チオ（２’−メチル−４’−ヒドロキシ−５’−ｔ−ブチルフェニル）−５−メチルフェニル］−１，６−ヘキサメチレン−ビス（Ｎ−ヒドロキシエチル−Ｎ−メチルセミカルバジド）ジホスファイト、テトラキス［２−ｔ−ブチル−４−チオ（２’−メチル−４’−ヒドロキシ−５’−ｔ−ブチルフェニル）−５−メチルフェニル］−１，１０−デカメチレン−ジ−カルボキシリックアシッド−ジ−ヒドロキシエチルカルボニルヒドラジド−ジホスファイト、テトラキス［２−ｔ−ブチル−４−チオ（２’−メチル−４’−ヒドロキシ−５’−ｔ−ブチルフェニル）−５−メチルフェニル］−１，１０−デカメチレン−ジ−カルボキシリックアシッド−ジ−サリシロイルヒドラジド−ジホスファイト、テトラキス［２−ｔ−ブチル−４−チオ（２’−メチル−４’−ヒドロキシ−５’−ｔ−ブチルフェニル）−５−メチルフェニル］−ジ（ヒドロキシエチルカルボニル）ヒドラジド−ジホスファイト、テトラキス［２−ｔ−ブチル−４−チオ（２’−メチル−４’−ヒドロキシ−５’−ｔ−ブチルフェニル）−５−メチルフェニル］−Ｎ，Ｎ’−ビス（ヒドロキシエチル）オキサミド−ジホスファイト、Ｎ，Ｎ’−ビス［２−〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシ〕エチル］オキサミド等を挙げることができる。
【００７７】
上記（ｉｉｉ）成分は、単独で使用しても、二種以上組み合わせて使用してもよく、その配合量は、（ｉ）成分の結晶性ポリプロピレン１００重量部に対して、好ましくは０．０１〜１重量部、さらに好ましくは０．０５〜０．５重量部である。量が少なすぎると、耐重金属性の向上効果が十分にでない場合があり、量が多すぎると、量に見合った耐重金属性の向上効果がでない場合があり、また引張強度などが低下する場合がある。
【００７８】
（ｉｖ）成分
本発明の組成物においては、必要によりラジカル発生剤を併用することによって、樹脂の流動性を改善することができる。
ラジカル発生剤として、具体的には、ベンゾイルパーオキサイド、ｔ−ブチルパーベンゾエート、ｔ−ブチルパーアセテート、ｔ−ブチルパーオキシイソプロピルカーボネート、２，５−ジ−メチル−２，５−ジ（ヘンゾイルパーオキシ）ヘキサン、２，５−ジ−メチル−２，５−ジ（ヘンゾイルパーオキシ）ヘキシン−３、ｔ−ブチル−ジ−パーアジペート、ｔ−ブチルパーオキシ−３，３，５−トリメチルヘキサノエート、メチル−エチルケトンパーオキサイド、シクロヘキサノンパーオキサイド、ジ−ｔ−ブチルパーオキサイド、ジキュミルパーオキサイド、２，５−ジ−メチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、２，５−ジ−メチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３、１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン、ｔ−ブチルキュミルパーオキサイド、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、ｐ−メンタンハイドロパーオキサイド、ジ−イソプロピルベンゼンハイドロパーオキサイド、キュメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド、ｐ−サイメンハイドロパーオキサイド、１，１，３，３−テトラ−メチルブチルハイドロパーオキサイド、２，５−ジ−メチル−２，５−ジ（ハイドロパーオキシ）ヘキサン、トリメチルシリル−キュミルパーオキサイド、２，５−ジ−メチル−２，５−ビス（トリメチルシリルパーオキシ）ヘキサン、２，５−ジ−メチル−２，５−ビス（トリメチルシリルパーオキシ）ヘキシン−３、１，３−ビス（トリメチルシリルパーオキシイソプロピル）ベンゼン等を挙げることができる。
【００７９】
上記（ｉｖ）成分は、単独で使用しても、二種以上組み合わせて使用してもよく、その配合量は、（ｉ）成分の結晶性ポリプロピレン１００重量部に対して、好ましくは０．００１〜０．５重量部、さらに好ましくは０．０１〜０．２重量部である。量が少なすぎると、樹脂の流動性向上効果が十分にでない場合があり、量が多すぎると、樹脂の成形加工が困難になる場合があり、また引張強度などが低下する場合がある。
【００８０】
本願の第二発明である成形体は、前記の結晶性ポリプロピレン樹脂組成物を用いて成形することにより得ることができる。本発明の成形体としては、自動車内装材、架電製品のハウジング材やフィルム、シート等を挙げることができる。また、成形方法としては、射出成形法、圧縮成形法、射出圧縮成形法、ガスアシスト射出成形法、押し出し成形法、ブロー成形法等を挙げることができる。
【００８１】
なお、本発明の成形体は、所望に応じ前記結晶性ポリプロピレン組成物に、帯電防止剤や防曇剤などの表面機能用添加剤、アンチブロッキンング剤、耐候剤、滑剤、造核剤、着色剤、無滴剤、難燃剤、難燃助剤、抗菌剤、無機又は有機充填剤などの公知の添加剤を配合して樹脂組成物を調製した上で製造してもよい。
【００８２】
【実施例】
以下、本発明を実施例により、さらに詳しく説明するが、本発明はこれらの例によってなんら限定されるものではない。
〔製造例１〕
（固体触媒成分の調製）
窒素で置換した内容積５リットルの攪拌器付三つ口フラスコにジエトキシマグネシウム１６０ｇを投入し、さらに脱水処理したオクタンを６００ミリリットル加えた。４０℃に加熱し四塩化珪素２４ミリリットルを加え、２０分攪拌し、ジブチルフタレートを１６ミリリットル加えた。溶液を８０℃まで昇温し、引き続き四塩化チタンを滴下ロートを用いて７７０ミリリットル滴下した。内温を１２５℃とし２時間接触反応させた。その後、１２５℃の脱水オクタンを用いて充分洗浄を行った。さらに四塩化チタンを１，２２０ミリリットル加え、内温を１２５℃とし２時間接触反応させた。その後１２５℃の脱水オクタンを用いて充分洗浄を行い固体成分［Ａ］を得た。
【００８３】
（予備重合）
窒素で置換した内容積１リットルの攪拌器付三つ口フラスコに固体成分［Ａ］を４８ｇ投入した。さらに脱水処理したｎ−ヘプタンを４００ミリリットル加えた。４０℃に加熱しトリエチルアルミニウム２．０ミリリットルとジイソペンチルジメトキシシランを６．３ミリリットル加えた。これにプロピレンを常圧で流通させ２時間反応させた。その後、固体成分を脱水ｎ−ヘプタンを用いて充分洗浄を行い触媒成分を得た。
【００８４】
（重合）
内容積１０リットルの攪拌器付ステンレス製オートクレーブを十分乾燥し、窒素置換の後、内部に脱水処理したヘプタンを６リットル加えた。攪拌しながら内温が８０℃になるまで昇温した。昇温後、トリエチルアルミニウム４０．０ミリモル、続いてジシクロペンチルジメトキシシラン５．０ミリモル加え、さらに上記固体触媒製分をＴｉ当たりで０．１ミリモル加え、水素３．０ｋｇ／ｃｍ² Ｇを導入後、全圧が８．０ｋｇ／ｃｍ² Ｇになるまでプロピレンを導入した。全圧が８．０ｋｇ／ｃｍ² Ｇになった時点から１時間重合を実施した。その後降温、脱圧し内容物を取り出し、エバポレーターで溶媒を除去し、真空乾燥してポリプロピレンを得た。
【００８５】
〔製造例２〕
製造例１において、重合時の水素導入量を２．８ｋｇ／ｃｍ² Ｇとした以外は製造例１と同様にしてポリプロピレンを製造した。
〔製造例３〕
製造例１において、重合時の水素導入量を１．０ｋｇ／ｃｍ² Ｇとした以外は製造例１と同様にしてポリプロピレンを製造した。
〔製造例４〕
製造例１において、重合時の水素導入量を０．５ｋｇ／ｃｍ² Ｇとした以外は製造例１と同様にしてポリプロピレンを製造した。
〔製造例５〕
製造例１において、重合時の水素導入量を０．１ｋｇ／ｃｍ² Ｇとした以外は製造例１と同様にしてポリプロピレンを製造した。
【００８６】
〔製造例６〕
（固体触媒成分の調製）
窒素で置換した内容積５リットルの攪拌器付三つ口フラスコにジエトキシマグネシウム１６０ｇを投入し、さらに脱水処理したｎ−ヘプタンを６００ミリリットル加えた。４０℃に加熱し四塩化珪素２４ミリリットルを加え、２０分攪拌し、ジエチルフタレートを２５ミリリットル加えた。溶液を８０℃まで昇温し、引き続き四塩化チタンを滴下ロートを用いて４７０ミリリットル滴下した。内温を１１０℃とし２時間接触反応させた。その後、９０℃の脱水ｎ−ヘプタンを用いて充分洗浄を行った。さらに四塩化チタンを７７０ミリリットル加え、内温を１１０℃とし２時間接触反応させた。その後９０℃の脱水ｎ−ヘプタンを用いて充分洗浄を行い固体成分［Ｂ］を得た。
【００８７】
（予備重合）
窒素で置換した内容積１リットルの攪拌器付三つ口フラスコに固体成分［Ｂ］を４８ｇ投入し、さらに脱水処理したｎ−ヘプタンを４００ミリリットル加えた。１０℃に保持しトリエチルアルミニウム２．７ミリリットルとシクロヘキシルメチルジメトキシシランを２．０ミリリットル加えた。これにプロピレンを常圧で流通させ２時間反応させた。その後、固体成分を脱水ｎ−ヘプタンを用いて充分洗浄を行い触媒成分を得た。
【００８８】
（重合）
内容積１０リットルの攪拌器付ステンレス製オートクレーブを十分乾燥し、窒素置換の後、内部に脱水処理したヘプタンを６リットル加えた。攪拌しながら内温が８０℃になるまで昇温した。昇温後、トリエチルアルミニウム４０．０ミリモル、続いてシクロヘキシルメチルジメトキシシラン５．０ミリモル加え、さらに上記固体触媒製分をＴｉ当たりで０．１ミリモル加え、水素１．１ｋｇ／ｃｍ² Ｇを導入後、全圧が８．０ｋｇ／ｃｍ² Ｇになるまでプロピレンを導入した。全圧が８．０ｋｇ／ｃｍ² Ｇになった時点から１時間重合を実施した。その後降温、脱圧し内容物を取り出し、エバポレーターで溶媒を除去し、真空乾燥してポリプロピレンを得た。
【００８９】
〔製造例７〕
製造例６において、重合時の水素導入量を０．５ｋｇ／ｃｍ² Ｇとした以外は製造例６と同様にポリプロピレンを製造した。
〔製造例８〕
製造例６において、重合時の水素導入量を０．２ｋｇ／ｃｍ² Ｇとした以外は製造例６と同様にポリプロピレンを製造した。
〔製造例９〕
製造例６において、重合時の水素導入量を０．０１ｋｇ／ｃｍ² Ｇとした以外は製造例６と同様にポリプロピレンを製造した。
実施例１〜１８及び比較例１〜４
上記の製造例１〜９により得られたポリプロピレンパウダーに第１表に示す添加剤を加え、よく混合した後、２０ｍｍ単軸混練押出機にて溶融混練造粒し、ペレットを作成した。ペレットの一部につき、所定の樹脂特性（構造特性）の測定を行い、残りのペレットを射出成形して下記の要領で各種試験片を作製し機械的特性の測定及び安定性の評価を実施した。その結果を第１表に示す。
【００９０】
なお、安定性の評価のうち耐金属老化性については、別の試験片を作成し評価した。
（機械的特性の測定用試験片）
東芝機械株式会社（製）のＩＳ１００ＦＩＩＩ型射出成形機を用い、樹脂温 度２００℃、金型温度４５℃で試験片を作製した。
（構造特性及び機械的特性の測定方法）
（１）極限粘度［η]
テトラリンに溶解し１３５℃で測定した。
（２）昇温分別法での０℃可溶分量および溶出曲線ピーク温度
重合により得られたポリプロピレンについて、昇温遊離分離法により求める。試料調製は、常温でｏ−ジクロルベンゼン１０ミリリットル中にポリマー７５ｍｇを秤量し、１３５〜１５０℃で１ｈｒ攪拌し溶解させる。カラム内に試料溶液を１３５℃の条件下で０．５ミリリットル注入後、１０℃／ｈｒで０℃まで徐冷してポリマーを充填剤表面に結晶化させる。その際結晶化せずに残ったポリマーの量を０℃可溶分量とした。溶出曲線は冷却後、ｏ−ジクロルベンゼンを２ミリリットル／ｍｉｎにて流通させながらカラム温度を４０℃／ｈｒで昇温させ、随時溶出されるポリマー濃度を赤外検出器にて連続的に測定することによって求める。得られた溶出曲線において、ピーク位置の温度をピーク温度とした。
【００９１】
なお、カラムは４．６ｍｍφ×１５０ｍｍ、充填剤はクロモソルブＰを使用し、溶出曲線の調整は標準試料として直鎖状ＰＥ（ＳＲＭ１４７５）を用い、上記条件で溶出させた際にピーク温度が１００℃( ±０．５）となるように調整した。検出には波長３．４１μｍを用いた。
（３）機械的特性の測定
射出成形で得た試験片について、引張り弾性率、曲げ弾性率、熱変形温度（ＨＤＴ) 、ロックウエル硬度（ＨＲ［Ｒ スケール])をそれぞれＪＩＳ Ｋ ７１１３，Ｋ ７２０３，Ｋ ７２０７，Ｋ ７２０２に準拠して測定した。
【００９２】
（安定性の評価）
（１）プロセス安定性
最初の溶融混練で得られたペレットのＭＩ（ＭＩ₀ ）と、そのペレットを２０ｍｍ単軸混練押出機２７０℃にて更に３回混練造粒して得られたペレットのＭＩ（ＭＩ₃ ）の比ＭＩ₃ ／ＭＩ₀ で比較評価を行った。
（２）発錆防止性
良く研磨した軟鋼板に厚さ５ｍｍのスペーサーを介してペレットを乗せ、２５０℃に加熱したプレス機で３０ｋｇ／ｃｍ² 、３０分間保持した。その後冷却プレスし、鋼板より試料剥取り、鋼板は２５℃、相対湿度１００％に保った容器中に１週間放置した。鋼板表面の発錆状態を標準板（発錆度０〜４）と比較し、評価した。発錆度０は錆なし、発錆度４は全面に非常に発錆した状態を示す。発錆度１以下なら実用上問題ない。
（３）耐金属老化性
樹脂組成物１００重量部に対して、市販の銅粉を０．５重量部配合した混合物を２０ｍｍφ単軸押出機により２００℃にて溶融混練し、次いで成形温度２００℃のプレス成形により厚み１ｍｍ、幅１０ｍｍ、長さ８０ｍｍの試験片を１０本作製した。得られた試験片を１５０℃、空気雰囲気中のギヤオーブン中に試験片の一方を吊るして入れ、試験片１０本中５本が劣化により割れるまでの時間を測定し、この時間を耐金属老化性の指標にした。
【００９３】
【表１】

【００９４】
【表２】

【００９５】
【表３】

【００９６】
【表４】

【００９７】
【表５】

【００９８】
なお、実施例と比較例に使用した添加剤は下記の通りである。
Ａ１：テトラキス［メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン（フェノール系酸化防止剤）
Ａ２：トリス（２，４−ジ−ｔ−ブチル）ホスファイト（リン系酸化防止剤）
Ａ３：３，３’−チオプロピオン酸ジミリスチル（イオウ系酸化防止剤）
Ａ４：２，５，７，８−テトラメチル−２（４’，８’，１２’−トリメチルトリトリデシル）クマロン−６−オール（ビタミン系酸化防止剤）
Ａ５：５，７−ジ−ブチル−３−（３，４−ジメチルフェニル）−３Ｈ−ベンゾフラン−２−オン（ラクトン系酸化防止剤）
【００９９】
Ｂ１：ステアリン酸カルシウム（高級脂肪酸金属塩）
Ｂ２：Ｍｇ_4.5 Ａｌ₁₂（ＯＨ）₁₃ＣＯ₃ ・３．５Ｈ₂ Ｏ（複化合物）
Ｂ３：酸化カルシウム（アルカリ土類金属化合物）
Ｂ４：乳酸カルシウム（乳酸金属塩）
Ｃ１：Ｎ，Ｎ’−ビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニル］ヒドラジン
Ｄ１：１，３−ビス（ｔ−ブチルパーオキシイソプロピル）ベンゼン
第１表において、ほぼ同じ［η］を示す実施例１２と比較例１で比較すると、本発明の結晶性ポリプロピレン組成物は、引張り弾性率、曲げ弾性率、熱変形温度およびロックウェル硬度が優れていることがわかる。同様に、実施例１５と比較例２、実施例１６と比較例３、実施例１８と比較例４の比較においても同様のことが言える。また、比較例２に示すように溶出ピークが本発明の範囲内にある場合でも、０℃可溶分量が多い場合は、物性が低下することも明らかである。また、酸化防止剤、発錆防止剤を使用することにより安定性も改良されていることは明らかである。
【０１００】
【発明の効果】
本発明の新規な結晶性ポリプロピレン樹脂組成物によれば、高剛性化による成形品の薄肉化が図られ、軽量化が可能となり、省資源や生産性の点で有効である。また剛性、耐熱性の向上により、従来ポリスチレン、ＡＢＳ樹脂などを用いていた用途への代替が可能である。また、本発明の成形体は、剛性、耐熱性、耐傷つき性及び安定性が優れているので、自動車内装材や家電製品のハウジング材やフィルム等に好適に使用することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a crystalline polypropylene composition and a molded article formed by molding the crystalline polypropylene composition, and more specifically, a crystalline polypropylene composition having excellent rigidity, heat resistance, scratch resistance and improved stability, and molding the same. It is related with the molded object formed.
[0002]
[Prior art]
Polypropylene resin has excellent heat resistance, chemical resistance, and electrical properties, and also has good rigidity, tensile strength, optical properties, and workability, and is used for injection molding, film molding, sheet molding, blow molding, etc. ing. In addition, it has a light specific gravity and is widely used in fields such as containers and packaging materials. However, depending on the application, these properties are not fully satisfied and their use is limited.
[0003]
Among the above performances, polypropylene is inferior to polystyrene and ABS resin, in particular, in rigidity, heat resistance and scratch resistance. Accordingly, polypropylene cannot be used as a material for producing a molded product that requires rigidity, heat resistance, and scratch resistance, and the polystyrene or ABS can be used as a material for a molded product that requires rigidity and heat resistance. In order to satisfy the quality equivalent to the resin, the molded product must be thick. This hinders the thickness of the molded product and increases the cost of the molded product, and the use of the polypropylene or the polypropylene composition cannot be expanded. If polypropylene has excellent rigidity, heat resistance, scratch resistance, etc., such polypropylene can be used as an alternative to polystyrene and ABS resin, and it can be used for a wide range of applications. Since it can be finished into a molded product, resource saving and cost reduction can be expected.
[0004]
Under such circumstances, known techniques for improving the rigidity of crystalline polypropylene include, for example, pt-butyl benzoic acid aluminum salt, 1,8-2,4-dibenzylidene sorbitol, phosphoric acid 2,2 -There is a method of molding by adding an organic nucleating agent such as methylene bis (4,6-di-t-butylphenyl) sodium, but the cost is not high and economical, and the addition of the organic nucleating agent gives gloss. There is a drawback that impact strength, tensile elongation, etc. are greatly reduced. In addition, as another means for improving the rigidity, there is a method of adding various inorganic fillers such as talc, calcium carbonate, kaolin, etc., but in addition to impairing the lightness and transparency that are characteristic of polypropylene, impact strength, There is a defect that gloss, tensile elongation, workability, etc. are lowered.
On the other hand, polypropylene resins need to further improve stability such as processing stability, heat aging resistance, and corrosion resistance.
[0005]
[Problems to be solved by the invention]
The present invention has been made from the above viewpoint, and provides a novel crystalline polypropylene resin composition having excellent rigidity, heat resistance, scratch resistance and improved stability, and a molded article formed by molding the same. It is intended.
[0006]
[Means for Solving the Problems]
As a result of extensive research, the present inventors have found a specific relationship between the 0 ° C. soluble content measured by the temperature rising fractionation method and the intrinsic viscosity [η] (deciliter / g) measured at 135 ° C. in a tetralin solvent. The present invention has been completed by finding that a resin composition in which an antioxidant or a rusting agent is blended with a novel crystalline polypropylene satisfying the above requirements meets this purpose.
[0007]
  That is, the gist of the present invention is as follows.
1. (I) Intrinsic viscosity [η] measured at 135 ° C. in a tetralin solvent is in the range of 0.5 to 4.0 deciliter / g, and 0 ° C. soluble amount α (% by weight) by a temperature rising fractionation method And the intrinsic viscosity [η] is the following formula (4)
α ≦ 1.11 × [η] ^-0.42 +0.50 ... (4)
A crystalline polypropylene resin composition comprising (ii) at least one compound selected from an antioxidant and a rust inhibitor in crystalline polypropylene satisfying the above relationship.
2. 2. The crystalline polypropylene resin composition as described in 1 above, wherein the intrinsic viscosity [η] is in the range of 0.5 to 3.0 deciliter / g.
3. (I) the crystalline polypropylene makes contact with (a) a magnesium compound, (b) a titanium compound, (c) an electron donor, and (d) a silicon compound at a temperature in the range of 120 to 150 ° C., and The crystalline polypropylene resin composition according to the above 1 or 2, which is polymerized using a solid catalyst component obtained by washing with an inert solvent at a temperature in the range of 100 to 150 ° C.
4). (Ii) The crystalline polypropylene resin composition according to any one of (1) to (3) above, wherein the total amount of components is 0.005 to 2 parts by weight per 100 parts by weight of component (i).
5). Furthermore, the crystalline polypropylene resin composition in any one of said 1-4 formed by mix | blending (iii) heavy metal deactivator and / or (iv) radical generator.
6). (I) In the component, elution curve peak temperature T by temperature rising fractionation method _P (° C.) and the intrinsic viscosity [η] (deciliter / g) measured at 135 ° C. in a tetralin solvent is represented by the following formula (2)
T _P > 1.21 × [η] +116.5 (2)
6. The crystalline polypropylene resin composition according to any one of 1 to 5 above, which is a crystalline polypropylene that satisfies the above relationship.
7). (Ii) The crystalline polypropylene resin composition according to any one of the above 1 to 6, wherein among the components, the antioxidant is a phenol-based, phosphorus-based, sulfur-based, vitamin-based or lactone-based compound.
8). (Ii) Among the components, the rust inhibitor is a higher fatty acid metal salt, a compound compound, an alkali metal compound, an alkaline earth metal compound, an alkyl lactic acid metal salt, or a lactic acid metal salt compound. The crystalline polypropylene resin composition described.
9. The molded object formed by shape | molding the crystalline polypropylene resin composition in any one of said 1-8.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The crystalline polypropylene as the component (i), which is a constituent element of the present invention, has a soluble amount α (wt%) of 0 ° C. by a temperature rising fractionation method and an intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C. It is necessary that g) satisfies the relationship of the following formula (1).
α ≦ 1.11 × [η]^-0.42+1.40 (1)
Preferably, the relationship of the following formula (3) is satisfied. Furthermore, preferably, the relationship of the following formula (4) is satisfied.
α ≦ 1.11 × [η]^-0.42+1.00 (3)
α ≦ 1.11 × [η]^-0.42+0.50 (4)
When the relationship of formula (1) is not satisfied, the rigidity when the resin composition is molded is lowered.
[0009]
Crystalline polypropylene has an elution curve peak temperature T determined by temperature rising fractionation._PIt is preferable that (° C.) and [η] satisfy the relationship of the following formula (2).
T_P> 1.21 × [η] +116.5 (2)
More preferably, the relationship of the following formula (5) is satisfied.
T_P> 1.21 × [η] +117.0 (5)
If the relationship of the above formula (2) is not satisfied, the rigidity when the resin composition is molded may be lowered.
[0010]
In addition, 0 degreeC soluble amount (alpha) (weight%) and elution curve peak temperature T by the temperature rising fractionation method in said crystalline polypropylene_P(° C.) is determined according to the following method.
For sample preparation, 75 mg of polymer is weighed in 10 ml of o-dichlorobenzene at room temperature, and stirred at 135 to 150 ° C. for 1 hour to dissolve. After injecting 0.5 ml of the sample solution into the column under the condition of 135 ° C., the polymer is crystallized on the surface of the filler by slowly cooling to 0 ° C. at 10 ° C./hr. At this time, the amount of polymer remaining without being crystallized was defined as a 0 ° C. soluble amount. The elution curve is that after cooling, the column temperature is raised at 40 ° C./hr while flowing o-dichlorobenzene at 2 ml / min, and the polymer concentration eluted at any time is continuously measured with an infrared detector. Ask for. In the obtained elution curve, the temperature at the peak position was defined as the peak temperature. The column uses 4.6 mmφ × 150 mm, the packing material uses chromosolve P, the elution curve is adjusted using linear PE (SRM1475) as a standard sample, and the peak temperature is 100 ° C. when eluting under the above conditions. It is adjusted to be (± 0.5). A wavelength of 3.41 μm was used for detection.
[0011]
The crystalline polypropylene as the component (i) of the present invention preferably has an intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C. in the range of 0.5 to 4.0 deciliter / g. More preferably, it is the range of 0.5-3.0 deciliter / g. If it is less than 0.5 deciliter / g, the heat resistance when the resin composition is molded may be lowered. Moreover, when it exceeds 4.0 deciliter / g, the rigidity at the time of shape | molding a resin composition may fall.
[0012]
Next, the manufacturing method of said crystalline polypropylene is demonstrated.
In the crystalline polypropylene as component (i) of the present invention, (A) a magnesium compound and a titanium compound were contacted at a temperature of 120 to 150 ° C. in the presence of an electron donating compound and, if necessary, a silicon compound. Thereafter, a solid catalyst component made of an inert solvent washed at a temperature of 100 to 150 ° C., (B) an organoaluminum compound, and (C) a catalyst made of an electron donating compound as the third component as required. Thus, it can be produced by polymerizing propylene or copolymerizing propylene and some α-olefin.
[0013]
Below, each catalyst component, a preparation method, a polymerization method, etc. are demonstrated.
Each catalyst component
(A) Solid catalyst component
The solid catalyst component contains magnesium, titanium, and an electron donor. The following (a) magnesium compound, (b) titanium compound, (c) electrophilic compound, and, if necessary, silicon compound (d) It is formed from the solid catalyst component which consists of these.
(A) Magnesium compound
Although there is no restriction | limiting in particular as a magnesium compound, General formula (I)
MgR¹R²... (I)
The magnesium compound represented by can be preferably used.
[0014]
In the above general formula (I), R¹And R²Is a hydrocarbon group, OR^ThreeGroup (R^ThreeRepresents a hydrocarbon group) or a halogen atom. Where R¹And R²As the hydrocarbon group, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and the like are represented by OR.^ThreeAs the group, R^ThreeRepresents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and the like, and examples of the halogen atom include chlorine, bromine, iodine, fluorine, and the like. R¹And R²May be the same or different.
[0015]
Specific examples of the magnesium compound represented by the general formula (I) include alkylmagnesium such as dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, diphenylmagnesium, and dicyclohexylmagnesium. Aryl magnesium; alkoxy magnesium such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium, dicyclohexyloxymagnesium, allyloxymagnesium; ethylmagnesium chloride, butyl Magnesium chloride, hexyl magnesi Alkylmagnesium halides such as muchloride, isopropylmagnesium chloride, isobutylmagnesium chloride, t-butylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, ethylmagnesium bromide, butylmagnesium bromide, phenylmagnesium chloride, butylmagnesium iodide, arylmagnesium halides; Alkoxymagnesium halides such as butoxymagnesium chloride, cyclohexyloxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide, ethoxymagnesium iodide; allyloxymagnesium halides; magnesium chloride, magnesium bromide, magnesium iodide, etc. It can be mentioned magnesium halide and the like.
[0016]
Among these magnesium compounds, magnesium halide, alkoxymagnesium, alkylmagnesium, and alkylmagnesium halide can be preferably used from the viewpoint of polymerization activity and stereoregularity.
The magnesium compound can be prepared from magnesium metal or a compound containing magnesium.
[0017]
As an example, a method of bringing metal magnesium into contact with halogen and alcohol can be mentioned.
Here, examples of halogen include iodine, chlorine, and fluorine. Examples of the alcohol include methanol, ethanol, propanol, butanol, cyclohexanol, octanol and the like.
[0018]
As another example, Mg (OR^Four)₂A magnesium alkoxy compound represented by the formula:^FourRepresents a hydrocarbon group having 1 to 20 carbon atoms. ) Can be mentioned a method of contacting a halide.
Examples of the halide include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, hydrogen chloride and the like. Among these, silicon tetrachloride is preferable from the viewpoint of polymerization activity and stereoregularity. R above^FourAs an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a hexyl group, an octyl group or a cyclohexyl group; an alkenyl group such as a propenyl group or a butenyl group; a phenyl group , Aryl groups such as tolyl group and xylyl group; aralkyl groups such as phenethyl group and 3-phenylpropyl group.
[0019]
Furthermore, the magnesium compound may be supported on a support such as silica, alumina, or polystyrene.
The above magnesium compounds may be used alone or in combination of two or more. Moreover, other elements, such as halogens, such as iodine, silicon, and aluminum, may be contained, and electron donors, such as alcohol, ether, and esters, may be contained.
[0020]
(B) Titanium compound
Although there is no restriction | limiting in particular as a titanium compound, General formula (II)
TiX¹ _p(OR^Five)_4-p  ... (II)
The titanium compound represented by can be preferably used.
In the above general formula (II), X¹Represents a halogen atom, and among them, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable. R^FiveIs a hydrocarbon group, which may be a saturated or unsaturated group, may have a straight or branched chain, or may be a cyclic group, and may be sulfur, nitrogen, oxygen, silicon, It may contain a heteroatom such as phosphorus. A hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group are preferable, and a linear or branched alkyl group is particularly preferable. OR^FiveWhen a plurality of are present, they may be the same as or different from each other. R^FiveSpecific examples of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, and phenethyl group. p shows the integer of 0-4.
[0021]
Specific examples of the titanium compound represented by the general formula (II) include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, Tetraalkoxy titanium such as tetracyclohexyloxy titanium and tetraphenoxy titanium; titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n -Trihalogenated alkoxytitanium such as butoxytitanium trichloride, ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride Dihalogenated dialkoxytitanium such as diethoxytitanium dibromide; monohalogen such as trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride, tri-n-butoxytitanium chloride And trialkoxy titanium. Among these, a high halogen-containing titanium compound, particularly titanium tetrachloride is preferable from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more.
[0022]
(C) electron donating compound
Examples of the electron-donating compound include alcohols, phenols, ketones, aldehydes, esters of organic acids or inorganic acids, oxygen-containing electron donors such as ethers such as monoethers, diethers or polyethers, ammonia, Nitrogen-containing electron donating compounds such as amines, nitriles and isocyanates can be mentioned. Among these, esters of polyvalent carboxylic acids are preferable, and esters of aromatic polyvalent carboxylic acids are more preferable. From the standpoint of polymerization activity, aromatic monocarboxylic acid monoesters and diesters are particularly preferred. In addition, an aliphatic hydrocarbon having a linear, branched or cyclic organic group in the ester portion is preferable.
[0023]
Specifically, phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid, 5,6,7, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl of dicarboxylic acids such as 8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid, indane-5,6-dicarboxylic acid, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methylhexyl Name dialkyl esters such as syl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 3-ethylpentyl, etc. Can do. Among these, phthalic acid diesters are preferable, and linear or branched aliphatic hydrocarbons having 4 or more carbon atoms in the organic group of the ester portion are preferable.
Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, diethyl phthalate and the like. These compounds may be used alone or in combination of two or more.
[0024]
(D) Silicon compound
In preparation of the solid catalyst component, in addition to the components (a), (b) and (c), optionally as component (d), the following general formula (III)
Si (OR⁶)_qX² _4-q  ... (III)
(R⁶Is a hydrocarbon group, X²Represents a halogen atom, and q represents an integer of 0 to 3. )
The silicon compound represented by these can be used. By using a silicon compound, catalytic activity and stereoregularity may be improved and the amount of fine powder in the produced polymer may be reduced.
[0025]
In the above general formula (III), X²Represents a halogen atom, and among these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R⁶Is a hydrocarbon group, which may be a saturated or unsaturated group, may have a straight or branched chain, or may be a cyclic group, and may be sulfur, nitrogen, oxygen, silicon, It may contain a heteroatom such as phosphorus. A hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group are preferred. OR⁶When a plurality of are present, they may be the same as or different from each other. R⁶Specific examples of these include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, and phenethyl group. q represents an integer of 0 to 3.
[0026]
Specific examples of the silicon compound represented by the general formula (III) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane, diethoxydichlorosilane, triethoxychlorosilane, and propoxytrichlorosilane. , Dipropoxydichlorosilane, tripropoxychlorosilane, and the like. Of these, silicon tetrachloride is particularly preferred. These silicon compounds may be used alone or in combination of two or more.
[0027]
(B) Organoaluminum compound
The organoaluminum compound (B) used for the production of the crystalline polypropylene as component (i) of the present invention is not particularly limited, but those having an alkyl group, halogen atom, hydrogen atom, alkoxy group, aluminoxane, and their Mixtures can be preferably used. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum; dialkyl such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride Examples include aluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; chain aluminoxanes such as methylaluminoxane. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable. Moreover, these organoaluminum compounds may be used alone or in combination of two or more.
[0028]
(C) Third component (electron-donating compound)
For the preparation of the crystalline polypropylene polymerization catalyst of the present invention, (C) an electron donating compound is used as necessary. As this (C) electron donating compound, an organosilicon compound having a Si—O—C bond, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among these, from the viewpoint of polymerization activity and stereoregularity, it is preferable to use an organosilicon compound having an Si—O—C bond, ethers and esters, and particularly an organosilicon compound having an Si—O—C bond. It is preferable.
[0029]
Specific examples of the organosilicon compound having a Si—O—C bond include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane. , Ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyl Dimethoxysilane, t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane, t-butylisobutyldi Toxisilane, t-butyl (s-butyl) dimethoxysilane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t- Butyldecyldimethoxysilane, t-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, cyclohexyl-t- Butyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis ( , 3-dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, t- Butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane , Cyclopentyl (t-butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t-butyl (Isobutoxy) dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, texyltrimethoxysilane, texylisopropoxydimethoxysilane, texyl (t-butoxy) dimethoxysilane, texylmethyldimethoxysilane, texylethyldimethoxysilane , Texylisopropyldimethoxysilane, texylcyclopentyldimethoxysilane, texylmyristyldimethoxysilane, texylcyclohexyldimethoxysilane, and the like.
In addition, the following general formula (IV)
[0030]
[Chemical 1]

[0031]
(Wherein R⁷~ R⁹Represents a hydrogen atom or a hydrocarbon group, which may be the same as or different from each other, and may be bonded to an adjacent group to form a ring. R^TenAnd R¹¹Represents a hydrocarbon group, which may be the same or different from each other, and may be bonded to an adjacent group to form a ring. R¹²And R¹³Represents an alkyl group having 1 to 20 carbon atoms, which may be the same as or different from each other. m is an integer of 2 or more, and n is an integer of 2 or more. )
The silicon compound represented by these can be used.
[0032]
In the above general formula (IV), specifically, R⁷~ R⁹As a straight chain hydrocarbon group such as a hydrogen atom, methyl group, ethyl group or n-propyl group, a branched hydrocarbon group such as isopropyl group, isobutyl group, t-butyl group or texyl group, cyclobutyl group, cyclopentyl And a saturated cyclic hydrocarbon group such as a cyclohexyl group, and an unsaturated cyclic hydrocarbon group such as a phenyl group and a pentamethylphenyl group. Of these, hydrogen and a straight-chain hydrocarbon group having 1 to 6 carbon atoms are preferable, and hydrogen, a methyl group, and an ethyl group are particularly preferable.
[0033]
In the above general formula (IV), R^TenAnd R¹¹As a straight chain hydrocarbon group such as a methyl group, an ethyl group or an n-propyl group, a branched hydrocarbon group such as an isopropyl group, an isobutyl group, a t-butyl group or a texyl group, a cyclobutyl group, a cyclopentyl group or a cyclohexyl group. And unsaturated cyclic hydrocarbon groups such as a phenyl group and a pentamethylphenyl group. These may be the same or different. Of these, a linear hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable.
[0034]
In the general formula (IV), R¹²And R¹³As methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, etc. And a linear or branched alkyl group. These may be the same or different. Among these, Preferably it is a C1-C6 linear hydrocarbon group, Most preferably, it is a methyl group.
[0035]
Specific examples of preferable compounds of the silicon compound represented by the general formula (IV) include neopentyl n-propyldimethoxysilane, neopentyl n-butyldimethoxysilane, neopentyl n-pentyldimethoxysilane, neopentyl n-hexyldimethoxysilane, and neopentyl. n-heptyldimethoxysilane, isobutyl n-propyldimethoxysilane, isobutyl n-butyldimethoxysilane, isobutyl n-pentyldimethoxysilane, isobutyl n-hexyldimethoxysilane, isobutyl n-heptyldimethoxysilane, 2-cyclohexylpropyl n-propyldimethoxysilane , 2-cyclohexylbutyl n-propyldimethoxysilane, 2-cyclohexylpentyl n-propyldimethoxysilane, 2-cyclohexylhe Sil n-propyldimethoxysilane, 2-cyclohexylheptyl n-propyldimethoxysilane, 2-cyclopentylpropyl n-propyldimethoxysilane, 2-cyclopentylbutyl n-propyldimethoxysilane, 2-cyclopentylpentyl n-propyldimethoxysilane, 2-cyclopentyl Hexyl n-propyldimethoxysilane, 2-cyclopentylheptyl n-propyldimethoxysilane, isopentyl n-propyldimethoxysilane, isopentyl n-butyldimethoxysilane, isopentyl n-pentyldimethoxysilane, isopentyl n-hexyldimethoxysilane, isopentyl n-heptyldimethoxy Silane, isopentylisobutyldimethoxysilane, isopentylneopentyldimethoxysilane, diisope Nthyldimethoxysilane, diisoheptyldimethoxysilane, diisohexyldimethoxysilane, and the like.
[0036]
Specific examples of particularly preferred compounds include neopentyl n-propyldimethoxysilane, neopentyl n-pentyldimethoxysilane, isopentylneopentyldimethoxysilane, diisopentyldimethoxysilane, diisoheptyldimethoxysilane, and diisohexyldimethoxysilane. Specific examples of more preferable compounds include neopentyl n-pentyldimethoxysilane and diisopentyldimethoxysilane.
The silicon compound represented by the general formula (IV) can be synthesized by any method. A typical synthesis route is as follows.
[0037]
[Chemical formula 2]

[0038]
In this synthetic route, the starting compound [1] is commercially available or can be obtained by known alkylation, halogenation, and the like. With respect to the compound [1], an organosilicon compound represented by the general formula (IV) can be obtained by a known Grignard reaction.
The above organosilicon compounds may be used alone or in combination of two or more.
[0039]
Specific examples of nitrogen-containing compounds include 2,6-substituted piperidines such as 2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, and N-methyl2,2,6,6-tetramethylpiperidine. 2,5-substituted azolidines such as 2,5-diisopropylazolidine, N-methyl 2,2,5,5-tetramethylazolidine; N, N, N ′, N′-tetramethylmethylenediamine, N Substituted methylenediamines such as 1, N, N ′, N′-tetraethylmethylenediamine; substituted imidazolidines such as 1,3-dibenzylimidazolidine, 1,3-dibenzyl-2-phenylimidazolidine, and the like. it can.
[0040]
Specific examples of phosphorus-containing compounds include triethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethylphenyl phosphite and the like. Phosphites and the like.
Specific examples of the oxygen-containing compound include 2,6-substituted tetrahydrofurans such as 2,2,6,6-tetramethyltetrahydrofuran and 2,2,6,6-tetraethyltetrahydrofuran; 1,1-dimethoxy-2,3 , 4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, dimethoxymethane derivatives such as diphenyldimethoxymethane, and the like.
[0041]
Preparation of solid catalyst components
As the method for preparing the solid catalyst component (A), the above-mentioned (a) magnesium compound, (b) titanium compound, (c) electron donor, and (d) silicon compound as necessary, except for the temperature, What is necessary is just to contact by a normal method and it does not ask | require in particular about a contact procedure. For example, each component may be contacted in the presence of an inert solvent such as a hydrocarbon, or each component may be diluted and previously contacted with an inert solvent such as a hydrocarbon. Examples of the inert solvent include aliphatic hydrocarbons such as octane, decane, and ethylcyclohexane, alicyclic hydrocarbons, and mixtures thereof.
[0042]
Here, a titanium compound is 0.5-100 mol normally with respect to 1 mol of magnesium of said magnesium compound, Preferably, 1-50 mol is used. When this molar ratio deviates from the above range, the catalyst activity may be insufficient. Moreover, said electron donor is 0.01-10 mol normally with respect to 1 mol of magnesium of said magnesium compound, Preferably, 0.05-1.0 mol is used. When this molar ratio deviates from the above range, catalyst activity and stereoregularity may be insufficient. Furthermore, when using a silicon compound, it is 0.001-100 mol normally with respect to 1 mol of magnesium of said magnesium compound, Preferably, 0.005-5.0 mol is used. When this molar ratio deviates from the above range, the effect of improving the catalytic activity and stereoregularity may not be sufficiently exhibited, and the amount of fine powder in the produced polymer may increase.
[0043]
Contact of said (a)-(d) component is performed in the temperature range of 120-150 degreeC after adding all the components, Preferably it is 125-140 degreeC. When the contact temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity is not sufficiently exhibited. The contact is usually performed for 1 minute to 24 hours, preferably 10 minutes to 6 hours. In this case, when the solvent is used, the range varies depending on the type, contact temperature, etc., but usually 0-50 kg / cm.²G, preferably 0-10 kg / cm²Perform in G range. Further, during the contact operation, stirring is preferably performed from the viewpoint of contact uniformity and contact efficiency.
[0044]
Further, it is preferable that the titanium compound is contacted twice or more and is sufficiently supported on the magnesium compound that serves as a catalyst carrier.
When a solvent is used in the contact operation, the solvent is usually used in an amount of 5,000 ml or less, preferably 10 to 1,000 ml, per 1 mol of the titanium compound. If this ratio deviates from the above range, contact uniformity and contact efficiency may deteriorate.
[0045]
The solid catalyst component obtained by the above contact is washed with an inert solvent at a temperature of 100 to 150 ° C, preferably 120 to 140 ° C. When this washing temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity may not be sufficiently exhibited. Examples of the inert solvent include aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarbons such as toluene and xylene, tetrachloroethane, chlorofluorocarbons, and the like. And halogenated hydrocarbons or mixtures thereof. Of these, aliphatic hydrocarbons are preferably used.
[0046]
There are no particular restrictions on the cleaning method, but methods such as decantation and filtration are preferred. The amount of inert solvent used, the washing time, and the number of washings are not particularly limited, but are usually 100 to 100,000 milliliters, preferably 1,000 to 50,000 milliliters of solvent per mole of magnesium compound. Is usually used for 1 minute to 24 hours, preferably 10 minutes to 6 hours. If this ratio deviates from the above range, cleaning may be incomplete.
[0047]
The range of the pressure at this time varies depending on the type of solvent, the washing temperature, etc., but is usually 0 to 50 kg / cm.²G, preferably 0-10 kg / cm²Perform in G range. Further, during the cleaning operation, it is preferable to perform stirring from the viewpoint of cleaning uniformity and cleaning efficiency.
The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as hydrocarbon.
[0048]
Polymerization method
The amount of the catalyst component used in the production of the crystalline polypropylene of the present invention is not particularly limited. However, the solid catalyst component of the component (A) is usually converted into titanium atoms per liter of reaction volume. An amount of 0.00005 to 1 mmol is used, and the organoaluminum compound (B) has an aluminum / titanium atomic ratio of usually 1 to 1,000, preferably 10 to 500. The correct amount is used. When this atomic ratio deviates from the above range, the catalyst activity may be insufficient. When (C) an electron donating compound such as an organosilicon compound is used as the third component, the (C) electron donating compound / (B) organoaluminum compound molar ratio is usually 0.001 to 5.0, The amount is preferably 0.01 to 2.0, more preferably 0.05 to 1.0. If this molar ratio is outside the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when prepolymerization is performed, it can be further reduced.
[0049]
In the polymerization of crystalline propylene according to the present invention, from the viewpoint of polymerization activity, stereoregularity, and polymer powder form, the olefin may be preliminarily polymerized first and then the main polymerization may be performed as desired. In this case, the olefin is usually 1 in the presence of a catalyst obtained by mixing (A) the solid catalyst component, (B) the organoaluminum compound and, if necessary, (C) the electron donating compound at a predetermined ratio. Normal pressure to 50 kg / cm at temperatures in the range of ~ 100 ° C²Prepolymerization is performed at a pressure of about G, and then propylene is main-polymerized in the presence of a catalyst and a prepolymerized product.
[0050]
As the olefin used in the prepolymerization, the general formula (V)
R¹⁴-CH = CH₂... (V)
The α-olefin represented by the formula is preferred.
In the above general formula (V), R¹⁴Is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be a saturated group or an unsaturated group. Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene, vinylcyclohexane , Butadiene, isoprene, piperylene and the like. These olefins may be used alone or in combination of two or more. Among the olefins, ethylene and propylene are particularly preferable.
[0051]
There are no particular restrictions on the type of polymerization in this main polymerization, and it can be applied to any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization, etc., and further applicable to both batch polymerization and continuous polymerization. Yes, it can be applied to two-stage polymerization and multi-stage polymerization under different conditions.
Furthermore, with respect to the reaction conditions, the polymerization pressure is not particularly limited, and is usually from atmospheric pressure to 80 kg / cm from the viewpoint of polymerization activity.²G, preferably 2-50 kg / cm²G and the polymerization temperature are usually selected appropriately in the range of 0 to 200 ° C, preferably 20 to 90 ° C, and more preferably 40 to 90 ° C. The polymerization time depends on the polymerization temperature of the raw material propylene and cannot be determined generally, but is usually 5 minutes to 20 hours, preferably about 10 minutes to 10 hours.
[0052]
The molecular weight can be adjusted by adding a chain transfer agent, preferably hydrogen. Further, an inert gas such as nitrogen may be present.
It is also possible to polymerize in two or more stages under different polymerization conditions.
In the polymerization for producing crystalline polypropylene as the component (i) of the present invention, the catalyst component is prepared by mixing the component (A), the component (B), and the component (C) at a predetermined ratio. After the contact, propylene may be introduced immediately for polymerization, or after the contact, after aging for about 0.2 to 3 hours, propylene may be introduced for polymerization. Further, the catalyst component can be supplied in a suspended state in an inert solvent or propylene.
[0053]
In the polymerization for producing the crystalline polypropylene as the component (i) of the present invention, the post-treatment after the polymerization can be performed by a conventional method. That is, in the gas phase polymerization method, after the polymerization, a nitrogen gas stream or the like may be passed through the polymer powder derived from the polymerization vessel in order to remove olefins contained therein, or as desired. Accordingly, pelletization may be performed by an extruder, and in this case, a small amount of water, alcohol, or the like may be added in order to completely deactivate the catalyst. In the bulk polymerization method, after polymerization, the monomer is completely separated from the polymer derived from the polymerization vessel, and then pelletized.
[0054]
In the main polymerization of propylene, in addition to propylene, some ethylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, as long as the produced crystalline polypropylene satisfies the relationship of the above formula (1). Copolymerization with an α-olefin such as heptene, 1-octene, 1-decene, 3-methyl-1-pentene, 4-methyl-1-pentene may be performed.
[0055]
Next, the additive of (ii) component mix | blended with the crystalline polypropylene of (i) component, (iii) component, and the additive of (iv) component mix | blended as needed are demonstrated.
(ii) completionMin
Among the components (ii), the antioxidant is not particularly limited, but can be suitably selected from phenol-based, phosphorus-based, sulfur-based, vitamin-based, and lactone-based antioxidants.
[0056]
As the phenolic antioxidant, a phenolic antioxidant conventionally used as an antioxidant can be used.
Specifically, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6- Di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6- t-butylphenol, 2-t-butyl-2-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, dl-α-tocopherol, t-butylhydroquinone, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-buty Denbis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), 4, 4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-) -T-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl)- 4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl Ester, tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tris (3,5-di-tert-butyl- -Hydroxybenzyl) isocyanurate, tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) ) Isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, tetrakis [methylene-3- (3 5-Di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,2′-methylenebis (4-methyl-6-tert-butylphenol) terephthalate, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2- (β- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- ( 3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester, etc. Can do.
[0057]
Among these, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearyl ester, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl- 4-hydroxybenzyl) benzene, dl-α-tocopherol, tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, tris [(3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5) Methylphenyl) propionyloxy} ethyl] -2,4,8,10-spiro [5,5] undecane is preferred.
[0058]
Commercially available products may also be used as the phenolic antioxidant, such as Irganox 1010 (Irganox 1010, Ciba Specialty Chemicals, Inc.), Irganox 1076 (Irganox 1076, Ciba Specialty Chemicals, Inc.), Irganox. 1330 (Irganox 1330, Ciba Specialty Chemicals, Trademark), Irganox 3114 (Irganox 3114, Ciba Specialty Chemicals, Trademark), Irganox 3125 (Irganox 3125, Ciba Specialty Chemicals, Trademark), BHT (Takeda Pharmaceutical Company Limited) ), Cyanox 1790 (Cyanox 1790, Cyanamid Co., Ltd.), Sumilizer GA-80 (Sumilizer GA- 0, Sumitomo Chemical Co., Ltd., trademark), and the like.
[0059]
As the phosphorus-based antioxidant, a phosphorus-based antioxidant conventionally used as an antioxidant can be used.
Specifically, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris (butoxy) Ethyl) phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) Butanediphosphite, tetra (C₁₂~ C₁₅Mixed alkyl) -4,4′-isopropylidene diphenyl diphosphite, tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite, tris (3,5-di-t- Butyl-4-hydroxyphenyl) phosphite, tris (mono-dimixed nonylphenyl) phosphite, hydrogenated-4,4′-isopropylidenediphenol polyphosphite, bis (octylphenyl) bis (4,4′- Butylidenebis (3-methyl-6-tert-butylphenol)] 1,6-hexanediol diphosphite, phenyl 4,4'-isopropylidenediphenol pentaerythritol diphosphite, tris [4,4'-isopropyl Redenbis (2-tert-butylphenol)] phosphite, Fe Di-isodecyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, tris (1,3-di-stearoyloxyisopropyl) phosphite, 4,4′-isopropylidenebis (2-t-butylphenol) di ( Nonylphenyl) phosphite, 9,10-di-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, bis (2,4-di-t-butyl-6-methylphenyl) .ethylphos Phyto, 2-[{2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo (D, F) (1,3,2) -dioxaphosphine-6-yl} oxy]- N, N-bis [[{2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo (D, F) (1,3,2) -dioxaphosphine , And the like down-6-yl} oxy] ethyl] ethanamine.
Bis (dialkylphenyl) pentaerythritol diphosphite ester is represented by the following general formula (VI)
[0060]
[Chemical 3]

[0061]
Spiro type represented by the following general formula (VII)
[0062]
[Formula 4]

[0063]
The cage type shown by can also be used. Usually, a mixture of both isomers can be used most often for economic reasons arising from the process for producing such phosphite esters.
Where R¹⁵, R¹⁶, R¹⁷Is preferably hydrogen or an alkyl group having 1 to 9 carbon atoms, particularly a branched alkyl group, especially a t-butyl group, and the substitution position in the phenyl group is most preferably 2,4,6. Suitable phosphite esters are bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) bentaerythritol diphosphite, and the like. Further, phosphonites having a structure in which carbon and phosphorus are directly bonded, for example, compounds such as tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite can also be mentioned.
[0064]
Commercially available products may be used as the phosphorus-based antioxidant, such as Irgafos 168 (Irgafos 168, Ciba Specialty Chemicals, Inc.), Irgafos 12 (Irgafos 12, Ciba Specialty Chemicals, Inc.), Irgafos 38 ( Irgafos 38, Ciba Specialty Chemicals, Inc., Adeka Stub 329K (ADKSTAB 329K, Asahi Denka Co., Ltd.), Adeka Stub PEP36 (ADKSTAB PEP36, Asahi Denka Co., Ltd.), Adeka Stub PEP-8 (ADKSTAB PEP-8, Asahi Denka) , Trademark), Sardstab P-EPQ (Clariant, Trademark), Weston 618 (Weston 618, GE, Trademark), Weston 619G (Weston 619G, GE) And Weston-624 (Weston-624, GE Corporation, trademark).
[0065]
In addition, as phosphorus-based antioxidants, JP-A-10-53595, JP-A-10-101687, JP-A-10-114784, JP-A-10-120691, JP-A-10-120893, JP-A-10-120694, JP-A-10-152494, JP-A-10-152696, JP-A-10-158283, JP-A-10-158285, JP-A-10-182675, JP-A-10-182675 Those described in JP-A-10-259190, JP-A-10-259193, JP-A-10-273493, JP-A-10-273494, and JP-A-10-298348 can also be suitably used.
[0066]
As a sulfur type antioxidant, the sulfur type antioxidant conventionally used as an antioxidant can be used.
Specifically, dialkylthiodipropionates such as dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, butylthiopropionic acid, octylthiopropionic acid, laurylthiopropionic acid, stearylthiol Mention may be made of alkylthiopropionic acid polyhydric alcohols such as propionic acid (eg glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) esters (eg pentaerythritol tetralaurylthiopropionate). it can.
[0067]
Commercially available products can be used as the sulfur-based antioxidant, such as DSTP (Yoshitomi) (trademark), DLTP (Yoshitomi) (trademark), DLTOIB (Yoshitomi Corp., trade mark), DMTP (Yoshitomi). ) (Yoshitomi, Trademark), Seenox 412S (Cipro Kasei, Trademark), Cyanox 1212 (Cyanamide, Trademark), and the like.
[0068]
As the vitamin-based antioxidant, vitamin-based antioxidants conventionally used as antioxidants can be used.
Specifically, d-α-tocopherol acetate, d-α-tocopherol succinate, d-α-tocopherol, d-β-tocopherol, d-γ-tocopherol, d-δ-tocopherol, d-α-tocotrienol, Natural products such as d-β-tocofetrienol, d-γ-tocofetrienol, d-δ-tocofetrienol, dl-α-tocopherol, dl-α-tocopherol acetate, dl-α-succinate Examples include synthetic products such as tocopherol calcium and dl-α-tocopherol nicotinate.
[0069]
Commercially available products can also be used as vitamin-based antioxidants, such as tocopherol (manufactured by Eisai Co., Ltd.), Irganox E201 (Irganox E201, Ciba Specialty Chemicals Co., Ltd., trademark, compound name; 2,5,7,8-tetra). Methyl-2 (4 ′, 8 ′, 12′-trimethyltridecyl) coumarone-6-ol) and the like.
[0070]
As the lactone antioxidant, a lactone antioxidant conventionally used as an antioxidant can be used. For example, those described in JP-A-7-233160 and JP-A-7-247278 can be used. In addition, HP-136 (Ciba Specialty Chemicals, trademark, compound name; 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one) and the like are commercially available. Goods can also be used.
[0071]
Of the components (ii), the rust inhibitor is not particularly limited, but is preferably a compound of higher fatty acid metal salt, double compound, alkali metal compound, alkaline earth metal compound, alkyl lactic acid metal salt, or lactic acid metal salt. You can choose.
Examples of higher fatty acid metal salts include alkali metal salts or alkaline earth metal salts of fatty acids having 8 to 23 carbon atoms. Examples of fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linolenic acid. Metals that form salts with these fatty acids include potassium, sodium, calcium, barium, magnesium, and aluminum. Can be mentioned.
[0072]
The double compound has the following general formula (VIII)
M_xAl_y(OH)_{2x + 3y-2z}(A)_z・ AH₂O (VIII)
(M represents Mg, Ca or Zn, and A represents CO._ThreeOr HPO_FourX, y and z are positive numbers, and a is 0 or a positive number. )
It is a compound represented by these. Specifically, Mg₆Al₂(OH)₁₆CO_Three・ 4H₂O, Mg₈Al₂(OH)₂₀CO_Three・ 5H₂O, Mg_FiveAl₂(OH)₁₄CO_Three・ 4H₂O, Mg_TenAl₂(OH)_{twenty two}(CO_Three)₂・ 4H₂O, Mg₆Al₂(OH)₁₆HPO_Four・ 4H₂O, Ca₆Al₂CO_Three・ 4H₂O, Zn₆Al₆(OH)₁₆CO_Three・ 4H₂O etc. can be mentioned. Also, compounds described in JP-A-7-316354 (Mg, Zn, Al-containing compound) and JP-B-7-2858 (Al, Li-containing compound) can be used.
[0073]
Examples of the alkali metal compound include sodium oxide, potassium oxide, sodium hydroxide, potassium hydroxide, sodium aluminate, sodium silicate, sodium carbonate, and potassium carbonate.
Examples of alkaline earth compounds include calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, and calcium calcium.
[0074]
The alkyl lactic acid metal salt is a mixture of lactic acid having a polymerization degree of 2 (2-lactyl lactic acid) and a calcium salt of a stearic esterification reaction product (stearyl lactic acid) as a main component and a salt of a small amount of related acids. Calcium stearyl can be mainly used. As the lactic acid metal salt, calcium lactate is generally used, but barium lactate, zinc lactate, magnesium lactate and the like can also be used.
[0075]
The amount of the component (ii) is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, particularly preferably 0, per 100 parts by weight of the crystalline polypropylene of the component (i). 0.02 to 0.5 parts by weight. If the amount is too small, the stability improvement effect such as processing stability, heat aging resistance, and corrosion resistance may not be sufficient. If the amount is too large, the stability improvement effect corresponding to the amount may not be sufficient. There are also cases where the tensile strength and the like are reduced.
[0076]
(iii) ingredients
In the composition of the present invention, heavy metal resistance (metal aging resistance) can be improved by using a heavy metal deactivator in combination.
Specific examples of the heavy metal deactivator include benzotriazole, 2,4,6-triamino-1,3,5-triazine, 3,9-bis [2- (3,5-diamino-2,4, 6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, ethylenediamine-tetraacetic acid, ethylenediamine-tetraacetic acid alkali metal salts (Li, Na, K ) Salt, N, N′-disalicylidene-ethylenediamine, N, N′-disalicylidene-1,2-propylenediamine, N, N ″ -disalicylidene-N′-methyl-dipropylenetriamine, 3-salicyloylamino-1 , 2,4-triazole, decamethylene dicarboxylic acid-bis (N′-salicyloyl hydrazide), nickel-bi (1-phenyl-3-methyl-4-decanoyl-5-pyrazolate), 2-ethoxy-2′-ethyloxanilide, N, N-diethyl-N ′, N′-diphenyloxamide, N, N ′ -Diethyl-N, N'-diphenyloxamide, oxalic acid-bis (benzylidenehydrazide), thiodipropionic acid-bis (benzylidenehydrazide), isophthalic acid-bis (2-phenoxypropionylhydrazide), bis ( Salicyloylhydrazine), N-salicylidene-N′-salicyloylhydrazone, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris [2 -T-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl)- -Methylphenyl] phosphite, bis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] pentaerythritol-diphosphite, tetrakis [ 2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,6-hexamethylene-bis (N-hydroxyethyl-N -Methylsemicarbazide) diphosphite, tetrakis [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di -Carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-t-butyl-4-thio ( 2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-salicyloylhydrazide-diphosphite, tetrakis [2- t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide-diphosphite, tetrakis [2-t-butyl -4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -N, N'-bis (hydroxyethyl) oxamide-diphosphite, N, N'-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] oxamide and the like Door can be.
[0077]
The above component (iii) may be used alone or in combination of two or more, and the blending amount thereof is preferably 0.01 with respect to 100 parts by weight of the crystalline polypropylene of component (i). To 1 part by weight, more preferably 0.05 to 0.5 part by weight. If the amount is too small, the effect of improving heavy metal resistance may not be sufficient, and if the amount is too large, the effect of improving heavy metal resistance may not be appropriate for the amount, and the tensile strength may decrease. There is.
[0078]
(iv) component
In the composition of this invention, the fluidity | liquidity of resin can be improved by using together a radical generator as needed.
Specific examples of radical generators include benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di (henzoyl). Peroxy) hexane, 2,5-di-methyl-2,5-di (henzoylperoxy) hexyne-3, t-butyl-di-peradipate, t-butylperoxy-3,3,5-trimethyl Hexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di (t-butylperoxy) hexane 2,5-di-methyl-2,5-di (t-butylperoxy) hexyne-3,1,3-bis (t-butyl par Oxyisopropyl) benzene, t-butylcumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2 , 2-bis (t-butylperoxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, 1,1 , 3,3-tetra-methylbutyl hydroperoxide, 2,5-di-methyl-2,5-di (hydroperoxy) hexane, trimethylsilyl-cumyl peroxide, 2,5-di-methyl-2, 5-bis (trimethylsilylperoxy) hexane, 2,5 Di - methyl-2,5-bis (trimethylsilyl peroxy) hexyne-3,1,3-bis (trimethylsilyl peroxy isopropyl) benzene and the like.
[0079]
The component (iv) may be used alone or in combination of two or more, and the blending amount thereof is preferably 0.001 with respect to 100 parts by weight of the crystalline polypropylene of the component (i). It is -0.5 weight part, More preferably, it is 0.01-0.2 weight part. If the amount is too small, the effect of improving the fluidity of the resin may not be sufficient. If the amount is too large, it may be difficult to mold the resin, and the tensile strength may decrease.
[0080]
The molded body which is the second invention of the present application can be obtained by molding using the crystalline polypropylene resin composition. Examples of the molded body of the present invention include automobile interior materials, housing materials for electrical products, films, sheets and the like. Examples of the molding method include an injection molding method, a compression molding method, an injection compression molding method, a gas assist injection molding method, an extrusion molding method, and a blow molding method.
[0081]
In addition, the molded article of the present invention may be added to the crystalline polypropylene composition as desired, with additives for surface functions such as antistatic agents and antifogging agents, anti-blocking agents, weathering agents, lubricants, nucleating agents, and coloring. You may manufacture, after preparing well-known additives, such as an agent, a dripping agent, a flame retardant, a flame retardant adjuvant, an antibacterial agent, and an inorganic or organic filler, and preparing a resin composition.
[0082]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[Production Example 1]
(Preparation of solid catalyst component)
160 g of diethoxymagnesium was charged into a 5-neck flask with a stirrer having an internal volume of 5 liters substituted with nitrogen, and 600 ml of dehydrated octane was further added. The mixture was heated to 40 ° C., 24 ml of silicon tetrachloride was added, stirred for 20 minutes, and 16 ml of dibutyl phthalate was added. The temperature of the solution was raised to 80 ° C., and subsequently 770 ml of titanium tetrachloride was added dropwise using a dropping funnel. The internal temperature was 125 ° C. and the contact reaction was carried out for 2 hours. Thereafter, it was sufficiently washed with 125 ° C. dehydrated octane. Further, 1,220 ml of titanium tetrachloride was added, the internal temperature was 125 ° C., and the contact reaction was performed for 2 hours. Thereafter, it was thoroughly washed with dehydrated octane at 125 ° C. to obtain a solid component [A].
[0083]
(Preliminary polymerization)
48 g of the solid component [A] was charged into a three-neck flask with a stirrer having an internal volume of 1 liter substituted with nitrogen. Further, 400 ml of dehydrated n-heptane was added. The mixture was heated to 40 ° C., and 2.0 ml of triethylaluminum and 6.3 ml of diisopentyldimethoxysilane were added. Propylene was passed through this at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated n-heptane to obtain a catalyst component.
[0084]
(polymerization)
A stainless steel autoclave with a stirrer with an internal volume of 10 liters was sufficiently dried, and after substitution with nitrogen, 6 liters of dehydrated heptane was added. While stirring, the temperature was raised until the internal temperature reached 80 ° C. After the temperature increase, 40.0 mmol of triethylaluminum was added, followed by 5.0 mmol of dicyclopentyldimethoxysilane, and 0.1 mmol of the above-mentioned solid catalyst was added per Ti, and 3.0 kg / cm of hydrogen was added.²After introducing G, the total pressure is 8.0 kg / cm²Propylene was introduced until G was reached. Total pressure is 8.0kg / cm²Polymerization was carried out for 1 hour from the time when G was reached. Thereafter, the temperature was lowered and the pressure was removed, the contents were taken out, the solvent was removed with an evaporator, and vacuum drying was performed to obtain polypropylene.
[0085]
[Production Example 2]
In Production Example 1, the amount of hydrogen introduced during polymerization was 2.8 kg / cm.²Except for G, polypropylene was produced in the same manner as in Production Example 1.
[Production Example 3]
In Production Example 1, the amount of hydrogen introduced during polymerization was 1.0 kg / cm.²Except for G, polypropylene was produced in the same manner as in Production Example 1.
[Production Example 4]
In Production Example 1, the amount of hydrogen introduced during polymerization was 0.5 kg / cm.²Except for G, polypropylene was produced in the same manner as in Production Example 1.
[Production Example 5]
In Production Example 1, the amount of hydrogen introduced during polymerization was 0.1 kg / cm.²Except for G, polypropylene was produced in the same manner as in Production Example 1.
[0086]
[Production Example 6]
(Preparation of solid catalyst component)
160 g of diethoxymagnesium was charged into a 5-neck flask with a stirrer having an internal volume of 5 liters substituted with nitrogen, and 600 ml of dehydrated n-heptane was further added. The mixture was heated to 40 ° C., 24 ml of silicon tetrachloride was added, stirred for 20 minutes, and 25 ml of diethyl phthalate was added. The temperature of the solution was raised to 80 ° C., and then 470 ml of titanium tetrachloride was added dropwise using a dropping funnel. The internal temperature was set to 110 ° C., and the contact reaction was performed for 2 hours. Thereafter, washing was sufficiently performed using dehydrated n-heptane at 90 ° C. Further, 770 milliliters of titanium tetrachloride was added, the internal temperature was set to 110 ° C., and contact reaction was performed for 2 hours. Thereafter, the solid component [B] was obtained by sufficiently washing with 90 ° C. dehydrated n-heptane.
[0087]
(Preliminary polymerization)
48 g of solid component [B] was charged into a three-neck flask with a stirrer having an internal volume of 1 liter substituted with nitrogen, and 400 ml of dehydrated n-heptane was further added. While maintaining at 10 ° C., 2.7 ml of triethylaluminum and 2.0 ml of cyclohexylmethyldimethoxysilane were added. Propylene was passed through this at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated n-heptane to obtain a catalyst component.
[0088]
(polymerization)
A stainless steel autoclave with a stirrer with an internal volume of 10 liters was sufficiently dried, and after substitution with nitrogen, 6 liters of dehydrated heptane was added. While stirring, the temperature was raised until the internal temperature reached 80 ° C. After the temperature increase, 40.0 mmol of triethylaluminum was added, followed by 5.0 mmol of cyclohexylmethyldimethoxysilane, and 0.1 mmol of the above solid catalyst was added per Ti, and 1.1 kg / cm2 of hydrogen was added.²After introducing G, the total pressure is 8.0 kg / cm²Propylene was introduced until G was reached. Total pressure is 8.0kg / cm²Polymerization was carried out for 1 hour from the time when G was reached. Thereafter, the temperature was lowered and the pressure was removed, the contents were taken out, the solvent was removed with an evaporator, and vacuum drying was performed to obtain polypropylene.
[0089]
[Production Example 7]
In Production Example 6, the amount of hydrogen introduced during polymerization was 0.5 kg / cm.²Except for G, polypropylene was produced in the same manner as in Production Example 6.
[Production Example 8]
In Production Example 6, the amount of hydrogen introduced during polymerization was 0.2 kg / cm.²Except for G, polypropylene was produced in the same manner as in Production Example 6.
[Production Example 9]
In Production Example 6, the amount of hydrogen introduced during polymerization was 0.01 kg / cm.²Except for G, polypropylene was produced in the same manner as in Production Example 6.
Examples 1-18 and Comparative Examples 1-4
The additives shown in Table 1 were added to the polypropylene powders obtained in the above Production Examples 1 to 9 and mixed well, and then melt-kneaded and granulated with a 20 mm single-screw kneading extruder to produce pellets. Measurements of predetermined resin properties (structural properties) were performed on a part of the pellets, the remaining pellets were injection molded, and various test specimens were prepared as described below, and mechanical properties were measured and stability was evaluated. . The results are shown in Table 1.
[0090]
In addition, about the metal aging resistance among stability evaluation, another test piece was created and evaluated.
(Measuring specimen for mechanical properties)
Test pieces were prepared at a resin temperature of 200 ° C. and a mold temperature of 45 ° C. using an IS100FIII type injection molding machine manufactured by Toshiba Machine Co., Ltd.
(Measuring method of structural characteristics and mechanical characteristics)
(1) Intrinsic viscosity [η]
It melt | dissolved in tetralin and measured at 135 degreeC.
(2) 0 ° C soluble fraction and elution curve peak temperature by temperature rising fractionation method
The polypropylene obtained by the polymerization is obtained by a temperature rising free separation method. For sample preparation, 75 mg of polymer is weighed in 10 ml of o-dichlorobenzene at room temperature, and stirred at 135 to 150 ° C. for 1 hour to dissolve. After injecting 0.5 ml of the sample solution into the column under the condition of 135 ° C., the polymer is crystallized on the surface of the filler by slowly cooling to 0 ° C. at 10 ° C./hr. At this time, the amount of polymer remaining without being crystallized was defined as a 0 ° C. soluble amount. The elution curve is cooled, the column temperature is raised at 40 ° C./hr while flowing o-dichlorobenzene at 2 ml / min, and the polymer concentration eluted at any time is continuously measured with an infrared detector. By seeking. In the obtained elution curve, the temperature at the peak position was defined as the peak temperature.
[0091]
The column uses 4.6 mmφ × 150 mm, the packing uses chromosolve P, the elution curve is adjusted using linear PE (SRM1475) as a standard sample, and the peak temperature is 100 ° C. when elution is performed under the above conditions. Adjustment was made to be (± 0.5). A wavelength of 3.41 μm was used for detection.
(3) Measurement of mechanical properties
For test specimens obtained by injection molding, the tensile modulus, flexural modulus, thermal deformation temperature (HDT), and Rockwell hardness (HR [R scale]) conform to JIS K7113, K7203, K7207, K7202, respectively. Measured.
[0092]
(Evaluation of stability)
(1) Process stability
MI (MI of pellets obtained by the first melt-kneading₀) And pellets obtained by kneading and granulating the pellets three more times at 270 ° C. in a 20 mm single-screw kneading extruder 270 ° C. (MI_Three) Ratio MI_Three/ MI₀A comparative evaluation was performed.
(2) Rust prevention
30 kg / cm in a press machine heated to 250 ° C. with pellets placed on a well-polished mild steel plate via a spacer with a thickness of 5 mm²For 30 minutes. Thereafter, the sample was peeled off from the steel plate, and the steel plate was left in a container kept at 25 ° C. and relative humidity of 100% for 1 week. The rusting state on the steel plate surface was compared with a standard plate (rusting degree 0 to 4) and evaluated. A rusting degree of 0 indicates no rusting, and a rusting degree of 4 indicates that the entire surface is very rusted. If the degree of rusting is 1 or less, there is no practical problem.
(3) Metal aging resistance
With respect to 100 parts by weight of the resin composition, a mixture containing 0.5 parts by weight of commercially available copper powder was melt-kneaded at 200 ° C. by a 20 mmφ single screw extruder, and then 1 mm thick by press molding at a molding temperature of 200 ° C. Ten test pieces having a width of 10 mm and a length of 80 mm were produced. The obtained test piece was suspended in a gear oven in an air atmosphere at 150 ° C., one of the test pieces was suspended, and the time until five of the ten test pieces were broken due to deterioration was measured. It was an index of sex.
[0093]
[Table 1]

[0094]
[Table 2]

[0095]
[Table 3]

[0096]
[Table 4]

[0097]
[Table 5]

[0098]
In addition, the additive used for the Example and the comparative example is as follows.
A1: Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (phenolic antioxidant)
A2: Tris (2,4-di-t-butyl) phosphite (phosphorus antioxidant)
A3: Dimyristyl 3,3'-thiopropionate (sulfur antioxidant)
A4: 2,5,7,8-tetramethyl-2 (4 ', 8', 12'-trimethyltritridecyl) coumaron-6-ol (vitamin antioxidant)
A5: 5,7-di-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one (lactone-based antioxidant)
[0099]
B1: Calcium stearate (higher fatty acid metal salt)
B2: Mg_4.5Al₁₂(OH)₁₃CO_Three・ 3.5H₂O (double compound)
B3: Calcium oxide (alkaline earth metal compound)
B4: Calcium lactate (metal lactate salt)
C1: N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine
D1: 1,3-bis (t-butylperoxyisopropyl) benzene
In Table 1, when compared with Example 12 and Comparative Example 1 showing substantially the same [η], the crystalline polypropylene composition of the present invention is excellent in tensile modulus, flexural modulus, heat distortion temperature and Rockwell hardness. You can see that Similarly, the same can be said for the comparison between Example 15 and Comparative Example 2, Example 16 and Comparative Example 3, and Example 18 and Comparative Example 4. In addition, even when the elution peak is within the range of the present invention as shown in Comparative Example 2, it is also clear that the physical properties decrease when the amount of soluble component at 0 ° C. is large. It is also clear that the stability is improved by using an antioxidant and an antirust agent.
[0100]
【The invention's effect】
According to the novel crystalline polypropylene resin composition of the present invention, it is possible to reduce the thickness of the molded product by increasing the rigidity and to reduce the weight, which is effective in terms of resource saving and productivity. In addition, the rigidity and heat resistance can be improved, so that it is possible to replace the conventional use of polystyrene, ABS resin and the like. Moreover, since the molded article of the present invention is excellent in rigidity, heat resistance, scratch resistance and stability, it can be suitably used for automobile interior materials, housing materials for household appliances, films, and the like.

Claims (9)

(I) Intrinsic viscosity [η] measured in a tetralin solvent at 135 ° C. is in the range of 0.5 to 4.0 deciliter / g, and 0 ° C. soluble amount α (wt%) by a temperature rising fractionation method the inherent viscosity [eta] is the following formula (4)
α ≦ 1.11 × [η] ^−0.42 +0.50 (4)
A crystalline polypropylene resin composition comprising (ii) at least one compound selected from antioxidants and rust inhibitors in crystalline polypropylene satisfying the above relationship. The crystalline polypropylene resin composition according to claim 1, wherein the intrinsic viscosity [η] is in the range of 0.5 to 3.0 deciliter / g. (I) the crystalline polypropylene makes contact with (a) a magnesium compound, (b) a titanium compound, (c) an electron donor, and (d) a silicon compound at a temperature in the range of 120 to 150 ° C., and The crystalline polypropylene resin composition according to claim 1 or 2 , which is polymerized using a solid catalyst component obtained by washing with an inert solvent at a temperature in the range of 100 to 150 ° C. The crystalline polypropylene resin composition according to any one of claims 1 to 3, wherein the total amount of component (ii) is 0.005 to 2 parts by weight per 100 parts by weight of component (i). Furthermore, the crystalline polypropylene resin composition of any one of Claims 1-4 formed by mix | blending (iii) heavy metal deactivator and / or (iv) radical generator. In the component (i), the elution curve peak temperature T _P (° C.) by the temperature rising fractionation method and the intrinsic viscosity [η] (deciliter / g) measured at 135 ° C. in a tetralin solvent are expressed by the following formula (2):
T _P > 1.21 × [η] +116.5 (2)
The crystalline polypropylene resin composition according to any one of claims 1 to 5 , which is a crystalline polypropylene satisfying the relationship: The crystalline polypropylene resin composition according to any one of claims 1 to 6 , wherein among the components (ii), the antioxidant is a phenol-based, phosphorus-based, sulfur-based, vitamin-based or lactone-based compound. (Ii) rust inhibitor of the component, higher fatty acid metal salts, double compound, alkali metal compound, an alkaline earth metal compound, any one of claims 1 to 7 which is a compound of the alkyl lactate metal salt or lactate metal salt 2. The crystalline polypropylene resin composition according to item 1. The molded object formed by shape | molding the crystalline polypropylene resin composition of any one of Claims 1-8 .