JP4161767B2 - Propylene resin composition and molded article thereof - Google Patents

Description

【００５５】
一般式（Ｉ）中、Ａ₁およびＡ₂は、共役５員環配位子であって、Ａ¹およびＡ²の少なくとも一方は、共役５員環配位子上の隣接した置換基が結合し、５員環の２原子を含めて形成された７〜１０員の縮合環を有し、Ｑは、２つの共役５員環配位子を任意の位置で架橋する結合性基、Ｍは、周期律表４族から選ばれる遷移金属原子を示し、そして、ＸおよびＹは、それぞれ独立して、Ｍと結合した水素原子、ハロゲン原子、炭化水素基、アルキルアミド基、ハロゲン化炭化水素基、酸素含有炭化水素基、窒素含有炭化水素基、リン含有炭化水素基、ケイ素含有炭化水素基、硫黄含有基を示す。
【００５６】
上記の共役５員環配位子の典型例としては、例えば、置換シクロペンタジエニル基を挙げることが出来る。該置換基の具体例としては、炭素数が通常１〜２０、好ましくは１〜１５の炭化水素基を挙げることができる。例えば、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、ｔ−ブチル基、イソブチル基、ペンチル基、シクロペンチル基、ヘキシル基、シクロヘキシル基、オクチル基、フェニル基、ナフチル基、ブテニル基、ブタジエニル基、トリフェニルカルビル基などが挙げられる。
【００５７】
上記の炭化水素基以外の置換基としては、ケイ素、酸素、窒素、リン、ホウ素、硫黄などの原子を含有する炭化水素残基が挙げられる。その典型例としては、メトキシ基、エトキシ基、フェノキシ基、フリル基、トリメチルシリル基、ジエチルアミノ基、ジフェニルアミノ基、ピラゾリル基、インドリル基、カルバゾリル基、ジメチルフォスフィノ基、ジフェニルフォスフィノ基、ジフェニルホウ素基、ジメトキシホウ素基、チエニル基などが挙げられる。
【００５８】
その他の置換基としては、ハロゲン原子又はハロゲン含有炭化水素基などが挙げられる。その典型的例としては、塩素、臭素、ヨウ素、フッ素、トリクロロメチル基、クロロフェニル基、クロロビフェニル基、クロロナフチル基、トリフルオロメチル基、フルオロフェニル基、フルオロビフェニル基、フルオロナフチル基、ペンタフルオロフェニル基などが挙げられる。
【００５９】
また、前記したように、Ａ₁およびＡ₂の少なくとも一方は、共役５員環配位子上の隣接した置換基が結合し、５員環の２原子を含めて７〜１０員の縮合環を形成する。このような具体例としては、アズレン等の化合物やその誘導体を挙げることができる。さらに具体的には、ヒドロアズレニル基、メチルヒドロアズレニル基、エチルヒドロアズレニル基、ジメチルヒドロアズレニル基、メチルエチルヒドロアズレニル基、メチルイソプロピルヒドロアズレニル基、メチルフェニルイソプロピルヒドロアズレニル基、各種アズレニル基の水添体、ビシクロ−［６．３．０］−ウンデカニル基、メチル−ビシクロ−［６．３．０］−ウンデカニル基、エチル−ビシクロ−［６．３．０］−ウンデカニル基、フェニル−ビシクロ−［６．３．０］−ウンデカニル基、メチルフェニル−ビシクロ−［６．３．０］−ウンデカニル基、エチルフェニル−ビシクロ−［６．３．０］−ウンデカニル基、メチルジフェニル−ビシクロ−［６．３．０］−ウンデカニル基、メチル−ビシクロ−［６．３．０］−ウンデカジエニル基、メチルフェニル−ビシクロ−［６．３．０］−ウンデカジエニル基、エチルフェニル−ビシクロ−［６．３．０］−ウンデカジエニル基、メチルイソプロピル−ビシクロ−［６．３．０］−ウンデカジエニル基、ビシクロ−［７．３．０］−ドデカニル基及びその誘導体、ビシクロ−［７．３．０］−ドデカジエニル基及びその誘導体、ビシクロ−［８．３．０］−トリデカニル基及びその誘導体、ビシクロ−［８．３．０］−トリデカジエニル基及びその誘導体などが例示される。
【００６０】
上記の各基の置換基としては、前述した炭化水素基、ケイ素、酸素、窒素、リン、ホウ素、硫黄などの原子を含有する炭化水素基、ハロゲン原子又はハロゲン含有炭化水素基などが挙げられる。
Ｑは、２つの共役５員環配位子を任意の位置で架橋する結合性基を示す。すなわち、Ｑは、２価の結合性基であり、Ａ₁とＡ₂とを架橋する。Ｑの種類に特に制限はないが、その具体例として、（ａ）炭素数が通常１〜２０、好ましくは１〜１２の２価の炭化水素基またはハロゲン化炭化水素基、具体的には、アルキレン基、シクロアルキレン基、アリーレン等の不飽和炭化水素基、ハロアルキレン基、ハロシクロアルキレン基、（ｂ）シリレン基またはオリゴシリレン基、（ｃ）炭素数が通常１〜２０、好ましくは１〜１２の炭化水素基またはハロゲン化炭化水素基を置換基として有するシリレン基またはオリゴシリレン基、（ｄ）ゲルミレン基、（ｅ）炭素数が通常１〜２０の炭化水素基またはハロゲン化炭化水素基を置換基として有するゲルミレン基などを挙げることができる。これらの中では、アルキレン基、シクロアルキレン基、アリーレン基、炭化水素基を置換基として有するシリレン基またはゲルミレン基が好ましい。
【００６１】
Ｍは、周期律表４族から選ばれる遷移金属原子を示し、好ましくは、ジルコニウムまたはハフニウムである。
ＸおよびＹは、それぞれ独立して、Ｍと結合した水素原子、ハロゲン原子、炭化水素基、アルキルアミド基、ハロゲン化炭化水素基、酸素含有炭化水素基、窒素含有炭化水素基、リン含有炭化水素基、ケイ素含有炭化水素基、硫黄含有基を示す。上記の各炭化水素基における炭素数は、通常１〜２０、好ましくは１〜１２である。これらの中では、水素原子、塩素原子、メチル基、イソブチル基、フェニル基、ジメチルアミド基、ジエチルアミド基、スルフィナト基が好ましい。
【００６２】
本発明における遷移金属化合物の具体例としては次の化合物が挙げられる。
(29) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−４Ｈ−１−アズレニル）］ハフニウム
(30) ジクロロ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(31) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−メチル−４ −フェニル−４Ｈ−１−アズレニル）］ハフニウム
(32) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−メチル−４ −イソプロピル−４Ｈ−１−アズレニル）］ハフニウム
(33) ジクロロ［ジメチルシリレン（２−エチル−１−シクロペンタジエニル） （２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(34) ジクロロ［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル− ４Ｈ−１−アズレニル）］ハフニウム
(35) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−エチル−４ −メチル−４Ｈ−１−アズレニル）］ハフニウム
(36) ジクロロ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(37) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−エチル−４ −フェニル−４Ｈ−１−アズレニル）］ハフニウム
(38) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−エチル−４ −イソプロピル−４Ｈ−１−アズレニル）］ハフニウム
(39) ジクロロ［ジメチルシリレン（９−フルオレニル）（２−エチル−４−メ チル−４Ｈ−１−アズレニル）］ハフニウム
(40) ジクロロ［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエ ニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(41) ジクロロ［エチレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ −１−アズレニル）］ハフニウム
(42) ジクロロ［エチレン（２−メチル−１−シクロペンタジエニル）（２，４ −ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(43) ジクロロ［エチレン（シクロペンタジエニル）（２−メチル−４−フェニ ル−４Ｈ−１−アズレニル）］ハフニウム
(44) ジクロロ［エチレン（シクロペンタジエニル）（２−メチル−４−イソプ ロピル−４Ｈ−１−アズレニル）］ハフニウム
(45) ジクロロ［エチレン（２−メチル−１−シクロペンタジエニル）（２，４ −ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(46) ジクロロ［エチレン（９−フルオレニル）（２，４−ジメチル−４Ｈ−１ −アズレニル）］ハフニウム
(47) ジクロロ［エチレン（シクロペンタジエニル）（２−エチル−４−メチル −４Ｈ−１−アズレニル）］ハフニウム
(48) ジクロロ［エチレン（２−メチル−１−シクロペンタジエニル）（２−エ チル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(49) ジクロロ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２−エチル−４−フェニル−４Ｈ−１−アズレニル）］ハフニウム
(50) ジクロロ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２−エチル−４−イソプロピル−４Ｈ−１−アズレニル）］ハフニウム
(51) ジクロロ［エチレン（９−フルオレニル）（２−エチル−４−メチル−４ Ｈ−１−アズレニル）］ハフニウム
(52) ジクロロ［エチレン（９−フルオレニル）（２−エチル−４−イソプロピ ル−４Ｈ−１−アズレニル）］ハフニウム
(53) ジクロロジメチルシリレン（シクロペンタジエニル）（２−ｎ−プロピル −４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(54) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−イソプロピ ル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(55) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−ｎ−ブチル −４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(56) ジクロロ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２−ｎ−プロピル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(57) ジクロロ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２−イソプロピル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(58) ジクロロ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２−ｎ−ブチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(59) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４，８−ト リメチル−４Ｈ−１−アズレニル）］ハフニウム
(60) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４，６−ト リメチル−４Ｈ−１−アズレニル）］ハフニウム
(61) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４，７−ト リメチル−４Ｈ−１−アズレニル）］ハフニウム
(62) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−６−イソプロピル−４Ｈ−１−アズレニル）］ハフニウム
(63) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−７−イソプロピル−４Ｈ−１−アズレニル）］ハフニウム
(64) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−８−イソプロピル−４Ｈ−１−アズレニル）］ハフニウム
(65) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−６−エチル−４Ｈ−１−アズレニル）］ハフニウム
(66) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−７−エチル−４Ｈ−１−アズレニル）］ハフニウム
(67) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−８−エチル−４Ｈ−１−アズレニル）］ハフニウム
(68) ジクロロ｛［ジ（クロロメチル）シリレン］（シクロペンタジエニル）（ ２，４−ジメチル−４Ｈ−１−アズレニル）｝ハフニウム
(69) ジクロロ｛［ジ（４−クロロフェニル）シリレン］（シクロペンタジエニ ル）（２，４−ジメチル−４Ｈ−１−アズレニル）｝ハフニウム
(70) ジクロロ［ジメチルメチレン（シクロペンタジエニル）（２，４−ジメチ ル−４Ｈ−１−アズレニル）］ハフニウム
(71) ジクロロ［ジメチルゲルミレン（シクロペンタジエニル）（２，４−ジメ チル−４Ｈ−１−アズレニル）］ハフニウム
(72) ジクロロ［ジメチルゲルミレン（２−メチル−１−シクロペンタジエニル ）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(73) ジクロロ［ジメチルゲルミレン（２，３−ジメチル−１−シクロペンタジ エニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(74) ジクロロ［ジメチルゲルミレン（９−フルオレニル）（２，４−ジメチル −４Ｈ−１−アズレニル）］ハフニウム
(75) ジクロロ［ジメチルゲルミレン（シクロペンタジエニル）（２−エチル− ４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(76) ジクロロ［ジメチルゲルミレン（シクロペンタジエニル）（２−ｎ−プロ ピル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(77) ジクロロ［ジメチルゲルミレン（シクロペンタジエニル）（２−イソプロ ピル−４Ｈ−１−アズレニル）］ハフニウム
(78) ジクロロ［ジメチルゲルミレン（シクロペンタジエニル）（２−ｎ−ブチ ル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(79) ジクロロ［ジメチルゲルミレン（２−メチル−１−シクロペンタジエニル ）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(80) ジクロロ［ジメチルゲルミレン（２，３−ジメチル−１−シクロペンタジ エニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウ ム
(81) ジクロロ［ジメチルゲルミレン（９−フルオレニル）（２−エチル−４− メチル−４Ｈ−１−アズレニル）］ハフニウム
(82) ジクロロ［ジメチルゲルミレン（２−メチル−１−シクロペンタジエニル ）（２−ｎ−プロピル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(83) ジクロロ［ジメチルゲルミレン（２，３−ジメチル−１−シクロペンタエ ニル）（２−ｎ−プロピル−４−メチル−４Ｈ−１−アズレニル）］ハフ ニウム
(84) ジクロロ［ジメチルゲルミレン（９−フルオレニル）（２−ｎ−プロピル −４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(85) ジクロロ［ジメチルシリレン（３−トリメチルシリル−１−シクロペンタ ジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(86) ジクロロ［ジメチルシリレン（３−トリメチルシリル−１−シクロペンタ ジエニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニ ウム
(87) ジクロロ［ジメチルゲルミレン（３−トリメチルシリル−１−シクロペン タジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(88) ジクロロ［ジメチルゲルミレン（３−トリメチルシリル−１−シクロペン タジエニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフ ニウム
(89) ジブロモ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−４Ｈ−１−アズレニル）］ハフニウム
(90) ジブロモ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(91) ジブロモ［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエ ニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(92) ジブロモ［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル− ４Ｈ−１−アズレニル）］ハフニウム
(93) ジヨード［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−４Ｈ−１−アズレニル）］ハフニウム
(94) ジヨード［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(95) ジヨード［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエ ニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(96) ジヨード［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル− ４Ｈ−１−アズレニル）］ハフニウム
(97) ジメチル［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチ ル−４Ｈ−１−アズレニル）］ハフニウム
(98) ジメチル［ジメチルシリレン（２−メチル−１−シクロペンタジエニル） （２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(99) ジメチル［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエ ニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(100) ジメチル［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(101) ジヒドリド［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(102) ジヒドリド［ジメチルシリレン（２−メチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(103) ジヒドリド［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(104) ジヒドリド［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(105) ビス（ジメチルアミド）［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(106) ビス（ジメチルアミド）［ジメチルシリレン（２−メチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(107) ビス（ジメチルアミド）［ジメチルシリレン（２，３−ジメチル−１−ロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(108) ビス（ジメチルアミド）［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(109) ビスフェノキシ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(110) ビスフェノキシ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(111) ビスフェノキシ［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム(112) ビスフェノキシ［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(113) ビスメタンスルフィナト［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(114) ビスメタンスルフィナト［ジメチルシリレン（２−メチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(115) ビスメタンスルフィナト［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(116) ビスメタンスルフィナト［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(117) ビストリフルオロメタンスルフィナト［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(118) ビストリフルオロメタンスルフィナト［ジメチルシリレン（２−メチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(119) ビストリフルオロメタンスルフィナト［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(120) ビストリフルオロメタンスルフィナト［ジメチルシリレン（９−フル オレニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(121) ビス−ｐ−トルエンスルフィナト［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(122) ビス−ｐ−トルエンスルフィナト［ジメチルシリレン（２−メチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(123) ビス−ｐ−トルエンスルフィナト［ジメチルシリレン（２，３−ジメチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(124) ビス−ｐ−トルエンスルフィナト［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(125) ジクロロ［ジメチルシリレン（１−インデニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(126) ジクロロ［ジメチルシリレン（２−メチル−１−インデニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(127) ジクロロ［ジメチルシリレン（１−インデニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(128) ジクロロ［ジメチルシリレン（２−メチル−１−インデニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(129) ジブロモ［ジメチルシリレン（１−インデニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(130) ジブロモ［ジメチルシリレン（２−メチル−１−インデニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(131) ジブロモ［ジメチルシリレン（１−インデニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(132) ジブロモ［ジメチルシリレン（２−メチル−１−インデニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(133) ジヨード［ジメチルシリレン（１−インデニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(134) ジヨード［ジメチルシリレン（２−メチル−１−インデニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(135) ジヨード［ジメチルシリレン（１−インデニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(136) ジヨード［ジメチルシリレン（２−メチル−１−インデニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(137) ジメチル［ジメチルシリレン（１−インデニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(138) ジメチル［ジメチルシリレン（２−メチル−１−インデニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ハフニウム
(139) ジメチル［ジメチルシリレン（１−インデニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(140) ジメチル［ジメチルシリレン（２−メチル−１−インデニル）（２−エチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(141) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−５，６，７，８−テトラヒドロ−１−アズレニル）］ハフニウム
(142) ジクロロ［ジメチルシリレン（２−メチル−１−シクロペンタジエニル）（２，４−ジメチル−４Ｈ−５，６，７，８−テトラヒドロ−１−アズレ ニル）］ハフニウム
(143) ジクロロ［ジメチルシリレン（２−メチル−１−インデニル）（２，４−ジメチル−４Ｈ−５，６，７，８−テトラヒドロ−１−アズレニル）］ハフニウム
(144) ジクロロ［ジメチルシリレン（９−フルオレニル）（２，４−ジメチル−４Ｈ−５，６，７，８−テトラヒドロ−１−アズレニル）］ハフニウム
(145) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−クロロメチル−４−メチル−４Ｈ−１−アズレニル）］ハフニウム
(146) ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２−メチル−４−クロロメチル−４Ｈ−１−アズレニル）］ハフニウム
また、先に例示した化合物の中心金属Ｍがハフニウムの代わりに、チタン、ジルコニウムに代わった化合物も例示することが出来る。これらは２種以上組み合わせて用いてもよい。また、重合の途中に、新たに遷移金属成分を追加してもよい。
触媒成分（ｂ）： 助触媒
本発明において、助触媒としては、（ア）有機アルミニウムオキシ化合物、（イ） 遷移金属成分と反応して、該成分をカチオンに交換することが可能なイオン性化合物、（ウ）ルイス酸、（エ）ケイ酸塩を除くイオン交換性層状化合物または無機ケイ酸塩、からなる群より選択される一種以上の物質を用いるのが好ましい。
【００６３】
（ア）の有機アルミニウムオキシ化合物としては、具体的には、次の一般式（ＩＩ）、（ＩＩＩ）、（ＩＶ）で表される化合物が挙げられる。
各一般式中、Ｒ⁴は、水素原子または炭化水素残基、好ましくは炭素数１〜１０、特に好ましくは、炭素数１〜６の炭化水素残基を示す。また、複数のＲ⁴はそれぞれ同一でも異なっていてもよい。またｐは０以上、好ましくは２以上であって、３００以下、好ましくは３０以下の整数を示す。
【００６４】
【化２】

【００６５】
一般式（ＩＩ）および（ＩＩＩ）で表される化合物は、アルミノキサンとも呼ばれる化合物であって、一種類のトリアルキルアルミニウムまたは二種類以上のトリアルキルアルミニウムと水との反応により得られる。具体的には、（ａ）一種類のトリアルキルアルミニウムと水とから得られる、メチルアルミノキサン、エチルアルミノキサン、プロピルアルミノキサン、ブチルアルミノキサン、イソブチルアルミノキサン、（ｂ）二種類のトリアルキルアルミニウムと水とから得られる、メチルエチルアルミノキサン、メチルブチルアルミノキサン、メチルイソブチルアルミノキサン等が挙げられる。これらの中では、メチルアルミノキサン、メチルイソブチルアルミノキサンが好ましい。上記のアルミノキサンは、複数種併用することも可能である。そして、上記のアルミノキサンは、公知の様々な条件下に調製することができる。
【００６６】
一般式（ＩＶ）で表される化合物は、一種類のトリアルキルアルミニウムまたは二種類以上のトリアルキルアルミニウムと次の一般式（Ｖ）で表されるアルキルボロン酸との１０：１〜１：１（モル比）の反応により得ることができる。一般式（Ｖ）中、Ｒ⁵は、炭素数１〜１０、好ましくは炭素数１〜６の炭化水素残基またはハロゲン化炭化水素基を示す。
【００６７】
【化３】
Ｒ⁵−Ｂ（ＯＨ）₂ （Ｖ）
具体的には、以下の様な反応生成物、すなわち、（ａ）トリメチルアルミニウムとメチルボロン酸の２：１の反応物、（ｂ）トリイソブチルアルミニウムとメチルボロン酸の２：１反応物、（ｃ）トリメチルアルミニウムとトリイソブチルアルミニウムとメチルボロン酸の１：１：１反応物、（ｄ）トリメチルアルミニウムとエチルボロン酸の２：１反応物、（ｅ）トリエチルアルミニウムとブチルボロン酸の２：１反応物などを挙げることができる。
【００６８】
また、（イ）遷移金属成分と反応して、該成分をカチオンに変換することが可能なイオン性化合物としては、一般式（ＶＩ）で表される化合物が挙げられる。
【００６９】
【化４】
［Ｋ］ⁿ⁺［Ｚ］^n- （VI）
一般式（ＶＩ）中、Ｋはカチオン成分であって、例えば、カルボニウムカチオン、トロピリウムカチオン、アンモニウムカチオン、オキソニウムカチオン、スルホニウムカチオン、ホスフォニウムカチオン等が挙げられる。また、それ自身が還元されやすい金属の陽イオンや有機金属の陽イオン等も挙げられる。
【００７０】
上記のカチオンの具体例としては、トリフェニルカルボニウム、ジフェニルカルボニウム、シクロヘプタトリエニウム、インデニウム、トリエチルアンモニウム、トリプロピルアンモニウム、トリブチルアンモニウム、Ｎ，Ｎ−ジメチルアニリニウム、ジプロピルアンモニウム、ジシクロヘキシルアンモニウム、トリフェニルホスホニウム、トリメチルホスホニウム、トリス（ジメチルフェニル）ホスホニウム、トリス（ジメチルフェニル）ホスホニウム、トリス（メチルフェニル）ホスホニウム、トリフェニルスルホニウム、トリフェニルスルホニウム、トリフェニルオキソニウム、トリエチルオキソニウム、ピリリウム、銀イオン、金イオン、白金イオン、銅イオン、パラジウムイオン、水銀イオン、フェロセニウムイオン等が挙げられる。
【００７１】
上記の一般式（ＶＩ）中、Ｚは、アニオン成分であり、遷移金属成分が変換されたカチオン種に対して対アニオンとなる成分（一般には非配位の成分）である。Ｚとしては、例えば、有機ホウ素化合物アニオン、有機アルミニウム化合物アニオン、有機ガリウム化合物アニオン、有機ヒ素化合物アニオン、有機アンチモン化合物アニオン等が挙げられ、具体的には次の化合物が挙げられる。すなわち、（ａ）テトラフェニルホウ素、テトラキス（３，４，５−トリフルオロフェニル）ホウ素、テトラキス｛３，５−ビス（トリフルオロメチル）フェニル｝ホウ素、テトラキス｛３，５−ジ（ｔ−ブチル）フェニル｝ホウ素、テトラキス（ペンタフルオロフェニル）ホウ素等、（ｂ）テトラフェニルアルミニウム、テトラキス（３，４，５−トリフルオロフェニル）アルミニウム、テトラキス｛３，５−ビス（トリフルオロメチル）フェニル｝アルミニウム、テトラキス｛３，５−ジ（ｔ−ブチル）フェニル｝アルミニウム、テトラキス（ペンタフルオロフェニル）アルミニウム等、（ｃ）テトラフェニルガリウム、テトラキス（３，４，５−トリフルオロフェニル）ガリウム、テトラキス｛３，５−ビス（トリフルオロメチル）フェニル｝ガリウム、テトラキス｛３，５−ジ（ｔ−ブチル）フェニル｝ガリウム、テトラキス（ペンタフルオロフェニル）ガリウム等、（ｄ） テトラフェニルリン、テトラキス（ペンタフルオロフェニル）リン等、（ｅ）テトラフェニルヒ素、テトラキス（ペンタフルオロフェニル）ヒ素等、（ｆ）テトラフェニルアンチモン、テトラキス（ペンタフルオロフェニル）アンチモン等、（ｇ）デカボレート、ウンデカボレート、カルバドデカボレート、デカクロロデカボレート等である。
【００７２】
（ウ）ルイス酸、特に遷移金属成分をカチオンに変換可能なルイス酸としては、種々の有機ホウ素化合物、金属ハロゲン化合物、固体酸などが例示され、その具体例としては次の化合物が挙げられる。すなわち、（ａ）トリフェニルホウ素、トリス（３，５−ジフルオロフェニル）ホウ素、トリス（ペンタフルオロフェニル）ホウ素等の有機ホウ素化合物、（ｂ）塩化アルミニウム、臭化アルミニウム、ヨウ化アルミニウム、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム、塩化臭化マグネシウム、塩化ヨウ化マグネシウム、臭化ヨウ化マグネシウム、塩化マグネシウムハイドライド、塩化マグネシウムハイドロオキシド、臭化マグネシウムハイドロオキシド、塩化マグネシウムアルコキシド、臭化マグネシウムアルコキシド等の金属ハロゲン化合物、（ｃ）アルミナ、シリカ・アルミナ等の固体酸などを挙げることができる。
【００７３】
（エ）ケイ酸塩を除くイオン交換性層状化合物は、イオン結合等によって構成される面が互いに弱い結合力で平行に積み重なった結晶構造をとる化合物であり、含有するイオンが交換可能なものを言う。
ケイ酸塩を除くイオン交換性層状化合物は、六方最密パッキング型、アンチモン型、ＣｄＣｌ₂ 型、ＣｄＩ₂型等の層状の結晶構造を有するイオン結晶性化合物等を例示することができる。具体的には、α−Ｚｒ（ＨＡｓＯ₄ ）₂・Ｈ₂Ｏ、α−Ｚｒ（ＨＰＯ₄）₂、α−Ｚｒ（ＫＰＯ₄）₂・３Ｈ₂Ｏ、α−Ｔｉ（ＨＰＯ₄）₂、α−Ｔｉ（ＨＡｓＯ₄）₂・Ｈ₂Ｏ、α−Ｓｎ（ＨＰＯ₄）₂・Ｈ₂Ｏ、(−Ｚｒ（ＨＰＯ₄）₂、(−Ｔｉ（ＨＰＯ₄）₂、(−Ｔｉ（ＮＨ₄ＰＯ₄）₂・Ｈ₂Ｏ等の多価金属の結晶性酸性塩があげられる。
【００７４】
また、無機ケイ酸塩としては、粘土、粘土鉱物、ゼオライト、珪藻土等が挙げられる。これらは、合成品を用いてもよいし、天然に産出する鉱物を用いてもよい。
粘土、粘土鉱物の具体例としては、アロフェン等のアロフェン族、ディッカイト、ナクライト、カオリナイト、アノーキサイト等のカオリン族、メタハロイサイト、ハロイサイト等のハロイサイト族、クリソタイル、リザルダイト、アンチゴライト等の蛇紋石族、モンモリロナイト、ザウコナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト等のスメクタイト、バーミキュライト等のバーミキュライト鉱物、イライト、セリサイト、海緑石等の雲母鉱物、アタパルジャイト、セピオライト、パイゴルスカイト、ベントナイト、木節粘土、ガイロメ粘土、ヒシンゲル石、パイロフィライト、リョクデイ石群等が挙げられる。これらは混合層を形成していてもよい。
【００７５】
人工合成物としては、合成雲母、合成ヘクトライト、合成サポナイト、合成テニオライト等が挙げられる。
これら具体例のうち好ましくは、ディッカイト、ナクライト、カオリナイト、アノーキサイト等のカオリン族、メタハロサイト、ハロサイト等のハロサイト族、クリソタイル、リザルダイト、アンチゴライト等の蛇紋石族、モンモリロナイト、ザウコナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト等のスメクタイト、バーミキュライト等のバーミキュライト鉱物、イライト、セリサイト、海緑石等の雲母鉱物、合成雲母、合成ヘクトライト、合成サポナイト、合成テニオライトが挙げられ、特に好ましくはモンモリロナイト、ザウコナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト等のスメクタイト、バーミキュライト等のバーミキュライト鉱物、合成雲母、合成ヘクトライト、合成サポナイト、合成テニオライトが挙げられる。
【００７６】
これら、ケイ酸塩を除くイオン交換性層状化合物、または無機ケイ酸塩は、そのまま用いてもよいが、塩酸、硝酸、硫酸等による酸処理および／または、ＬｉＣｌ、ＮａＣｌ、ＫＣｌ、ＣａＣｌ₂ 、ＭｇＣｌ₂ 、Ｌｉ₂ＳＯ₄、ＭｇＳＯ₄、ＺｎＳＯ₄、Ｔｉ（ＳＯ₄）₂、Ｚｒ（ＳＯ₄ ）₂、Ａｌ₂ （ＳＯ₄ ）₃等の塩類処理を行ったほうが好ましい。なお、処理にあたり、対応する酸と塩基を混合して反応系内で塩を生成させて処理を行ってもよい。また、粉砕や造粒等の形状制御を行ってもよく、粒子流動性に優れた固体触媒成分を得るためには、造粒することが好ましい。また、上記成分は、通常脱水乾燥してから用いる。これら助触媒成分としては、重合活性等の触媒性能の面で、（エ）のケイ酸塩を除くイオン交換性層状化合物または無機ケイ酸塩を用いることが好ましい。
【００７７】
本発明の重合においては、助触媒成分の任意成分として、有機アルミニウム化合物を用いてもよい。このような有機アルミニウム化合物は、ＡｌＲ¹ _mＺ_3-m（式中、Ｒ¹は、炭素数１〜２０の炭化水素基、Ｚは、水素、ハロゲン、アルコキシ基もしくはアリールオキシ基、ｍは０＜ｍ≦３の数）で示される化合物である。
【００７８】
具体的にはトリメチルアルミニウム、トリエチルアルミニウム、トリプロピルアルミニウム、トリイソブチルアルミニウム等のトリアルキルアルミニウム、またはジエチルアルミニウムモノクロライド、ジエチルアルミニウムエトキシド等のハロゲンもしくはアルコキシ含有アルキルアルミニウム、または、ジエチルアルミニウムハイドライド、ジイソブチルアルミニウムハイドライド等の水素含有有機アルミニウム化合物である。またこの他、メチルアルミノキサン等のアルミノキサン等も使用できる。これらのうち、特に好ましいのはトリアルキルアルミニウムである。これら任意成分は２種以上組み合わせて用いてもよい。また、重合開始後等に、新たに該任意成分を追加してもよい。
▲２▼ 触媒調製方法
本発明の触媒は、遷移金属成分、助触媒成分、任意に有機アルミニウム化合物成分の接触によって得られるが、その接触方法については特に限定がない。この接触は、触媒調製時だけでなく、プロピレンによる予備重合時または重合時に行ってもよい。
【００７９】
触媒各成分の接触時、または接触後にポリエチレン、ポリプロピレン等の重合体、シリカ、アルミナ等の無機酸化物の固体を共存させるか、もしくは接触させてもよい。
接触は窒素等の不活性ガス中で行ってもよいし、ペンタン、ヘキサン、ヘプタン、トルエン、キシレン等の不活性炭化水素溶媒中で行ってもよい。これらの溶媒は、水や硫黄化合物などの被毒物質を除去する操作を施したものを使用するのが好ましい。接触温度は、２０℃ないし、使用する溶媒の沸点の間で行い、特には、室温から使用する溶媒の沸点の間で行うのが好ましい。
▲３▼ 触媒使用量
触媒各成分の使用量に特に制限はないが、助触媒成分として、ケイ酸塩を除くイオン交換性層状化合物、または無機ケイ酸塩を用いる場合は、助触媒成分１ｇあたり、遷移金属成分が通常０．０００１ｍｍｏｌ以上、好ましくは０．００１ｍｍｏｌ以上であって、通常１０ｍｍｏｌ以下、好ましくは５ｍｍｏｌ以下であり、任意成分である有機アルミニウム化合物が通常０ｍｍｏｌ以上、好ましくは０．０１ｍｍｏｌ以上であって、通常１０，０００ｍｍｏｌ以下、好ましくは１００ｍｍｏｌ以下となるように設定することにより、重合活性などの点で好適な結果が得られる。また、遷移金属成分中の遷移金属と任意成分である有機アルミニウム化合物中のアルミニウムの原子比が通常１：０以上、好ましくは１：０．１以上であって、通常１：１，０００，０００以下、好ましくは、１：１００，０００以下となるように制御することが、同様に重合活性などの点で好ましい。
▲４▼ 触媒洗浄
このようにして得られた触媒は、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、トルエン、キシレン等の不活性炭化水素溶媒で洗浄して使用してもよいし、洗浄せずに用いてもよい。
【００８０】
洗浄の際に、必要に応じて、新たに上述の有機アルミニウム化合物を組合せて用いてもよい。この際に用いられる有機アルミニウム化合物の量は、遷移金属成分中の遷移金属に対する有機アルミニウム化合物中のアルミニウムの原子比で１：０〜１０，０００になるようにするのが好ましい。
▲５▼ 予備重合
触媒として、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−オクテン、４−メチル−１−ペンテン、３−メチル−１−ブテン、ビニルシクロアルカン、スチレン等のα−オレフィンを予備的に重合し、必要に応じて洗浄したものを使用することもできる。この予備重合は窒素等の不活性ガス中、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、トルエン、キシレン等の不活性炭化水素溶媒中で行ってもよい。
▲６▼ 重合反応
本発明におけるプロピレンとエチレンの共重合反応は、プロパン、ｎ−ブタン、イソブタン、ｎ−ヘキサン、ｎ−ヘプタン、トルエン、キシレン、シクロヘキサン、メチルシクロヘキサン等の不活性炭化水素や液化α−オレフィン等の液体の存在下あるいは不在下に行われる。これらのうち、上述の不活性炭化水素存在下で共重合を行うのが好ましい。また、ここで記載した化合物の混合物を溶媒として使用してもよい。
【００８１】
具体的には、遷移金属成分と助触媒成分、もしくは、遷移金属成分、助触媒成分および任意成分としての有機アルミニウム化合物の存在下に、プロピレン系共重合体を製造するのが好ましい。
▲７▼ 重合反応条件
重合温度、重合圧力および重合時間に特に制限はないが、通常は、以下の範囲から生産性やプロセスの能力を考慮して、最適な設定を行うことができる。すなわち、重合温度は通常２０℃から１５０℃、好ましくは０℃から１００℃、重合圧力は、０．１ＭＰａから１００ＭＰａ、好ましくは、０．３ＭＰａから１０ａ、さらに好ましくは、０．５ＭＰａから４ＭＰａ、重合時間は、０．１時間から１０時間、好ましくは、０．３時間から７時間、さらに好ましくは０．５時間から６時間の範囲から選ぶことができる。
【００８２】
本発明において、重合体の重量平均分子量Ｍｗを調製する必要がある場合には、従来公知の方法を使用することができる。すなわち、重合温度を制御して分子量を調節する方法、モノマー濃度を制御して分子量を調節する方法、連鎖移動剤を使用して分子量を制御する方法等が挙げられる。また、触媒の構造によって分子量を制御することもできる。特に、架橋メタロセンを用いる場合には、架橋基の橋頭を基点としてα−位の構造が重要である。一般的に、α−位が水素原子である場合には、重合時に成長ポリマー鎖からのβ−水素脱離が起きやすいため、生成する重合体は低分子量になりやすい。これに対して、α−位になんらかの置換基（たとえば、メチル基など）がある場合には、成長ポリマー鎖からのβ−水素脱離が抑制されるので、高分子量の重合体が生成しやすい。
【００８３】
本発明の極性基含有プロピレン系重合体においては、主鎖におけるプロピレン連鎖部分が、アイソタクチックブロックと非晶性ブロックからなるステレオブロック構造を有していることが必要である。このためには、重合時に立体選択性を制御して、ステレオブロック構造を形成させるのが好ましい。
立体選択性の制御方法に特に制限はないが、一般的には、触媒の構造で制御する方法、重合条件を制御して制御する方法等が挙げられる。触媒の構造で制御する場合には、遷移金属成分を構成する配位子の構造が重要である。特に、架橋メタロセンを用いる場合には、架橋基の橋頭を基点としてα−位の置換基が重要である。一般的には、α−位にある程度かさだかい置換基がある場合に、立体選択性が向上しやすい。さらに、インデニル基やアズレニル基などの縮合環を有する配位子を含む架橋メタロセンを用いる場合には、４−位の置換基の構造も立体選択性に大きな影響を与える。一般的には、４−位にある程度かさだかい置換基がある場合に、立体選択性が向上しやすい。逆に、４−位に、立体的に比較的小さい置換基を導入することにより、効果的に立体選択性を低下させ、生成重合体の結晶性を低下させるという制御が可能となる。
【００８４】
本発明の極性基含有プロピレン系重合体の製造を、Ｃ₁−対称アンサメタロセンを用いて行う場合、位置不規則単位、すなわち、２，１−挿入したプロピレン単量体および／または１，３−挿入したプロピレン単量体に基づく位置不規則単位が、該極性基含有プロピレン系重合体主鎖中に存在し、全プロピレン挿入に対する該２，１−挿入と１，３−挿入に基づく位置不規則単位のそれぞれの比率の和が０．０５％以上であることが好ましい。
【００８５】
プロピレンの重合は、メチレン基が触媒の活性サイトと結合する１，２−挿入で進行するのが普通であるが、まれに、２，１−挿入あるいは１，３−挿入することがある。プロピレン連鎖において２，１−挿入されたプロピレン単量体は、下記部分構造（Ｉ）および（ＩＩ）で表される位置不規則単位を形成する。このように、部分構造（Ｉ）および（ＩＩ）の両者が主鎖中に存在するのは、本発明のプロピレン系共重合体の特徴のひとつである。また、プロピレン連鎖において１，３−挿入されたプロピレン単量体は、重合体主鎖中において、下記部分構造（ＩＩＩ）で表される位置不規則単位を形成する。
【００８６】
また、該極性基含有プロピレン系重合体の主鎖がプロピレンとエチレンの共重合体の場合には、プロピレンが２，１−挿入した後に、エチレンが挿入し、ついでプロピレンが正常に１，２−挿入するという構造（部分構造IV）も、好ましい部分構造のひとつである。
【００８７】
【化５】

【００８８】
本発明において、全プロピレン挿入に対する２，１−挿入したプロピレンの割合、および、１，３−挿入したプロピレンの割合は、下記式で計算される。
【００８９】
【数１】

【００９０】
式中、ΣＩ（ｘ−ｙ）は、¹³Ｃ−ＮＭＲスペクトルにおいて、ｘｐｐｍからｙｐｐｍに現れる信号の積分強度和を表す。
なお、１４．２〜１８．０ｐｐｍに現れる信号は、２，１−挿入したプロピレンのメチル基の炭素に由来するものであり、３３．５〜３４．２ｐｐｍに現れる信号は、^tＰＥＰなる構造において、２，１−挿入したプロピレンのメチル基の炭素に由来する。ここで、Ｐはプロピレン、^tＰは２，１−挿入したプロピレン、Ｅはエチレンを示す。１４．２〜２３．５ｐｐｍに現れる信号は、１，２−挿入および２，１−挿入したプロピレンのメチル基の炭素に由来するものであり、また、２７．５〜２８．０ｐｐｍに現れる信号は、１，３−挿入したプロピレン中の２個のメチレン炭素に由来するものである。
【００９１】
このような位置不規則単位は、一般に重合体の結晶性を低下させるため、本発明においては、該極性基含有プロピレン系重合体の成形体表面への偏在性を向上させる作用をしているものと考えられる。なお、プロピレン重合体の結晶性を低下させる別の手段として、メチル基の立体規則性を低下させる方法があるが、一般に、この手法でできたポリマーを用いると、成形体表面のべたつきが顕著になる傾向があり、応用上好ましくない。このため、べたつきを抑制しようとしてメチル基の立体規則性を上げると、今度は、該極性基含有プロピレン系重合体の成形体表面への偏在性が低下し、塗装性が損なわれる傾向があり、これも応用上好ましくない。このように、成形体表面への偏在性ならびに塗装性を考慮すると、位置不規則単位を適度に主鎖に持つ構造が、両者のバランス上好ましいと言える。
【００９２】
本発明においては、２，１−挿入したプロピレン単量体および１，３−挿入したプロピレン単量体の両者に基づく位置不規則単位が主鎖中に存在するものが、より効果的に結晶性を低下させ、溶媒への溶解度を向上させるうえで好ましい。また、１，３−挿入に基づく位置不規則単位の比率が２，１−挿入に基づく位置不規則単位の比率よりも多い方が、成形体表面への偏在性や塗装性などを総合した性能において良好な物性となるため、より一層好ましい。
【００９３】
主鎖中における２，１−挿入および／または１，３−挿入の量を制御する方法については、（ｉ）重合触媒の構造によって制御する方法、（ｉｉ）重合温度によって制御する方法、（ｉｉｉ）モノマー濃度によって制御する方法等を挙げることができる。２，１−挿入および／または１，３−挿入量の温度依存性や、モノマー濃度依存性は、使用する触媒によって異なるので一概に言うことはできない。したがって、使用する触媒の性質にもとづいて、これらの条件を制御することが肝要である。
▲８▼ 変性方法
本発明において、はじめにプロピレン重合体を製造し、その後極性モノマーにて変性する方法にて極性基含有プロピレン重合体を製造する場合、変性前のプロピレン重合体は、末端に不飽和結合を有するものが好ましい。不飽和結合があることによって、例えば、ラジカルグラフト法によって極性モノマーを導入する場合、グラフト効率が向上する。このような末端不飽和プロピレン重合体は、一般に、メタロセン触媒を用い、無水素条件下で重合を行うことによって製造することができる。
【００９４】
グラフト変性重合体中におけるカルボキシル基等を含有する重合性単量体の変性重合体中の含有量について特に制限はないが、塗装性と外観が共に良好となるように、通常０．０１重量％以上、好ましくは０．１重量％以上であって、通常２５重量％以下、好ましくは１５重量％以下となるようにグラフト共重合する。極性基を有する重合性単量体をグラフト共重合させる方法としては、種々の公知の方法が挙げられる。例えば、プロピレン系重合体を有機溶媒に溶解し、重合性単量体およびラジカル重合開始剤を添加して加熱攪拌することによりグラフト共重合反応を行う方法、実質的に溶媒を使用することなく、プロピレン重合体、重合性単量体およびラジカル重合開始剤を加熱溶融させて攪拌することによりグラフト共重合反応を行う方法、押出機を用いて、プロピレン重合体、重合性単量体およびラジカル重合開始剤を溶融混練することによりグラフト共重合反応を行う方法が挙げられる。これらのうち、プロピレン系重合体を有機溶媒に溶解し、重合性単量体およびラジカル重合開始剤を添加して加熱攪拌することによりグラフト共重合反応を行う方法が、変性率の制御が比較的容易であるうえ、変性後に変性重合体を容易に洗浄できるため好ましい。
（ｉｉ）プロピレンと極性モノマーを直接共重合する方法
この方法は、プロピレンの重合触媒として、ＩＶ族の遷移金属を有する触媒を用いる方法と、Ｖ〜ＶＩＩＩ族の遷移金属を有する触媒を用いる方法に大別できる。両者に共通して応用可能な方法のひとつは、極性モノマーの極性基をマスクして、触媒を被毒しないようにしてプロピレンと共重合する方法である。たとえば、水酸基を有するビニルモノマーに、有機アルミニウム化合物を反応させることによって、水酸基をマスクすることができる。また、別の方法としては、極性モノマーの極性基と重合に関わる炭素−炭素二重結合のあいだに、メチレン基のようなスペーサーをいれ、両者の距離を遠くすることによってプロピレンと共重合する方法が挙げられる。また、Ｖ〜ＶＩＩＩ族の遷移金属を有する触媒を用いる場合には、これらの遷移金属は、比較的極性基に対する耐性が強いので、極性基をマスクすることなく、直接プロピレンとの共重合が可能な場合がある。
【００９５】
又、共重合方法としては前記（ｉ）で記載したのと同様のものが挙げられる。［３］ 配合成分の混練
本発明のプロピレン系樹脂組成物は、特に制限なく、従来公知の方法で、各配合成分を混合し、溶融混練することにより製造される。
すなわち、本発明のプロピレン系樹脂組成物は、各配合成分を配合し、一軸押出機、二軸押出機、バンバリーミキサー、ロールミキサー、ブラベンダープラストグラフ、ニーダー等の通常の混練機を用いて混練・造粒することによって得られる。
【００９６】
この場合、各成分の分散を良好にすることができる混練・造粒方法を選択することが好ましく、通常は二軸押出機を用いて行われる。この混練・造粒の際には、各成分の配合物を同時に混練してもよく、また性能向上をはかるべく各成分を分割して混練する、例えば、まずプロピレン系重合体の一部または全部とエラストマーとを混練し、その後に残りの成分を混練・造粒するといった方法を採用することもできる。
【００９７】
（Ｂ）成分と（Ａ）成分との混合比率は特に制限はないが、好ましくは、（Ａ）成分１００重量部に対して、通常１重量部以上、好ましくは２重量部以上、より好ましくは３重量部以上、通常１５重量部以下、好ましくは１３重量部以下、より好ましくは１０重量部以下、さらに好ましくは８重量部以下となるように混合される。混合比率が１重量部未満では、塗装性が劣る傾向があり、１５重量部を超えると、耐衝撃性、耐熱性等の物性低下が大きくなる傾向がある。
【００９８】
（Ｂ）成分と（Ａ）成分の相対的な分子量については特に制限はないが、一般的には、（Ｂ）成分の分子量を（Ａ）成分の分子量よりも低くすることが、（Ｂ）成分の分散性向上の観点から好ましい。
（ｉ）許容可能な配合剤
本発明のプロピレン系樹脂組成物には、上述した成分の他に、必要に応じて、本発明の効果が著しく損なわれない範囲内で、その他の成分が配合されていてもよい。このようなその他の配合成分としては、着色するための顔料、フェノール系、イオウ系、リン系などの酸化防止剤、帯電防止剤、ヒンダードアミン等光安定剤、紫外線吸収剤、有機アルミ・タルク等の各種核剤、分散剤、中和剤、発泡剤、銅害防止剤、滑剤、難燃剤、等を挙げることができる。
【００９９】
また、必要に応じて、ポリヒドロキシポリオレフィンを配合してもよい。ここで、必要に応じて使用されるポリヒドロキシポリオレフィンは、分子末端に水酸基を有する低分子量ポリオレフィンであり、好ましくは、分子量が１０００〜５０００のものである。このようなポリヒドロキシポリオレフィンは、共役ジエンモノマーをアニオン重合等により重合させ、それを加水分解して得たポリマーを水素添加することにより得られる。具体的には、三菱化学社製の商品名ポリテールＨ （Ｐｏｌｙｔａｉｌ Ｈ）が挙げられる。
【０１００】
本発明において、必要に応じて使用されるポリヒドロキシポリオレフィンは、水酸基価（ｍｇＫＯＨ／ｇ）で、２０以上１００以下が好ましい。水酸基価が２０未満では塗膜との反応性が不足し、１００を超えると樹脂との相溶性が悪化するため、それぞれ塗膜との密着性が低下し、好ましくない。
また、必要に応じて、エチレン・オクテンランダム共重合体および／またはエチレン・ブテンランダム共重合体を配合してもよい。本発明で使用されるエチレン・オクテンおよび／またはエチレン・ブテンランダム共重合体成分は、耐衝撃性を向上しつつ、かつ良好な成形性、物性、収縮特性を発現させる目的で用いるものである。これらの共重合体において、エチレンと共重合されるコモノマーは１−オクテンまたは１−ブテンであり、そのコモノマー含量は通常２８重量％以上、通常６０重量％以下、好ましくは５０重量％以下である。これらの共重合体のＭＦＲは、通常０．５ ｇ／１０ｍｉｎ以上、好ましくは０．７ｇ／１０ｍｉｎ以上、特に好ましくは０．９ｇ／１０ｍｉｎ以上であって、通常２０ｇ／１０ｍｉｎ以下、好ましくは１５ｇ／１０ｍｉｎ以下、特に好ましくは１０ｇ／１０ｍｉｎ以下の範囲である。共重合コモノマー含量やＭＦＲが上記範囲を逸脱した場合、プロピレン系樹脂組成物の耐衝撃性や引張伸び、脆化温度等が不十分となりやすく、好ましくない。上記エチレン・オクテンランダム共重合体および／またはエチレン・ブテンランダム共重合体は、１種類である必要はなく、２種類以上の混合物であってもよい。
【０１０１】
さらに、本発明のプロピレン系樹脂組成物には、必要に応じて、スチレン系水添ブロック共重合ゴムを配合してもよい。エチレン・オクテンランダム共重合体および／またはエチレン・ブテンランダム共重合体とスチレン系ブロック共重合ゴムの併用により、高度な物性バランスと成形性が可能となる。スチレン系水添ブロック共重合ゴムは、ポリスチレン構造を有するＡセグメントの含量が通常１重量％、好ましくは５重量％、さらに好ましくは７重量％以上であって、通常２５重量％以下、好ましくは２２重量％以下で、エチレン・ブテンまたはエチレン・プロピレン構造を示すＢセグメントと共に、Ａ−ＢまたはＡ−Ｂ−Ａタイプの構造を有するブロック共重合体である。Ａセグメントの含有量が２５重量％を超えると、脆化温度が劣るため好ましくない。なお、ポリスチレン構造単位の含有量は、赤外スペクトル分析法、¹³Ｃ−ＮＭＲ法などの常法によって測定される値である。スチレン系水添ブロック共重合ゴムの具体例としては、スチレン・エチレン・ブテン・スチレンブロック共重合体（ＳＥＢＳ）、スチレン・エチレン・プロピレン・スチレンブロック共重合体（ＳＥＰＳ）が挙げられる。該ブロック構造を有するエラストマー共重合体は、上記構造式に示すようなトリブロック構造とジブロック構造の混合物であってもよい。
【０１０２】
本発明において、必要に応じて用いられるタルクは、平均粒径が１０μｍ以下、好ましくは０．５〜８μｍである。平均粒径が上記範囲を逸脱すると、剛性が劣る。該平均粒径の測定は、レーザー回折法（例えば、堀場製作所製ＬＡ９２０Ｗ）や、液層沈降方式光透過法（例えば、島津製作所製ＣＰ型等）によって測定した粒度累積分布曲線から読み取った、累積量５０重量％の粒径値より求めることができる。これらタルクは、天然に産出されたものを機械的に微粉砕化することにより得られたものをさらに精密に分級することによって得られる。又、この分級操作は複数回重ねて行ってもよい。機械的に粉砕する方法としては、ジョークラッシャー、ハンマークラッシャー、ロールクラッシャー、スクリーンミル、ジェット粉砕機、コロイドミル、ローラーミル、振動ミル等の粉砕機を用いる方法が挙げられる。これらの粉砕されたタルクは、本発明で示される平均粒径に調整するために、サイクロン、サイクロンエアセパレーター、ミクロセパレーター、シャープカットセパレーター等の装置で、１回又は繰り返し湿式又は乾式分級する。本発明で用いるタルクを製造する際は、特定の粒径に粉砕した後、シャープカットセパレーターにて分級操作を行うのが好ましい。これらのタルクは、重合体との接着性或いは分散性を向上させる目的で、各種有機チタネート系カップリング剤、有機シランカップリング剤、不飽和カルボン酸、又はその無水物をグラフトした変性ポリオレフィン、脂肪酸、脂肪酸金属塩、脂肪酸エステル等によって表面処理したものを用いてもよい。
（ｉｉ）混合条件
前記した配合可能な配合剤は、任意の形態で配合できる。たとえば、固体で配合してもよいし、溶剤に溶解した溶液として、あるいは、溶剤に分散させたスラリーとして配合してもよい。
［４］ 成形
本発明のプロピレン系樹脂組成物は、公知の各種方法による成形に用いることができる。例えば射出成形（ガス射出成形も含む）、射出圧縮成形（プレスインジェクション）、押出成形、中空成形、カレンダー成形、インフレーション成形、一軸延伸フィルム成形、二軸延伸フィルム成形等にて成形することによって各種成形品を得ることができる。このうち、射出成形、射出圧縮成形がより好ましい。
＜プロピレン系樹脂組成物＞
上記の方法により、下記成分（Ａ）および（Ｂ）を含むプロピレン系樹脂組成物が得られる。
（Ａ）プロピレン単独重合体、プロピレンとプロピレン以外のα−オレフィンとの共重合体、または、これらの混合物。
（Ｂ）極性官能基を有するプロピレン系重合体であって、主鎖におけるプロピレン連鎖部分が、アイソタクチックブロックと非晶性ブロックからなるステレオブロック構造を有していることを特徴とする極性基含有プロピレン系重合体。
【０１０３】
本発明の組成物において、（Ａ）成分と（Ｂ）成分は互いに混合されて混合物を形成する。場合により、（Ａ）成分の一部と（Ｂ）成分の一部が化学的結合を形成してもよい。
なお、塗装性を向上させるためには、（Ｂ）成分の極性基が成形体の表面近傍に存在することが好ましい。具体的には、該極性基中のあるヘテロ原子に注目した場合、このヘテロ原子をＸ、炭素原子をＣとした場合、成形体の表面をＥＳＣＡで測定した際に、Ｘ／Ｃが、０．００１以上、１以下、好ましくは、０．００２以上０．８以下になるように調整することが好ましい。Ｘ／Ｃが０．００１未満では、成形体に塗装した際に、十分な塗膜密着性が得られない。また、Ｘ／Ｃが高すぎると、成形体スキン層の力学的強度が損なわれるため、これも好ましくない。Ｘ／Ｃを調整する方法に特に制限はないが、たとえば、（Ｂ）成分中の極性基含量を調整する方法、（Ｂ）成分の（Ａ）成分に対する混合比を調整する方法、射出成形時のｓｈｅａｒ ｒａｔｅを変える方法、多層成形を行う方法、成形後に表面を水や極性溶媒などで処理する方法などを挙げることができる。また、成形がしやすいことから、本発明の組成物のＭＦＲは通常０．１以上、好ましくは１以上、より好ましくは１０以上であり、通常１０００以下、好ましくは５００以下、より好ましくは３００以下である。
＜用途＞
本発明のプロピレン系樹脂組成物は、剛性、耐衝撃性、塗装性において高度な物性バランスを有しているため、各種工業部品分野、特に薄肉化、高機能化、大型化された各種成形品、例えばテレビケース、冷蔵庫外板、洗濯機外板などの家電機器部品などの各種工業部品用成形材料として、実用に十分な性能を有している。
【０１０４】
【実施例】
次に実施例によって本発明をさらに具体的に説明するが、本発明はその要旨を逸脱しない限りこれら実施例によって制約を受けるものではない。
以下の諸例において、メタロセンの合成工程は全て精製窒素雰囲気下で行い、エーテルおよびＴＨＦはＮａ−ベンゾフェノンで乾燥したものを用いた。トルエン及びｎ−ヘキサンは関東化学から購入した脱水溶媒を用いた。重合工程は、全て精製窒素雰囲気下で行い、溶媒は、モレキュラーシーブ（ＭＳ−４Ａ）で脱水した後に、精製窒素でバブリングして脱気して使用した。プロピレン系重合体の分子量ならびに融点の測定については、本明細書記載の方法で行った。
【０１０５】
各種物性の測定は、下記要領に従った。
（１） ＭＦＲ： ＪＩＳＫ７２１０に準拠し、２３０℃、２．１６ ｋｇ荷重で行った。
（２） 曲げ弾性率（単位： ＭＰａ）： ＪＩＳ−Ｋ７２０３に準拠して２３℃で測定した。
（３） アイゾット（Ｉｚｏｄ）衝撃強度（単位： ｋＪ／ｍ²）： ＪＩＳ−Ｋ７１１０に準拠し、２３℃、及び(３０℃で測定した。
（４） 荷重たわみ温度（単位： ℃）： ＪＩＳ−Ｋ７２０７に準拠して、４．６ ｋｇｆ／ｃｍ²の条件で測定した。
（５） 塗装性： 射出成形により成形した平板に、前処理を全く施すこと無く、エアースプレーガンを用いて、直接、水性メラミン系塗料を厚さ約１５ミクロンとなるようにスプレー塗布し、１２０℃で１時間焼付け乾燥した後、室温で４８時間放置する。この後、試験片表面に片刃カミソリを用い、直交する縦横１１本ずつの平行線を２ ｍｍ間隔で引き、碁盤目を１００個作る。その上にセロハン粘着テープ（ＪＩＳ−Ｚ１５２２）を充分圧着し、塗装面と粘着テープの角度を約３０度に保ちながら、一気に引き剥がす作業を５回繰り返し、碁盤目で囲まれた部分の状態を観察して、剥離しなかった碁盤目の数を評価する。
【０１０６】
成分（Ａ）としては、表１に示された物性を有するプロピレン・エチレンブロック共重合体（ＢＰＰ１〜ＢＰＰ３）を用いた。
【０１０７】
【表１】

【０１０８】
成分（Ｂ）の製造例
（製造例１）＜ステレオブロック構造を有している極性基含有プロピレン系重合体＞
（１）ジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ジルコニウムの合成
（１）−１ 配位子合成
２−メチルアズレン（１２．１０ｇ，０．０８５ｍｏｌ）をテトラヒドロフラン（１６８ｍｌ）に溶解し、アイスバスにて５℃に冷却した後、同温度でメチルリチウムのジエチルエーテル溶液１．０４ ｍｏｌ／ｌ，８３ｍｌ，０．０８６ｍｏｌ）を滴下した。滴下終了後、アイスバスを外して３時間攪拌した。この溶液を、アイスバスにて５℃に冷却したジメチルシリルジクロリド（２２．５ ｍｌ，０．１８５ｍｏｌ）のテトラヒドロフラン溶液（４２０ｍｌ）にゆっくり滴下した。滴下終了後、アイスバスを外して３時間攪拌した後、減圧下に溶媒および未反応のジメチルシリルジクロリドを留去した。残渣にテトラヒドロフラン（２４０ｍｌ）を加えて０℃まで冷却し、シクロペンタジエニルナトリウム（２．１ ｍｏｌ／ｌ，８１ ｍｌ，０．１６０ｍｏｌ）を徐々に滴下した。その後、徐々に室温まで上げ、昼夜撹拌を行った。攪拌終了後、水を加え、ジエチルエーテルで目的とする化合物を抽出した。抽出溶液を硫酸マグネシウムで脱水した後、乾固することにより配位子の未精製品を得た（２３．５４ｇ，収率９８．８％）。
（１）−２ 錯体合成
（１）−１で得られた配位子（１０．５６ｇ，３７．６ｍｍｏｌ）をテトラヒドロフラン（９０ｍｌ）で溶解し、アイスバスにて５℃に冷却した。同温度に保ちながら、そこにｎ−ブチルリチウムのｎ−ヘキサン溶液（１．５９ｍｏｌ／ｌ，４７．３ｍｌ，７５．２ｍｍｏｌ）をゆっくり滴下した。滴下終了後、アイスバスをはずして２時間攪拌し、減圧下に溶媒を留去した。留去後得られた残渣にテトラヒドロフラン（１０ｍｌ）とトルエン（２００ｍｌ）を加えた後、７８℃に冷却した。そこにジルコニウムテトラクロリド（８．７３ｇ，３７．５ｍｍｏｌ）をゆっくり添加した。その後、冷却浴をはずして終夜攪拌した。攪拌終了後、反応液をＧ３フリットで濾過した。フリット上の固体をさらにトルエンで洗浄し、濾液を濃縮することにより、褐色の粉末が得られた。得られた褐色粉末に、トルエン（７０ｍｌ）および、ｎ−ヘキサン（１００ｍｌ）を加えた。上澄み液を分取した後、それを濃縮した。濃縮後の残渣をｎ−ヘキサン（２０ｍｌ，２回）、ジエチルエーテル（１５ｍｌ，２回）で洗浄した。この洗浄操作を更に２回繰り返した後、乾固することにより目的錯体を得た（２．２９ ｇ，収率１３．８％）。
【０１０９】
¹Ｈ−ＮＭＲ（ＣＤＣｌ₃）：δ ０．８５（ｓ，３Ｈ），０．８８（ｓ，３Ｈ），１．４７（ｄ，Ｊ＝７．２Ｈｚ，３Ｈ），２．１６（ｓ，３Ｈ），３．３８−３．５０（ｍ，１Ｈ），５．２７（ｄｄ，Ｊ＝４．８，６．０ Ｈｚ，１Ｈ），５．８０−５．８５（ｍ，２Ｈ），５．９５−５．９９（ｍ，１Ｈ），６．６５（ｄｄ，Ｊ＝５．４０，１１．３Ｈｚ，１Ｈ），６．３２（ｓ，１Ｈ），６．５８（ｄ，Ｊ＝１１．７Ｈｚ，１Ｈ），６．９０−６．９５（ｍ，１Ｈ），７．０８−７．１０（ｍ，１Ｈ）。
（２） 粘土鉱物の化学処理
３００ｍｌ丸底フラスコに、脱塩水（９３．６ｍｌ）、硫酸リチウム・１水和物（１４．５ｇ）および硫酸（２２．１ｇ）を採取し、攪拌下に溶解させた。この溶液に、モンモリロナイト（水澤化学製水澤スメクタイト） ２９．４ｇを添加し、昇温して還流下に１２０分間処理した。処理後、脱塩水４００ｍｌを加えて遠心分離後、上澄み液を除去した。さらに脱塩水４００ｍｌを加え、遠心分離ならびに上澄み液の除去を２回繰り返し、最後に残留物を濾過した。得られた固体を１００℃で乾燥した。次に、ここで得られた乾燥固体を、１００ｍｌ丸底フラスコに０．５ｇ採取し、減圧下２００℃で２時間加熱乾燥させた。終了後、精製窒素下でトリエチルアルミニウムのトルエン溶液（０．４５ｍｍｏｌ／ｍｌ）を２．３ｍｌ添加し、室温で３０分反応させた後、トルエン２０ｍｌで２回洗浄し、化学処理モンモリロナイトのトルエンスラリーを得た。
（３） 触媒調製
トリイソブチルアルミニウムのトルエン溶液（０．１ｍｍｏｌ／ｍｌ）３．９ｍｌと、（１）で合成したジクロロ［ジメチルシリレン（シクロペンタジエニル）（２，４−ジメチル−４Ｈ−１−アズレニル）］ジルコニウム１７ｍｇおよびトルエン９．１ｍｌを５０ｍｌのナスフラスコに加え、室温で５分間攪拌した。この錯体溶液４．７ｍｌを、（２）で得られた化学処理モンモリロナイトのトルエンスラリー０．９ｍｌ（固形分として４６９．６ｍｇを含有）に添加し、室温で１０分間攪拌し、触媒スラリーを得た。
（４） プロピレン重合
いかり型攪拌翼を内蔵する２リッターの誘導攪拌式オートクレーブを精製窒素で置換し、トリイソブチルアルミニウムのトルエン溶液（０．１ｍｍｏｌ／ｍｌ）を２．５ｍｌ装入した。（３）で得られた触媒スラリーを、該オートクレーブに全量装入し、さらに、液化プロピレン６２５ｇを装入した。オートクレーブを昇温し、内温が８０℃で一定になるよう調整しながらプロピレンの重合を行った。内温が８０℃に到達した時点から８０分後に、未反応のプロピレンをパージして重合を停止させた。さらに、オートクレーブ内にメタノール５ｍｌを圧入し、残存する有機アルミニウム化合物および触媒を失活させた。次いで、内温を１２０℃まで昇温し、減圧下でメタノールなどの溶媒を留去した。最終的に得られたプロピレン重合体の収量は３８０ｇであった。
【０１１０】
得られた重合体の一部を分取して分析したところ、以下の結果が得られた。ＧＰＣによるＭｗ：１１，０００、Ｍｗ／Ｍｎ＝２．６。¹³Ｃ−ＮＭＲによるｈｅａｄ ｔｏ ｔａｉｌ結合からなるプロピレン単位連鎖部のメチル基の炭素原子に由来するピーク： Ｓ₁／Ｓ＝３３．３（％）、４＋２Ｓ₁／Ｓ₂＝７．９、¹³Ｃ−ＮＭＲにより測定した全プロピレン挿入に対する２，１−挿入の比率は０．０４（％）であり、１，３−挿入の比率は０．１４（％）であった。¹Ｈ−ＮＭＲにより停止末端の不飽和結合量を測定したところ、ビニリデン末端が１９．４（％）、ビニル末端が６．４（％）であった。得られた重合体についてＤＳＣを測定したところ、明確な融点ピークは観測されなかった。また、得られた重合体の溶解度を測定したところ、以下の結果が得られた。ｎ−ヘプタンへの溶解度（温度＝９８℃，濃度＝１０ｗｔ％）：ポリマーは完全に溶解し、不溶分は観察されなかった。トルエンへの溶解度（温度＝２５℃，濃度＝１０ｗｔ％）：ポリマーは完全に溶解し、不溶分は観察されなかった。
（５） 無水マレイン酸変性重合体の製造
（４）で得られたオートクレーブ内のプロピレン重合体３６８ｇ（１００部）に、キシレン１８．４ｇ（５部）に加熱溶解させた無水マレイン酸１８．４ｇ（５部）を装入後、さらにキシレン１８．４ｇ（５部）を追加した。オートクレーブ内温を１７０℃まで昇温させた後、パーブチルＩ（日本油脂（株）製）３．６８ｇ（１部）をキシレン１８．４ｇ（５部）に分散させた液を、分割して５分おきに３０分かけて圧入した。パーブチルＩの添加を終えた後、引き続き１７０℃で６０分間反応を行った。反応終了後、減圧下、２００℃で未反応の無水マレイン酸を６０分間留去した。得られた変性重合体の一部を取り出して分析したところ、変性重合体中の無水マレイン酸含量は、１．４ｍｏｌ％であった。
（６） イミド変性重合体の製造
（５）で得られた無水マレイン酸変性重合体を、オートクレーブから取り出すことなく、１２０℃に昇温した。次いで、２−アミノエタノール９．２ｇを圧入し、さらにキシレンを２０ｍｌずつ５回装入した。１２０℃で６０分間イミド化反応を行い、反応終了後、イミド変性重合体を、大量のアセトンを用いて再沈させた。さらにアセトン洗浄を３回行い、未反応物を除去したうえで、１２０℃にて６時間減圧乾燥を行った。この変性体のイミド含量をＩＲスペクトルで定量したところ、０．９ｍｏｌ％であった。平均分子量、分子量分布、主鎖の立体構造およびその他の物性は、（４）で得たポリマーに対して変化が見られなかった。（製造例２）＜ステレオブロック構造を有している極性基含有プロピレン系重合体＞
製造例１ （４）で得られたプロピレン重合体に対して、無水マレイン酸の使用量を３６．８ｇにした以外は、製造例１（５）と同様の操作により無水マレイン酸変性重合体の製造を行った。得られた無水マレイン酸変性重合体の一部を取り出して分析したところ、変性重合体中の無水マレイン酸含量は２．１ｍｏｌ％であった。
【０１１１】
つぎに、２−アミノエタノールの使用量を２７．６ｇとした以外は、製造例１（６）と同様にして、イミド変性重合体の製造を行った。得られた変性重合体中のイミド含量は１．４ｍｏｌ％であった。
（製造例３）＜ステレオブロック構造を有している極性基含有プロピレン系重合体＞
製造例１（４）で得られたプロピレン重合体に対して、無水マレイン酸の使用量を８．１ｇにした以外は、製造例１（５）と同様の操作により無水マレイン酸変性重合体の製造を行った。得られた無水マレイン酸変性重合体の一部を取り出して分析したところ、変性重合体中の無水マレイン酸含量は０．６ｍｏｌ％であった。
【０１１２】
つぎに、２−アミノエタノールの使用量を４．０ｇとした以外は、製造例１（６）と同様にして、イミド変性重合体の製造を行った。得られた変性重合体中のイミド含量は０．４ｍｏｌ％であった。
（製造例４）＜アイソタクチック構造の極性基含有ポリプロピレン＞
数平均分子量３０００のアイソタクチックポリプロピレンワックス（Ｓ₁／Ｓ＞９５％）３００重量部、無水マレイン酸２３重量部を、還流管を付けた反応器の中に仕込んだ。次いで、キシレン７００重量部を加え、反応器内部を窒素置換した。攪拌下、窒素を少量導入しながら１５０℃に昇温し、均一溶液を得た後、ジクミルパーオキサイド１６．５重量部を３時間かけて添加し、さらに４時間反応を続けた。その後、最初常圧で、次いで１８０℃、３ｍｍＨｇの減圧下、２時間かけてキシレンおよび未反応の無水マレイン酸を除去した。続いて、トルエン１２５０重量部を添加し、トルエン溶液中に酸変性ポリプロピレンを溶解させた後、モノエタノールアミン１２重量部を加え、５０℃で６０分間反応させた。得られた変性ポリプロピレンは、重量平均分子量７５００、グラフト率３．０ ｗｔ％であった。
（実施例１〜１０、比較例１〜４）
表２に示した配合組成に従い、成分（Ａ）（プロピレン・エチレンブロック共重合体）および成分（Ｂ）を配合し、フェノール系酸化防止剤（チバスペシャルティケミカルズ社製ＩＲＧＡＮＯＸ １０１０）０．１重量部、リン系酸化防止剤（チバスペシャルティケミカルズ社製Ｉｒｇａｆｏｓ １６８）０．０５重量部、ステアリン酸カルシウム０．３重量部と共に混合した後、２軸押出機（日本製鋼所製ＴＥＸ３０α）を用いて、スクリュー回転数３００ｒｐｍ、押出レート１５ ｋｇ／ｈで溶融混練し、プロピレン系樹脂組成物ペレットを得た。得られたペレットを用いて、金型温度４０℃、シリンダ温度２２０℃の条件で射出成形し、プロピレン系樹脂組成物の試験片とした。
【０１１３】
得られた試験片を用いて、上述の方法により、各種物性を評価した。評価結果を表２に示す。
【０１１４】
【表２】

【０１１５】
以上の実施例、比較例から明らかなとおり、成分（Ａ）であるプロピレン・エチレンブロック共重合体に対して配合する成分（Ｂ）が、ステレオブロック構造を有さない場合には、たとえその配合量を変化させても強度（アイゾッド衝撃）および耐熱性（荷重たわみ温度）と塗装性（碁盤目５回剥離後の残存率）とを両立させることはできないが、成分（Ｂ）として本発明に規定したステレオブロック構造を有する極性基含有プロピレン系重合体を用いると、これらの物性をバランス良く達成することができる。
【０１１６】
【発明の効果】
特定の構造を有する変性ポリプロピレンが配合された、本発明のプロピレン系樹脂組成物は、衝撃強度、曲げ剛性等の強度バランスに優れ、かつ、溶剤プライマーを塗布すること無く塗膜を密着せしめることが可能であるため、工業的に非常に有用なものである。さらに本発明のプロピレン系樹脂組成物は、水性塗料に対してプライマーレスで塗膜密着を実現するため、プライマーに起因する有機溶媒のみならず、塗料溶媒に起因する有機溶媒の使用量削減を実現せしめることが可能となり、環境負荷の低減に多大な効果をもたらす。さらに、本発明のプロピレン系樹脂組成物は、強度バランスにも優れるため、成形品の薄肉化が実現可能であり、特にその使用量が増大している自動車部品等では、軽量化に伴う燃費効率の向上にも繋がる技術である。このことは、エネルギー資源の節約、地球環境の保護といった近年の社会的な問題を解決する一つの有効な手段であると言うことができ、その工業的価値は極めて大きい。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a propylene-based resin composition having excellent paintability. Specifically, the present invention relates to a propylene-based resin composition having an excellent balance between paintability and mechanical properties.
[0002]
[Prior art]
Polypropylene is widely used as an injection molding material in the industrial parts field represented by parts for automobiles and home appliances. In particular, parts such as automobile bumpers, televisions, refrigerators, washing machines and vacuum cleaners are mainly made of polypropylene materials.
[0003]
In many cases, these parts are painted on the surface for designability, but since polypropylene has poor adhesion to the coating film, a primer is applied to the surface of the polypropylene part to make the coating film intimate. ing. However, since this primer contains an organic solvent as a solvent, it causes exhausted VOC and increases the environmental load.
[0004]
For this reason, attempts have been made to reduce the environmental load by imparting coating film adhesion to polypropylene itself, thereby allowing the coating film to adhere without applying a primer component.
In JP-A-62-2579946 (Patent Document 1), JP-A-9-48885 (Patent Document 2), etc., modified polypropylene obtained by grafting a polar functional group to polypropylene is kneaded into polypropylene as a coating modifier. A method for adhering a coating film without applying a primer is shown. However, in these methods, in order to adhere the coating film, a large amount of modified polypropylene has to be added, and this has the disadvantage that mechanical properties such as impact strength are greatly reduced. .
[0005]
Moreover, it is also desired to change the paint solvent from a conventional organic solvent to water due to the recent demand for reducing the environmental load. However, when the solvent is changed to water, the wettability between the paint solvent and the polypropylene is lowered, so that a larger amount of modified polypropylene must be added as compared with the case of using a conventional solvent-based paint. For this reason, in the conventional method, in order to satisfy the paintability with respect to the water-based paint, it is necessary to greatly sacrifice the mechanical properties.
[0006]
Against this background, the development of a propylene resin composition capable of primerless coating, in particular, a propylene resin composition capable of primerless coating which has an excellent balance between paintability and mechanical properties for water-based paints has been awaited.
[0007]
[Patent Document 1]
Japanese Patent Laid-Open No. 62-257946
[Patent Document 2]
JP-A-9-48885
[0008]
[Problems to be solved by the present invention]
An object of the present invention is to provide a propylene-based resin composition excellent in the balance between paintability and mechanical properties on the premise of primer-less coating of a water-based paint.
[0009]
[Means for Solving the Problems]
As a result of intensive studies on the propylene-based resin composition excellent in the balance between paintability and mechanical properties, the present inventors have used a polar group-containing propylene-based polymer having a specific structure as a coating modifying component. As a result, it was found that the paintability can be improved with a small blending amount. As a result, it was found that a propylene-based resin composition having an excellent balance between mechanical properties and paintability could be obtained, and the present invention was completed.
[0010]
  That is, the present invention is (A) a propylene homopolymer, a copolymer of propylene and an α-olefin other than propylene, or a mixture thereof, and (B) a propylene-based polymer having a polar functional group. The propylene chain portion in the main chain has a stereo block structure consisting of an isotactic block and an amorphous block.The propylene chain moiety is (a) ¹³ In the C-NMR spectrum, a peak derived from the carbon atom of the methyl group of the propylene unit chain part consisting of a head-to-tail bond was observed, and the chemical shift of the peak top of the peak attributed to the pentad represented by mmmm 21. The area of the peak of 8 ppm is S ₁ And the area of the peak having 21.5 to 21.6 ppm as the peak top attributed to the pentad represented by mmr is S ₂ 4 + 2S ₁ / S ₂ > 5, and (b) Similarly, the peak area S having a peak top of 21.8 ppm with respect to the total area S of peaks appearing at 19.8 to 22.2 ppm ₁ Ratio S ₁ / S is 10% or more and 90% or lessPolar group-containing propylene polymer,A novel propylene-based resin composition.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Embodiments of the present invention will be described below. The propylene resin composition of the present invention comprises a propylene polymer and a specific propylene polymer having a polar functional group.
<Method for producing propylene-based resin composition>
[1] Compounding ingredients
(A) Propylene polymer
The component (A) of the present invention is a propylene polymer. Here, the propylene-based polymer is a polymer having propylene as a main constituent unit, and is a propylene homopolymer, a copolymer of propylene and an α-olefin other than propylene, or a mixture thereof. . The structure of the propylene-based polymer, for example, stereoregularity, molecular weight, molecular weight distribution, propylene content, etc. is not particularly limited, and those having a necessary structure can be used depending on the purpose.
[0012]
When applied to industrial parts, generally, (i) propylene / ethylene block copolymer, (ii) propylene homopolymer, and (iii) propylene / ethylene random copolymer are preferably used. Hereinafter, these will be described in more detail.
(I) Propylene / ethylene block copolymer
The propylene / ethylene block copolymer preferably used is a propylene homopolymer portion having an isotactic pentad fraction of 0.9 or more, a glass transition temperature of −30 ° C. or less, and 135 ° C. in decalin. The measured intrinsic viscosity [η] has an ethylene / propylene copolymer portion of 3 to 15 (dl / g).
[0013]
The isotactic pentad fraction of the propylene homopolymer portion is 0.9 or more and 1.0 or less, preferably 0.950 or more, more preferably 0.980 or more, and usually 0.995 or less. . In general, the higher the isotactic pentad fraction, the more improved the rigidity and heat resistance of the molded body.
What is the isotactic pentad fraction?¹³It is an isotactic fraction of pentad units in a polypropylene molecular chain measured by a method using C-NMR. In other words, the isotactic pentad fraction is the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are connected and meso-bonded. In particular¹³The isotactic pentad fraction is measured as the intensity fraction of the mmmm peak in the total absorption peak of the methyl carbon region in the C-NMR spectrum.
[0014]
In the present invention¹³The measuring method of C-NMR spectrum is as follows.
350-500 mg of sample is completely dissolved in about 10 ml of NMR sample tube using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene is added as a lock solvent and homogenized, and then measurement is performed at 130 ° C. by a proton complete decoupling method. Measurement conditions are flip angle 90 °, pulse interval 5T.₁(T₁Is the longest value of the spin-lattice relaxation time of the methyl group. In the propylene polymer, since the spin lattice relaxation times of the methylene group and methine group are shorter than that of the methyl group, the recovery of the magnetization of all the carbons is 99% or more under this measurement condition. In order to improve the quantitative accuracy,¹³It is preferable to perform integration for 20 hours or more using an NMR apparatus having a resonance frequency of C nucleus of 125 MHz or more.
[0015]
The chemical shift is a methyl branch of 10 types of pentads (mmmm, mmr, rmmr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrr, mrrm) of propylene unit linkages composed of head-to-tail bonds. The absolute configuration of all is the same, that is, the chemical shift of the peak top of the peak based on the methyl group of the third unit of the 5-unit propylene unit expressed in mmmm is set as 21.8 ppm, and this is used as a reference. The chemical shift of the peak top of the peak based on the methyl group of the 3rd unit of the 5-unit chain is determined. According to this standard, for example, in the case of other five propylene units, the chemical shift at the peak top is generally as follows. That is, mmmr: 21.5 to 21.7 ppm, rmmr: 21.3 to 21.5 ppm, mmrr: 21.0 to 21.1 ppm, mmrm and rmrr: 20.8 to 21.0 ppm, rmrm: 20.6 ˜20.8 ppm, rrrr: 20.3 to 20.5 ppm, rrrm: 20.1 to 20.3 ppm, mrrm: 19.9 to 20.1 ppm. The chemical shift of the peak derived from these pentads varies somewhat depending on the NMR measurement conditions, and the peak is not necessarily a single peak, but a complex splitting pattern based on a fine structure ( It is necessary to perform the assignment with attention to the fact that it often indicates a split pattern).
[0016]
A propylene homopolymer portion having an isotactic pentad fraction of 0.9 or more can be produced using a stereoregular catalyst. Examples of the stereoregular catalyst include (a) a titanium trichloride-based catalyst, (b) a magnesium compound-supported catalyst, and (c) a single site catalyst. As a typical example of a titanium trichloride-based catalyst, titanium tetrachloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating with various electron donors and electron acceptors, an organoaluminum compound, and The catalyst which combined carboxylic acid ester can be mentioned. As a typical example of the magnesium compound-supported catalyst, a catalyst in which a solid catalyst component obtained by contacting titanium tetrachloride and an electron donor with magnesium halide, an organoaluminum compound, and an alkoxysilane can be given. Single-site catalysts can be broadly classified into two types: metallocene catalysts with cyclopentadienyl ligands and so-called post-metallocene catalysts without cyclopentadienyl ligands, both of which are transition metal complexes and activators. It is a catalyst consisting of a combination.
[0017]
The melt flow rate (MFR) of the propylene homopolymer portion is usually 10 g / 10 min or more, preferably 15 g / 10 min or more, and usually 300 g / 10 min or less, preferably 250 g / 10 min or less. If the MFR is less than 10, the fluidity of the propylene-based resin composition is inferior, and if it exceeds 300, the impact resistance is inferior. The MFR of the propylene homopolymer portion is measured at a temperature of 230 ° C. and a load of 21.18 N based on JIS K7210 condition 14. The MFR of the propylene homopolymer portion can be adjusted by controlling the polymerization temperature and the hydrogen concentration during the polymerization of the propylene homopolymer portion.
[0018]
In the propylene / ethylene copolymer part, ethylene and propylene are copolymerized under the above-mentioned catalyst, but other α-olefins such as butene, pentene, hexene, octene are also used as other copolymerization monomers. can do. The most preferred copolymer is a copolymer of propylene and ethylene from the viewpoint of compatibility with the propylene homopolymer and toughness.
[0019]
The intrinsic viscosity [η] of the propylene / ethylene copolymer portion measured in decalin at 135 ° C. is usually 3 dl / g or more, preferably 4 dl / g or more, more preferably 5 dl / g or more, usually 15 dl / g. Hereinafter, it is preferably 12 dl / g or less, more preferably 10 dl / g or less. When the intrinsic viscosity is less than 3, the toughness of the copolymer component itself is inferior, and when it exceeds 15, the dispersibility of the copolymer component is lowered, each of which becomes a factor of reducing impact resistance. The intrinsic viscosity of the propylene / ethylene copolymer portion is controlled by adjusting the polymerization temperature and the amount of hydrogen added when polymerizing the copolymer component.
[0020]
The propylene / ethylene copolymer component preferably has a glass transition temperature of −30 ° C. or lower. When the glass transition temperature is higher than −30 ° C., the impact resistance at low temperatures is deteriorated, so that it is not preferable particularly in applications requiring low temperature impact resistance. The glass transition temperature of the propylene / ethylene copolymer component is measured by a dynamic solid viscoelasticity measuring apparatus. The glass transition temperature of the propylene / ethylene copolymer component can be controlled by the copolymerization ratio of ethylene and the comonomer. In general, the copolymerization ratio of propylene to ethylene and / or α-olefin (excluding ethylene and propylene) is usually 1/99 or more, preferably 10/90 or more, more preferably 20 /, in weight ratio. 80 or more, usually 99/1 or less, preferably 90/10 or less, more preferably 80/20 or less.
[0021]
This propylene / ethylene block copolymer can be polymerized by any conventionally known method. For example, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, a slurry polymerization method, and the like can be mentioned. Polymerization can be carried out batchwise in one reactor, or polymerized in a continuous manner by combining a plurality of reactors. Also good.
(Ii) Propylene homopolymer
Preferably used as a propylene homopolymer is an isotactic pentad fraction of 0.9 or more and an MFR of usually 0.1 g / 10 min or more, preferably 0.2 g / 10 min or more, more preferably 0.5 g / The propylene homopolymer is 10 g or more and usually 300 g / 10 min or less, preferably 250 g / 10 min or less, more preferably 200 g / 10 min or less. As a catalyst for obtaining this polymer, the catalyst described in the section of (i) propylene / ethylene block copolymer can be used. The same applies to the MFR control method and manufacturing process.
[0022]
(Iii) Propylene / ethylene random copolymer
The propylene / ethylene random copolymer is preferably used with an ethylene content of 0.1 to 10 wt% and an MFR of usually 0.1 g / 10 min or more, preferably 0.2 g / 10 min or more, more preferably 0.5 g / It is a propylene / ethylene random copolymer of 10 min or more and 300 g / 10 min or less, preferably 250 g / 10 min or less, more preferably 200 g / 10 min or less. As a catalyst for obtaining this polymer, the catalyst described in the section of (1) propylene / ethylene block copolymer can be used. The same applies to the MFR control method. In addition to propylene and ethylene, a small amount of other α-olefins may be copolymerized. The ethylene content can be controlled by changing the ratio of propylene and ethylene in the polymerization vessel. Generally, the ethylene content is 0.1% by weight or more, preferably 0.5% by weight or more and 10% by weight or less, preferably 8% by weight or less.
[0023]
(B) Propylene polymer having a polar functional group
The propylene polymer having a polar functional group used in the present invention has a structure in which the propylene chain portion in the main chain has a structure having two or more isotactic blocks and amorphous blocks alternately. Containing propylene-based polymer. Here, the propylene-based polymer means a polymer mainly composed of propylene, and has a monomer unit having a polar group as a comonomer in a part of its structure. In addition to propylene and a monomer having a polar group, ethylene or a C 4-20 olefin may be included as a comonomer. In this case, the content of ethylene or a C 4-20 olefin is 10 mol% or less.
[0024]
(I) Stereo block structure
The polar group-containing propylene polymer in the present invention has a structure in which the propylene chain portion in the main chain has two or more isotactic blocks and amorphous blocks alternately as described above. ,¹³The following requirements defined by the C-NMR spectrum are satisfied.
That is,
(A)¹³In the C-NMR spectrum, a peak derived from the carbon atom of the methyl group in the propylene unit chain part consisting of a head-to-tail bond was observed, and the chemical shift of the peak top of the peak attributed to the pentad represented by mmmm was 21. The area of the peak with S.8 ppm and the peak top of 21.5-21.6 ppm attributed to the pentad represented by mmr is S₂4 + 2S₁/ S₂> 5.
(B) Similarly, the peak area S having 21.8 ppm as the peak top with respect to the total area S of peaks appearing from 19.8 ppm to 22.2 ppm.₁Ratio S₁/ S is 10% or more and 90% or less.
These are the two requirements.
[0025]
In the above requirement (a), 4 + 2S₁/ S₂The relational expression> 5 is closely related to an index named as isotactic block index (BI) by Waymouth et al. (See Japanese Patent Publication No. 9-510745). BI is an index representing the stereoblock property of the polymer. More specifically, BI represents the average chain length of an isotactic block having 4 or more propylene units, and is defined by BI = 4 + 2 [mmmm] / [mmmr]. (JW Collette et al., Macromol., 22, 3858 (1989); JC Randall, J. Polym. Sci. Polym. Phys. Ed., 14, 2083 (1976)). For statistically perfect atactic polypropylene, BI = 5. Therefore, BI = 4 + 2 [mmmm] / [mmmr]> 5 means that the average chain length of the isotactic block contained in the polymer is longer than that of the so-called atactic polypropylene. 4 + 2S₁/ S₂The requirement of> 5 indicates that the polymer of the present invention contains crystallizable chain length isotactic blocks, unlike atactic PP. Of the above BI, it is preferably 6 or more, more preferably 7 or more, and usually 500 or less, preferably 300 or less.
[0026]
On the other hand, the requirement (b) is that the polar group-containing propylene polymer of the present invention has incomplete isotacticity of the main chain, and the ratio of mmmm pentads in all pentads is 10% or more and 90% or less. Among these, 15% or more is preferable and 20% or more is more preferable. Further, the upper limit is preferably 80% or less, more preferably 60% or less, further preferably 50% or less, and most preferably less than 40%.
[0027]
Therefore, the polar group-containing propylene-based polymer of the present invention has both an isotactic block and a block composed of a sequence with disordered stereospecificity, that is, an amorphous block, in the main chain. Means.
S₁And S₂Examples of the method for controlling the amount to be in the range specified above include a method of controlling by the structure of the polymerization catalyst, a method of controlling by the polymerization temperature, a method of controlling by the monomer concentration, and the like. S₁, S₂The temperature dependency and the monomer concentration dependency depend on the catalyst used, and cannot be generally stated. Therefore, it is important to control these conditions based on the nature of the catalyst used. A method of controlling by the structure of the polymerization catalyst will be described later.
(Ii) Polar group
The polar group-containing propylene-based polymer in the present invention has a polar group at the same time as the main chain has a stereo block structure as described above. As the polar group, any functional group can be used as long as it is a functional group that reacts with the coating resin, and among them, a carboxyl group, a carboxylic acid group, an ester group, an amide group, an imide group, an acid anhydride group, and a hydroxyl group are included. It is preferably used, particularly preferably an acid anhydride group or a hydroxyl group.
[0028]
There is no restriction | limiting in particular in the introduction method of a polar group, A conventionally well-known method can be used. That is, a method of copolymerizing a monomer having a polar group with propylene, a solution method in which a propylene polymer and a monomer having a polar group are graft-reacted using an organic peroxide as an initiator in an organic solvent solution, an extruder, etc. Examples thereof include a melt kneading method in which a monomer having a polar group is grafted to a propylene polymer using a melt kneading apparatus. In addition, about introduction | transduction of a polar group, you may combine the method quoted here or may implement the same or different method in multiple times.
[0029]
The content of the monomer having a polar group in the component (B) is generally 0.2% by weight or more, preferably 2.0% by weight or more, 6% by weight or less, and 5.0% by weight or less. If the graft ratio is less than 0.2% by weight, the coating film adhesion is poor, and if it exceeds 6% by weight, the dispersibility of the component (B) decreases, and the component (B) is agglomerated in the propylene-based resin composition. Each tends to disperse, which is not preferable.
[0030]
Content in the (B) component of the monomer which has a polar group is measured with the following method.
First, after removing unreacted components by dissolution reprecipitation method or the like, the component (B) is formed into a film having a thickness of 0.15 mm by hot press molding at 200 ° C., and this film is acetone with a Soxhlet extractor. Extract with a solvent at 85 ° C. for 1.5 hours and dry in an oven at 70 ° C. for 20 minutes. After the extraction and drying treatment, the infrared absorption peak intensity is quantified using IR, and the monomer pigment having a polar group is calculated from the calibration curve.
(Iii) Specific examples of polar groups
When graft copolymerizing a polar monomer having a carboxyl group to a propylene polymer, examples of the polar monomer include (meth) acrylic acid and its acid derivative, monoolefin dicarboxylic acid, its anhydride and its monoester.
[0031]
Specifically, as (meth) acrylic acid and ester derivatives thereof, (meth) acrylic acid, (meth) acrylic acid ester monomers having an alkyl group having 1 to 12 carbon atoms, such as (meth) Methyl acrylate, (meth) ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- (meth) acrylic acid Butyl, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth) acryl Decyl acid, dodecyl (meth) acrylate, etc., an aryl group having 6 to 12 carbon atoms or arylalkyl Having Le group (meth) monomers acrylic acid esters, for example, (meth) acrylate, phenyl (meth) toluyl acrylate include benzyl (meth) acrylate and the like.
[0032]
Furthermore, as another (meth) acrylic acid derivative, a monomer of a (meth) acrylic acid ester having a C1-C20 alkyl group containing a hetero atom, for example, hydroxyethyl (meth) acrylate, (meth) Dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid-2-aminoethyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-methoxypropyl, (meth) Monomers of (meth) acrylate esters having an alkyl group having 1 to 20 carbon atoms containing fluorine atoms, such as glycidyl acrylate and adducts of (meth) acrylate ethylene oxide, such as trifluoromethyl (meth) acrylate , (Meth) acrylic acid-2-trifluoromethylethyl, (meth) acrylic acid 2-perfluoroethyl, etc., (meth) acrylamide monomer, e.g., (meth) acrylamide, (meth) acrylic dimethyl amides.
[0033]
Examples of the monoolefin dicarboxylic acid include maleic acid, chloromaleic acid, citraconic acid, itaconic acid, glutaconic acid, 3-methyl-2-pentene diacid, 2-methyl-2-pentene diacid, 2-hexene. -Diacid etc. are mentioned.
Examples of monoolefin dicarboxylic acid monoalkyl esters include monoesters of alkyl alcohols having 1 to 12 carbon atoms and these dicarboxylic acids. Examples of alkyl alcohols include methyl alcohol, ethyl alcohol, and propyl alcohol. Butyl alcohol, pentyl alcohol, octyl alcohol, cyclohexyl alcohol and the like. A modified polymer having a monoolefin dicarboxylic acid monoalkyl ester as a graft copolymer unit is, for example, a method of graft copolymerizing a monoolefin dicarboxylic acid monoalkyl ester to a polymer: a monoolefin dicarboxylic acid or an anhydride thereof, propylene-based After graft copolymerization with the polymer, it can be obtained by a method of esterifying one of the carboxylic acid groups with an alkyl alcohol.
[0034]
A polar group-containing propylene polymer containing an amide group, an imide group or a hydroxyl group can be produced by further modifying the above-mentioned carboxyl group-containing modified polypropylene with an amine or the like. Moreover, a hydroxyl group-containing propylene polymer can be produced by modifying again the above-mentioned carboxyl group-containing modified polypropylene using a polar monomer having both an amino group and a hydroxyl group. In addition, these functional group conversion can use a conventionally well-known method, for example, reduction | restoration of an ester group, etc.
[0035]
The radical polymerization initiator used for the graft copolymerization can be appropriately selected from ordinary radical initiators, and examples thereof include organic peroxides and azonitriles. Organic peroxides include diisopropyl peroxide, di (t-butyl) peroxide, t-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, cumyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide Methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate, dicyclohexyl peroxycarbonate and the like. Examples of the azonitrile include azobisbutyronitrile and azobisisopropylnitrile. Of these, benzoyl peroxide and dicumyl peroxide are preferred.
[0036]
When the graft copolymerization reaction is carried out using an organic solvent, specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic systems such as hexane, heptane, octane and decane. Hydrocarbons: Halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chlorobenzene, o-dichlorobenzene, etc., and among these, aromatic hydrocarbons or halogenated hydrocarbons are preferred, particularly toluene, xylene, chlorobenzene. Is preferred.
(Iv) Physical properties
In order to improve the coating adhesion of the molded product comprising the component (A) of the present invention, it is necessary to have as many polar functional groups as possible on the surface of the molded product. For this purpose, it is conceivable to increase the blending amount of the modified polypropylene. However, this method leads to a decrease in mechanical properties as described above in the section of the prior art and lacks practicality.
[0037]
A feature of the present invention is that a polar group-containing propylene polymer having a component (B), that is, a stereo block structure, is used. When such a (B) component is used, even if there are few compounding quantities with respect to (A) component, paintability will improve. Accordingly, the paintability can be improved without deteriorating the mechanical properties.
(1) Crystallinity
In kneading of polypropylene, it is generally known that a component having low crystallinity is more likely to be unevenly distributed on the surface than a component having high crystallinity. Since the component (B) of the present invention has a stereo block structure, it is a component having low crystallinity as compared with normal isotactic polypropylene. For this reason, the component (B) of the present invention is likely to be unevenly distributed on the surface when kneaded. On the other hand, when the component (B) is completely amorphous, the surface may move relatively easily during the kneading. This leads to stickiness of the surface, which in turn leads to a decrease in paintability. On the other hand, the component (B) of the present invention has a stereo block structure as a main chain, so that even when it is unevenly distributed on the surface of the molded body, there is little stickiness and the effect of improving paintability is high.
[0038]
Thus, in this invention, the uneven distribution property to the surface of a molded object is raised by reducing the crystallinity of the polar group containing propylene polymer used as (B) component. This uneven distribution is particularly noticeable when the heat of fusion by DSC of the polar group-containing propylene polymer is less than 1 J / g. The DSC measurement method is as follows. Measurement was carried out by the following method using a thermal analysis system TA2000 manufactured by DuPont. A sample (about 5 to 10 mg) is melted at 200 ° C. for 5 minutes, cooled to 20 ° C. at a rate of 10 ° C./min, held at the same temperature for 5 minutes, and then heated to 200 ° C. at 10 ° C./min. Thus, a melting curve was obtained, and the peak top temperature of the main endothermic peak in the final temperature rising stage was determined as the melting point. The amount of heat of fusion was determined from the area of the region surrounded by this main endothermic peak and the baseline. By the way, when the amount of heat of fusion is small, it may be difficult to distinguish between baseline fluctuations and true endothermic peaks. In this case, it is confirmed whether or not there is an exothermic peak due to crystallization in the temperature lowering process described above, and this corresponds to the endothermic peak. If there is a corresponding exothermic peak, it is determined that there is a true endothermic peak based on crystal melting, and if not, it is determined that there is a baseline variation.
[0039]
(2) Solubility in hydrocarbon solvents
The polar group-containing propylene-based polymer of the present invention has a stereoblock structure and has low crystallinity as compared with ordinary isotactic polypropylene, and therefore generally has high solubility in a hydrocarbon solvent. When the polar group-containing propylene-based polymer is produced by modification of polypropylene, the original polypropylene has an insoluble content of 1% by weight or less when dissolved in n-heptane at 98 ° C. at a concentration of 10% by weight. Is preferably selected. Further, as the original polypropylene, one having an insoluble content of 1% by weight or less when dissolved in toluene at 25 ° C. at a concentration of 10% by weight is more preferably used. The insoluble content is measured by the following method.
[0040]
In a solvent (n-heptane or toluene), a propylene polymer is charged at a concentration of 10% by weight into a separable flask equipped with a stirring blade. The temperature rises to 110 ° C for n-heptane and 120 ° C for toluene. Warm to dissolve the polymer. After the internal temperature becomes constant, stirring is continued for 2 hours. In the case of n-heptane, it is quickly at the boiling temperature, and in the case of toluene, it is naturally cooled to 30 ° C., left to stand for 1 hour, and filtered through a SUS wire mesh No. 400. What remains in the wire mesh is insoluble, and what has passed through the wire mesh as a solution is soluble. The insoluble matter is dried at 80 ° C. and 1 mmHg or less for 4 hours in a vacuum dryer. Weigh and calculate the fraction of insoluble matter.
(3) Molecular weight
The polar group-containing propylene polymer of the present invention is not particularly limited with respect to molecular weight. However, in consideration of moldability and the like, generally, the weight average molecular weight Mw is preferably 500 or more, preferably 1000 or more, and 1 million or less, preferably 500,000 or less. Here, the weight average molecular weight Mw of the polar group-containing propylene polymer is measured by GPC under the following conditions.
[0041]
Apparatus: Waters HLC / GPC 150C
Column temperature: 135 ° C
Solvent: o-dichlorobenzene
Flow rate: 1.0 ml / min
Column: Tosoh Corporation GMH_HR-H (S) HT 60 cm x 1
Injection volume: 0.15 ml (no filtration treatment)
Solution concentration: 1.5 mg / ml
Sample preparation: Using o-dichlorobenzene, the solution is adjusted to 1.5 mg / ml and dissolved at 140 ° C. for 1 to 3 hours.
[0042]
Calibration curve: Use standard polystyrene samples.
Calibration curve order: primary
Mw: Polystyrene equivalent molecular weight x 0.639h
[2] Method for producing component (B)
There are two methods for producing component (B): (i) a method of producing a propylene polymer having a stereoblock structure and then modifying with a polar monomer, and (ii) a method of directly copolymerizing propylene and a polar monomer. Can be divided roughly.
(I) A method of producing a propylene polymer having a stereoblock structure and then modifying with a polar monomer
Among these methods, a preferable production method includes a method of producing a propylene polymer with a single site catalyst and modifying it with a polar monomer.
[0043]
The reason for this is that, in general, the single-site catalyst can control the microtacticity by the design of the ligand, the molecular weight distribution and the stereoregular distribution are sharp, and a polymer having a relatively low molecular weight can be easily produced. It is done. As the single site catalyst, a metallocene catalyst or a so-called post-metallocene catalyst can be used as a catalyst for producing the copolymer of the present invention. Here, the metallocene catalyst is a catalyst containing a transition metal compound having a cyclopentadienyl ligand, and the post metallocene catalyst does not contain a cyclopentadienyl ligand, such as nitrogen, oxygen, phosphorus, etc. The catalyst containing the transition metal compound containing the ligand which has these heteroatoms is pointed out. These catalysts are generally compounds called co-catalysts and are usually used in combination with compounds capable of activating these transition metals. Among these, the metallocene catalyst is preferably used in that the microtacticity can be precisely controlled.
[0044]
(1) Metallocene catalyst
The metallocene catalyst preferably contains the following catalyst component (a) as an essential component and contains the catalyst component (b).
Catalyst component (a): metallocene
Catalyst component (b): promoter
Hereinafter, each component will be described.
Catalyst component (a): metallocene
The metallocene used for the production of the component (B) of the present invention is C having a crosslinking group.₁Symmetric answer metallocenes are preferred. C₁-By using a symmetric answer metallocene, in general, a stereo block structure can be effectively formed in the main chain of the propylene polymer. Non-crosslinked metallocenes can also be applied to the production of the propylene polymer of the present invention. In general, ansa metallocenes having a crosslinking group are preferable from an industrial standpoint because they are superior in thermal stability and the like.
[0045]
The ansa metallocene having a bridging group preferably used in the present invention is a C-group of a bridged Group 4 transition metal compound having a conjugated 5-membered ring ligand.₁-Metallocene with symmetry. Such transition metal compounds are known, and it is also known to use them as catalyst components for α-olefin polymerization.
The metallocene preferably used for the production of the propylene polymer of the present invention has the general formula: Q (C_FiveH_4aR² _a) (C_FiveH_4bR^Three _b) MXY and C₁-A compound having symmetry. A plurality of metallocenes represented by the general formula may be mixed and used.
[0046]
Hereinafter, the metallocene having the general formula will be described in detail. In the general formula, Q is a bonding group that bridges two conjugated 5-membered ring ligands, M is a group 4 transition metal in the periodic table, and X and Y are each independently hydrogen, halogen, carbon. A hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms The silicon-containing hydrocarbon group of²And R^ThreeAre each independently a hydrocarbon group having 1 to 20 carbon atoms, halogen, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, nitrogen A hydrocarbon-containing group or a boron-containing hydrocarbon group. Two adjacent Rs²And / or R^ThreeMay be bonded to each other to form a 4- to 10-membered ring. a and b are each independently an integer satisfying 0 ≦ a ≦ 4 and 0 ≦ b ≦ 4.
[0047]
Specific examples of the binding group Q that bridges between two conjugated 5-membered ring ligands include the following. That is, an alkylene group such as methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group, alkylidene group such as diphenylmethylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group , Silicon-containing cross-linking groups such as diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisilylene group, dimethylgermylene group, diethylgermylene group, diphenyl Germanium-containing cross-linking groups such as germanyl group and methylphenylgermylene group, alkylphosphine, amine and the like. Among these, an alkylene group, an alkylidene group, a silicon-containing crosslinking group, and a germanium-containing crosslinking group are particularly preferably used.
[0048]
In the above general formula, R²And / or R^ThreeAre methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl Group, nonyl group, decyl group, phenyl group, t-butylphenyl group, naphthyl group and the like, optionally substituted hydrocarbon group having 1 to 20 carbon atoms, fluoromethyl group, fluoroethyl group, fluorophenyl group, fluoro C1-C20 hydrocarbon group which may contain halogen such as naphthyl group, fluorobiphenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, chloronaphthyl group, chlorobiphenyl group, fluorine, chlorine, bromine, Halogen such as iodine, alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group Aryloxy group such as phenoxy group, methylphenoxy group, pentamethylphenoxy group, silicon-containing hydrocarbon group such as trimethylsilyl group, triethylsilyl group, triphenylsilyl group, or phosphorus-containing hydrocarbon group, nitrogen-containing hydrocarbon group, Boron-containing hydrocarbon group.
[0049]
R²Are present, they may be the same or different. Two R²Are present on adjacent carbon atoms of the cyclopentadienyl ring to form a 4- to 10-membered ring, indenyl group, tetrahydroindenyl group, fluorenyl group, octahydrofluorenyl group, azulenyl Group, hexahydroazurenyl group and the like. Similarly, R^ThreeAre present, they may be the same or different. Two R^ThreeAre present on adjacent carbon atoms of the cyclopentadienyl ring to form a 4- to 10-membered ring, indenyl group, tetrahydroindenyl group, fluorenyl group, octahydrofluorenyl group, azulenyl Group, hexahydroazurenyl group and the like. In the present invention, the general formula: Q (C_FiveH_4aR² _a) (C_FiveH_4bR^Three _b) The metallocene represented by MXY is C₁-As long as it has symmetry, C₁As long as symmetry is maintained, R²And R^ThreeMay be the same or different.
[0050]
M is titanium, zirconium or hafnium, which is a group 4 transition metal of the periodic table, and preferably zirconium or hafnium.
X and Y are each hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkylamide group, and 1 to 20 carbon atoms. Preferably a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms, and a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. X and Y may be the same or different. Of these, halogen, hydrocarbon group and alkylamide group are preferred.
[0051]
When M is zirconium, specific examples of the transition metal compound include
(1) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-1-indenyl) zirconium]
(2) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-1-indenyl) zirconium]
(3) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-phenyl-1-indenyl) zirconium]
(4) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-isopropyl-1-indenyl) zirconium]
(5) Dichloro [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-1-indenyl) zirconium]
(6) Dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-methyl-1-indenyl) zirconium]
(7) Dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-phenyl-1-indenyl) zirconium]
(8) Dichloro [ethylene (cyclopentadienyl) (2-methyl-1-indenyl) zirconium]
(9) Dichloro [ethylene (cyclopentadienyl) (2,4-dimethyl-1-indenyl) zirconium]
(10) Dichloro [ethylene (cyclopentadienyl) (2-methyl-4-phenyl-1-indenyl) zirconium]
(11) Dichloro [ethylene (cyclopentadienyl) (2-methyl-4-isopropyl-1-indenyl) zirconium]
(12) Dichloro [ethylene (9-fluorenyl) (2,4-dimethyl-1-indenyl) zirconium]
(13) Dichloro [ethylene (cyclopentadienyl) (2-ethyl-4-methyl-1-indenyl) zirconium]
(14) Dichloro [ethylene (cyclopentadienyl) (2-ethyl-4-phenyl-1-indenyl) zirconium]
(15) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyltetrahydro-1-indenyl) zirconium]
(16) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyltetrahydro-1-indenyl) zirconium]
(17) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-phenyltetrahydro-1-indenyl) zirconium]
(18) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-isopropyltetrahydro-1-indenyl) zirconium]
(19) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyltetrahydro-1-indenyl) zirconium]
(20) Dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-methyltetrahydro-1-indenyl) zirconium]
(21) Dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-phenyltetrahydro-1-indenyl) zirconium]
(22) Dichloro [ethylene (cyclopentadienyl) (2-methyltetrahydro-1-indenyl) zirconium]
(23) Dichloro [ethylene (cyclopentadienyl) (2,4-dimethyltetrahydro-1-indenyl) zirconium]
(24) Dichloro [ethylene (cyclopentadienyl) (2-methyl-4-phenyltetrahydro-1-indenyl) zirconium]
(25) Dichloro [ethylene (cyclopentadienyl) (2-methyl-4-isopropyltetrahydro-1-indenyl) zirconium]
(26) Dichloro [ethylene (9-fluorenyl) (2,4-dimethyltetrahydro-1-indenyl) zirconium]
(27) Dichloro [ethylene (cyclopentadienyl) (2-ethyl-4-methyl tetrahydro-1-indenyl) zirconium]
(28) Dichloro [ethylene (cyclopentadienyl) (2-ethyl-4-phenyltetrahydro-1-indenyl) zirconium]
Etc. are exemplified.
[0052]
In addition, the same compounds as described above can be used for other Group 4 to 6 transition metal compounds such as a titanium compound and a hafnium compound. In addition, about these compounds, you may use the mixture of the compound which has a several different structure. Furthermore, a known solid catalyst mainly composed of titanium trichloride or a carrier-supported catalyst containing magnesium, titanium, and halogen as essential components can be supplementarily used.
[0053]
The transition metal compound particularly preferably used is represented by the following general formula (I) and C₁-A compound having symmetry.
[0054]
[Chemical 1]

[0055]
In general formula (I), A₁And A₂Is a conjugated 5-membered ring ligand, and A¹And A²At least one of them has a 7 to 10 membered fused ring formed by including adjacent atoms of a conjugated 5-membered ring ligand and including two atoms of the 5-membered ring, A binding group that bridges the conjugated 5-membered ring ligand at an arbitrary position, M represents a transition metal atom selected from Group 4 of the periodic table, and X and Y are each independently bonded to M Hydrogen atom, halogen atom, hydrocarbon group, alkylamide group, halogenated hydrocarbon group, oxygen-containing hydrocarbon group, nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon group, silicon-containing hydrocarbon group, sulfur-containing group .
[0056]
Typical examples of the conjugated 5-membered ring ligand include a substituted cyclopentadienyl group. Specific examples of the substituent include hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, phenyl group, naphthyl group, Examples include butenyl, butadienyl, and triphenylcarbyl groups.
[0057]
Examples of the substituent other than the hydrocarbon group include hydrocarbon residues containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur. Typical examples include methoxy group, ethoxy group, phenoxy group, furyl group, trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, carbazolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group. , Dimethoxyboron group, thienyl group and the like.
[0058]
Examples of other substituents include a halogen atom or a halogen-containing hydrocarbon group. Typical examples are chlorine, bromine, iodine, fluorine, trichloromethyl group, chlorophenyl group, chlorobiphenyl group, chloronaphthyl group, trifluoromethyl group, fluorophenyl group, fluorobiphenyl group, fluoronaphthyl group, pentafluorophenyl. Groups and the like.
[0059]
As described above, A₁And A₂In at least one of the groups, adjacent substituents on the conjugated 5-membered ring ligand are bonded to form a 7-10 membered condensed ring including 2 atoms of the 5-membered ring. Specific examples thereof include compounds such as azulene and derivatives thereof. More specifically, hydroazurenyl group, methylhydroazurenyl group, ethylhydroazurenyl group, dimethylhydroazurenyl group, methylethylhydroazurenyl group, methylisopropylhydroazurenyl group, methylphenylisopropylhydroazurenyl group, various types Hydrogenated azulenyl group, bicyclo- [6.3.0] -undecanyl group, methyl-bicyclo- [6.3.0] -undecanyl group, ethyl-bicyclo- [6.3.0] -undecanyl group, Phenyl-bicyclo- [6.3.0] -undecanyl group, methylphenyl-bicyclo- [6.3.0] -undecanyl group, ethylphenyl-bicyclo- [6.3.0] -undecanyl group, methyldiphenyl- Bicyclo- [6.3.0] -undecanyl group, methyl-bicyclo- [6.3.0] -u Decadienyl group, methylphenyl-bicyclo- [6.3.0] -undecadienyl group, ethylphenyl-bicyclo- [6.3.0] -undecadienyl group, methylisopropyl-bicyclo- [6.3.0] -undecadienyl group Bicyclo- [7.3.0] -dodecanyl group and derivatives thereof, bicyclo- [7.3.0] -dodecadienyl group and derivatives thereof, bicyclo- [8.3.0] -tridecanyl group and derivatives thereof, bicyclo -[8.3.0] -Tridecadienyl group and derivatives thereof are exemplified.
[0060]
Examples of the substituent for each group include the hydrocarbon groups described above, hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur, halogen atoms, or halogen-containing hydrocarbon groups.
Q represents a binding group that bridges two conjugated 5-membered ring ligands at an arbitrary position. That is, Q is a divalent linking group, and A₁And A₂And crosslink. The type of Q is not particularly limited, and specific examples thereof include: (a) a divalent hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, specifically, An unsaturated hydrocarbon group such as an alkylene group, a cycloalkylene group, and an arylene, a haloalkylene group, a halocycloalkylene group, (b) a silylene group or an oligosilylene group, and (c) a carbon number of usually 1 to 20, preferably 1 to A silylene group or an oligosilylene group having 12 hydrocarbon groups or a halogenated hydrocarbon group as a substituent, (d) a germylene group, (e) a hydrocarbon group or a halogenated hydrocarbon group usually having 1 to 20 carbon atoms. Examples thereof include a germylene group as a substituent. Among these, a silylene group or a germylene group having an alkylene group, a cycloalkylene group, an arylene group or a hydrocarbon group as a substituent is preferable.
[0061]
M represents a transition metal atom selected from Group 4 of the periodic table, and is preferably zirconium or hafnium.
X and Y are each independently a hydrogen atom bonded to M, a halogen atom, a hydrocarbon group, an alkylamide group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a phosphorus-containing hydrocarbon. Group, silicon-containing hydrocarbon group, sulfur-containing group. Carbon number in each said hydrocarbon group is 1-20 normally, Preferably it is 1-12. Among these, a hydrogen atom, a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethylamide group, a diethylamide group, and a sulfinato group are preferable.
[0062]
Specific examples of the transition metal compound in the present invention include the following compounds.
(29) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(30) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(31) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium
(32) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-isopropyl-4H-1-azurenyl)] hafnium
(33) Dichloro [dimethylsilylene (2-ethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(34) Dichloro [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(35) Dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(36) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(37) Dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium
(38) Dichloro [dimethylsilylene (cyclopentadienyl) (2-ethyl-4-isopropyl-4H-1-azurenyl)] hafnium
(39) Dichloro [dimethylsilylene (9-fluorenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(40) Dichloro [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(41) Dichloro [ethylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(42) Dichloro [ethylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(43) Dichloro [ethylene (cyclopentadienyl) (2-methyl-4-phenyl-4H-1-azurenyl)] hafnium
(44) Dichloro [ethylene (cyclopentadienyl) (2-methyl-4-isopropyl-4-H-1-azurenyl)] hafnium
(45) Dichloro [ethylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(46) Dichloro [ethylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(47) Dichloro [ethylene (cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azulenyl)] hafnium
(48) Dichloro [ethylene (2-methyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(49) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-ethyl-4-phenyl-4H-1-azurenyl)] hafnium
(50) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-ethyl-4-isopropyl-4H-1-azurenyl)] hafnium
(51) Dichloro [ethylene (9-fluorenyl) (2-ethyl-4-methyl-4H-1-azulenyl)] hafnium
(52) Dichloro [ethylene (9-fluorenyl) (2-ethyl-4-isopropyl-4H-1-azurenyl)] hafnium
(53) Dichlorodimethylsilylene (cyclopentadienyl) (2-n-propyl-4-methyl-4H-1-azulenyl)] hafnium
(54) Dichloro [dimethylsilylene (cyclopentadienyl) (2-isopropyl-4-methyl-4H-1-azulenyl)] hafnium
(55) Dichloro [dimethylsilylene (cyclopentadienyl) (2-n-butyl-4-methyl-4H-1-azurenyl)] hafnium
(56) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-n-propyl-4-methyl-4H-1-azurenyl)] hafnium
(57) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-isopropyl-4-methyl-4H-1-azurenyl)] hafnium
(58) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2-n-butyl-4-methyl-4H-1-azulenyl)] hafnium
(59) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4,8-trimethyl-4H-1-azurenyl)] hafnium
(60) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4,6-trimethyl-4H-1-azurenyl)] hafnium
(61) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4,7-trimethyl-4H-1-azurenyl)] hafnium
(62) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-6-isopropyl-4H-1-azulenyl)] hafnium
(63) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-7-isopropyl-4H-1-azulenyl)] hafnium
(64) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-8-isopropyl-4H-1-azurenyl)] hafnium
(65) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-6-ethyl-4H-1-azulenyl)] hafnium
(66) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-7-ethyl-4H-1-azulenyl)] hafnium
(67) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-8-ethyl-4H-1-azulenyl)] hafnium
(68) Dichloro {[di (chloromethyl) silylene] (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)} hafnium
(69) Dichloro {[di (4-chlorophenyl) silylene] (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)} hafnium
(70) Dichloro [dimethylmethylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(71) Dichloro [dimethylgermylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(72) Dichloro [dimethylgermylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(73) Dichloro [dimethylgermylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(74) Dichloro [dimethylgermylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(75) Dichloro [dimethylgermylene (cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(76) Dichloro [dimethylgermylene (cyclopentadienyl) (2-n-propyl-4-methyl-4H-1-azurenyl)] hafnium
(77) Dichloro [dimethylgermylene (cyclopentadienyl) (2-isopropyl-4H-1-azurenyl)] hafnium
(78) Dichloro [dimethylgermylene (cyclopentadienyl) (2-n-butyl-4-methyl-4H-1-azulenyl)] hafnium
(79) Dichloro [dimethylgermylene (2-methyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(80) Dichloro [dimethylgermylene (2,3-dimethyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(81) Dichloro [dimethylgermylene (9-fluorenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(82) Dichloro [dimethylgermylene (2-methyl-1-cyclopentadienyl) (2-n-propyl-4-methyl-4H-1-azurenyl)] hafnium
(83) Dichloro [dimethylgermylene (2,3-dimethyl-1-cyclopentaenyl) (2-n-propyl-4-methyl-4H-1-azurenyl)] hafnium
(84) Dichloro [dimethylgermylene (9-fluorenyl) (2-n-propyl-4-methyl-4H-1-azurenyl)] hafnium
(85) Dichloro [dimethylsilylene (3-trimethylsilyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(86) Dichloro [dimethylsilylene (3-trimethylsilyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(87) Dichloro [dimethylgermylene (3-trimethylsilyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(88) Dichloro [dimethylgermylene (3-trimethylsilyl-1-cyclopentadienyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(89) Dibromo [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(90) Dibromo [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(91) Dibromo [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(92) Dibromo [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(93) Diiodo [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(94) Diiodo [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(95) Diiodo [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(96) Diiodo [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(97) Dimethyl [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(98) Dimethyl [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(99) Dimethyl [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(100) Dimethyl [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium
(101) Dihydrido [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(102) Dihydrido [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(103) Dihydrido [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(104) Dihydrido [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(105) Bis (dimethylamide) [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(106) Bis (dimethylamide) [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(107) Bis (dimethylamide) [dimethylsilylene (2,3-dimethyl-1-lopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(108) Bis (dimethylamide) [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(109) Bisphenoxy [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(110) Bisphenoxy [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(111) Bisphenoxy [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium (112) Bisphenoxy [dimethylsilylene (9-fluorenyl) (2,4-Dimethyl-4H-1-azulenyl)] hafnium
(113) Bismethanesulfinato [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(114) Bismethanesulfinato [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(115) Bismethanesulfinato [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(116) Bismethanesulfinato [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(117) Bistrifluoromethanesulfinato [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(118) Bistrifluoromethanesulfinato [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(119) Bistrifluoromethanesulfinato [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(120) Bistrifluoromethanesulfinato [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(121) Bis-p-toluenesulfinato [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(122) Bis-p-toluenesulfinato [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(123) Bis-p-toluenesulfinato [dimethylsilylene (2,3-dimethyl-1-cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(124) Bis-p-toluenesulfinato [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(125) Dichloro [dimethylsilylene (1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(126) Dichloro [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(127) Dichloro [dimethylsilylene (1-indenyl) (2-ethyl-4-methyl-4H-1-azulenyl)] hafnium
(128) Dichloro [dimethylsilylene (2-methyl-1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(129) Dibromo [dimethylsilylene (1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(130) Dibromo [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(131) Dibromo [dimethylsilylene (1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(132) Dibromo [dimethylsilylene (2-methyl-1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(133) Diiodo [dimethylsilylene (1-indenyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium
(134) Diiodo [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(135) Diiodo [dimethylsilylene (1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(136) Diiodo [dimethylsilylene (2-methyl-1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(137) Dimethyl [dimethylsilylene (1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(138) Dimethyl [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium
(139) Dimethyl [dimethylsilylene (1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(140) Dimethyl [dimethylsilylene (2-methyl-1-indenyl) (2-ethyl-4-methyl-4H-1-azurenyl)] hafnium
(141) Dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-5,6,7,8-tetrahydro-1-azulenyl)] hafnium
(142) Dichloro [dimethylsilylene (2-methyl-1-cyclopentadienyl) (2,4-dimethyl-4H-5,6,7,8-tetrahydro-1-azulenyl)] hafnium
(143) Dichloro [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-5,6,7,8-tetrahydro-1-azulenyl)] hafnium
(144) Dichloro [dimethylsilylene (9-fluorenyl) (2,4-dimethyl-4H-5,6,7,8-tetrahydro-1-azulenyl)] hafnium
(145) Dichloro [dimethylsilylene (cyclopentadienyl) (2-chloromethyl-4-methyl-4H-1-azurenyl)] hafnium
(146) Dichloro [dimethylsilylene (cyclopentadienyl) (2-methyl-4-chloromethyl-4H-1-azurenyl)] hafnium
In addition, compounds in which the central metal M of the compound exemplified above is replaced with titanium or zirconium instead of hafnium can also be exemplified. Two or more of these may be used in combination. Further, a transition metal component may be newly added during the polymerization.
Catalyst component (b): cocatalyst
In the present invention, the promoter includes (a) an organoaluminum oxy compound, (b) an ionic compound capable of reacting with a transition metal component and exchanging the component for a cation, (c) Lewis acid, ( D) It is preferable to use one or more substances selected from the group consisting of ion-exchangeable layered compounds excluding silicates or inorganic silicates.
[0063]
Specific examples of the organoaluminum oxy compound (a) include compounds represented by the following general formulas (II), (III), and (IV).
In each general formula, R^FourRepresents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Also, multiple R^FourMay be the same or different. P is 0 or more, preferably 2 or more, and is an integer of 300 or less, preferably 30 or less.
[0064]
[Chemical 2]

[0065]
The compounds represented by the general formulas (II) and (III) are also called aluminoxanes, and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) obtained from one kind of trialkylaluminum and water, obtained from methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, (b) obtained from two kinds of trialkylaluminum and water. And methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane. Of these, methylaluminoxane and methylisobutylaluminoxane are preferred. A plurality of the above aluminoxanes can be used in combination. And said aluminoxane can be prepared on well-known various conditions.
[0066]
The compound represented by general formula (IV) is 10: 1 to 1: 1 of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and alkylboronic acid represented by the following general formula (V). It can be obtained by a (molar ratio) reaction. In general formula (V), R^FiveRepresents a hydrocarbon residue or halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
[0067]
[Chemical 3]
R^Five-B (OH)₂        (V)
Specifically, the following reaction products are obtained: (a) a 2: 1 reaction product of trimethylaluminum and methylboronic acid, (b) a 2: 1 reaction product of triisobutylaluminum and methylboronic acid, (c) Examples include 1: 1: 1 reactant of trimethylaluminum, triisobutylaluminum and methylboronic acid, (d) 2: 1 reactant of trimethylaluminum and ethylboronic acid, (e) 2: 1 reactant of triethylaluminum and butylboronic acid, and the like. be able to.
[0068]
In addition, examples of the ionic compound capable of reacting with the transition metal component (a) to convert the component into a cation include a compound represented by the general formula (VI).
[0069]
[Formula 4]
[K]^{n +}[Z]^n-          (VI)
In general formula (VI), K is a cation component, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Moreover, the cation of the metal which is easy to reduce itself, the cation of an organic metal, etc. are mentioned.
[0070]
Specific examples of the cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, Triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium, triphenylsulfonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, Gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion, etc. .
[0071]
In the above general formula (VI), Z is an anion component, which is a component (generally a non-coordinating component) that becomes a counter anion with respect to the cation species in which the transition metal component is converted. Examples of Z include an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic arsenic compound anion, and an organic antimony compound anion. Specific examples include the following compounds. (A) tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis {3,5-bis (trifluoromethyl) phenyl} boron, tetrakis {3,5-di (t-butyl) ) Phenyl} boron, tetrakis (pentafluorophenyl) boron, etc. (b) tetraphenylaluminum, tetrakis (3,4,5-trifluorophenyl) aluminum, tetrakis {3,5-bis (trifluoromethyl) phenyl} aluminum , Tetrakis {3,5-di (t-butyl) phenyl} aluminum, tetrakis (pentafluorophenyl) aluminum, etc., (c) tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis {3 , 5-Bis (trifluoromethyl) fur Nil} gallium, tetrakis {3,5-di (t-butyl) phenyl} gallium, tetrakis (pentafluorophenyl) gallium, etc. (d) tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, etc. (e) tetraphenyl Arsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, etc. (g) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, etc.
[0072]
(C) Lewis acids, particularly Lewis acids capable of converting transition metal components into cations, include various organic boron compounds, metal halogen compounds, solid acids and the like, and specific examples thereof include the following compounds. (A) organoboron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron, tris (pentafluorophenyl) boron, (b) aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, Metals such as magnesium bromide, magnesium iodide, magnesium chlorobromide, magnesium chloroiodide, magnesium bromoiodide, magnesium chloride hydride, magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide alkoxide Examples include halogen compounds, (c) solid acids such as alumina, silica and alumina.
[0073]
(D) The ion-exchangeable layered compound excluding silicate is a compound having a crystal structure in which the surfaces constituted by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the ions contained therein can be exchanged. To tell.
The ion-exchange layered compounds excluding silicate are hexagonal close-packed type, antimony type, CdCl₂Type, CdI₂Examples thereof include ionic crystalline compounds having a layered crystal structure such as a mold. Specifically, α-Zr (HAsO_Four)₂・ H₂O, α-Zr (HPO_Four)₂, Α-Zr (KPO_Four)₂・ 3H₂O, α-Ti (HPO_Four)₂, Α-Ti (HAsO_Four)₂・ H₂O, α-Sn (HPO_Four)₂・ H₂O, (-Zr (HPO_Four)₂, (-Ti (HPO_Four)₂, (-Ti (NH_FourPO_Four)₂・ H₂Examples thereof include crystalline acidic salts of polyvalent metals such as O.
[0074]
Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. A synthetic product may be used for these, and the mineral produced naturally may be used.
Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite and anorcite, halloysites such as metahalloysite and halloysite, and serpentine such as chrysotile, lizardite and antigolite. Stone group, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc. Examples include clay, gyrome clay, hysingelite, pyrophyllite, and ryokdeite group. These may form a mixed layer.
[0075]
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.
Among these specific examples, preferably, kaolins such as dickite, nacrite, kaolinite, anorcite, halosites such as metahalosite, halosite, chrysotile, lizardite, serpentine such as antigolite, montmorillonite, Smectites such as sauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, sea chlorite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite Particularly preferred are montmorillonite, sauconite, beidellite, nontronite, saponite, smectite such as hectorite, vermiculite mineral such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic Taeniolite.
[0076]
These ion-exchange layered compounds excluding silicates or inorganic silicates may be used as they are. However, acid treatment with hydrochloric acid, nitric acid, sulfuric acid and / or LiCl, NaCl, KCl, CaCl₂MgCl₂, Li₂SO_Four, MgSO_FourZnSO_Four, Ti (SO_Four)₂, Zr (SO_Four)₂, Al₂(SO_Four)_ThreeIt is preferable to perform a salt treatment such as the above. In the treatment, the corresponding acid and base may be mixed to produce a salt in the reaction system. In addition, shape control such as pulverization and granulation may be performed, and granulation is preferable in order to obtain a solid catalyst component having excellent particle fluidity. The above components are usually used after being dehydrated and dried. As these co-catalyst components, it is preferable to use an ion-exchange layered compound or inorganic silicate excluding the silicate (d) in terms of catalyst performance such as polymerization activity.
[0077]
In the polymerization of the present invention, an organoaluminum compound may be used as an optional component of the promoter component. Such organoaluminum compounds are AlR¹ _mZ_3-m(Wherein R¹Is a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrogen, halogen, alkoxy group or aryloxy group, and m is a compound represented by 0 <m ≦ 3.
[0078]
Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, or halogen or alkoxy-containing alkylaluminum such as diethylaluminum monochloride, diethylaluminum ethoxide, diethylaluminum hydride, diisobutylaluminum Hydrogen-containing organoaluminum compounds such as hydride. In addition, aluminoxane such as methylaluminoxane can also be used. Of these, trialkylaluminum is particularly preferred. Two or more of these optional components may be used in combination. Moreover, you may add this arbitrary component newly after superposition | polymerization start.
(2) Catalyst preparation method
The catalyst of the present invention can be obtained by contacting a transition metal component, a promoter component, and optionally an organoaluminum compound component, but the contacting method is not particularly limited. This contact may be performed not only during catalyst preparation, but also during prepolymerization with propylene or during polymerization.
[0079]
A polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or may be brought into contact with or after contacting each component of the catalyst.
Contact may be performed in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene. These solvents are preferably used after an operation for removing poisoning substances such as water and sulfur compounds. The contact temperature is 20 ° C. to the boiling point of the solvent to be used, and particularly preferably from room temperature to the boiling point of the solvent to be used.
(3) Catalyst usage
The amount of each catalyst component used is not particularly limited, but when an ion-exchange layered compound excluding silicate or an inorganic silicate is used as a promoter component, the transition metal component is usually per gram of the promoter component. 0.0001 mmol or more, preferably 0.001 mmol or more, usually 10 mmol or less, preferably 5 mmol or less, and the optional organoaluminum compound is usually 0 mmol or more, preferably 0.01 mmol or more, By setting it to be not more than 1,000 mmol, preferably not more than 100 mmol, a favorable result can be obtained in terms of polymerization activity. Further, the atomic ratio of the transition metal in the transition metal component to the aluminum in the organoaluminum compound which is an optional component is usually 1: 0 or more, preferably 1: 0.1 or more, and usually 1: 1,000,000. Hereinafter, it is preferable to control the ratio to be 1: 100,000 or less from the viewpoint of polymerization activity and the like.
▲ 4 ▼ Catalyst cleaning
The catalyst thus obtained may be used after washing with an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene, xylene or the like, or may be used without washing. Good.
[0080]
At the time of washing, the above-described organoaluminum compound may be newly used in combination as necessary. The amount of the organoaluminum compound used in this case is preferably 1: 0 to 10,000 in terms of the atomic ratio of aluminum in the organoaluminum compound to the transition metal in the transition metal component.
(5) Prepolymerization
Preliminarily polymerized α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and styrene as catalysts And what was washed can also be used as needed. This prepolymerization may be carried out in an inert gas such as nitrogen, or in an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene, or xylene.
(6) Polymerization reaction
The copolymerization reaction of propylene and ethylene in the present invention is carried out by liquids such as inert hydrocarbons such as propane, n-butane, isobutane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, and liquefied α-olefins. In the presence or absence of Of these, the copolymerization is preferably performed in the presence of the above-described inert hydrocarbon. Moreover, you may use the mixture of the compound described here as a solvent.
[0081]
Specifically, the propylene-based copolymer is preferably produced in the presence of a transition metal component and a promoter component, or a transition metal component, a promoter component, and an organoaluminum compound as an optional component.
(7) Polymerization reaction conditions
The polymerization temperature, polymerization pressure, and polymerization time are not particularly limited, but usually optimum settings can be made in consideration of productivity and process capability from the following ranges. That is, the polymerization temperature is usually 20 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., the polymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 10a, more preferably 0.5 MPa to 4 MPa. The time can be selected from the range of 0.1 to 10 hours, preferably 0.3 to 7 hours, more preferably 0.5 to 6 hours.
[0082]
In the present invention, when it is necessary to prepare the weight average molecular weight Mw of the polymer, a conventionally known method can be used. That is, a method for adjusting the molecular weight by controlling the polymerization temperature, a method for controlling the molecular weight by controlling the monomer concentration, a method for controlling the molecular weight by using a chain transfer agent, and the like can be mentioned. Further, the molecular weight can be controlled by the structure of the catalyst. In particular, when a bridged metallocene is used, the α-position structure with respect to the bridge head of the bridge group is important. In general, when the α-position is a hydrogen atom, β-hydrogen elimination from the growing polymer chain tends to occur during polymerization, so that the resulting polymer tends to have a low molecular weight. On the other hand, if there is any substituent (for example, methyl group) at the α-position, β-hydrogen elimination from the growing polymer chain is suppressed, so that a high molecular weight polymer is likely to be formed. .
[0083]
In the polar group-containing propylene-based polymer of the present invention, it is necessary that the propylene chain portion in the main chain has a stereo block structure composed of an isotactic block and an amorphous block. For this purpose, it is preferable to control the stereoselectivity during polymerization to form a stereo block structure.
The method for controlling the stereoselectivity is not particularly limited, but generally, a method for controlling by the structure of the catalyst, a method for controlling by controlling the polymerization conditions, and the like can be mentioned. When controlling by the structure of a catalyst, the structure of the ligand which comprises a transition metal component is important. In particular, when a bridged metallocene is used, a substituent at the α-position with respect to the bridge head of the bridge group is important. In general, stereoselectivity is likely to improve when there is a substituent that is somewhat bulky at the α-position. Furthermore, when a bridged metallocene containing a ligand having a condensed ring such as an indenyl group or an azulenyl group is used, the structure of the 4-position substituent also greatly affects the stereoselectivity. In general, stereoselectivity is likely to improve when there is a somewhat bulky substituent at the 4-position. Conversely, by introducing a sterically small substituent at the 4-position, it is possible to effectively reduce the stereoselectivity and reduce the crystallinity of the resulting polymer.
[0084]
The production of the polar group-containing propylene-based polymer of the present invention is carried₁When carried out with symmetrical ansa metallocenes, regioregular units, i.e. regioregular units based on 2,1-inserted propylene monomers and / or 1,3-inserted propylene monomers, The sum of the ratio of each of the position irregular units based on the 2,1-insertion and the 1,3-insertion with respect to the total propylene insertion is 0.05% or more in the main chain containing propylene-based polymer. Is preferred.
[0085]
The polymerization of propylene usually proceeds with a 1,2-insertion where the methylene group binds to the active site of the catalyst, but in rare cases it may have a 2,1-insertion or a 1,3-insertion. The propylene monomer having 2,1-insertion in the propylene chain forms regioregular units represented by the following partial structures (I) and (II). Thus, both the partial structures (I) and (II) are present in the main chain, which is one of the characteristics of the propylene-based copolymer of the present invention. Moreover, the 1,3-inserted propylene monomer in the propylene chain forms a position irregular unit represented by the following partial structure (III) in the polymer main chain.
[0086]
In the case where the main chain of the polar group-containing propylene polymer is a copolymer of propylene and ethylene, propylene is inserted after 2,1-insertion, then ethylene is inserted, and then propylene is normally 1,2- The structure of inserting (partial structure IV) is also a preferable partial structure.
[0087]
[Chemical formula 5]

[0088]
In the present invention, the ratio of 2,1-inserted propylene and the ratio of 1,3-inserted propylene to the total propylene insertion are calculated by the following formulas.
[0089]
[Expression 1]

[0090]
Where ΣI (xy) is¹³In the C-NMR spectrum, the integrated intensity sum of signals appearing from xppm to yppm is represented.
The signal appearing at 14.2 to 18.0 ppm is derived from the carbon of the methyl group of 2,1-inserted propylene, and the signal appearing at 33.5 to 34.2 ppm is^tIn the structure of PEP, it is derived from the carbon of the methyl group of 2,1-inserted propylene. Where P is propylene,^tP represents 2,1-inserted propylene, and E represents ethylene. The signal appearing at 14.2 to 23.5 ppm is derived from the carbon of the methyl group of 1,2-inserted and 2,1-inserted propylene, and the signal appearing at 27.5 to 28.0 ppm is , Derived from two methylene carbons in 1,3-inserted propylene.
[0091]
Such a position irregular unit generally lowers the crystallinity of the polymer. Therefore, in the present invention, it has an effect of improving the uneven distribution of the polar group-containing propylene-based polymer on the surface of the molded product. it is conceivable that. As another means of reducing the crystallinity of the propylene polymer, there is a method of reducing the stereoregularity of the methyl group. Generally, when a polymer made by this method is used, the stickiness of the surface of the molded product is noticeable. This is not preferable for application. For this reason, when increasing the stereoregularity of the methyl group in an attempt to suppress stickiness, this time, the uneven distribution of the polar group-containing propylene-based polymer on the surface of the molded product tends to be reduced, and the paintability tends to be impaired. This is also not preferable in application. Thus, in view of uneven distribution on the surface of the molded body and paintability, it can be said that a structure having a position irregular unit in the main chain appropriately is preferable in terms of the balance between the two.
[0092]
In the present invention, those having regioregular units based on both 2,1-inserted propylene monomer and 1,3-inserted propylene monomer in the main chain are more effectively crystalline. Is preferable in terms of lowering the solubility and improving the solubility in a solvent. In addition, when the ratio of the position irregular units based on 1,3-insertion is larger than the ratio of the position irregular units based on 2,1-insertion, the performance that integrates uneven distribution on the surface of the molded body, paintability, etc. Is more preferable because of good physical properties.
[0093]
Regarding the method for controlling the amount of 2,1-insertion and / or 1,3-insertion in the main chain, (i) a method controlled by the structure of the polymerization catalyst, (ii) a method controlled by the polymerization temperature, (iii) ) A method of controlling by the monomer concentration can be mentioned. The temperature dependency and the monomer concentration dependency of the 2,1-insertion and / or 1,3-insertion amount depend on the catalyst used, and thus cannot be generally described. Therefore, it is important to control these conditions based on the nature of the catalyst used.
(8) Denaturation method
In the present invention, when a polar group-containing propylene polymer is produced by first producing a propylene polymer and then modifying with a polar monomer, the propylene polymer before modification has an unsaturated bond at the terminal. preferable. Due to the presence of the unsaturated bond, for example, when a polar monomer is introduced by a radical grafting method, the grafting efficiency is improved. Such a terminal unsaturated propylene polymer can be generally produced by using a metallocene catalyst and performing polymerization under hydrogen-free conditions.
[0094]
There is no particular limitation on the content of the polymerizable monomer containing a carboxyl group or the like in the graft-modified polymer in the modified polymer, but usually 0.01% by weight so that both the paintability and appearance are good. The graft copolymerization is carried out so that the amount is preferably 0.1% by weight or more and usually 25% by weight or less, preferably 15% by weight or less. As a method for graft copolymerizing a polymerizable monomer having a polar group, various known methods may be mentioned. For example, a method of conducting a graft copolymerization reaction by dissolving a propylene-based polymer in an organic solvent, adding a polymerizable monomer and a radical polymerization initiator and stirring under heating, substantially without using a solvent, Propylene polymer, polymerizable monomer, and radical polymerization initiator are heated, melted and stirred for a graft copolymerization reaction method, using an extruder, propylene polymer, polymerizable monomer, and radical polymerization start A method of carrying out a graft copolymerization reaction by melting and kneading the agent is mentioned. Among these, the method of dissolving a propylene polymer in an organic solvent, adding a polymerizable monomer and a radical polymerization initiator, and performing heating and stirring to carry out a graft copolymerization reaction is relatively easy to control the modification rate. It is preferable because it is easy and the modified polymer can be easily washed after modification.
(Ii) A method of directly copolymerizing propylene and a polar monomer
This method can be roughly divided into a method using a catalyst having a group IV transition metal as a propylene polymerization catalyst and a method using a catalyst having a group V to VIII transition metal. One of the methods that can be applied in common to both is a method of copolymerizing with propylene by masking the polar group of the polar monomer so as not to poison the catalyst. For example, a hydroxyl group can be masked by reacting a vinyl monomer having a hydroxyl group with an organoaluminum compound. Another method is to copolymerize with propylene by inserting a spacer such as a methylene group between the polar group of the polar monomer and the carbon-carbon double bond involved in the polymerization, and increasing the distance between the two. Is mentioned. In addition, when using a catalyst having a V to VIII group transition metal, these transition metals have a relatively strong resistance to polar groups, and thus can be directly copolymerized with propylene without masking the polar groups. There are cases.
[0095]
Examples of the copolymerization method include the same methods as described in (i) above. [3] Mixing of ingredients
The propylene-based resin composition of the present invention is produced by mixing each compounding component and melt-kneading by a conventionally known method without any particular limitation.
That is, the propylene-based resin composition of the present invention is compounded with each compounding component and kneaded using a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, or a kneader. -Obtained by granulation.
[0096]
In this case, it is preferable to select a kneading and granulating method capable of improving the dispersion of each component, and it is usually performed using a twin-screw extruder. In this kneading and granulation, the blend of each component may be kneaded at the same time, and each component is kneaded in order to improve performance. For example, first, a part or all of the propylene-based polymer It is also possible to employ a method of kneading an elastomer and kneading and granulating the remaining components.
[0097]
The mixing ratio of the component (B) and the component (A) is not particularly limited, but is preferably 1 part by weight or more, preferably 2 parts by weight or more, more preferably 100 parts by weight of the component (A). 3 parts by weight or more, usually 15 parts by weight or less, preferably 13 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 8 parts by weight or less. If the mixing ratio is less than 1 part by weight, the paintability tends to be inferior, and if it exceeds 15 parts by weight, the physical properties such as impact resistance and heat resistance tend to decrease.
[0098]
The relative molecular weight of the component (B) and the component (A) is not particularly limited, but in general, the molecular weight of the component (B) is lower than the molecular weight of the component (A). It is preferable from the viewpoint of improving the dispersibility of the components.
(I) Acceptable formulation
In addition to the above-described components, other components may be blended with the propylene-based resin composition of the present invention as necessary within the range where the effects of the present invention are not significantly impaired. Examples of such other ingredients include pigments for coloring, antioxidants such as phenols, sulfurs, and phosphoruss, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, and organic aluminum and talc. Various nucleating agents, dispersing agents, neutralizing agents, foaming agents, copper damage preventing agents, lubricants, flame retardants and the like can be mentioned.
[0099]
Moreover, you may mix | blend polyhydroxy polyolefin as needed. Here, the polyhydroxy polyolefin used as needed is a low molecular weight polyolefin having a hydroxyl group at the molecular end, and preferably has a molecular weight of 1000 to 5000. Such a polyhydroxy polyolefin can be obtained by polymerizing a conjugated diene monomer by anionic polymerization or the like and hydrolyzing it to hydrogenate a polymer. Specifically, trade name Polytail H (Polytail H) manufactured by Mitsubishi Chemical Corporation may be mentioned.
[0100]
In the present invention, the polyhydroxypolyolefin used as necessary has a hydroxyl value (mgKOH / g) of preferably 20 or more and 100 or less. When the hydroxyl value is less than 20, the reactivity with the coating film is insufficient, and when it exceeds 100, the compatibility with the resin is deteriorated.
If necessary, an ethylene / octene random copolymer and / or an ethylene / butene random copolymer may be blended. The ethylene / octene and / or ethylene / butene random copolymer component used in the present invention is used for the purpose of improving impact resistance and exhibiting good moldability, physical properties and shrinkage characteristics. In these copolymers, the comonomer copolymerized with ethylene is 1-octene or 1-butene, and the comonomer content is usually 28% by weight or more, usually 60% by weight or less, preferably 50% by weight or less. The MFR of these copolymers is usually 0.5 g / 10 min or more, preferably 0.7 g / 10 min or more, particularly preferably 0.9 g / 10 min or more, and usually 20 g / 10 min or less, preferably 15 g / min. The range is 10 min or less, particularly preferably 10 g / 10 min or less. When the copolymerized comonomer content and MFR deviate from the above ranges, the impact resistance, tensile elongation, embrittlement temperature and the like of the propylene-based resin composition tend to be insufficient, which is not preferable. The ethylene / octene random copolymer and / or ethylene / butene random copolymer need not be one kind, and may be a mixture of two or more kinds.
[0101]
Furthermore, you may mix | blend a styrene-type hydrogenated block copolymer rubber with the propylene-type resin composition of this invention as needed. The combined use of ethylene / octene random copolymer and / or ethylene / butene random copolymer and styrene block copolymer rubber makes it possible to achieve a high degree of physical property balance and moldability. In the styrene-based hydrogenated block copolymer rubber, the content of the A segment having a polystyrene structure is usually 1% by weight, preferably 5% by weight, more preferably 7% by weight or more, and usually 25% by weight or less, preferably 22%. It is a block copolymer having a structure of AB or ABA type together with a B segment having an ethylene / butene or ethylene / propylene structure at a weight percent or less. When the content of the A segment exceeds 25% by weight, the embrittlement temperature is inferior. In addition, the content of the polystyrene structural unit is an infrared spectrum analysis method,¹³It is a value measured by a conventional method such as C-NMR method. Specific examples of the styrene-based hydrogenated block copolymer rubber include styrene / ethylene / butene / styrene block copolymer (SEBS) and styrene / ethylene / propylene / styrene block copolymer (SEPS). The elastomer copolymer having the block structure may be a mixture of a triblock structure and a diblock structure as shown in the above structural formula.
[0102]
In the present invention, the talc used as necessary has an average particle size of 10 μm or less, preferably 0.5 to 8 μm. If the average particle size deviates from the above range, the rigidity is poor. The average particle size was measured by reading from a cumulative particle size distribution curve measured by a laser diffraction method (for example, LA920W manufactured by Horiba, Ltd.) or a liquid layer sedimentation type light transmission method (for example, CP type manufactured by Shimadzu Corp.). It can be determined from the particle size value of 50% by weight. These talcs can be obtained by further precisely classifying those obtained by mechanically pulverizing naturally produced ones. Further, this classification operation may be repeated a plurality of times. Examples of the mechanical pulverization method include a method using a pulverizer such as a jaw crusher, a hammer crusher, a roll crusher, a screen mill, a jet pulverizer, a colloid mill, a roller mill, and a vibration mill. These pulverized talcs are subjected to wet or dry classification once or repeatedly in an apparatus such as a cyclone, a cyclone air separator, a micro separator, or a sharp cut separator in order to adjust to the average particle size shown in the present invention. When producing the talc used in the present invention, it is preferable to perform a classification operation with a sharp cut separator after pulverization to a specific particle size. These talcs are modified polyolefins, fatty acids grafted with various organic titanate coupling agents, organic silane coupling agents, unsaturated carboxylic acids, or anhydrides for the purpose of improving the adhesion or dispersibility with the polymer. Alternatively, a surface treated with a fatty acid metal salt, a fatty acid ester or the like may be used.
(Ii) Mixing conditions
The compounding agent which can be blended can be blended in any form. For example, it may be blended as a solid, as a solution dissolved in a solvent, or as a slurry dispersed in a solvent.
[4] Molding
The propylene-based resin composition of the present invention can be used for molding by various known methods. For example, various types of molding by molding by injection molding (including gas injection molding), injection compression molding (press injection), extrusion molding, hollow molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, etc. Goods can be obtained. Of these, injection molding and injection compression molding are more preferable.
<Propylene-based resin composition>
By the above method, a propylene-based resin composition containing the following components (A) and (B) is obtained.
(A) A propylene homopolymer, a copolymer of propylene and an α-olefin other than propylene, or a mixture thereof.
(B) A polar group having a polar functional group, wherein the propylene chain portion in the main chain has a stereo block structure composed of an isotactic block and an amorphous block Contains propylene polymer.
[0103]
In the composition of the present invention, the component (A) and the component (B) are mixed with each other to form a mixture. In some cases, a part of the component (A) and a part of the component (B) may form a chemical bond.
In addition, in order to improve paintability, it is preferable that the polar group of the (B) component exists in the surface vicinity of a molded object. Specifically, when attention is paid to a certain hetero atom in the polar group, when the hetero atom is X and the carbon atom is C, X / C is 0 when the surface of the molded body is measured by ESCA. It is preferable to adjust it to be 0.001 or more and 1 or less, preferably 0.002 or more and 0.8 or less. When X / C is less than 0.001, sufficient coating film adhesion cannot be obtained when the molded body is coated. Moreover, since X / C is too high, since the mechanical strength of a molded object skin layer will be impaired, this is also unpreferable. The method for adjusting X / C is not particularly limited. For example, the method for adjusting the polar group content in component (B), the method for adjusting the mixing ratio of component (B) to component (A), and injection molding Examples include a method of changing the shear rate, a method of performing multilayer molding, and a method of treating the surface with water or a polar solvent after molding. Further, since it is easy to mold, the MFR of the composition of the present invention is usually 0.1 or more, preferably 1 or more, more preferably 10 or more, and usually 1000 or less, preferably 500 or less, more preferably 300 or less. It is.
<Application>
Since the propylene-based resin composition of the present invention has a high balance of physical properties in rigidity, impact resistance, and paintability, various industrial parts fields, in particular, various molded products that are thin, highly functional, and large in size. As a molding material for various industrial parts such as home appliance parts such as TV cases, refrigerator outer plates, washing machine outer plates, etc., it has sufficient performance for practical use.
[0104]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention will not be restrict | limited by these Examples, unless it deviates from the summary.
In the following examples, all the metallocene synthesis steps were performed under a purified nitrogen atmosphere, and ether and THF were dried with Na-benzophenone. Toluene and n-hexane were dehydrated solvents purchased from Kanto Chemical. All of the polymerization steps were performed under a purified nitrogen atmosphere, and the solvent was dehydrated with molecular sieve (MS-4A) and then degassed by bubbling with purified nitrogen. The molecular weight and melting point of the propylene polymer were measured by the method described in this specification.
[0105]
Various physical properties were measured according to the following procedures.
(1) MFR: Measured according to JISK7210 at 230 ° C. and 2.16 kg load.
(2) Flexural modulus (unit: MPa): Measured at 23 ° C. according to JIS-K7203.
(3) Izod impact strength (unit: kJ / m²): Measured at 23 ° C. and (30 ° C. in accordance with JIS-K7110.
(4) Deflection temperature under load (unit: ° C): 4.6 kgf / cm according to JIS-K7207²It measured on condition of this.
(5) Paintability: A flat plate molded by injection molding is directly spray-coated with a water-based melamine-based paint to a thickness of about 15 microns using an air spray gun without any pretreatment. Bake and dry at 1 ° C. for 1 hour, then leave at room temperature for 48 hours. Thereafter, using a single-edged razor on the surface of the test piece, 11 parallel lines of 11 vertical and horizontal directions are drawn at intervals of 2 mm to make 100 grids. The cellophane adhesive tape (JIS-Z1522) is fully crimped on top of it, and the work of peeling off at a stretch is repeated 5 times while keeping the angle between the coated surface and the adhesive tape at about 30 degrees, and the state of the part surrounded by the grid is confirmed. Observe and evaluate the number of grids that did not peel.
[0106]
As the component (A), propylene / ethylene block copolymers (BPP1 to BPP3) having the physical properties shown in Table 1 were used.
[0107]
[Table 1]

[0108]
Production example of component (B)
(Production Example 1) <Polar group-containing propylene polymer having a stereo block structure>
(1) Synthesis of dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] zirconium
(1) -1 Ligand synthesis
2-Methylazulene (12.10 g, 0.085 mol) was dissolved in tetrahydrofuran (168 ml), cooled to 5 ° C. in an ice bath, and then methyllithium diethyl ether solution 1.04 mol / l, 83 ml at the same temperature. , 0.086 mol) was added dropwise. After completion of dropping, the ice bath was removed and the mixture was stirred for 3 hours. This solution was slowly added dropwise to a tetrahydrofuran solution (420 ml) of dimethylsilyl dichloride (22.5 ml, 0.185 mol) cooled to 5 ° C. in an ice bath. After completion of the dropping, the ice bath was removed and the mixture was stirred for 3 hours, and then the solvent and unreacted dimethylsilyl dichloride were distilled off under reduced pressure. Tetrahydrofuran (240 ml) was added to the residue and cooled to 0 ° C., and cyclopentadienyl sodium (2.1 mol / l, 81 ml, 0.160 mol) was gradually added dropwise. Thereafter, the temperature was gradually raised to room temperature, and stirring was performed day and night. After completion of the stirring, water was added and the target compound was extracted with diethyl ether. The extracted solution was dehydrated with magnesium sulfate and then dried to obtain a crude ligand product (23.54 g, yield 98.8%).
(1) -2 Complex synthesis
The ligand (10.56 g, 37.6 mmol) obtained in (1) -1 was dissolved in tetrahydrofuran (90 ml) and cooled to 5 ° C. with an ice bath. While maintaining the same temperature, an n-hexane solution of n-butyllithium (1.59 mol / l, 47.3 ml, 75.2 mmol) was slowly added dropwise thereto. After completion of dropping, the ice bath was removed and the mixture was stirred for 2 hours, and the solvent was distilled off under reduced pressure. Tetrahydrofuran (10 ml) and toluene (200 ml) were added to the residue obtained after the distillation, and the mixture was cooled to 78 ° C. Zirconium tetrachloride (8.73 g, 37.5 mmol) was slowly added thereto. Thereafter, the cooling bath was removed and the mixture was stirred overnight. After completion of stirring, the reaction solution was filtered through a G3 frit. The solid on the frit was further washed with toluene and the filtrate was concentrated to give a brown powder. Toluene (70 ml) and n-hexane (100 ml) were added to the obtained brown powder. After separating the supernatant, it was concentrated. The residue after concentration was washed with n-hexane (20 ml, twice) and diethyl ether (15 ml, twice). This washing operation was further repeated twice and then dried to obtain the target complex (2.29 g, yield 13.8%).
[0109]
¹H-NMR (CDCl_Three): Δ 0.85 (s, 3H), 0.88 (s, 3H), 1.47 (d, J = 7.2 Hz, 3H), 2.16 (s, 3H), 3.38-3 .50 (m, 1H), 5.27 (dd, J = 4.8, 6.0 Hz, 1H), 5.80-5.85 (m, 2H), 5.95-5.99 (m , 1H), 6.65 (dd, J = 5.40, 11.3 Hz, 1H), 6.32 (s, 1H), 6.58 (d, J = 11.7 Hz, 1H), 6.90. -6.95 (m, 1H), 7.08-7.10 (m, 1H).
(2) Chemical treatment of clay minerals
Demineralized water (93.6 ml), lithium sulfate monohydrate (14.5 g) and sulfuric acid (22.1 g) were collected in a 300 ml round bottom flask and dissolved with stirring. To this solution, 29.4 g of montmorillonite (Mizusawa Chemical's Mizusawa smectite) was added, and the temperature was raised and treated under reflux for 120 minutes. After the treatment, 400 ml of demineralized water was added and centrifuged, and then the supernatant was removed. Further, 400 ml of demineralized water was added, centrifugation and removal of the supernatant were repeated twice, and finally the residue was filtered. The resulting solid was dried at 100 ° C. Next, 0.5 g of the dry solid obtained here was collected in a 100 ml round bottom flask and dried by heating at 200 ° C. under reduced pressure for 2 hours. After completion, 2.3 ml of a toluene solution of triethylaluminum (0.45 mmol / ml) was added under purified nitrogen, reacted at room temperature for 30 minutes, washed twice with 20 ml of toluene, and a chemically treated montmorillonite toluene slurry was added. Obtained.
(3) Catalyst preparation
3.9 ml of a toluene solution of triisobutylaluminum (0.1 mmol / ml) and 17 mg of dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] zirconium synthesized in (1) Then, 9.1 ml of toluene was added to a 50 ml eggplant flask and stirred at room temperature for 5 minutes. 4.7 ml of this complex solution was added to 0.9 ml of the chemically treated montmorillonite toluene slurry (containing 469.6 mg as a solid content) obtained in (2) and stirred at room temperature for 10 minutes to obtain a catalyst slurry. .
(4) Propylene polymerization
A 2-liter induction stirring autoclave containing a built-in stirring blade was replaced with purified nitrogen, and 2.5 ml of a toluene solution of triisobutylaluminum (0.1 mmol / ml) was charged. The entire amount of the catalyst slurry obtained in (3) was charged into the autoclave, and 625 g of liquefied propylene was further charged. The autoclave was heated, and propylene was polymerized while adjusting the internal temperature to be constant at 80 ° C. After 80 minutes from the time when the internal temperature reached 80 ° C., unreacted propylene was purged to terminate the polymerization. Further, 5 ml of methanol was injected into the autoclave to deactivate the remaining organoaluminum compound and catalyst. Next, the internal temperature was raised to 120 ° C., and a solvent such as methanol was distilled off under reduced pressure. The yield of the finally obtained propylene polymer was 380 g.
[0110]
When a part of the obtained polymer was collected and analyzed, the following results were obtained. Mw by GPC: 11,000, Mw / Mn = 2.6.¹³Peak derived from carbon atom of methyl group of propylene unit chain part consisting of head to tail bond by C-NMR: S₁/S=33.3(%), 4 + 2S₁/ S₂= 7.9,¹³The ratio of 2,1-insertion to the total propylene insertion measured by C-NMR was 0.04 (%), and the ratio of 1,3-insertion was 0.14 (%).¹When the unsaturated bond amount at the terminal end was measured by 1 H-NMR, it was 19.4 (%) at the vinylidene terminal and 6.4 (%) at the vinyl terminal. When DSC was measured for the obtained polymer, no clear melting point peak was observed. Moreover, when the solubility of the obtained polymer was measured, the following results were obtained. Solubility in n-heptane (temperature = 98 ° C., concentration = 10 wt%): The polymer was completely dissolved and no insoluble matter was observed. Solubility in toluene (temperature = 25 ° C., concentration = 10 wt%): The polymer was completely dissolved and no insoluble matter was observed.
(5) Production of maleic anhydride modified polymer
After charging 18.4 g (5 parts) of maleic anhydride dissolved in 18.4 g (5 parts) of xylene into 368 g (100 parts) of the propylene polymer in the autoclave obtained in (4), xylene was further added. 18.4 g (5 parts) was added. After raising the internal temperature of the autoclave to 170 ° C., a liquid in which 3.68 g (1 part) of perbutyl I (manufactured by NOF Corporation) was dispersed in 18.4 g (5 parts) of xylene was divided into 5 parts. Press-fitted every 30 minutes. After the addition of perbutyl I was completed, the reaction was continued at 170 ° C. for 60 minutes. After completion of the reaction, unreacted maleic anhydride was distilled off at 200 ° C. under reduced pressure for 60 minutes. When a part of the obtained modified polymer was taken out and analyzed, the maleic anhydride content in the modified polymer was 1.4 mol%.
(6) Production of imide-modified polymer
The maleic anhydride-modified polymer obtained in (5) was heated to 120 ° C. without taking it out of the autoclave. Next, 9.2 g of 2-aminoethanol was injected, and further 20 ml of xylene was charged 5 times. An imidization reaction was performed at 120 ° C. for 60 minutes, and after completion of the reaction, the imide-modified polymer was reprecipitated using a large amount of acetone. Furthermore, acetone washing | cleaning was performed 3 times, and after removing an unreacted substance, it dried under reduced pressure at 120 degreeC for 6 hours. When the imide content of this modified product was quantified by IR spectrum, it was 0.9 mol%. The average molecular weight, molecular weight distribution, steric structure of the main chain and other physical properties were not changed with respect to the polymer obtained in (4). (Production Example 2) <Polar group-containing propylene polymer having a stereoblock structure>
Production Example 1 The maleic anhydride modified polymer was prepared in the same manner as in Production Example 1 (5), except that the amount of maleic anhydride used was 36.8 g relative to the propylene polymer obtained in (4). Manufactured. When a part of the obtained maleic anhydride-modified polymer was taken out and analyzed, the maleic anhydride content in the modified polymer was 2.1 mol%.
[0111]
Next, an imide-modified polymer was produced in the same manner as in Production Example 1 (6) except that the amount of 2-aminoethanol used was 27.6 g. The imide content in the obtained modified polymer was 1.4 mol%.
(Production Example 3) <Polar group-containing propylene polymer having stereoblock structure>
The maleic anhydride modified polymer was prepared in the same manner as in Production Example 1 (5) except that the amount of maleic anhydride used was 8.1 g with respect to the propylene polymer obtained in Production Example 1 (4). Manufactured. When a part of the obtained maleic anhydride-modified polymer was taken out and analyzed, the maleic anhydride content in the modified polymer was 0.6 mol%.
[0112]
Next, an imide-modified polymer was produced in the same manner as in Production Example 1 (6) except that the amount of 2-aminoethanol used was 4.0 g. The imide content in the obtained modified polymer was 0.4 mol%.
(Production Example 4) <Isotactic structure polar group-containing polypropylene>
Isotactic polypropylene wax with a number average molecular weight of 3000 (S₁/ S> 95%) 300 parts by weight and 23 parts by weight of maleic anhydride were charged into a reactor equipped with a reflux tube. Next, 700 parts by weight of xylene was added, and the inside of the reactor was purged with nitrogen. While stirring, the temperature was raised to 150 ° C. while introducing a small amount of nitrogen to obtain a homogeneous solution, and 16.5 parts by weight of dicumyl peroxide was added over 3 hours, and the reaction was continued for further 4 hours. Thereafter, xylene and unreacted maleic anhydride were removed at a normal pressure first and then at 180 ° C. under a reduced pressure of 3 mmHg over 2 hours. Subsequently, 1250 parts by weight of toluene was added to dissolve the acid-modified polypropylene in the toluene solution, and then 12 parts by weight of monoethanolamine was added and reacted at 50 ° C. for 60 minutes. The obtained modified polypropylene had a weight average molecular weight of 7,500 and a graft ratio of 3.0 wt%.
(Examples 1-10, Comparative Examples 1-4)
In accordance with the composition shown in Table 2, component (A) (propylene / ethylene block copolymer) and component (B) were blended, and 0.1 parts by weight of a phenolic antioxidant (IRGANOX 1010, manufactured by Ciba Specialty Chemicals) , Phosphorus antioxidant (Irgafos 168 manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.05 parts by weight and calcium stearate 0.3 parts by weight, and then screw rotation using a twin-screw extruder (Nippon Steel Works TEX30α) It was melt-kneaded at several 300 rpm and an extrusion rate of 15 kg / h to obtain propylene-based resin composition pellets. Using the obtained pellets, injection molding was performed under conditions of a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C. to obtain a test piece of a propylene-based resin composition.
[0113]
Various physical properties were evaluated by the above-described methods using the obtained test pieces. The evaluation results are shown in Table 2.
[0114]
[Table 2]

[0115]
As is clear from the above Examples and Comparative Examples, when the component (B) to be blended with the propylene / ethylene block copolymer as the component (A) does not have a stereo block structure, even if blended Even if the amount is changed, strength (Izod impact) and heat resistance (deflection temperature under load) and paintability (residual rate after 5th cross-cut peel) cannot be achieved at the same time, but as component (B) in the present invention When a polar group-containing propylene polymer having a defined stereo block structure is used, these physical properties can be achieved in a well-balanced manner.
[0116]
【The invention's effect】
The propylene-based resin composition of the present invention, in which a modified polypropylene having a specific structure is blended, is excellent in strength balance such as impact strength and bending rigidity, and can adhere a coating film without applying a solvent primer. Since it is possible, it is very useful industrially. Furthermore, since the propylene-based resin composition of the present invention achieves adhesion of a coating film to a water-based paint without a primer, not only the organic solvent attributed to the primer but also the reduction in the amount of organic solvent attributed to the paint solvent is realized. It is possible to reduce the environmental load, and it has a great effect on the reduction of the environmental load. Furthermore, since the propylene-based resin composition of the present invention is excellent in strength balance, it is possible to reduce the thickness of a molded product. Particularly in automobile parts and the like in which the amount of use is increasing, fuel efficiency associated with weight reduction is achieved. It is a technology that leads to improvement. This can be said to be one effective means for solving recent social problems such as saving energy resources and protecting the global environment, and its industrial value is extremely large.

Claims (7)

A propylene-based resin composition containing the following components (A) and (B) as essential components.
(A) A propylene homopolymer, a copolymer of propylene and an α-olefin other than propylene, or a mixture thereof.
(B) a propylene polymer having a polar functional group consisting of a carboxyl group, a carboxylic acid group, an ester group, an amide group, an imide group, an acid anhydride group, or a hydroxyl group, wherein the propylene chain portion in the main chain is A polar group-containing propylene-based polymer having a stereo block structure composed of a tactic block and an amorphous block , the propylene chain portion of which satisfies the following requirements (a) and (b) .
(A) In a ¹³ C-NMR spectrum, a peak derived from a carbon atom of a methyl group in a propylene unit chain part composed of a head-to-tail bond was observed, and the peak top of a peak attributed to a pentad represented by mmmm 4 + 2S ₁ , where S ₁ is the peak area with a chemical shift of 21.8 ppm and S ₂ is the peak area with a peak top of 21.5-21.6 ppm attributed to the pentad represented by mmmr. / S ₂ > 5.
(B) Similarly, the ratio S ₁ / S of the peak area S ₁ having 21.8 ppm as the peak top to the total area S of peaks appearing at 19.8 to 22.2 ppm is 10% or more and 90% or less.   The propylene-based resin composition according to claim 1, wherein the polar group-containing propylene-based polymer has a heat of crystal melting by DSC of less than 1 J / g. The propylene-based resin composition according to claim 1 or 2, wherein the polar group-containing propylene-based polymer is a modified polymer of a propylene-based polymer having the following requirement (1).
(1) When dissolved in n-heptane at 98 ° C. at a concentration of 10% by weight, the insoluble content is 1% by weight or less. The propylene-based resin composition according to any one of claims 1 to 3, wherein the polar group-containing propylene-based polymer is a modified polymer of a propylene-based polymer having the following requirement (2).
(2) When dissolved at a concentration of 10% by weight in toluene at 25 ° C., the insoluble content is 1% by weight or less.   The propylene-based resin composition according to any one of claims 1 to 4, wherein the polar group-containing propylene-based polymer is a modified polymer of a propylene-based polymer having an unsaturated bond at a terminal. The propylene-based resin composition according to any one of claims 1 to 5, wherein the polar group-containing propylene-based polymer is a modified polymer of a propylene-based polymer having the following requirement (3).
(3) 2,1-inserted propylene monomer and 1, 3-inserted propylene monomer to based position irregular units are present in the main chain, and 2,1-insertion to all propylene insertions The sum of the ratios of position irregular units based on 1,3-insertion is 0.05% or more. The molded object formed by shape | molding the propylene-type resin composition of any one of Claims 1-6 .