JP4142390B2 - PROPYLENE POLYMER, COMPOSITION CONTAINING THE SAME, AND USE - Google Patents

Description

【００３１】
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。
【００３２】
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、炭素原子数１〜１０、好ましくは炭素原子数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。
【化３】

【００３３】
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。
【００３４】
また、（２）［Ａ］成分の遷移金属と反応して［Ａ］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。
【化４】

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、ホスホ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。
【００３５】
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。
【００３６】
上記の一般式（ＶＩ）中、Ｚは、アニオン成分であり、［Ａ］成分の遷移金属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）アルミニウム等が挙げられる。
【００３７】
他の具体的化合物として、（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が挙げられる。
【００３８】
また、（３）ルイス酸、特に［Ａ］成分の遷移金属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。
【００３９】
（４）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、γ−Ｚｒ（ＨＰＯ₄）₂、γ−Ｔｉ（ＨＰＯ₄）₂、γ−Ｔｉ（ＮＨ₄ＰＯ₄）₂・Ｈ₂Ｏ等の多価金属の結晶性酸性塩があげられる。
【００４０】
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。
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。
【００４１】
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。
【００４２】
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［Ｂ］成分の必須成分としては、重合活性等の触媒性能の面で、（４）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。
【００４３】
本発明のプロピレン重合体主鎖の製造で、共触媒［Ｂ］成分の他に任意成分［Ｃ］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、一般式、ＡｌＲ¹ _mＺ_3-m（式中、Ｒ¹は、炭素原子数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。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、新たに任意成分［Ｃ］を追加してもよい。
【００４４】
プロピレン重合用触媒は、［Ａ］成分、［Ｂ］成分、任意の［Ｃ］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されない。この接触は、触媒調製時だけでなく、プロピレンの予備重合時または重合時に行ってもよい。触媒各成分の接触時、または接触後にプロピレン重合体、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、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。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℃乃至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。
【００４５】
触媒各成分の使用量に特に制限はないが、［Ｂ］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、［Ｂ］成分１ｇあたり［Ａ］成分が０．０００１〜１０ｍｍｏｌ、好ましくは０．００１〜５ｍｍｏｌであり、［Ｃ］成分が０〜１０，０００ｍｍｏｌ、好ましくは０．０１〜１００ｍｍｏｌである。また、［Ａ］成分中の遷移金属と［Ｃ］成分中のアルミニウムの原子比が１：０〜１，０００，０００、好ましくは、１：０．１〜１００，０００となるように制御することが、重合活性などの点で好ましい。
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。
洗浄の際に、必要に応じて新たに［Ｃ］成分を組合せて用いてもよい。この際に用いられる［Ｃ］成分の量は、［Ａ］成分中の遷移金属に対する［Ｃ］成分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。
【００４６】
触媒として、プロピレ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、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。
プロピレンの重合反応は、プロパン、ｎ−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プロピレン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重合を行うのが好ましい。
具体的には、［Ａ］成分と［Ｂ］成分、もしくは［Ａ］成分、［Ｂ］成分および［Ｃ］成分の存在下に、主鎖のプロピレン重合体を製造する。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０から１５０℃、好ましくは２０から１００℃、重合圧力は、０．１ＭＰａから１００ＭＰａ、好ましくは、０．３ＭＰａから１０ＭＰａ、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時間の範囲から選ばれる。
【００４７】
本発明においては、前記したように、重合体の重量平均分子量Ｍｗを５，０００〜２００，０００の範囲にするのが好ましい。このために、重合体の分子量調節には、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が挙げられる。連鎖移動剤を使用する場合には、水素が好ましい。
【００４８】
また、本発明において頭−尾結合からなるプロピレン単位連鎖部の立体選択性を制御して製造されるプロピレン重合体主鎖は、前述のように¹³Ｃ−ＮＭＲにて、頭−尾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を観測し、ｍｍｍｍで表されるペンタッドに帰属されるピークのピークトップのケミカルシフトを２１．８ｐｐｍとした際に、１９．８ｐｐｍから２２．２ｐｐｍの範囲に現れる全ペンタッドに属するピークの総面積Ｓに対する、２１．８ｐｐｍをピークトップとするピークの面積Ｓ₁の比率（Ｓ₁／Ｓ）が１０％以上、６０％以下であり、且つ２１．５〜２１．７ｐｐｍをピークトップとするピーク（ｍｍｍｒ）の面積をＳ₂としたとき４＋２Ｓ₁ ／Ｓ₂＞５であることが好ましい。
【００４９】
プロピレン重合体主鎖のこのような特性に係わる立体選択性の制御方法については特に制限はないが、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が挙げられる。重合条件を制御して立体選択性を制御する場合には、重合温度やモノマー濃度を制御することにより、そして、場合により、上述の触媒の構造制御ともあわせて、所望とする立体規則性を有するプロピレン重合体主鎖を得ることができる。
【００５０】
本発明に用いるプロピレン重合体主鎖は、溶媒に溶解させることができる。溶媒の具体例としては、ベンゼン、トルエン、キシレン等の芳香族系炭化水素；ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｎ−デカン等の脂肪族系炭化水素；シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン等の脂環式脂肪族系炭化水素、塩化メチレン、四塩化炭素、トリクロロエチレン、パークロルチレン、クロルベンゼン、ｏ−ジクロロベンゼン等のハロゲン化炭化水素、ｎ−エチルアセテート、ｎ−ブチルアセテート等のエステル類、メチルイソブチルケトン、シクロヘキサノン等のケトン類、テトラヒドロフラン、ジメチルスルホキシド等の極性溶媒類などが挙げられ、これらの中でも、芳香族炭化水素もしくはハロゲン化炭化水素が好ましく、特にトルエン、キシレン、クロルベンゼンが好ましい。
【００５１】
その溶解性は通常の高立体規則性アイソタクチックポリプロピレン変性体に比べ非常に優れており、室温のトルエン（２５℃）に１０重量％濃度で溶解した場合、その不溶成分がその重合体全量の１重量％以下である。好ましくは０．１重量％以下であり、さらに好ましくは不溶成分が無い状態である。同様に、沸騰ヘプタン（９８℃）に１０重量％濃度で溶解した際にも、その不溶成分がその重合体全量の１重量％以下である。
測定方法としては、例えば次のように所定温度・所定濃度で溶解した溶液をその温度付近にて（温度が高い場合によっては熱時濾過）濾過し、その時用いた濾紙もしくはＳＵＳ製金網（あらかじめ重量を測ってある）を乾燥し、不溶分の重量を測定する方法が用いられる。
【００５２】
本発明のプロピレン重合体から成る主鎖と、カルボン酸基もしくは酸無水物基又はカルボン酸エステル基を含む側鎖とを有するプロピレン系重合体を製造する方法は特に限定されないが、上記プロピレン重合体主鎖にカルボン酸基等を含有する重合性単量体をグラフト共重合させて得る方法が一般的である。グラフト共重合させるカルボン酸基等を含有する重合性単量体としては、（メタ）アクリル酸およびその酸誘導体並びにモノオレフィンジカルボン酸、その無水物およびそのモノエステル類が挙げられ、これらから選ばれる少なくとも１種が用いられる。具体的に例示するならば、（メタ）アクリル酸およびそのエステル誘導体としては（メタ）アクリル酸；炭素原子数１〜１２のアルキル基を有する（メタ）アクリル酸エステル系モノマー、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル等；炭素原子数６〜１２のアリール基又はアリールアルキル基を有する（メタ）アクリル酸エステルのモノマー、例えば（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイル、（メタ）アクリル酸ベンジル等が挙げられる。
【００５３】
更に、他の（メタ）アクリル酸誘導体としてはヘテロ原子を含有する炭素原子数１〜２０のアルキル基を有する（メタ）アクリル酸エステルのモノマー、例えば（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸−２−アミノエチル、（メタ）アクリル酸−２−メトキシエチル、（メタ）アクリル酸−３−メトキシプロピル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸エチレンオキサイドの付加物等；フッ素原子を含有する炭素原子数１〜２０のアルキル基を有する（メタ）アクリル酸エステルのモノマー、例えば（メタ）アクリル酸トリフルオロメチルメチル、（メタ）アクリル酸２−トリフルオロメチルエチル、（メタ）アクリル酸２−パーフルオロエチルエチル等；（メタ）アクリルアミド系モノマー、例えば（メタ）アクリルアミド、（メタ）アクリルジメチルアミド等が挙げられる。
【００５４】
モノオレフィンジカルボン酸およびその酸無水物並びにモノオレフィンジカルボン酸のモノアルキルエステルが挙げられるが、そのモノオレフィンジカルボン酸としては、例えば、マレイン酸、クロロマレイン酸、シトラコン酸、イタコン酸、グルタコン酸、３−メチル−２−ペンテン・二酸、２−メチル−２−ペンテン・二酸、２−ヘキセン・二酸等が挙げられる。また、モノオレフィンジカルボン酸モノアルキルエステルとしては、炭素原子数１〜１２のアルキルアルコールとこれらのジカルボン酸とのモノエステルが挙げられ、アルキルアルコールとしては、具体的にはメチルアルコール、エチルアルコール、プロピルアルコール、ブチルアルコール、ペンチルアルコール、オクチルアルコール、シクロヘキシルアルコール等が挙げられる。
本発明のグラフト変性したプロピレン系重合体を用いて塗膜を形成した場合、塗膜と塗料との接着性の面から、これらのグラフトするカルボン酸基等を含有する重合性単量体としては、溶解度パラメーターが高い方が好ましく、すなわち炭素原子数３〜１０の不飽和カルボン酸、その酸無水物およびそのエステルからなる不飽和カルボン酸誘導体成分が好ましい。特に無水マレイン酸が好ましい。
【００５５】
本発明におけるグラフト変性したプロピレン系重合体の内で、グラフト共重合単位としてモノオレフィンジカルボン酸モノアルキルエステルを有する変性重合体は、例えば、モノオレフィンジカルボン酸モノアルキルエステルを主鎖のプロピレン重合体にグラフト共重合する方法：モノオレフィンジカルボン酸もしくはその酸無水物を、プロピレン重合体主鎖にグラフト共重合させた後に、アルキルアルコールによりカルボン酸基の１つをエステル化する方法によって得ることができる。
【００５６】
グラフト変性したプロピレン系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から選ばれる少なくとも１種のグラフト共重合単位のグラフト量、すなわち該プロピレン系重合体中の含有量（グラフト率）が、０．０１〜２５重量％、好ましくは０．１〜１５重量％となるようにグラフト共重合するのが良い。グラフト率がこの範囲内であるプロピレン系重合体は、これをプライマーとして成型品に塗布した際、塗料の付着性が高い塗膜が得られ、また該塗膜と成型品との付着性も良好で、外観が良好となる点で好ましい。
更に、本発明のプロピレン系重合体は、後述するように、２５℃にてトルエンに１０重量％濃度で溶解した際に、その不溶分がその重合体全量の１重量％以下であるという優れた溶解性を有するが、加えて基材となるポリプロピレン成形体に対し高い密着性も有するのである。即ち、本発明のプロピレン系重合体は、ポリプロピレン成形体への密着性が優れており、密着性試験（碁盤目テープ法）による密着性が５０／１００以上である。好ましくは８０／１００以上であり、さらに好ましくは１００／１００である。
特に、このような特性に優れたプロピレン系重合体としては、上述の如きプロピレン重合体主鎖にカルボン酸基等を含有する重合性単量体をグラフト共重合させたものを挙げることが出来る。
【００５７】
本発明において、プロピレン系重合体の密着性は以下の密着試験法によるものとする。
密着試験法
（Ａ）密着試験は、ＪＩＳ Ｋ５４００ ８．５．２に記載されている碁盤目テープ法に準じて行う。
(1) 要旨 試験片の塗膜を貫通して、素地面に達する切り傷を碁盤目状に付け、この碁盤目の上に粘着テープをはり、はがした後の塗膜の付着状態を目視によって観察する。
(2) 装置および材料
（ａ）カッターナイフ ＪＩＳ Ｋ５４００ ７．２(2) (e)による。
（ｂ）カッターガイド ＪＩＳ Ｋ５４００ ８．５．１(2) (b)による。
（ｃ）セロハン粘着テープ ＪＩＳ Ｚ１５２２に規定するセロハン粘着テープで、幅１８ｍｍ又は２４ｍｍ、粘着力２．９４Ｎ／１０ｍｍ以上のもの
（ｄ）試験板 ポリプロピレン成形体（１５０mm×７０mm×３mm）とする
（ｅ）消しゴム ＪＩＳ Ｓ６０５０に規定するもの
【００５８】
(3) 試験片の作成
試料を試験片の片面に、ＪＩＳ Ｋ５４００ ３．３によって試料の製品規格に規定する方法で塗装して乾燥した後、標準状態で２４時間放置したものを使用
(4) 操作
ＪＩＳ Ｋ５４００ ８．５．２．（４）に従う
(5) 評価
評価は次の通りとする。
（ａ）試験片の塗面に付けた碁盤目状の傷の状態を観察し、碁盤目１００個のうちで剥離されなかった碁盤目の数を数え「残留碁盤目数／１００個」で表記し、密着性とする。
【００５９】
本発明の密着試験に用いられるポリプロピレン基材は、結晶性ポリプロピレンが用いられる。結晶性ポリプロピレンとしては、プロピレン単独重合体、及び／またはプロピレン単独重合体部とプロピレン・エチレン共重合体部からなるプロピレン・エチレンブロック共重合体等が挙げられる。中でもＭＦＲ（２３０℃、21.18Ｎ荷重）が５〜３０(ｇ／１０分）のプロピレン単独重合体を用いるのが好ましい。
【００６０】
前記主鎖のプロピレン重合体にモノオレフィンジカルボン酸、その酸無水物およびモノオレフィンジカルボン酸モノアルキルエステル等の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、該プロピレン重合体主鎖を有機溶媒に溶解し、前記グラフトする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；該プロピレン重合体主鎖を加熱して溶解し、該溶融物にグラフトする重合性単量体およびラジカル重合開始剤を添加し攪拌することによりグラフト共重合する方法；あるいは各成分を押出機に供給して加熱混練しながらグラフト共重合する方法；該プロピレン重合体のパウダーに前記グラフトする重合性単量体およびラジカル重合開始剤を有機溶媒に溶解した溶液を含浸させた後、パウダーが溶解しない温度まで加熱し、グラフト共重合する方法などが挙げられる。
このとき、ラジカル重合開始剤／グラフトする重合性単量体の使用割合は、通常モル比で１／１００〜３／５、好ましくは１／２０〜１／２の範囲である。
反応温度は、５０℃以上、特に８０〜２００℃の範囲が好適であり、反応時間は２〜１０時間程度である。
【００６１】
上記グラフト共重合に用いられるラジカル重合開始剤としては、通常のラジカル開始剤から適宜選択して使用することができ、有機過酸化物、アゾニトリル等を挙げることができる。有機過酸化物としては、ジイソプロピルパーオキシド、ジ（ｔ−ブチル）パーオキシド、ｔ−ブチルヒドロパーオキシド、ベンゾイルパーオキシド、ジクミルパーオキシド、クミルヒドロパーオキシド、ジラウロイルパーオキシド、ジベンゾイルパーオキシド、メチルエチルケトンパーオキシド、シクロヘキサノンパーオキシド、クメンヒドロパーオキシド、ジイソプロピルパーオキシカルボナート、ジシクロヘキシルパーオキシカルボナート等が挙げられる。アゾニトリルとしてはアゾビスブチロニトリル、アゾビスイソプロピルニトリル等が挙げられる。これらの中で、ベンゾイルパーオキシド、ジクミルパーオキシドが好ましい。
【００６２】
上記グラフト共重合反応を有機溶媒を用いて行う場合、その有機溶媒の具体的な例としては、ベンゼン、トルエン、キシレン等の芳香族系炭化水素；ヘキサン、ヘプタン、オクタン、デカン等の脂肪族系炭化水素；トリクロロエチレン、パークロルエチレン、クロルベンゼン、ｏ−ジクロロベンゼン等のハロゲン化炭化水素などが挙げられ、これらの中でも、芳香族炭化水素もしくはハロゲン化炭化水素が好ましく、特にトルエン、キシレン、クロルベンゼンが好ましい。
【００６３】
本発明のプロピレン系重合体も、プロピレン重合体主鎖が可溶な前記の溶媒と同様の溶媒に溶解させることができる。その溶解性は通常の高立体規則性アイソタクチックポリプロピレン重合体に比べ非常に優れており、２５℃にてトルエンに１０重量％濃度で溶解した際に、その不溶分がその重合体全量の１重量％以下である。好ましくは０．１重量％以下であり、さらに好ましくは不溶成分が無い状態である。また本発明のプロピレン系重合体は、溶媒の中でも特に溶解度パラメーターが１１（cal/cm³）^1/2以下の溶媒には溶解性が高いので、このグラフト変性したプロピレン系重合体を溶解度パラメーターが１１（cal/cm³）^1/2以下の溶剤に１重量部以上溶解した組成物は接着性組成物として利用することができる。
【００６４】
溶解度パラメーターが１１（cal/cm³）^1/2以下の溶媒の具体例としては、ベンゼン、トルエン、キシレン等の芳香族系炭化水素；ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｎ−デカン等の脂肪族系炭化水素；シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン等の脂環式脂肪族系炭化水素、塩化メチレン、クロロホルム、四塩化炭素、トリクロロエチレン、パークロルエチレン、クロルベンゼン、ｏ−ジクロロベンゼン等のハロゲン化炭化水素、ｎ−メチルアセテート、ｎ−エチルアセテート、ｎ−ブチルアセテート等のエステル類、メチルイソブチルケトン、シクロヘキサノン等のケトン類、テトラヒドロフラン等のエーテル類などが挙げられ、これらの中でも、芳香族炭化水素もしくはハロゲン化炭化水素が好ましく、特にトルエン、キシレン、クロルベンゼンが好ましい。
【００６５】
また、本発明のプロピレン系重合体は、プロピレン重合体主鎖同様、ポリマー主鎖中のメチル基の立体規則性分布が適度であるので、その結晶性も比較的低く溶媒に対する溶解性に優れる特徴を有する。具体的には、該重合体をオルトジクロロベンゼンにて昇温溶出分別した際に、実質的にすべての成分が６０℃以下で溶出するという特性である。６０℃よりも高い温度で溶出する成分は、結晶性がかなり高い成分であるので、重合体がこのような成分を含んでいる場合には、重合体を溶媒に溶解させた際に、こうした結晶性の高い成分が不溶成分となったり、ゲル化が発生したりするといった不都合が起きやすい。本発明のプロピレン系重合体は、実質的にすべての成分が６０℃以下で溶出するので、こうした不都合を回避することが出来るが、好ましくは５０℃以下、さらに好ましくは４０℃以下で実質的にすべての成分が溶出することが好ましい。
【００６６】
本発明のプロピレン系重合体は、上述のように溶媒に可溶なので、結晶性を有するオレフィン系重合体の成形体（基材）に塗布することができる。基材としてのオレフィン系重合体としては、高圧法ポリエチレン、中低圧法ポリエチレン、ポリプロピレン、ポリ−４−メチル−１−ペンテン、ポリ−１−ブテン、ポリスチレン等のオレフィン系重合体、エチレン・プロピレン共重合体、エチレン・ブテン共重合体、プロピレン・ブテン共重合体等のオレフィン共重合体等が挙げられる。これらのオレフィン共重合体のうち、プロピレン共重合体が好ましく用いられる。また、ポリプロピレンと合成ゴムとからなる成型品、ポリアミド樹脂、不飽和ポリエステル樹脂、ポリブチレンテレフタレート樹脂、ポリカーボネート樹脂等からなる成型品、例えば自動車用バンパー等の成型品、さらには鋼板や電着処理用鋼板等の表面処理にも用いることができる。さらに、ポリウレタン樹脂、脂肪酸変性ポリエステル樹脂、オイルフリーポリエステル樹脂、メラミン樹脂、エポキシ樹脂等を主成分とする塗料、プライマー、接着剤等を塗布した表面に下塗りし、その表面への塗料等の付着性を改善すると共に、鮮映性、低温衝撃性等にも優れる塗膜を形成するためにも用いることができる。
【００６７】
本発明のプロピレン系重合体をオレフィン系重合体からなる基材に塗布した際に形成される塗膜は、前述の通り基材に対して良好な密着性を示すので、本発明の該プロピレン系重合体は、オレフィン系重合体に対する接着性樹脂として使用することができる。なお、オレフィン系重合体の基材に対して良好な密着性を得るためには、塗布後に加熱することが好ましい。加熱温度に特に制限はないが、実用性を考慮して５０〜１５０℃、さらには６０〜１３０℃とするのが好ましい。塗布の方法にも特に制限はなく、スプレーで塗布する方法、ローラーで塗布する方法、刷毛で塗布する方法など、従来公知の方法が使用できる。
【００６８】
本発明のプロピレン系重合体を塗布し、塗膜を形成した成形品の表面には、静電塗装、吹き付け塗装、刷毛塗り等の方法によって、塗料を塗布することができる。
塗料の塗布は、下塗りした後、上塗りする方法で行ってもよい。塗料を塗布した後、電熱、赤外線、高周波等によって加熱する通常の方法に従って塗膜を硬化させて、所望の塗膜を表面に有する成形品を得ることができる。塗膜を硬化させる方法は、成形品の材質、形状、使用する塗料の性状等によって適宜選ばれる。
【００６９】
本発明のプロピレン系重合体を溶剤に溶解した組成物は、主たる成分としてα−オレフィン共重合体やその他の重合体からなる成型品の表面に塗布し、その表面への塗料の付着性、耐水性及び耐ガソリン性といった塗膜性能を改善するためのプライマー等として用いることができる。また付着性、剥離強度および耐水性に優れる特徴を生かして、上記の成形品のプライマーとしての用途以外にも、広範囲の用途に適用可能なものであり、例えば、接着剤や塗料のための添加剤、インクバインダー等の用途にも適用可能であることは言うまでもない。
上記記載の具体的用途としては自動車外装用（バンパー用）プライマー、建材・化粧シート用接着剤、自動車部品用接着剤、包装材料用接着剤、自動車内装用塗料添加剤、グラビアインキ用インキバインダー等が挙げられる。
さらに、本発明の組成物は、上記以外に必要に応じて酸化防止剤、耐候安定剤、耐熱防止剤等の各種安定剤；酸化チタン、有機顔料等の着色剤、カーボンブラック、フェライト等の導電性付与剤等を含有していてもよい。
【００７０】
また本発明の上記組成物が適用される成型品は、上記の各種重合体あるいは樹脂が、射出成形、圧縮成型、中空成形、押出成形、回転成形等の公知の成形法のいずれの方法によって成型されたものであってもよい。
本発明のプロピレン系重合体を含有する組成物を成型品に塗布する際、成形品がタルク、亜鉛華、ガラス繊維、チタン白、硫酸マグネシウム等の無機充填剤、顔料等が配合されている場合にも、特に付着性の良い塗膜を形成することができる。
また、本発明のプロピレン系重合体を塗布する成形品は、上記以外に、種々の安定剤、紫外線吸収剤等を含有しても差し支えない。
【００７１】
本発明の上記組成物に好ましく用いられる安定剤としては、例えば、２，６−ジ−ｔ−ブチル−４−メチルフェノール、テトラキス［メチレン（３，５−ジ−４−ヒドロキシヒドロシンナメート）］メタン、メタオクタデシル−３−（４’−ヒドロキシ−３，５−ジ−ｔ−ブチル−フェニル）プロピオネート、２，２’−メチレンビス（４−メチル−６−ｔ−ブチル−フェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチル−フェノール）、２，２−チオビス（４−メチル−６−ｔ−ブチルフェノール）、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、１，３，５−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェノール）ブタン等のフェノール系安定剤；ジラウリルチオジプロポネート、ジステアリルチオジプロピオネート等のイオウ系安定剤；トリデシルホスファイト、トリノニルフェニルホスファイト等のリン系安定剤などを挙げることができる。
また用いられる紫外線吸収剤としては、例えば、２−ヒドロキシ−４−オクトキシベンゾフェノン、２−エチルヘキシル−２−シアノ−３，３−ジフェニルアクリレート、パラオクチルフェニルサリチレート等を挙げることができる。
【００７２】
【実施例】
次に実施例及び比較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。
なお、以下の実施例及び比較例において重合体の物性・性能測定は次の通り行った。また、各例において、触媒合成工程および重合工程は、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。
【００７３】
＜物性測定＞
（ｉ）主鎖のプロピレン重合体の物性測定
（１）プロピレン重合体主鎖の分子量の測定
重量平均分子量Ｍｗ、数平均分子量Ｍｎおよび分子量分布Ｍｗ／ＭｎのＧＰＣによる測定は、ウオーターズ社（Ｗａｔｅｒｓ社）製ＧＰＣ１５０ＣＶ型を使用して行った。溶媒としては、ｏ−ジクロロベンゼンを使用し、測定温度は１３５℃とした。分子量算出は、標準試料として市販の単分散のポリスチレンを使用し、該ポリスチレン標準試料およびポリプロピレンの粘度式から、保持時間と分子量に関する校正曲線を作成し分子量の算出を行った。
【００７４】
（２）プロピレン単位連鎖部のペンタッドの、¹³Ｃ−ＮＭＲスペクトルによる測定は次の通り行った。
試料３５０〜５００ｍｇを、１０ｍｍφのＮＭＲ用サンプル管中で、約２．２ｍｌのオルトジクロロベンゼンを用いて完全に溶解させる。次いで、ロック溶媒として約０．２ｍｌの重水素化ベンゼンを加え、均一化させた後、１３０℃でプロトン完全デカップリング法により測定を行う。測定条件は、フリップアングル９０°、パルス間隔５Ｔ₁以上（Ｔ₁は、メチル基のスピン−格子緩和時間のうち最長の値）とする。プロピレン重合体において、メチレン基およびメチン基のスピン−格子緩和時間はメチル基のそれよりも短いので、この測定条件では、すべての炭素の磁化の回復は９９％以上である。なお、定量精度を上げるため、¹³Ｃ核の共鳴周波数として１２５ＭＨｚ以上のＮＭＲ装置を使用し、２０時間以上の積算を行うのが好ましい。
【００７５】
（３）結晶化度は広角Ｘ線結晶回折により測定し、多重ピーク分離法により決定した（対称透過法 （２θ／θ＝５〜６０゜、０．１゜／ｓｔｅｐ））。
（４）融点Ｔｍおよび結晶融解熱はＤｕＰｏｎｔ社製熱分析システムＴＡ２０００を使用して、以下の方法で求めた。
試料（約５〜１０ｍｇ）を２００℃で３分間融解後、１０℃／ｍｉｎの速度で３０℃まで降温した後に、１０℃／ｍｉｎで２００℃まで昇温することにより融解曲線を得て、最後の昇温段階における主吸熱ピークのピークトップ温度を融点として求めた。
【００７６】
（５）ｏ−ジクロロベンゼンによる昇温溶出分別は、三菱化学ＣＦＣ−Ｔ−１０２Ｌを用いて行った（１００％溶出温度として記載。溶出分別は５℃から開始し、４〜５℃刻みで昇温して測定した。）。
（６）溶解性試験は以下の方法により行った。
溶剤（ヘプタン又はトルエン）にプロピレン系重合体を濃度１０重量％で攪拌翼付きセパラブルフラスコに仕込み、ヘプタンは外温１１０℃、トルエンは外温１２０℃に昇温し溶解する。内温が一定となった後２時間攪拌を続ける。ヘプタンは沸騰時の温度で素早く、トルエンは３０℃まで自然冷却してから１時間静置し、ＳＵＳ金網４００番にてろ過する。金網に残ったものを不溶分、溶液として通ったものを可溶分とし、真空乾燥器で８０℃、１ｍｍＨｇ以下、４時間乾燥させる。秤量し、不溶分の分率を計算する。
評価基準 ○：不溶分１％以下、×：不溶分１％以上。
【００７７】
（７）ノンタック性は指触タック性試験により評価した。
○：ノンタック性優れる、△：タック性ややあり、×：タック性有り。
【００７８】
（ｉｉ） プロピレン系重合体の密着性試験
（１） 密着性試験は、前述した密着試験法に従って行った。
尚、試験片の作成条件は、後述の［参考例］に示した。
（２） 耐水性試験はプロピレン系重合体またはそれ以外のポリマーをプライマーとして基材上に塗膜を形成し、その塗膜の上からベースコートを塗装して焼き付け、室温にて養生した塗装物を４０℃に保った温水中に１０日間浸漬する。その後、表面の水分を乾燥させた後、前記密着性試験と同様にして試験を行った。
【００７９】
（３） 耐ガソホール性試験はプロピレン系重合体またはそれ以外のポリマーをプライマーとして基材上に塗膜を形成し、その塗膜の上からベースコートを塗装して焼き付け、室温にて養生した塗装物を２０℃に保ったレギュラーガソリン：エタノール＝９：１混合溶液中に浸漬してその塗膜に顕著な剥離が生じるまでの時間を測定した。
【００８０】
＜試験片（基材）の作成＞
［参考例１］
配合物組成
ポリプロピレンブロック共重合体
（商品名：ＢＣ０６Ｃ 日本ポリケム社製 MFR=60） ６０重量部
エチレン・プロピレンランダム共重合体ゴム
（商品名：ＥＰＯ７Ｐ ＪＳＲ社製） ３０重量部
タルク
（商品名：ＭＴ７ 富士タルク社製） １０重量部
【００８１】
上記配合物に酸化防止剤としてテトラキス［メチレン−３−（３’５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（チバガイギー社製 IRGANOX 1010）０．１重量部を配合して、ヘンシェルミキサーで５分間混合した後、神戸製鋼社製二軸混練機(KCM50)にて２１０℃の設定温度で混練造粒することにより熱可塑性樹脂組成物を得た。更に、この組成物を東芝機械社製射出成型機（東芝ＩＳ１７０）を用いて、成形温度２２０℃の設定で１５０mm×７０mm×３mmから成る形状の試験片を成形した。
【００８２】
［参考例２］
日本ポリケム社製ポリプロピレン ＭＡ３Ｕ（プロピレン単独重合体、MFR：15g/10分(230℃、21.18N荷重)を、東芝機械社製射出成型機（東芝ＩＳ１７０）を用いて、成形温度２２０℃の設定で１５０mm×７０mm×３mmから成る形状の試験片を成形した。
【００８３】
［製造例１］
（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）］ハフニウムの合成
（１）−１ 配位子合成
２−メチルアズレン（４．０１ｇ）をテトラヒドロフラン（５６ｍｌ）に溶解し、アイスバスにて０℃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（１．１４ｍｏｌ／ｌ）２４．８ｍｌを滴下した。滴下終了後、アイスバスを外して２時間攪拌した。この溶液を、アイスバスにて０℃に冷却したジメチルシリルジクロリド（３４．０ ｍｌ，０．２８０ｍｏｌ）のテトラヒドロフラン溶液（１４０ｍｌ）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。テトラヒドロフラン（８０ｍｌ）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（２．１ｍｏｌ／ｌ，２６．９ｍｌ，５６．５ｍｍｏｌ）を徐々に滴下し、滴下終了後、室温で１２時間撹拌した。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目的配位子の未精製品を得た。ｎ−ヘキサンを溶出溶媒とするシリカゲルカラムクロマトグラフィーで、該未精製品を精製することにより、目的の配位子（６．２９ｇ）を収率７９％で得た。
【００８４】
（１）−２ 錯体合成
（１）−１で得られた配位子（６．２９ｇ）をテトラヒドロフラン（１００ｍｌ）に溶解し、アイスバスにて０℃に冷却した。ここに同温度で、ｎ−ブチルリチウムのｎ−ヘキサン溶液（１．５６ｍｏｌ／ｌ，２８．４ｍｌ）を、ゆっくり滴下した。滴下終了後、アイスバスをはずして３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トルエン（６０ｍｌ）を加えた後、−７８℃に冷却した。ここに、−７８℃に冷却したハフニウムテトラクロリド（７．１７ｇ）のトルエン（１４０ｍｌ）懸濁液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フリットを用いて濾過した。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。この褐色の粉末から、ホットｎ−ヘキサン（１８０ｍｌ×３回）で目的錯体を抽出した。抽出溶液を乾固させた後、得られた固体をｎ−ヘキサン（２０ｍｌ×５回）で懸濁洗浄した後、減圧下で乾燥させることにより、目的とするジクロロ［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（２．９０ｇ）を得た（収率２５％）。
【００８５】
上記化合物の¹H-NMR測定した結果を以下にのせる。
¹H-NMR(CDCl₃):δ0.85(s,3H),0.86(s,3H),1.47 (d,J = 7.1 Hz, 3H), 2.25 (s,3H), 3.42-3.52 (m,1H), 5.42 (dd,J = 4.7, 10.1 Hz,1H), 5.80-5.85 (m,2H), 5.90-5.95 (m,1H), 6.16-6.20 (m,2H), 6.65 (d,J = 11.4H), 6.80-6.85 (m,1H), 6.98-7.02 (m,1H)。
【００８６】
（２） 粘土鉱物の化学処理
１，０００ｍｌ丸底フラスコに、脱塩水（１１０ｍｌ）、硫酸マグネシウム・７水和物（２２．２ｇ）および硫酸（１８．２ｇ）を採取し、攪拌下に溶解させた。この溶液に、市販の造粒モンモリロナイト（水澤化学社製ベンクレイＳＬ，１６．７ｇ）を分散させ、２時間かけて１００℃まで昇温し、１００℃で２時間攪拌を行った。その後、１時間かけて室温まで冷却し、得られたスラリーを濾過してウェットケーキを回収した。回収したケーキを１，０００ｍｌ丸底フラスコにて、脱塩水（５００ｍｌ）にて再度スラリー化し、濾過を行った。この操作を２回繰り返した。最終的に得られたケーキを、窒素雰囲気下１１０℃で終夜乾燥し、化学処理モンモリロナイト（１３．３ｇ）を得た。
【００８７】
（３） 重合
製造例１（２）で得られた化学処理モンモリロナイト（０．４４ｇ）に、トリエチルアルミニウムのトルエン溶液（０．４ｍｍｏｌ／ｍｌ，２．０ｍｌ）を加え、室温で１時間攪拌した。この懸濁液にトルエン（８ｍｌ）を加え、攪拌後、上澄みを除いた。この操作を２回繰り返した後、トルエンを加えて、粘土スラリー（スラリー濃度＝９９ｍｇ粘土／ｍｌ）を得た。
別のフラスコに、東ソー・アクゾ社製トリイソブチルアルミニウム（０．１１４ｍｍｏｌ）を採取し、ここで得られた粘土スラリー（３．８ｍｌ）および製造例１（１）−２で得られた錯体（６．０２ｍｇ，１１．４μｍｏｌ）のトルエン希釈液を加え、室温で１０分間撹拌し、触媒スラリーを得た。
【００８８】
次いで、内容積２リッターの誘導攪拌式オートクレーブ内に、トルエン（７５０ｍｌ）、トリイソブチルアルミニウム（１．９ｍｍｏｌ）および液体プロピレン（１８０ｍｌ）を導入した。室温で、上記触媒スラリーを全量導入し、６０℃まで昇温し重合時の全圧を０．７ＭＰａで一定に保持しながら、同温度で１時間攪拌を継続した。攪拌終了後、未反応プロピレンをパージして重合を停止した。オートクレーブを開放してポリマーのトルエン溶液を全量回収し、溶媒ならびに粘土残渣を除去したところ、２３．２ｇのプロピレン重合体が得られた。得られた重合体を分析した結果を表１にまとめて示す。
【００８９】
［製造例２］
粘土スラリー用物質として、錯体を１７．８ｍｇ（３４．２ｍｍｏｌ）、トリイソブチルアルミニウム（０．３４２ｍｍｏｌ）、粘土スラリー（１１．４ｍｌ）を用い、またトルエン（１１００ｍｌ）、トリイソブチルアルミニウム（０．５ｍｍｏｌ）、液体プロピレン（２６４ｍｌ）、重合時の温度を８０℃、全圧を０．８Ｍｐａ、重合時間を１．８３時間とした以外は全て製造例１と同様の操作にて行った。その結果、２４５ｇのプロピレン重合体が得られた。得られた重合体を分析した結果を表１にまとめて示す。
【００９０】
［製造例３］
トルエン（１３５０ｍｌ）、液体プロピレン（９０ｍｌ）、重合時の温度を７０℃、全圧を０．３１Ｍｐａ、重合時間を２時間とした以外は全て製造例２と同様の操作にて行った。その結果、４４ｇのプロピレン重合体が得られた。得られた重合体を分析した結果を表１にまとめて示す。
【００９１】
［製造例４］
液体プロピレン（１８２ｍｌ），トリイソブチルアルミニウム（０．５ｍｍｏｌ）とした以外は全て製造例１と同様の操作にて行った。その結果、３９．６ｇのプロピレン重合体が得られた。得られた重合体を分析した結果を表１にまとめて示す。
【００９２】
［製造例５］
（１） ジクロロ｛１，１’−ジメチルシリレンビス［２−エチル−４−（２−フルオロ−４−ビフェニリル）−４Ｈ−アズレニル］｝ハフニウムのラセミ体の合成
２−フルオロ−４−ブロモビフェニル（６．３５ｇ，２５．３ｍｍｏｌ）を、ジエチルエーテル（５０ｍｌ）とｎ−ヘキサン（５０ｍｌ）の混合溶媒に溶かし、ｔ−ブチルリチウムのｎ−ペンタン溶液（３３ｍｌ，５０．６ｍｍｏｌ，１．５４Ｎ）を−７８℃で滴下した。−１０℃で２時間攪拌し、この溶液に２−エチルアズレン（３．５５ｇ，２２．８ｍｍｏｌ）を加え、室温で２時間攪拌した。ｎ−ヘキサン（３０ｍｌ）を加え、上澄みをデカンテーションで除去した。さらに、この操作をもう一度繰り返した。得られた黄色沈殿に、０℃でｎ−ヘキサン（３０ｍｌ）とテトラヒドロフラン（４０ｍｌ）を加えた。次いで、Ｎ−メチルイミダゾール（５０ｍｌ）とジメチルジクロロシラン（１．４ｍｌ，１１．４ｍｍｏｌ）を加え、室温まで昇温し、室温で１時間攪拌した。この後、希塩酸を加え、分液した後有機相を硫酸マグネシウムで乾燥し、減圧下に溶媒を留去すると、ジメチルシリレンビス（２−エチル−４−（２−フルオロ−４−ビフェニル）−１，４−ジヒドロアズレン）の粗生成物（８．３ｇ）が得られた。
【００９３】
次に、上記で得られた粗生成物をジエチルエーテル（３０ｍｌ）に溶かし、−７０℃でｎ−ブチルリチウムのｎ−ヘキサン溶液（１４．９ｍｌ，２２．８ｍｍｏｌ，１．５３Ｎ）を滴下し、徐々に昇温して、室温で一夜攪拌した。さらに、トルエン（２００ｍｌ）を加え、−７０℃に冷却し、四塩化ハフニウム（３．６ｇ，１１．４ｍｍｏｌ）を加え、徐々に昇温し、室温で４時間攪拌した。得られたスラリーから、減圧下に大部分の溶媒を留去し、ジエチルエーテル（５０ｍｌ）を加え、得られたスラリーを濾過した。ジエチルエーテル（５ｍｌ×２）、エタノール（１５ｍｌ×２）、ｎ−ヘキサン（１０ｍｌ×２）で洗浄すると、ジクロロ｛１，１’−ジメチルシリレンビス［２−エチル−４−（２−フルオロ−４−ビフェニリル）−４Ｈ−アズレニル］｝ハフニウムのラセミ・メソ混合物（４．５３ｇ，収率４２％）が得られた。得られたラセミ・メソ混合物を¹Ｈ−ＮＭＲで分析した結果、ラセミ体７６．６％、メソ体２３．４％の混合物であることがわかった。
ここで得られたラセミ・メソ混合物（４．５ｇ）をジクロロメタン（３５ｍｌ）に懸濁し、高圧水銀灯（１００Ｗ）を用いて１時間光照射した。減圧下に溶媒を留去し、得られた固体にトルエン（２５ｍｌ）とジクロロメタン（１１ｍｌ）を加え、６０℃に加熱すると均一溶液となった。減圧下にジクロロメタンを留去すると結晶が析出した。得られた結晶を濾過して、ヘキサン（５ｍｌ）で２回洗浄し、減圧下乾燥すると、ラセミ体（１．７９ｇ）が得られた。
【００９４】
（２） 粘土鉱物の化学処理
５００ｍｌ丸底フラスコに、脱塩水５５．８５ｇと硫酸３２．７０ｇおよび水酸化リチウム８．０１ｇを加えて攪拌した後、モンモリロナイト（水澤化学製：水澤スメクタイト）５１．６５ｇを添加し、昇温して還流下に１４０分間処理した。脱塩水３００ｍｌを加えて吸引濾過した後、脱塩水６００ｍｌに固体成分を分散させて吸引濾過した。この操作をさらにもう１度繰り返した。濾過して得られた残留物を１００℃で乾燥し、酸および金属塩処理モンモリロナイトを得た。ここで得られた酸および金属塩処理モンモリロナイト１．０５ｇを１００ｍｌ丸底フラスコに採取し、減圧下、２００℃で２時間加熱乾燥させた。これに、トリエチルアルミニウムのトルエン溶液（０．５ｍｍｏｌ／ｍｌ）を、精製窒素下で４．０ｍｌ添加して、室温で３０分反応させた後、トルエン３０ｍｌで２回洗浄し、化学処理モンモリロナイトを含有するトルエンスラリーを得た。
【００９５】
（３） 予備重合
製造例５（２）で得られたトルエンスラリー（固形分として９１４．２ｍｇ含有）からトルエンを抜き出し、残存トルエン量を１．０ｍｌとした。このスラリーに、トリイソブチルアルミニウムのトルエン溶液（０．５ｍｍｏｌ／ｍｌ，０．５ｍｌ）を加え、さらに、製造例５（１）で合成したジクロロ｛１，１’−ジメチルシリレンビス［２−エチル−４−（２−フルオロ−４−ビフェニリル）−４Ｈ−アズレニル］｝ハフニウムのラセミ体のトルエン溶液（３．０ｍｍｏｌ／ｍｌ，９．２ｍｌ）を加え、室温で１時間攪拌し、触媒スラリーを得た。
２リッターの誘導攪拌式オートクレーブに、精製窒素下、トルエン４０ｍｌと上記触媒スラリー全量を導入した。攪拌下にプロピレン１１．０ｇを導入し、３０℃で２時間、次いで５０℃で０．５時間予備重合を行った。予備重合後、未反応のプロピレンをパージし、精製窒素０．５ＭＰａで２回加圧置換した後予備重合触媒を取り出した。このものは、化学処理モンモリロナイト成分１ｇあたり９．７ｇの重合体を含有していた。
【００９６】
（４） 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、次いで、２５℃で液化プロピレン７５０ｇを装入した。トリイソブチルアルミニウムのトルエン溶液（０．１ｍｍｏｌ／ｍｌ，５．０ｍｌ）を同温度で圧入後、７０℃まで昇温した。水素を、気相中の水素濃度で０．２ｍｏｌ％になるように加えた後、７０℃で、上記（３）で得られた予備重合触媒を３０．０ｍｇ加え、重合を開始した。１時間後、未反応のプロピレンをパージし、重合を終了した。得られたプロピレン重合体の量は３８４ｇであった。
【００９７】
得られた重合体を分析した結果を表１に纏めて示す。
なお、¹³Ｃ−ＮＭＲによる頭−尾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：［ｍｍｍｍ］＞９９．９（％）であり、他のペンタッドに由来するピークはほとんど見られなかった。
【００９８】
［製造例６］
内容積５００ｍＬの誘導攪拌式ミクロオートクレーブ内に、高立体特異性アイソタクチックポリプロピレン（３１．１ ｇ）、ヘプタン（１８０ｍｌ）、Ｐｄ／Ｃ（アルドリッチ社：１０ｗｔ％Ｐｄ／Ｃ）（７．８７ｇ）を加えた後、系を密閉系にし、窒素置換を行った。その後、水素を８．０ＭＰａ導入し、２７５℃まで昇温して、６時間攪拌を継続した。冷却後、水素をパージして反応を停止した。オートクレーブを開放してポリマーのヘプタン溶液を全量回収し、溶媒ならびにＰｄ／Ｃ残渣を除去したところ、３０．６ｇのプロピレン重合体が得られた。得られた重合体を分析した結果を表１に纏めて示す。
なお、使用した高立体特異性アイソタクチックポリプロピレンの物性は、次の通りである。
ＭＦＲ：１５，０００；
Ｔｍ：１５４．９；
Ｍｗ：３７，０００；Ｍｎ：１８，０００；Ｍｗ／Ｍｎ：２．１；
［ｍｍｍｍ］：９８．４％；［ｍｍｍｒ］：０．０％；［ｒｍｒｍ］：０．１％；［ｒｒｒｒ］：０．２％。
【００９９】
［対照例１］
宇部興産（株）社製ウベタックＵＴ−２１１５の物性を同様に測定した。結果を表１に纏めて示す。
【０１００】
【表１】

【０１０１】
［実施例１］
（１） プロピレン重合体の無水マレイン酸変性
温度計、攪拌機のついたステンレス耐圧反応容器中に、クロロベンゼン（８０ｇ）、製造例１（３）で得られたプロピレン重合体（２０ｇ）および無水マレイン酸（４ｇ）を加え、容器内を窒素ガスで置換し、１３２℃に昇温した。昇温後、ジクミルペルオキシド（DCPO）のクロロベンゼン溶液（２０ｗｔ％）８ｇを、定量ポンプを用いて５．５時間で供給した後、３時間同温度で攪拌を続けて反応を行った。反応終了後、系を室温付近まで冷却し、アセトンを加えて、沈殿したポリマーを濾別した。さらにアセトンで沈殿・濾別を繰り返し、最終的に得られたポリマーをアセトンで洗浄した。洗浄後に得られたポリマーを減圧乾燥することにより、白色粉末状の変性ポリマーが得られた。この変性ポリマーの赤外線吸収スペクトル測定および中和滴定等を行った結果、無水マレイン酸基の含量は、３．３ｗｔ％であった。
ここで得られた無水マレイン酸変性プロピレン重合体１５ｇにトルエン１３５ｇを加え、１００℃に昇温し、１時間かけて溶解させた。得られた溶液を室温付近まで冷却した後、＃４００のＳＵＳ金網を通して、無水マレイン酸変性プロピレン重合体の１０ｗｔ％溶液を調製した。
【０１０２】
（２） 変性プロピレン重合体の物性評価
参考例１および２で作成した射出成形試験片（イソプロピルアルコールで表面を清拭したもの）に、実施例１（１）で得られた無水マレイン酸変性プロピレン重合体のトルエン溶液を噴霧塗布した。なお、塗布量は、３〜５ｇ／ｍ²とした。次にこの成形試験片を２５℃にて１時間静置した後、セーフベンドライヤー中にて８０℃、３０分間乾燥させた。次いで、この乾燥品を２５℃にて１時間静置させた後、その塗膜の上からベースコートとしてアクリルポリオールウレタン塗料 レタンＰＧ・８０III（関西ペイント社製：商品名）を、所定量の硬化剤を配合し、フォードカップ４番にて専用シンナーで粘度調整を行い、粘度が１２〜１３秒となるように調整した後、乾燥塗布量が５０〜６０ｇになるように噴霧塗装し、セーフベンドライヤー中にて１００℃、３０分間焼き付けを行った。さらに、２５℃にて１０日間静置し養生した。得られた塗装物について層間密着性試験を行った。また、耐水性試験及び耐ガソホール性試験も行った。その結果を纏めて表２−１に示す。
【０１０３】
［実施例２］
製造例２で合成したプロピレン重合体２０ｇ及び無水マレイン酸を１０ｇ、ジクミルペルオキシド（DCPO）のクロロベンゼン溶液（２０ｗｔ％）７ｇを用い、１１０℃にて反応を行った以外は、実施例１と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−１に示す。
［実施例３］
製造例２で合成したプロピレン重合体を用いた以外は、実施例１と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−１に示す。
【０１０４】
［実施例４］
製造例３で合成したプロピレン重合体を用いた以外は、実施例１と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−１に示す。
［実施例５］
製造例４で合成したプロピレン重合体を用いた以外は、実施例１と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−１に示す。
【０１０５】
［実施例６］
無水マレイン酸（４ｇ）の代わりに、メタクリル酸（５ｇ）を加え、ジクミルペルオキシド（DCPO）のクロロベンゼン溶液（２０ｗｔ％）の使用量を２．５ｇとした以外は、実施例１と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−１に示す。
［実施例７］
メタクリル酸（５ｇ）の代わりに、２−ヒドロキシエチルメタクリレート（５ｇ）を加えた以外は、実施例６と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−１に示す。
【０１０６】
［実施例８］
メタクリル酸（５ｇ）の代わりに、２−ヒドロキシエチルメタクリレート（５ｇ）およびスチレン（５ｇ）を加えた以外は、実施例６と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−１に示す。
【０１０７】
［比較例１］
製造例５で合成したプロピレン重合体を用いた以外は、実施例１と同様の操作にて変性処理及び塗装物の作成を行った。得られた変性ポリプロピレン重合体は、トルエンへの溶解性が悪く、その９６％が不溶解物であったため塗装評価できなかった。
［比較例２］
製造例６で合成したプロピレン重合体を用いた以外は、実施例１と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−２に示す。
【０１０８】
［比較例３］
宇部興産（株）社製ウベタックＵＴ−２１１５（チーグラー・ナッタ触媒系ポリプロピレン）を用い、実施例１と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−２に示す。
［比較例４］
三井化学（株）社製タフマーＸＲ−１１０Ｔ（プロピレン−ブテン−１共重合体、プロピレン成分：ブテン−１成分＝７６：２４）を用い、実施例１と同様の操作にて変性処理及び塗装物の作成を行い、同様に物性評価試験を行った。その結果を纏めて表２−２に示す。
【０１０９】
［比較例５］
変性重合体として、Ｅａｓｔｍａｎ社のＣＰ−３４３−１（無水マレイン酸変性塩素化ポリプロピレン）を用いて、実施例１（２）と同様にして評価を行った。その結果を纏めて表２−２に示す。
【０１１０】
【表２】

【０１１１】
【表３】

【０１１２】
【発明の効果】
本発明のプロピレン系重合体を用いることにより、塩素のようなハロゲンを含有せず、かつ、結晶性のプロピレン重合体基材に対して良好な接着性、塗装性を付与することが可能である。よって、本発明は工業的に価値が高い。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel propylene-based polymer. More specifically, propylene-based polymers, particularly graft-modified propylene, which have good solubility in organic solvents such as toluene and are used as materials for surface treatment agents, adhesives, paints, etc., especially for olefin polymers having crystallinity. The present invention relates to a polymer and an adhesive composition containing the polymer.
[0002]
[Prior art]
Propylene polymers and propylene / α-olefin copolymers are inexpensive and have excellent mechanical properties, heat resistance, chemical resistance, water resistance, and the like, and thus are used in a wide range of fields. However, such a propylene-based polymer generally has a low polarity because it does not have a polar group in the molecule, and has a drawback that it is difficult to paint or bond. In order to remedy this drawback, various treatments such as chemically treating the surface of the molded body of these propylene polymers with chemicals or oxidizing the surface of the molded body by means of corona discharge treatment, plasma treatment, flame treatment, etc. Techniques have been tried. However, these methods require not only a special device but also cannot be said to be sufficient in improving paintability and adhesiveness.
[0003]
Thus, so-called chlorinated polypropylene has been developed as a device for imparting good paintability and adhesion to a propylene polymer or the like by a relatively simple method. Chlorinated polypropylene is generally soluble in a hydrocarbon solvent such as toluene and xylene, and has relatively good adhesion to a propylene polymer or the like serving as a base material. Therefore, the coating properties and adhesion of propylene polymers can be improved with a relatively simple method by applying the hydrocarbon solution of the chlorinated polypropylene to the surface of the propylene polymer as the base material and removing the solvent. can do. It is known that modified chlorinated polypropylene obtained by further modifying chlorinated polypropylene by graft copolymerization with a polar monomer is further excellent in improving paintability and adhesiveness.
[0004]
Thus, chlorinated polypropylene and modified chlorinated polypropylene can improve the paintability and adhesiveness of propylene polymers and the like relatively easily, but the problem is that they contain a large amount of chlorine. Is mentioned. In recent years, the use of vinyl chloride resin has become a social problem due to the generation of harmful substances due to resin recycling and incineration, and in addition, problems such as poor weather resistance remain for chlorine-containing resins. . Therefore, for chlorinated polypropylene, like vinyl chloride resin, development of an alternative resin containing no halogen such as chlorine is strongly desired.
[0005]
Against this background, on the other hand, the development of resins that do not contain chlorine has been carried out. For example, Japanese Patent Publication No. 44-958 discloses a treating agent in which an amorphous polypropylene polymer modified with a specific proportion of maleic acid or its anhydride is dissolved in a solvent. Here, the amorphous polypropylene polymer optionally contains an amorphous polypropylene and a copolymer containing at least about 20 mol% propylene unit, and is an amorphous polypropylene copolymer comprising at least one copolymer monomer and propylene. It is a polymer. Further, as a similar treating agent, there is JP-A-8-217835, in which an amorphous polypropylene or an amorphous propylene-1-butene copolymer is graft copolymerized with an unsaturated carboxylic acid having 3 to 10 carbon atoms. A crystalline polymer is disclosed. When such a graft-modified product is used, the solubility is improved and the paintability is superior compared to general modified propylene resins, but the solubility in a solvent at room temperature is still low, stickiness and adhesion Inferior. For this reason, chlorinated polypropylene or modified chlorinated polypropylene is considered to be a relatively excellent resin at present for use as a surface treatment agent, an adhesive, or a paint.
[Patent Document 1]
Japanese Patent Publication No. 44-958
[Patent Document 2]
JP-A-8-217835
[0006]
[Problems to be solved by the invention]
The present invention does not contain a halogen such as chlorine, is not sticky, has excellent solubility, and imparts good adhesiveness and paintability to a crystalline propylene polymer as a substrate. The present invention provides a novel propylene polymer, particularly a graft-modified propylene polymer, and a composition containing the same.
[0007]
[Means for Solving the Problems]
  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
  That is, the gist of the present invention has a stereo block structure including an isotactic block.Consisting essentially of a propylene homopolymerIt has a main chain and a side chain containing a carboxylic acid group or an acid anhydride group or a carboxylic acid ester group (hereinafter collectively referred to as “carboxylic acid group etc.”).Per propylene homopolymer main chain, ¹³ In C-NMR, 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 was 21. The peak area S having a peak top of 21.8 ppm with respect to the total area S of peaks appearing from 19.8 ppm to 22.1 ppm when 8 ppm is set. ₁ Ratio (S ₁ / S) is 10% or more and 60% or less,And a propylene-based polymer whose insoluble content is 1% by weight or less based on the total polymer when dissolved in toluene at 25 ° C. at a concentration of 10% by weight, andA monomer substantially consisting of propylene is converted to C having a transition metal-containing crosslinking group. ₁ -The propylene homopolymer main chain is obtained by polymerization in the presence of a single-site catalyst that is a symmetric answer-metallocene compound, and a polymerizable monomer having a carboxylic acid group or the like is grafted onto the propylene polymer main chain. A process for producing the propylene polymer comprising polymerizingAnd adhesiveness containing the propylene-based polymerofPresent in the composition.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
In the propylene-based polymer of the present invention, a polymer having a carboxyl group in a propylene polymer main chain having a stereo block structure mainly containing an isotactic block (hereinafter sometimes abbreviated as a propylene polymer main chain). A monomer is graft-copolymerized, and the main chain of the propylene polymer is a polymer of propylene substantially containing propylene as a monomer. Here, the substantially propylene-only polymer is a polymer having a propylene content of 99% by weight or more, but a small amount of other monomers are copolymerized within the range not detracting from the gist of the present invention. You may contain as a component. In the present invention, the propylene content is preferably 99.7% by weight or more, more preferably 99.9% by weight or more.
[0009]
Other monomers of the copolymer component that the propylene polymer main chain may contain include monomers having an olefinic double bond, such as ethylene, butene, pentene, hexene, octene, decene, butadiene, hexadiene, Suitable ones can be selected from octadiene, cyclobutene, cyclopentene, cyclohexene, norbornene, norbornadiene, styrene and derivatives thereof. Of these, ethylene, butene, pentene, hexene and octene are preferred, and ethylene and butene are more preferred.
[0010]
The propylene polymer of the main chain in the present invention is required to have a stereo block structure containing an isotactic block, but the weight average molecular weight Mw measured by GPC (Gel Permeation Chromatography) is 5,000 to 200, 000 is preferred. When Mw is smaller than 5,000, the film-forming property deteriorates after coating on a substrate using a propylene-based polymer modified by graft copolymerization (hereinafter sometimes referred to as graft-modified polymer). Is not only undesirable, but also stickiness is remarkable. On the other hand, when Mw exceeds 200,000, there is no significant problem with respect to film-forming properties and stickiness, but the viscosity when the graft-modified polymer is dissolved in a solvent becomes too high, resulting in production or the graft-modified weight. This is not preferable because it causes inconvenience in handling the combined solution. In the present invention, the preferred range of the weight average molecular weight Mw is 5,000 to 200,000, more preferably 10,000 to 180,000, still more preferably 30,000 to 150,000.
The molecular weight measurement by GPC can be performed by a conventionally known method using a commercially available apparatus using orthodichlorobenzene or the like as a solvent and polystyrene as a standard sample.
[0011]
The molecular weight distribution of the propylene polymer main chain in the present invention is not particularly limited, but an excessively wide molecular weight distribution should be avoided because it means that the content of low molecular weight components is inevitably high. When the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is used as an index of the molecular weight distribution, preferably Mw / Mn <20, more preferably Mw / Mn <10, most preferably Mw / Mn <5. Are preferably used.
[0012]
Although the propylene polymer main chain in the present invention has a stereo block structure containing an isotactic block as described above, it is preferably one having a small amount of insoluble heptane produced with a specific catalyst. Above all,¹³What has the characteristic prescribed | regulated as mentioned above by a C-NMR spectrum is more preferable. This characteristic is that the propylene polymer main chain has a structure in which a highly crystalline block and a highly amorphous block coexist in a well-balanced manner, and a highly crystalline block is rich in isotacticity. Represents. In other words, if there are too many highly crystalline blocks in the polymer main chain, the solubility in the solvent will deteriorate, so the balance between the highly crystalline block and the highly amorphous block is important and represents this balance. As part of the indicator,¹³The requirements defined by the C-NMR spectrum apply.
[0013]
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 time of the methylene group and methine group is 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.
[0014]
The chemical shift is a methyl branch of 10 types of pentads (mmmm, mmmr, rmrr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrr, mrrm) of propylene unit linkages composed of head-to-tail bonds. The absolute chemical configuration of all is the same, that is, the chemical shift of the peak based on the methyl group of the third unit of 5 units of propylene units expressed in mmmm is set as 21.8 ppm, and other carbon peaks are based on this. Determine the chemical shift. According to this standard, for example, in the case of other five propylene units, the chemical shift of the peak based on the methyl group of the third unit 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 to 20.8 ppm, rrrr: 20.3-20.5 ppm, rrrm: 20.1-20.3 ppm, mrrm: 19.9-20.1 ppm. The chemical shift of the peak derived from these pentads varies slightly 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 should be noted that the split pattern) is often shown.
[0015]
The propylene polymer main chain in the present invention is the above-mentioned one appearing in the range of 19.8 ppm to 22.2 ppm when the peak top chemical shift of the peak represented by mmmm is 21.8 ppm. The peak area S having a peak top of 21.8 ppm with respect to the total area S of the pentads, that is, all the peaks belonging to all pentads of mmmm, mmr, rmmr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrr, mrrm₁Ratio (S₁/ S) is 10% or more and 60% or less, and the area of the peak (mmmmr) having 21.5 to 21.7 ppm as the peak top is S.₂4 + 2S₁ / S₂> 5 is preferred.
[0016]
A preferred propylene polymer main chain of the present invention has a ratio of the peak area attributed to a specific pentad to the total area (S) of all pentad peaks appearing at 19.8 ppm to 22.2 ppm as described below ( The requirements of 1) to (4) are satisfied. Here,% represents the ratio of the peak area attributed to a specific pentad to the total area of all pentad peaks appearing from 19.8 ppm to 22.2 ppm.
(1) The area of a peak (rrrr) having a peak top of 20.3 to 20.5 ppm is S_ThreeThe area S_ThreeRatio (S_Three/ S) is 0.2% or more and 3% or less,
(2) The area of the peak (rmrm) having a peak top of 20.6 to 20.8 ppm is S_FourThe area S_FourRatio (S_Four/ S) is 0.3% or more and 7% or less,
(3) S_FourArea is S_ThreeLarger than the area of
(4) S₂Area is 25> 4 + 2S₁ / S₂> 5
[0017]
Further preferred propylene polymer main chains satisfy the following requirements (1) to (4) (S, S₁~ S_FourIs as defined above).
(1) Area S₁Ratio (S₁/ S) is 30% or more and 50% or less.
(2) Area S_ThreeRatio (S_Three/ S) is 1% or more and 3% or less,
(3) Area S_FourRatio (S_Four/ S) is 4% or more and 7% or less,
(4) S₂Area> 10> 4 + 2S₁ / S₂> 7
Among these requirements, the requirements of each (1) to (3) are as follows: in the main chain of the propylene polymer of the present invention, a highly crystalline block and a highly amorphous block coexist in the main chain, and This is related to the fact that a highly crystalline block has a structure with high isotacticity. S for S₁If the ratio is less than 10%, the crystallinity is too low, sufficient adhesion cannot be obtained, and problems such as stickiness are liable to occur. On the other hand, S against S₁If the ratio exceeds 60%, on the contrary, the crystallinity is too high and the solubility in a solvent is lowered, which is also not preferable. S for S defined in the present invention₁The range of the ratio is from 10% to 60%, preferably from 20% to 50%, more preferably from 30% to 50%.
[0018]
The propylene polymer main chain in the present invention is 4 + 2S as described above.₁/ S₂It is preferable to satisfy the relationship> 5. This relational expression is closely related to an index named by Waymouth et al. As an isotactic block index (BI) (see Japanese translation of PCT publication No. 9-510745). BI is an index representing the stereoblock property of the polymer, and is defined by BI = 4 + 2 [mmmm] / [mmmr]. More specifically, BI represents the average chain length of isotactic blocks having 4 or more propylene units (JWCollete et al., Macromol., 22, 3858 (1989); JCRandall, 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 isotactic blocks contained in the polymer is longer than that of atactic polypropylene.
[0019]
4 + 2S required by the propylene polymer main chain of the present invention₁/ S₂Is not exactly the same as the above-mentioned BI, but is roughly compatible with 4 + 2S₁/ S₂The requirement> 5 means that the propylene polymer of the main chain of the present invention contains an isotactic block with a chain length that can be crystallized, unlike atactic polypropylene. The presence of an isotactic block means that, in other words, a block composed of a sequence having a disordered stereospecificity is also present in the main chain. Thus, in the propylene polymer main chain of the present invention, as described above, the block having crystallinity and the amorphous block coexist in the main chain, and the block having crystallinity is relatively long. It is a unique structure that is formed from an isotactic block having an average chain length and has a structure rich in isotacticity.
In the present invention, 5 <4 + 2S₁/ S₂But preferably 5 <4 + 2S₁/ S₂<25, more preferably 7 <4 + 2S₁/ S₂<10.
[0020]
Furthermore, since the propylene polymer main chain of the present invention has an appropriate stereoregular distribution of methyl groups in the polymer main chain, the propylene polymer main chain has a characteristic that the crystallinity is relatively low and the solvent solubility is excellent. Specifically, when the polymer main chain is fractionated by elution with orthodichlorobenzene at a temperature, substantially all components are eluted at 60 ° C. or lower. The component that elutes at a temperature higher than 60 ° C. is a component having a considerably high crystallinity. Therefore, when the polymer main chain contains such a component, the polymer main chain is dissolved in a solvent. In addition, such a high crystallinity component tends to be an insoluble component or gelation easily occurs. In the propylene polymer main chain of the present invention, substantially all of the components are eluted at 60 ° C. or lower, so that such inconvenience can be avoided, but preferably 50 ° C. or lower, more preferably 40 ° C. or lower. It is preferable that all components are eluted.
[0021]
The propylene polymer main chain of the present invention is obtained by a method of polymerizing with a single site catalyst. This is because, in general, single-site catalysts can control microtacticity by ligand design, can easily produce polymers with relatively low molecular weights, and are particularly sharp in the molecular weight distribution and stereoregularity distribution of polymers. Etc. If the molecular weight distribution or the stereoregular distribution is irregular, the solubility may be different, and a partially insoluble one may be formed. Of the single-site catalysts, metallocene catalysts are preferably used in that the microtacticity can be precisely controlled.
As the single site catalyst for producing the propylene polymer main chain of the present invention, a metallocene catalyst having a metallocene compound ([A] component) and a cocatalyst ([B] component) as essential components is preferably used.
[0022]
As the metallocene compound ([A] component), C having a transition metal-containing crosslinking group₁Symmetric ansa-metallocene is preferred. Non-crosslinked metallocene can also be applied to the production of the propylene polymer of the present invention. In general, an ansa-metallocene having a crosslinking group is preferable from an industrial standpoint because it is superior in thermal stability and the like.
The ansa-metallocene having a transition group containing a transition metal used in the present invention is a C 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 of [A] component preferably used for the production of a propylene polymer is represented by the following general formula (I) and C₁-A compound having symmetry. A plurality of metallocenes represented by the general formula may be mixed and used.
[Chemical 1]
Q (C_FiveH_4-aR² _a) (C_FiveH_4-bR^Three _b) MXY (I)
[0023]
Hereinafter, the metallocene having the general formula will be described in detail.
In the general formula (I), Q is a bonding group that bridges two conjugated 5-membered ring ligands, M is a group 4 transition metal of the periodic table, X and Y are each independently hydrogen, Halogen, hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, phosphorus-containing hydrocarbon having 1 to 20 carbon atoms A group or a silicon-containing hydrocarbon group of 1 to 20 carbon atoms, R²And 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, or a phosphorus-containing hydrocarbon group. Represents a nitrogen-containing hydrocarbon 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.
[0024]
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.
[0025]
In the above general formula (I), R²And R^ThreeSpecifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, A hydrocarbon group having 1 to 20 carbon atoms, such as a heptyl group, an octyl group, a nonyl group, a decyl group, a phenyl group, a t-butylphenyl group, a naphthyl group, a fluoromethyl group, a fluoroethyl group, A hydrocarbon group having 1 to 20 carbon atoms which may contain halogen such as fluorophenyl group, fluoronaphthyl group, fluorobiphenyl group, chloromethyl group, chloroethyl group, chlorophenyl group, chloronaphthyl group, chlorobiphenyl group, Halogen such as fluorine, chlorine, bromine, iodine, methoxy group, ethoxy group, propoxy group, buto Alkoxy groups such as Si groups, aryloxy groups such as phenoxy groups, methylphenoxy groups, and pentamethylphenoxy groups, silicon-containing hydrocarbon groups such as trimethylsilyl groups, triethylsilyl groups, and triphenylsilyl groups, or phosphorus-containing hydrocarbon groups A nitrogen-containing hydrocarbon group and a boron-containing hydrocarbon group. R²Are present, they may be the same or different.
[0026]
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 (I): Q (C_FiveH_4-aR² _a) (C_FiveH_4-bR^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.
[0027]
M is a transition metal of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, 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 a carbon atom number. Examples thereof include a phosphorus-containing hydrocarbon group having 1-20, preferably 1-12, a silicon-containing hydrocarbon group having 1-20 carbon atoms, preferably 1-12. X and Y may be the same or different. Of these, halogen, hydrocarbon group and alkylamide group are preferred.
Among the metallocenes represented by the above general formula (I), propyl [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H- 1-azurenyl)] hafnium is most preferred, and dichloro [dimethylgermylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azurenyl)] hafnium or dichloro [dimethylsilylene (2-methyl-1-). Indenyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium is also a suitable catalyst.
[0028]
In addition, about a [A] component metallocene compound, the mixture of the compound which has several different structure may be used, and may be used in combination of 2 or more types. Further, a known solid catalyst mainly composed of titanium trichloride and a carrier-supported catalyst containing magnesium, titanium, and halogen as essential components can be used supplementarily. Further, the [A] component may be newly added at the end of the first stage of polymerization or before the start of polymerization in the second stage.
[0029]
The co-catalyst used as a cocatalyst (component [B]) in the present invention includes (1) an organoaluminum oxy compound as an essential component, and (2) a reaction with a transition metal of [A] component to convert [A] component into a cation. One or more substances selected from the group consisting of ionic compounds that can be exchanged with (3) Lewis acids, (4) ion-exchangeable layered compounds excluding silicates, and inorganic silicates are used.
Specific examples of the organoaluminum oxy compound (1) 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 represents an integer of 0 to 40, preferably 2 to 30.
[0030]
[Chemical 2]

[0031]
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.
[0032]
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.
[Chemical 3]

[0033]
Specifically, the following reaction products are: (a) a 2: 1 reaction product of trimethylaluminum and methylboronic acid, (b) a 2: 1 reaction product of triisobutylaluminum and methylboronic acid, (c) trimethyl. List 1: 1 1: 1 reactant of aluminum, triisobutylaluminum and methylboronic acid, (d) 2: 1 reactant of trimethylaluminum and ethylboronic acid, (e) 2: 1 reactant of triethylaluminum and butylboronic acid, etc. Can do.
[0034]
Moreover, (2) As an ionic compound which can react with the transition metal of [A] component and can convert [A] component into a cation, the compound represented by general formula (VI) is mentioned.
[Formula 4]

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.
[0035]
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. .
[0036]
In said general formula (VI), Z is an anion component and is a component (generally non-coordinating component) which becomes a counter anion with respect to the cation seed | species in which the transition metal of [A] component was 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 and the like.
[0037]
Other specific compounds include (c) tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis {3,5-bis (trifluoromethyl) phenyl} gallium, tetrakis {3,5- Di (t-butyl) phenyl} gallium, tetrakis (pentafluorophenyl) gallium, etc. (d) tetraphenylphosphorus, tetrakis (pentafluorophenyl) phosphorus, etc. (e) tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, etc. (F) tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, etc. (g) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate and the like.
[0038]
Further, (3) Lewis acids, in particular, Lewis acids capable of converting the transition metal of the component [A] into cations include various organic boron compounds, metal halogen compounds, solid acids and the like. The compound of this is mentioned. (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.
[0039]
(4) 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 a weak binding force, and can contain exchangeable ions. 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, γ-Zr (HPO_Four)₂, Γ-Ti (HPO_Four)₂, Γ-Ti (NH_FourPO_Four)₂・ H₂Examples thereof include crystalline acidic salts of polyvalent metals such as O.
[0040]
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.
Examples of the artificial compound include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.
[0041]
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.
[0042]
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 an essential component of these [B] components, it is preferable to use the ion-exchangeable layered compound excluding the silicate of (4) or an inorganic silicate in terms of catalyst performance such as polymerization activity.
[0043]
In the production of the propylene polymer main chain of the present invention, an organoaluminum compound may be used as an optional component [C] in addition to the cocatalyst [B] component. Such organoaluminum compounds have the general formula AlR¹ _mZ_3-m(Wherein R¹Is a hydrocarbon group having 1 to 20 carbon atoms, Z is hydrogen, halogen, alkoxy group or aryloxy group, and m is a number of 0 <m ≦ 3). 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. Further, an optional component [C] may be newly added after the start of polymerization.
[0044]
The propylene polymerization catalyst can be obtained by contacting the [A] component, the [B] component, and any [C] component, but the contacting method is not particularly limited. This contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization or polymerization of propylene. A solid of an inorganic oxide such as a propylene polymer, silica, alumina, or the like may be allowed to coexist or contact when the catalyst components are contacted or after contact.
The contact may be performed in an inert gas such as nitrogen, or may be performed in an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene and xylene. These solvents are preferably used after an operation for removing poisoning substances such as water and sulfur compounds. The contact temperature is between −20 ° C. and the boiling point of the solvent used, and particularly preferably between room temperature and the boiling point of the solvent used.
[0045]
Although there is no restriction | limiting in particular in the usage-amount of each component of a catalyst, When using the ion-exchange layered compound except a silicate, or an inorganic silicate as a [B] component, [A] component per 1g of [B] component Is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, and the [C] component is 0 to 10,000 mmol, preferably 0.01 to 100 mmol. The atomic ratio of the transition metal in the [A] component and the aluminum in the [C] component is controlled to be 1: 0 to 1,000,000, preferably 1: 0.1 to 100,000. Is preferable in terms of polymerization activity.
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.
In washing, a new [C] component may be used in combination as necessary. The amount of the [C] component used in this case is preferably 1: 0 to 10,000 in terms of the atomic ratio of aluminum in the [C] component to the transition metal in the [A] component.
[0046]
As the catalyst, it is also possible to use a polymer obtained by preliminarily polymerizing propylene and washing it as necessary. This prepolymerization may be carried out in an inert gas such as nitrogen or in an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, xylene.
The polymerization reaction of propylene is performed in the presence or absence of an inert hydrocarbon such as propane, n-butane, n-hexane, n-heptane, toluene, xylene, cyclohexane, methylcyclohexane, or a liquid of liquefied propylene. Of these, the polymerization is preferably performed in the presence of the above-described inert hydrocarbon.
Specifically, the main chain propylene polymer is produced in the presence of the [A] component and the [B] component, or the [A] component, the [B] component, and the [C] component. 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 from 0 to 150 ° C., preferably from 20 to 100 ° C., the polymerization pressure is from 0.1 MPa to 100 MPa, preferably from 0.3 MPa to 10 MPa, more preferably from 0.5 MPa to 4 MPa, the polymerization time. Is selected from the range of 0.1 to 10 hours, preferably 0.3 to 7 hours, more preferably 0.5 to 6 hours.
[0047]
In the present invention, as described above, the weight average molecular weight Mw of the polymer is preferably in the range of 5,000 to 200,000. For this reason, conventionally known methods can be used to adjust the molecular weight of the polymer. That is, a method of controlling the molecular weight by controlling the polymerization temperature, a method of controlling the molecular weight by controlling the monomer concentration, and a method of controlling the molecular weight by using a chain transfer agent. Hydrogen is preferred when a chain transfer agent is used.
[0048]
Further, in the present invention, the propylene polymer main chain produced by controlling the stereoselectivity of the propylene unit chain portion composed of the head-to-tail bond is as described above.¹³In C-NMR, 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 was 21. The peak area S having a peak top of 21.8 ppm with respect to the total area S of peaks belonging to all pentads appearing in the range of 19.8 ppm to 22.2 ppm when 8 ppm is set.₁Ratio (S₁/ S) is 10% or more and 60% or less, and the area of the peak (mmmmr) having 21.5 to 21.7 ppm as the peak top is S.₂4 + 2S₁ / S₂> 5 is preferred.
[0049]
There are no particular restrictions on the method of controlling the stereoselectivity related to such properties of the propylene polymer main chain, but generally there are a method of controlling by the structure of the catalyst and a method of controlling by controlling the polymerization conditions. It is done. When controlling the stereoselectivity by controlling the polymerization conditions, the desired stereoregularity can be achieved by controlling the polymerization temperature and the monomer concentration, and, in some cases, in conjunction with the above-described catalyst structure control. A propylene polymer main chain can be obtained.
[0050]
The propylene polymer main chain used in the present invention can be dissolved in a solvent. Specific examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane and n-decane; cyclohexane and methyl Cycloaliphatic aliphatic hydrocarbons such as cyclohexane and dimethylcyclohexane, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, trichloroethylene, perchloroethylene, chlorobenzene, o-dichlorobenzene, n-ethyl acetate, n-butyl Examples include esters such as acetate, ketones such as methyl isobutyl ketone and cyclohexanone, and polar solvents such as tetrahydrofuran and dimethyl sulfoxide. Among these, aromatic hydrocarbons and halogenated hydrocarbons are preferable, and toluene, xylene are particularly preferable. , Chlorobenzene is preferred There.
[0051]
Its solubility is very superior to that of an ordinary highly stereoregular isotactic polypropylene modified product. When dissolved in toluene (25 ° C.) at room temperature at a concentration of 10% by weight, the insoluble component is the total amount of the polymer. 1% by weight or less. Preferably it is 0.1 weight% or less, More preferably, it is a state without an insoluble component. Similarly, when dissolved in boiling heptane (98 ° C.) at a concentration of 10% by weight, the insoluble component is 1% by weight or less of the total amount of the polymer.
As a measuring method, for example, a solution dissolved at a predetermined temperature and a predetermined concentration is filtered around the temperature (filtered when hot if the temperature is high), and the filter paper or SUS wire mesh (weight in advance) is used. The method of measuring the weight of insoluble matter is used.
[0052]
A method for producing a propylene polymer having a main chain composed of the propylene polymer of the present invention and a side chain containing a carboxylic acid group, an acid anhydride group or a carboxylic acid ester group is not particularly limited. A method obtained by graft copolymerization of a polymerizable monomer containing a carboxylic acid group or the like in the main chain is common. Examples of the polymerizable monomer containing a carboxylic acid group to be graft-copolymerized include (meth) acrylic acid and acid derivatives thereof, and monoolefin dicarboxylic acid, anhydrides and monoesters thereof. At least one is used. Specifically, (meth) acrylic acid and its ester derivatives include (meth) acrylic acid; (meth) acrylic acid ester monomers having an alkyl group having 1 to 12 carbon atoms, such as (meth) acrylic Methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate , Pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic acid Decyl, dodecyl (meth) acrylate, etc .; aryl group or arylal having 6 to 12 carbon atoms Having Le group (meth) monomers acrylic acid ester, for example (meth) acrylate, phenyl (meth) toluyl acrylate include benzyl (meth) acrylate and the like.
[0053]
Further, as other (meth) acrylic acid derivatives, monomers of (meth) acrylic acid esters having an alkyl group containing 1 to 20 carbon atoms containing hetero atoms, such as hydroxyethyl (meth) acrylate and (meth) acrylic Dimethylaminoethyl acid, diethylaminoethyl (meth) acrylate, (meth) acrylic acid-2-aminoethyl, (meth) acrylic acid-2-methoxyethyl, (meth) acrylic acid-3-methoxypropyl, (meth) acrylic Glycidyl acid, adduct of (meth) acrylic acid ethylene oxide, etc .; monomer of (meth) acrylic acid ester having a fluorine atom-containing alkyl group having 1 to 20 carbon atoms, such as trifluoromethyl methyl (meth) acrylate , (Meth) acrylic acid 2-trifluoromethylethyl, (meth) acrylic Acid 2-perfluoroethyl ethyl, and the like; (meth) acrylamide monomers such as (meth) acrylamide, (meth) acrylic dimethyl amides.
[0054]
Monoolefin dicarboxylic acid and acid anhydrides thereof, and monoalkyl esters of monoolefin dicarboxylic acid may be mentioned. Examples of monoolefin dicarboxylic acid include maleic acid, chloromaleic acid, citraconic acid, itaconic acid, glutaconic acid, 3 -Methyl-2-pentene / diacid, 2-methyl-2-pentene / dioic acid, 2-hexene / dioic acid and the like. Examples of monoolefin dicarboxylic acid monoalkyl esters include monoesters of alkyl alcohols having 1 to 12 carbon atoms and these dicarboxylic acids. Specific examples of alkyl alcohols include methyl alcohol, ethyl alcohol, and propyl. Examples include alcohol, butyl alcohol, pentyl alcohol, octyl alcohol, cyclohexyl alcohol and the like.
In the case of forming a coating film using the graft-modified propylene polymer of the present invention, from the viewpoint of adhesion between the coating film and the coating material, as a polymerizable monomer containing these grafted carboxylic acid groups, etc. The solubility parameter is preferably higher, that is, an unsaturated carboxylic acid derivative component composed of an unsaturated carboxylic acid having 3 to 10 carbon atoms, an acid anhydride and an ester thereof is preferable. Maleic anhydride is particularly preferable.
[0055]
Among the graft-modified propylene polymers in the present invention, the modified polymer having a monoolefin dicarboxylic acid monoalkyl ester as a graft copolymer unit is, for example, a monoolefin dicarboxylic acid monoalkyl ester converted to a main chain propylene polymer. Graft copolymerization method: A monoolefin dicarboxylic acid or an acid anhydride thereof can be graft-copolymerized to a propylene polymer main chain and then esterified with one of carboxylic acid groups with an alkyl alcohol.
[0056]
The graft amount of at least one graft copolymerized unit selected from polymerizable monomers containing a carboxyl group or the like in the graft-modified propylene polymer, that is, the content (graft ratio) in the propylene polymer is The graft copolymerization is preferably carried out so as to be 0.01 to 25% by weight, preferably 0.1 to 15% by weight. When a propylene polymer having a graft ratio within this range is applied to a molded product using this as a primer, a coating film with high paint adhesion is obtained, and the adhesion between the coating film and the molded product is also good. And it is preferable at the point that an external appearance becomes favorable.
Further, as described later, the propylene-based polymer of the present invention is excellent in that the insoluble content is 1% by weight or less of the total amount of the polymer when dissolved in toluene at 25 ° C. at a concentration of 10% by weight. Although it has solubility, it also has high adhesion to a polypropylene molded body that is a base material. That is, the propylene-based polymer of the present invention has excellent adhesion to a polypropylene molded product, and the adhesion by an adhesion test (cross-cut tape method) is 50/100 or more. Preferably it is 80/100 or more, More preferably, it is 100/100.
In particular, examples of the propylene polymer excellent in such properties include those obtained by graft copolymerization of a polymerizable monomer containing a carboxylic acid group or the like in the propylene polymer main chain as described above.
[0057]
In the present invention, the adhesion of the propylene polymer is determined by the following adhesion test method.
Adhesion test method
(A) The adhesion test is performed according to the cross-cut tape method described in JIS K5400 8.5.2.
(1) AbstractCut through the coating film of the test piece and make cuts that reach the ground surface in a grid pattern, apply adhesive tape on the grid pattern, and visually observe the state of adhesion of the coating film after peeling.
(2) Equipment and materials
(A) Cutter knife According to JIS K5400 7.2 (2) (e).
(B) Cutter guide According to JIS K5400 8.5.1 (2) (b).
(C) Cellophane adhesive tape Cellophane adhesive tape specified in JIS Z1522, having a width of 18 mm or 24 mm and an adhesive strength of 2.94 N / 10 mm or more
(D) Test plate A polypropylene molded body (150 mm × 70 mm × 3 mm)
(E) Eraser Specified in JIS S6050
[0058]
(3) Creating specimens
The sample is coated on one side of the test piece by the method specified in the product standard of the sample according to JIS K5400 3.3, dried, and then left in the standard state for 24 hours.
(Four) operation
JIS K5400 8.5.2. Follow (4)
(Five) Evaluation
Evaluation is as follows.
(A) Observe the state of the grid-like scratches on the coated surface of the test piece, count the number of grids that were not peeled out of the 100 grids, and indicate the number of residual grids / 100. And adherence.
[0059]
Crystalline polypropylene is used for the polypropylene substrate used in the adhesion test of the present invention. Examples of crystalline polypropylene include a propylene homopolymer and / or a propylene / ethylene block copolymer composed of a propylene homopolymer portion and a propylene / ethylene copolymer portion. Among them, it is preferable to use a propylene homopolymer having an MFR (230 ° C., 21.18 N load) of 5 to 30 (g / 10 minutes).
[0060]
Various known methods can be used as a method of graft copolymerizing a main chain propylene polymer with a polymerizable monomer such as a monoolefin dicarboxylic acid, an acid anhydride thereof and a monoolefin dicarboxylic acid monoalkyl ester. For example, a method of conducting a graft copolymerization reaction by dissolving the propylene polymer main chain in an organic solvent, adding the polymerizable monomer and radical polymerization initiator to be grafted, and stirring with heating; the propylene polymer main A method in which a chain is heated and dissolved, and a graft copolymerization is carried out by adding a polymerizable monomer and a radical polymerization initiator that are grafted to the melt and stirring; or, each component is supplied to an extruder and heated and kneaded. Graft copolymerization while impregnating the propylene polymer powder with a solution prepared by dissolving the grafting polymerizable monomer and radical polymerization initiator in an organic solvent, and then heating to a temperature at which the powder does not dissolve. Examples thereof include a copolymerization method.
At this time, the ratio of radical polymerization initiator / polymerizable monomer to be grafted is usually in the range of 1/100 to 3/5, preferably 1/20 to 1/2 in terms of molar ratio.
The reaction temperature is preferably 50 ° C. or higher, particularly 80 to 200 ° C., and the reaction time is about 2 to 10 hours.
[0061]
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.
[0062]
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.
[0063]
The propylene polymer of the present invention can also be dissolved in the same solvent as the above-mentioned solvent in which the propylene polymer main chain is soluble. Its solubility is very superior to that of a normal highly stereoregular isotactic polypropylene polymer. When dissolved in toluene at a concentration of 10% by weight at 25 ° C., the insoluble matter is 1% of the total amount of the polymer. % By weight or less. Preferably it is 0.1 weight% or less, More preferably, it is a state without an insoluble component. The propylene-based polymer of the present invention has a solubility parameter of 11 (cal / cm) among solvents.^Three)^1/2Since this solvent is highly soluble in the following solvents, this graft-modified propylene polymer has a solubility parameter of 11 (cal / cm^Three)^1/2A composition in which 1 part by weight or more is dissolved in the following solvent can be used as an adhesive composition.
[0064]
Solubility parameter is 11 (cal / cm^Three)^1/2Specific examples of the following solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane and n-decane; cyclohexane , Cycloaliphatic aliphatic hydrocarbons such as methylcyclohexane and dimethylcyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, chlorobenzene and o-dichlorobenzene, n-methyl acetate , Esters such as n-ethyl acetate and n-butyl acetate, ketones such as methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran, etc. Among these, aromatic hydrocarbons or halogenated hydrocarbons are preferable. , Especially toluene, xylene Chlorobenzene is preferred.
[0065]
In addition, the propylene polymer of the present invention, like the propylene polymer main chain, has an appropriate stereoregular distribution of methyl groups in the polymer main chain, and therefore has a relatively low crystallinity and excellent solubility in a solvent. Have Specifically, when the polymer is fractionated at elevated temperature with orthodichlorobenzene, substantially all components are eluted at 60 ° C. or lower. The component that elutes at a temperature higher than 60 ° C. is a component having a considerably high crystallinity. Therefore, when the polymer contains such a component, such a crystal is dissolved when the polymer is dissolved in a solvent. Inconveniences such as highly soluble components becoming insoluble components and gelation tend to occur. In the propylene-based polymer of the present invention, substantially all of the components are eluted at 60 ° C. or lower, so that such inconvenience can be avoided, but preferably 50 ° C. or lower, more preferably 40 ° C. or lower. It is preferred that all components elute.
[0066]
Since the propylene polymer of the present invention is soluble in a solvent as described above, it can be applied to a molded body (base material) of an olefin polymer having crystallinity. Examples of the olefin polymer as a base material include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, polystyrene, and other olefin polymers, ethylene / propylene copolymer. Examples thereof include olefin copolymers such as polymers, ethylene / butene copolymers, and propylene / butene copolymers. Of these olefin copolymers, a propylene copolymer is preferably used. Also, molded products made of polypropylene and synthetic rubber, molded products made of polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, polycarbonate resin, etc., such as molded products such as automobile bumpers, and further for steel plate and electrodeposition treatment It can also be used for surface treatment of steel plates and the like. In addition, the surface is coated with paint, primer, adhesive, etc. mainly composed of polyurethane resin, fatty acid-modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, etc., and adherence of paint, etc. to the surface Can be used to form a coating film that is excellent in sharpness and low-temperature impact properties.
[0067]
Since the coating film formed when the propylene-based polymer of the present invention is applied to a substrate made of an olefin-based polymer exhibits good adhesion to the substrate as described above, the propylene-based polymer of the present invention The polymer can be used as an adhesive resin for an olefin polymer. In addition, in order to acquire favorable adhesiveness with respect to the base material of an olefin polymer, it is preferable to heat after application | coating. Although there is no restriction | limiting in particular in heating temperature, Considering practicality, it is preferable to set it as 50-150 degreeC, Furthermore, it is 60-130 degreeC. There is no restriction | limiting in particular also in the method of application | coating, A conventionally well-known method, such as the method of apply | coating with a spray, the method of apply | coating with a roller, the method of applying with a brush, can be used.
[0068]
A coating material can be applied to the surface of the molded article on which the propylene-based polymer of the present invention has been applied to form a coating film by a method such as electrostatic coating, spray coating, or brush coating.
The coating may be applied by a method of overcoating after undercoating. After applying the coating material, the coating film is cured according to a normal method of heating by electric heating, infrared rays, high frequency, etc., and a molded product having a desired coating film on the surface can be obtained. The method for curing the coating film is appropriately selected depending on the material and shape of the molded product, the properties of the paint used, and the like.
[0069]
A composition in which the propylene polymer of the present invention is dissolved in a solvent is applied to the surface of a molded product composed of an α-olefin copolymer or other polymer as a main component, and the adhesion of the paint to the surface, water resistance It can be used as a primer or the like for improving coating film performance such as property and gasoline resistance. In addition to the use as a primer for the above-mentioned molded product, taking advantage of its excellent adhesion, peel strength, and water resistance, it can be applied to a wide range of applications. For example, it can be added for adhesives and paints. Needless to say, the present invention is also applicable to applications such as an agent and an ink binder.
Specific applications described above include automotive exterior (bumper) primers, adhesives for building materials and decorative sheets, adhesives for automotive parts, adhesives for packaging materials, paint additives for automotive interiors, ink binders for gravure inks, etc. Is mentioned.
In addition to the above, the composition of the present invention includes various stabilizers such as antioxidants, weathering stabilizers, heat resistance inhibitors, etc. as necessary; colorants such as titanium oxide and organic pigments, and conductive materials such as carbon black and ferrite. It may contain a property-imparting agent.
[0070]
In addition, the molded product to which the composition of the present invention is applied is formed by any of the above-mentioned various polymers or resins by any of known molding methods such as injection molding, compression molding, hollow molding, extrusion molding, and rotational molding. It may be what was done.
When the composition containing the propylene polymer of the present invention is applied to a molded product, the molded product is blended with inorganic fillers such as talc, zinc white, glass fiber, titanium white, magnesium sulfate, pigments, etc. In addition, a coating film having particularly good adhesion can be formed.
In addition to the above, the molded product to which the propylene polymer of the present invention is applied may contain various stabilizers, ultraviolet absorbers and the like.
[0071]
Examples of the stabilizer preferably used in the composition of the present invention include 2,6-di-t-butyl-4-methylphenol and tetrakis [methylene (3,5-di-4-hydroxyhydrocinnamate)]. Methane, metaoctadecyl-3- (4′-hydroxy-3,5-di-tert-butyl-phenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butyl-phenol), 4,4 '-Butylidenebis (3-methyl-6-tert-butyl-phenol), 2,2-thiobis (4-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris ( Phenols such as 3,5-di-tert-butyl-4-hydroxybenzyl) benzene and 1,3,5-tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane Stabilizers; can be mentioned tridecyl phosphite, and the like phosphorus-based stabilizers such as trinonylphenyl phosphite; dilauryl thio dipropoxy sulfonates, sulfur-based stabilizers such as distearyl thiodipropionate.
Examples of the ultraviolet absorber used include 2-hydroxy-4-octoxybenzophenone, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, paraoctylphenyl salicylate, and the like.
[0072]
【Example】
EXAMPLES Next, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not restrict | limited by these Examples, unless it deviates from the summary.
In the following examples and comparative examples, the physical properties and performance of the polymers were measured as follows. In each example, the catalyst synthesis step and the polymerization step were all carried out in a purified nitrogen atmosphere, and the solvent was dehydrated with molecular sieve (MS-4A) and then degassed by bubbling with purified nitrogen.
[0073]
<Measurement of physical properties>
(I) Physical property measurement of main chain propylene polymer
(1) Measurement of molecular weight of propylene polymer main chain
The weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution Mw / Mn were measured by GPC using a GPC150CV type manufactured by Waters. As a solvent, o-dichlorobenzene was used, and the measurement temperature was 135 ° C. The molecular weight was calculated by using a commercially available monodisperse polystyrene as a standard sample, creating a calibration curve for the retention time and molecular weight from the viscosity formula of the polystyrene standard sample and polypropylene, and calculating the molecular weight.
[0074]
(2) of pentad of propylene unit chain part¹³Measurement by C-NMR spectrum was performed 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 time of the methylene group and methine group is 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.
[0075]
(3) Crystallinity was measured by wide-angle X-ray crystal diffraction and determined by multiple peak separation method (symmetric transmission method (2θ / θ = 5-60 °, 0.1 ° / step)).
(4) The melting point Tm and the heat of crystal fusion were determined by the following method using a thermal analysis system TA2000 manufactured by DuPont.
After melting the sample (about 5-10 mg) at 200 ° C. for 3 minutes, the temperature was lowered to 30 ° C. at a rate of 10 ° C./min, and then the temperature was raised to 200 ° C. at 10 ° C./min. The peak top temperature of the main endothermic peak in the temperature rising stage was determined as the melting point.
[0076]
(5) Elevated temperature elution fractionation with o-dichlorobenzene was performed using Mitsubishi Chemical CFC-T-102L (described as 100% elution temperature. Elution fractionation starts at 5 ° C and increases in increments of 4-5 ° C. Measured by warming).
(6) The solubility test was performed by the following method.
A propylene polymer is charged into a solvent (heptane or toluene) at a concentration of 10% by weight in a separable flask equipped with a stirring blade, and heptane is heated to an external temperature of 110 ° C. and toluene is heated to an external temperature of 120 ° C. to dissolve. Stirring is continued for 2 hours after the internal temperature becomes constant. Heptane is quickly heated at the boiling temperature, and toluene is naturally cooled to 30 ° C., then left to stand for 1 hour, and filtered through SUS wire mesh No. 400. What remains in the wire mesh is insoluble, and what is passed as a solution is soluble, and is dried in a vacuum dryer at 80 ° C., 1 mmHg or less for 4 hours. Weigh and calculate the fraction of insoluble matter.
Evaluation criteria ○: Insoluble matter 1% or less, x: Insoluble matter 1% or more.
[0077]
(7) Non-tack property was evaluated by a finger tuck property test.
○: Excellent non-tackiness, Δ: Slightly tacky, ×: Tacky.
[0078]
(Ii) Adhesion test of propylene polymer
(1) The adhesion test was performed according to the adhesion test method described above.
In addition, the preparation conditions of the test piece are shown in [Reference Example] described later.
(2) In the water resistance test, a coating film is formed on a base material using a propylene-based polymer or other polymer as a primer, and a base coat is applied and baked on the coating film. Immerse in warm water kept at 40 ° C. for 10 days. Thereafter, after moisture on the surface was dried, the test was performed in the same manner as the adhesion test.
[0079]
(3) The gasohol resistance test is a coating that forms a coating on a substrate using a propylene polymer or other polymer as a primer, coats and coats the base coat on the coating, and is cured at room temperature. Was immersed in a regular gasoline: ethanol = 9: 1 mixed solution kept at 20 ° C., and the time until significant peeling occurred in the coating film was measured.
[0080]
<Creation of test piece (base material)>
[Reference Example 1]
Formulation composition
Polypropylene block copolymer
(Product name: BC06C Nippon Polychem MFR = 60) 60 parts by weight
Ethylene / propylene random copolymer rubber
(Product name: EPO7P JSR) 30 parts by weight
talc
(Product name: MT7 manufactured by Fuji Talc) 10 parts by weight
[0081]
0.1 parts by weight of tetrakis [methylene-3- (3′5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (IRGANOX 1010, manufactured by Ciba Geigy) as an antioxidant After mixing for 5 minutes with a Henschel mixer, a thermoplastic resin composition was obtained by kneading and granulating at a set temperature of 210 ° C. with a twin screw kneader (KCM50) manufactured by Kobe Steel. Further, a test piece having a shape of 150 mm × 70 mm × 3 mm was molded from this composition using an injection molding machine (Toshiba IS170) manufactured by Toshiba Machine Co., Ltd. at a molding temperature of 220 ° C.
[0082]
[Reference Example 2]
Nippon Polychem Polypropylene MA3U (Propylene Homopolymer, MFR: 15 g / 10 min (230 ° C, 21.18N load) is used at a molding temperature of 220 ° C using an injection molding machine (Toshiba IS170) manufactured by Toshiba Machine Co., Ltd. A test piece having a shape of 150 mm × 70 mm × 3 mm was molded.
[0083]
[Production Example 1]
(1) Synthesis of dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium
(1) -1 Ligand synthesis
2-Methylazulene (4.01 g) was dissolved in tetrahydrofuran (56 ml), cooled to 0 ° C. with an ice bath, and then 24.8 ml of methyl lithium in diethyl ether (1.14 mol / l) was added dropwise at the same temperature. did. After completion of dropping, the ice bath was removed and the mixture was stirred for 2 hours. This solution was slowly added dropwise to a tetrahydrofuran solution (140 ml) of dimethylsilyl dichloride (34.0 ml, 0.280 mol) cooled to 0 ° 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 (80 ml) was added and the mixture was cooled to 0 ° C., and cyclopentadienyl sodium (2.1 mol / l, 26.9 ml, 56.5 mmol) was gradually added dropwise. After completion of the addition, the mixture was stirred at room temperature for 12 hours. 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 an unpurified product of the target ligand. The crude product was purified by silica gel column chromatography using n-hexane as an elution solvent to obtain the target ligand (6.29 g) in a yield of 79%.
[0084]
(1) -2 Complex synthesis
The ligand (6.29 g) obtained in (1) -1 was dissolved in tetrahydrofuran (100 ml) and cooled to 0 ° C. with an ice bath. At the same temperature, an n-hexane solution of n-butyllithium (1.56 mol / l, 28.4 ml) was slowly added dropwise. After completion of dropping, the ice bath was removed and the mixture was stirred for 3 hours, and the solvent was distilled off under reduced pressure. Toluene (60 ml) was added to the residue obtained after distilling off, followed by cooling to -78 ° C. A suspension of toluene (140 ml) in hafnium tetrachloride (7.17 g) cooled to -78 ° C was slowly added thereto. Thereafter, the cooling bath was removed and the mixture was stirred overnight. After completion of the stirring, the reaction solution was filtered using a G3 frit. The solid on the frit was further washed with toluene and the filtrate was concentrated to give a brown powder. The target complex was extracted from this brown powder with hot n-hexane (180 ml × 3 times). After the extract solution was dried to dryness, the obtained solid was suspended and washed with n-hexane (20 ml × 5 times) and then dried under reduced pressure to obtain the desired dichloro [dimethylsilylene (cyclopentadienyl). ) (2,4-dimethyl-4H-1-azulenyl)] hafnium (2.90 g) was obtained (yield 25%).
[0085]
Of the above compounds¹The results of H-NMR measurement are listed below.
¹H-NMR (CDCl_Three): δ0.85 (s, 3H), 0.86 (s, 3H), 1.47 (d, J = 7.1 Hz, 3H), 2.25 (s, 3H), 3.42-3.52 (m, 1H), 5.42 (dd, J = 4.7, 10.1 Hz, 1H), 5.80-5.85 (m, 2H), 5.90-5.95 (m, 1H), 6.16-6.20 (m, 2H), 6.65 (d, J = 11.4H), 6.80-6.85 (m, 1H), 6.98-7.02 (m, 1H).
[0086]
(2) Chemical treatment of clay minerals
Demineralized water (110 ml), magnesium sulfate heptahydrate (22.2 g) and sulfuric acid (18.2 g) were collected in a 1,000 ml round bottom flask and dissolved with stirring. In this solution, commercially available granulated montmorillonite (Menzawa Chemical Co., Ltd. Benclay SL, 16.7 g) was dispersed, heated to 100 ° C. over 2 hours, and stirred at 100 ° C. for 2 hours. Then, it cooled to room temperature over 1 hour, and obtained slurry was filtered and the wet cake was collect | recovered. The collected cake was slurried again with demineralized water (500 ml) in a 1,000 ml round bottom flask and filtered. This operation was repeated twice. The finally obtained cake was dried at 110 ° C. overnight under a nitrogen atmosphere to obtain chemically treated montmorillonite (13.3 g).
[0087]
(3) Polymerization
To the chemically treated montmorillonite (0.44 g) obtained in Production Example 1 (2) was added a toluene solution of triethylaluminum (0.4 mmol / ml, 2.0 ml), and the mixture was stirred at room temperature for 1 hour. Toluene (8 ml) was added to this suspension, and after stirring, the supernatant was removed. After repeating this operation twice, toluene was added to obtain a clay slurry (slurry concentration = 99 mg clay / ml).
In another flask, triisobutylaluminum (0.114 mmol) manufactured by Tosoh Akzo Corporation was collected, and the clay slurry (3.8 ml) obtained here and the complex (6) obtained in Production Example 1 (1) -2 were used. (0.02 mg, 11.4 μmol) of toluene diluted solution was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry.
[0088]
Subsequently, toluene (750 ml), triisobutylaluminum (1.9 mmol) and liquid propylene (180 ml) were introduced into an induction stirring autoclave having an internal volume of 2 liters. The whole amount of the catalyst slurry was introduced at room temperature, the temperature was raised to 60 ° C., and the total pressure during polymerization was kept constant at 0.7 MPa, and stirring was continued for 1 hour at the same temperature. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened and the whole toluene solution of the polymer was recovered, and the solvent and the clay residue were removed. As a result, 23.2 g of a propylene polymer was obtained. The results of analyzing the obtained polymer are summarized in Table 1.
[0089]
[Production Example 2]
As a material for clay slurry, 17.8 mg (34.2 mmol) of the complex, triisobutylaluminum (0.342 mmol) and clay slurry (11.4 ml) were used, and toluene (1100 ml) and triisobutylaluminum (0.5 mmol) were used. The procedure was the same as in Production Example 1, except that liquid propylene (264 ml), the polymerization temperature was 80 ° C., the total pressure was 0.8 Mpa, and the polymerization time was 1.83 hours. As a result, 245 g of a propylene polymer was obtained. The results of analyzing the obtained polymer are summarized in Table 1.
[0090]
[Production Example 3]
All operations were performed in the same manner as in Production Example 2, except that toluene (1350 ml), liquid propylene (90 ml), the polymerization temperature was 70 ° C., the total pressure was 0.31 Mpa, and the polymerization time was 2 hours. As a result, 44 g of a propylene polymer was obtained. The results of analyzing the obtained polymer are summarized in Table 1.
[0091]
[Production Example 4]
All operations were performed in the same manner as in Production Example 1 except that liquid propylene (182 ml) and triisobutylaluminum (0.5 mmol) were used. As a result, 39.6 g of a propylene polymer was obtained. The results of analyzing the obtained polymer are summarized in Table 1.
[0092]
[Production Example 5]
(1) Racemic synthesis of dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} hafnium
2-Fluoro-4-bromobiphenyl (6.35 g, 25.3 mmol) was dissolved in a mixed solvent of diethyl ether (50 ml) and n-hexane (50 ml), and a solution of t-butyllithium in n-pentane (33 ml, 50 ml). .6 mmol, 1.54 N) was added dropwise at -78 ° C. The mixture was stirred at −10 ° C. for 2 hours, 2-ethylazulene (3.55 g, 22.8 mmol) was added to this solution, and the mixture was stirred at room temperature for 2 hours. n-Hexane (30 ml) was added and the supernatant was removed by decantation. This operation was repeated once more. N-Hexane (30 ml) and tetrahydrofuran (40 ml) were added to the obtained yellow precipitate at 0 ° C. Next, N-methylimidazole (50 ml) and dimethyldichlorosilane (1.4 ml, 11.4 mmol) were added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1 hour. After this, dilute hydrochloric acid was added and the layers were separated, and then the organic phase was dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -1 , 4-dihydroazulene) (8.3 g) was obtained.
[0093]
Next, the crude product obtained above was dissolved in diethyl ether (30 ml), and an n-butyllithium n-hexane solution (14.9 ml, 22.8 mmol, 1.53N) was added dropwise at -70 ° C. The temperature was gradually raised and the mixture was stirred overnight at room temperature. Furthermore, toluene (200 ml) was added, and the mixture was cooled to −70 ° C., hafnium tetrachloride (3.6 g, 11.4 mmol) was added, the temperature was gradually raised, and the mixture was stirred at room temperature for 4 hours. From the resulting slurry, most of the solvent was distilled off under reduced pressure, diethyl ether (50 ml) was added, and the resulting slurry was filtered. After washing with diethyl ether (5 ml × 2), ethanol (15 ml × 2), n-hexane (10 ml × 2), dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4 A racemic meso mixture (4.53 g, 42% yield) of -biphenylyl) -4H-azurenyl]} hafnium was obtained. The resulting racemic / meso mixture¹As a result of analysis by 1 H-NMR, it was found to be a mixture of racemic 76.6% and meso 23.4%.
The racemic / meso mixture (4.5 g) obtained here was suspended in dichloromethane (35 ml) and irradiated with light using a high pressure mercury lamp (100 W) for 1 hour. The solvent was distilled off under reduced pressure. Toluene (25 ml) and dichloromethane (11 ml) were added to the obtained solid, and the mixture was heated to 60 ° C. to obtain a homogeneous solution. When dichloromethane was distilled off under reduced pressure, crystals were precipitated. The obtained crystals were filtered, washed twice with hexane (5 ml), and dried under reduced pressure to obtain a racemate (1.79 g).
[0094]
(2) Chemical treatment of clay minerals
To a 500 ml round bottom flask, 55.85 g of demineralized water, 32.70 g of sulfuric acid and 8.01 g of lithium hydroxide were added and stirred. Treated under reflux for 140 minutes. After adding 300 ml of demineralized water and suction filtration, the solid component was dispersed in 600 ml of demineralized water and subjected to suction filtration. This operation was repeated once more. The residue obtained by filtration was dried at 100 ° C. to obtain acid and metal salt-treated montmorillonite. 1.05 g of the acid and metal salt-treated montmorillonite obtained here was collected in a 100 ml round bottom flask and dried by heating at 200 ° C. for 2 hours under reduced pressure. To this, 4.0 ml of a toluene solution of triethylaluminum (0.5 mmol / ml) was added under purified nitrogen, reacted at room temperature for 30 minutes, washed twice with 30 ml of toluene, and containing chemically treated montmorillonite. A toluene slurry was obtained.
[0095]
(3) Prepolymerization
Toluene was extracted from the toluene slurry (containing 914.2 mg as a solid content) obtained in Production Example 5 (2), and the amount of residual toluene was 1.0 ml. To this slurry, a toluene solution of triisobutylaluminum (0.5 mmol / ml, 0.5 ml) was added, and dichloro {1,1′-dimethylsilylenebis [2-ethyl-] synthesized in Production Example 5 (1) was further added. 4- (2-Fluoro-4-biphenylyl) -4H-azurenyl]} hafnium racemic toluene solution (3.0 mmol / ml, 9.2 ml) was added and stirred at room temperature for 1 hour to obtain a catalyst slurry. .
Into a 2-liter induction stirring autoclave, 40 ml of toluene and the total amount of the catalyst slurry were introduced under purified nitrogen. 11.0 g of propylene was introduced with stirring, and prepolymerization was performed at 30 ° C. for 2 hours and then at 50 ° C. for 0.5 hour. After pre-polymerization, unreacted propylene was purged and pressure-replaced twice with purified nitrogen 0.5 MPa, and then the pre-polymerization catalyst was taken out. This contained 9.7 g of polymer per gram of chemically treated montmorillonite component.
[0096]
(4) Polymerization
A 2-liter induction-stirring autoclave containing a built-in stirring blade was replaced with purified nitrogen, and then 750 g of liquefied propylene was charged at 25 ° C. A toluene solution of triisobutylaluminum (0.1 mmol / ml, 5.0 ml) was injected at the same temperature, and then heated to 70 ° C. Hydrogen was added so that the hydrogen concentration in the gas phase was 0.2 mol%, and then 30.0 mg of the prepolymerized catalyst obtained in (3) above was added at 70 ° C. to initiate polymerization. After 1 hour, unreacted propylene was purged to complete the polymerization. The amount of the obtained propylene polymer was 384 g.
[0097]
The results of analyzing the obtained polymer are summarized in Table 1.
In addition,¹³Peak derived from carbon atom of methyl group of propylene unit chain part consisting of head-to-tail bond by C-NMR: [mmmm]> 99.9 (%), and few peaks derived from other pentads are seen It was.
[0098]
[Production Example 6]
Highly stereospecific isotactic polypropylene (31.1 g), heptane (180 ml), Pd / C (Aldrich: 10 wt% Pd / C) (7.87 g) in an induction stirring type micro autoclave having an internal volume of 500 mL Was added, and the system was closed and replaced with nitrogen. Thereafter, 8.0 MPa of hydrogen was introduced, the temperature was raised to 275 ° C., and stirring was continued for 6 hours. After cooling, hydrogen was purged to stop the reaction. The autoclave was opened and the entire amount of the polymer heptane solution was recovered, and the solvent and the Pd / C residue were removed. As a result, 30.6 g of a propylene polymer was obtained. The results of analyzing the obtained polymer are summarized in Table 1.
The physical properties of the highly stereospecific isotactic polypropylene used are as follows.
MFR: 15,000;
Tm: 154.9;
Mw: 37,000; Mn: 18,000; Mw / Mn: 2.1;
[Mmmm]: 98.4%; [mmmmr]: 0.0%; [rmrm]: 0.1%; [rrrr]: 0.2%.
[0099]
[Control Example 1]
The physical properties of Ubetac UT-2115 manufactured by Ube Industries, Ltd. were measured in the same manner. The results are summarized in Table 1.
[0100]
[Table 1]

[0101]
[Example 1]
(1) Maleic anhydride modification of propylene polymer
Chlorobenzene (80 g), the propylene polymer (20 g) obtained in Production Example 1 (3) and maleic anhydride (4 g) are added to a stainless steel pressure-resistant reaction vessel equipped with a thermometer and a stirrer, and the inside of the vessel is filled with nitrogen gas. And heated to 132 ° C. After raising the temperature, 8 g of a chlorobenzene solution (20 wt%) of dicumyl peroxide (DCPO) was supplied in 5.5 hours using a metering pump, and then the reaction was continued for 3 hours at the same temperature. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was filtered off. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after washing was dried under reduced pressure to obtain a white powdery modified polymer. As a result of infrared absorption spectrum measurement and neutralization titration of this modified polymer, the content of maleic anhydride groups was 3.3 wt%.
To 15 g of the maleic anhydride-modified propylene polymer obtained here was added 135 g of toluene, and the temperature was raised to 100 ° C. and dissolved for 1 hour. After cooling the obtained solution to near room temperature, a 10 wt% solution of maleic anhydride-modified propylene polymer was prepared through a # 400 SUS wire mesh.
[0102]
(2) Physical property evaluation of modified propylene polymer
The toluene solution of the maleic anhydride-modified propylene polymer obtained in Example 1 (1) was spray-coated on the injection-molded test pieces prepared in Reference Examples 1 and 2 (surfaces wiped with isopropyl alcohol). The coating amount is 3 to 5 g / m.²It was. Next, this molded test piece was allowed to stand at 25 ° C. for 1 hour, and then dried in a safe ben dryer at 80 ° C. for 30 minutes. Next, the dried product was allowed to stand at 25 ° C. for 1 hour, and then an acrylic polyol urethane paint Retan PG 80III (trade name, manufactured by Kansai Paint Co., Ltd.) was used as a base coat on the coating film. After adjusting the viscosity with a dedicated thinner in Ford Cup No. 4, adjusting the viscosity to 12-13 seconds, spray-coating so that the dry coating amount is 50-60 g, Safe Ben dryer Baking was performed at 100 ° C. for 30 minutes. Furthermore, it left still at 25 degreeC for 10 days, and was cured. An interlayer adhesion test was performed on the obtained coated product. In addition, a water resistance test and a gasohol resistance test were also performed. The results are summarized in Table 2-1.
[0103]
[Example 2]
The same as Example 1 except that 20 g of the propylene polymer synthesized in Production Example 2, 10 g of maleic anhydride, and 7 g of a chlorobenzene solution of dicumyl peroxide (DCPO) (20 wt%) were used at 110 ° C. The modification treatment and the preparation of the coated product were performed by the above operation, and the physical property evaluation test was similarly conducted. The results are summarized in Table 2-1.
[Example 3]
Except for using the propylene polymer synthesized in Production Example 2, modification treatment and preparation of a coated product were performed in the same manner as in Example 1, and the physical property evaluation test was conducted in the same manner. The results are summarized in Table 2-1.
[0104]
[Example 4]
Except for using the propylene polymer synthesized in Production Example 3, modification treatment and preparation of a coated product were performed in the same manner as in Example 1, and physical property evaluation tests were performed in the same manner. The results are summarized in Table 2-1.
[Example 5]
Except for using the propylene polymer synthesized in Production Example 4, modification treatment and preparation of a coated product were performed in the same manner as in Example 1, and the physical property evaluation test was performed in the same manner. The results are summarized in Table 2-1.
[0105]
[Example 6]
Operation similar to Example 1 except that methacrylic acid (5 g) was added instead of maleic anhydride (4 g) and the amount of dichlorobenzene solution (20 wt%) of dicumyl peroxide (DCPO) was changed to 2.5 g. The material was subjected to modification treatment and preparation of a coated product, and a physical property evaluation test was similarly conducted. The results are summarized in Table 2-1.
[Example 7]
A modification treatment and preparation of a coated product were performed in the same manner as in Example 6 except that 2-hydroxyethyl methacrylate (5 g) was added instead of methacrylic acid (5 g), and a physical property evaluation test was performed in the same manner. . The results are summarized in Table 2-1.
[0106]
[Example 8]
A modification treatment and preparation of a coated product were performed in the same manner as in Example 6 except that 2-hydroxyethyl methacrylate (5 g) and styrene (5 g) were added instead of methacrylic acid (5 g), and physical properties were similarly obtained. An evaluation test was conducted. The results are summarized in Table 2-1.
[0107]
[Comparative Example 1]
Except for using the propylene polymer synthesized in Production Example 5, modification treatment and creation of a coated product were performed in the same manner as in Example 1. The obtained modified polypropylene polymer was poorly soluble in toluene, and 96% of the modified polypropylene polymer was an insoluble matter, and thus could not be evaluated for coating.
[Comparative Example 2]
Except for using the propylene polymer synthesized in Production Example 6, modification treatment and preparation of a coated product were performed in the same manner as in Example 1, and a physical property evaluation test was performed in the same manner. The results are summarized in Table 2-2.
[0108]
[Comparative Example 3]
Using Ubetac UT-2115 (Ziegler-Natta catalyst polypropylene) manufactured by Ube Industries, Ltd., modification treatment and preparation of a coated product were performed in the same manner as in Example 1, and physical property evaluation tests were performed in the same manner. The results are summarized in Table 2-2.
[Comparative Example 4]
Modification treatment and coated product in the same manner as in Example 1 using Tafmer XR-110T (propylene-butene-1 copolymer, propylene component: butene-1 component = 76: 24) manufactured by Mitsui Chemicals, Inc. The physical property evaluation test was conducted in the same manner. The results are summarized in Table 2-2.
[0109]
[Comparative Example 5]
Evaluation was performed in the same manner as in Example 1 (2) using CP-343-1 (maleic anhydride-modified chlorinated polypropylene) manufactured by Eastman as the modified polymer. The results are summarized in Table 2-2.
[0110]
[Table 2]

[0111]
[Table 3]

[0112]
【The invention's effect】
By using the propylene-based polymer of the present invention, it is possible to impart good adhesion and paintability to a crystalline propylene polymer substrate that does not contain halogen such as chlorine. . Therefore, the present invention is industrially valuable.

Claims (21)

A main chain consisting essentially of propylene homopolymer having a stereo-block structure containing an isotactic block, has a side chain containing a carboxylic acid group or acid anhydride group or carboxylic acid ester group, the propylene For the homopolymer main chain, 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 by ¹³ C-NMR, and the peak attributed to the pentad represented by mmmm When the chemical shift of the peak top is 21.8 ppm, the ratio of the peak area S ₁ having 21.8 ppm as the peak top to the total peak area S appearing from 19.8 ppm to 22.1 ppm (S ₁ / S ) is 10% or more and 60% or less, and when dissolved in a concentration of 10 wt% in toluene at 25 ° C., the insoluble matter Propylene polymer wherein the total polymer to 1% by weight or less. Propylene homopolymer polymer main chain, a propylene-based polymer according to claim 1, characterized in that it is manufactured by a single site catalyst. Propylene homopolymer polymer main chain, when dissolved at a concentration of 10 wt% in heptane at 98 ° C., to claim 1 or 2 that insoluble matter is characterized in that 1% by weight or less relative to the total polymer The propylene-based polymer described. Per propylene homopolymer polymer main ^chain, at 13 C-NMR, head - when observed a peak derived from a carbon atom of the methyl group of the propylene unit chain consisting of tail bonds, peak top of 21.5~21.7ppm when the area of the peak (mmmr) which was _{S 2} and ₄ + 2S 1 _{/ S} 2> propylene polymer according to claim 1, characterized in that the 5 (where, S, S ₁ and S ₂ have the same meaning as in claim 1 ). Per propylene homopolymer polymer main chain, at ^{13 C-NMR,} head - when observed a peak derived from a carbon atom of the methyl group of the propylene unit chain consisting of tail bonds, the following characteristics (1) to (4) 5. The propylene polymer according to claim ₁ , wherein S, S ₁ and S ₂ are as defined in claim 1 .
(1) the area ratio of the area _{S 3} upon the _{S 3} peaks having a peak top of _{20.3~20.5ppm (rrrr) (S 3 /} S) is 0.2% or more, 3% or less And
(2) a ratio area of the area _{S 4} upon the _{S 4} peak to peak top of _{20.6~20.8ppm (rmrm) (S 4 /} S) is 0.3% or more, 7% or less And
(3) the area of _{S 4} is larger than the area of _{S 3,}
(4) the area of _{S 2 is, 25> 4 + 2S 1 /} S 2> 5 is that. Per propylene homopolymer polymer main chain, at ^{13 C-NMR,} head - when observed a peak derived from a carbon atom of the methyl group of the propylene unit chain consisting of tail bonds, the following characteristics (1) to (4) The propylene-based polymer according to claim 5 , wherein
(1) The ratio of area S ₁ (S ₁ / S) is 30% or more and 50% or less, and (2) the ratio of area S ₃ (S ₃ / S) is 1% or more and 3% or less,
(3) The ratio of the area S ₄ (S ₄ / S) is 4% or more and 7% or less,
(4) the area of _{S 2 is, 10> 4 + 2S 1 /} S 2> It is 7. Propylene homopolymer polymer backbone has a weight average molecular weight Mw measured by GPC is 5,000 or more, propylene-based polymer according to any one of claims 1 to 6 200,000 or less. Propylene homopolymer polymer main chain, in any one of claims 1 to 7, characterized in that distinct peaks crystal fusion heat of melting point (Tm) measured by DSC is equivalent to more than 1joule / g does not exist The propylene-based polymer described. Symmetry ansa - - propylene polymer according to any one of claims 2-8, characterized in that a metallocene compound C ₁ having single-site catalyst, a transition metal-containing crosslinking group. When propylene homopolymer polymer main chain and / or propylene-based polymer, and Atsushi Nobori elution fractionation at o- dichlorobenzene, claim 1, substantially all of the components are characterized by elution with 60 ° C. or less the propylene-based polymer according to any one of 1-9. Carboxylic acid group or acid anhydride group or carboxylic acid ester group of the side chain in claim 1, characterized in propylene homopolymer polymer backbone, to a polymerizable compound having a base which is introduced by graft copolymerization The propylene-based polymer according to any one of claims 1 to 10 . 12. The propylene-based polymer according to claim 11 , wherein the polymerizable compound is an unsaturated carboxylic acid derivative component comprising an unsaturated carboxylic acid having 3 to 25 carbon atoms, an acid anhydride thereof or an ester thereof. The propylene-based polymer according to claim 12, wherein the polymerizable compound is maleic anhydride. Propylene polymer according to any one of claims 1 to 13, characterized by having the following characteristics (b).
(B) Adhesion according to an adhesion test to a polypropylene substrate (cross-cut tape method) is 50/100 or more. Propylene polymer solubility parameter of 11 (cal ^/ cm ^{3) 1/2} or less of the adhesive composition by dissolving 1 part by weight or more in the solvent according to any one of claims 1-14. Propylene comprising a polymer, an adhesive for an olefin polymer base material having a crystallinity of any one of claims 1-14. Comprising the composition of claim 15, the adhesive for an olefin polymer base material having a crystallinity. A production method for the propylene-based polymer according to claim 1, the monomer consists essentially of propylene, C ₁ having a transition metal-containing bridging group - single-site catalyst is a metallocene compound - symmetry answer obtain a main chain consisting of polymerized in the presence of propylene homopolymer polymer having a stereo-block structure containing an isotactic block, the propylene homopolymer backbone at ^{13 C-NMR,} head - tail bond When the peak derived from the carbon atom of the methyl group of the propylene unit chain portion is observed and the chemical shift of the peak top of the peak represented by mmmm is 21.8 ppm, 19.8 ppm to 22 The ratio of the peak area S ₁ having a peak top of 21.8 ppm to the total peak area S appearing at ₁ ppm (S ₁ / S ) 10% or more and 60% or less, then the propylene homopolymer polymer backbone obtained, a polymerizable monomer containing a carboxylic acid group or acid anhydride group or carboxylic acid ester group by graft copolymerization A method for producing a propylene polymer, characterized by being a propylene polymer. In the propylene polymer, the graft amount of at least one graft copolymer unit selected from the polymerizable monomer containing the carboxylic acid group or acid anhydride group or carboxylic acid ester group is 0.01 to 25. The method for producing a propylene-based polymer according to claim 18 , wherein the propylene-based polymer is in wt%. C ₁ having a crosslinkable group in the transition metal-containing - Symmetry ansa - metallocene compounds, C ₁ Group 4 transition metal compounds are crosslinked with a conjugated five-membered ring ligands - that the metallocene have symmetry The method for producing a propylene-based polymer according to claim 18 or 19 , characterized in that A main chain consisting essentially of propylene homopolymer a polymer having a stereo-block structure containing an isotactic block, has a side chain containing a carboxylic acid group or acid anhydride group or carboxylic acid ester group, the propylene For the homopolymer main chain, 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 by ¹³ C-NMR, and the peak attributed to the pentad represented by mmmm When the chemical shift of the peak top is 21.8 ppm, the ratio of the peak area S ₁ having 21.8 ppm as the peak top to the total peak area S appearing from 19.8 ppm to 22.1 ppm (S ₁ / S ) 10% or more and 60% or less, the propylene polymer der and having the following characteristics (a) or (a) and (b) Te,
A monomer having substantially propylene is polymerized in the presence of a single-site catalyst that is a C ₁ -symmetric ansa-metallocene compound having a transition group-containing bridging group to form a stereo block structure containing an isotactic block. give the propylene homopolymer polymer backbone having,
To the resulting propylene homopolymer polymer main chain, a propylene-based heavy, characterized in that the polymerizable monomer containing a carboxylic acid group or acid anhydride group or carboxylic acid ester groups formed by produced by graft copolymerization Coalescence.
(A) when dissolved in toluene at 25 ° C. at a concentration of 10% by weight, the insoluble content is 1% by weight or less based on the total polymer,
(B) Adhesion according to an adhesion test to a polypropylene substrate (cross-cut tape method) is 50/100 or more.