JP2004083686A - Polypropylene-based coated molded form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polypropylene-based coated molded form obtained by coating an elastomer-containing crystalline polypropylene molded form with a coating component comprising a polar group-containing propylene-based polymer. <P>SOLUTION: The propylene-based coated molded form is obtained by coating a substrate(B) with a coating component(A). In this molded form, the coating component(A) comprises the polar group-containing propylene-based polymer composed of the main chain consisting of a propylene-based polymer having the characteristics(1) and (2) described below and side chains containing carboxy groups, carboxylic anhydride groups or carboxylic ester groups: (1) produced using a single-site catalyst and (2) ≤1 wt.% in insolubles when dissolved at 10 wt.% concentration in heptane at 98°C; and the substrate(B) is a molded form of a resin composition comprising a crystalline polypropylene and an elastomer component. <P>COPYRIGHT: (C)2004,JPO

Description

なお、これらのペンタッドに由来するピークのケミカルシフトは、ＮＭＲの測定条件によって多少の変動があること、および、ピークは必ずしも単一ピーク（ｓｉｎｇｌｅ　ｐｅａｋ）ではなく、微細構造にもとづく複雑な分裂パターン（ｓｐｌｉｔ　ｐａｔｔｅｒｎ）を示すことが多い点に注意して帰属を行う必要がある。本発明でいうアイソタクチックブロックとは、ｍｍｍｍペンタッドを指称し、非晶性ブロックとは、少なくとも１個のｒダイアドを含む他の全てのペンタッドを指称する。
【００２７】
本発明において、ステレオブロック構造の特徴として重要なところは、下記要件▲１▼及び▲２▼である。
▲１▼　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、１９．８〜２２．２ｐｐｍの範囲に現れる上記１０種類の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Ｓ_１の比率（Ｓ_１／Ｓ）が１０〜６０％であること
▲２▼　２１．５〜２１．７ｐｐｍにピークトップを有するピーク（ｍｍｍｒ）の面積をＳ_２としたとき、Ｓ_１とＳ_２の関係が、４＋２Ｓ_１　／Ｓ_２＞５を満たすこと。
【００２８】
Ｓに対するＳ_１の比率が１０％未満である場合には、結晶性が低すぎ、十分な塗膜密着性が得られず、さらに、べたつきなどの問題も起こりやすいために好ましくない。一方、Ｓに対するＳ_１の比率が６０％を越える場合には、逆に結晶性が高すぎ、溶媒への溶解性が低下するため、これも好ましくない。Ｓに対するＳ_１の比率は、好ましくは２０〜５０％、更に好ましくは３０〜５０％である。
【００２９】
Ｓ_１とＳ_２を上記の要件▲２▼で規定した範囲となるように制御する方法としては、（ｉ）　重合触媒の構造によって制御する方法、（ｉｉ）　重合温度によって制御する方法、（ｉｉｉ）　モノマー濃度によって制御する方法；　等を挙げることができる。Ｓ_１、　Ｓ_２の温度依存性や、モノマー濃度依存性は、使用する触媒によって異なるので一概に言うことはできない。したがって、使用する触媒の性質にもとづいて、これらの条件を制御することが肝要である。また、重合触媒の構造によって制御する場合には、遷移金属成分を構成する配位子の構造が重要である。特に、架橋メタロセンを用いる場合には、架橋基の橋頭を基点として　α−位の置換基が重要である。一般的には、α−位にある程度かさだかい置換基がある場合に、立体選択性が向上しやすい。さらに、インデニル基やアズレニル基などの縮合環を有する配位子を含む架橋メタロセンを用いる場合には、４−位の置換基の構造も立体選択性に大きな影響を与える。一般的には、４−位にある程度かさだかい置換基がある場合に、立体選択性が向上しやすい。逆に、４−位に、立体的に比較的小さい置換基を導入することにより、効果的に立体選択性を低下させ、生成重合体の結晶性を低下させるという制御が可能となる。
【００３０】
更に本発明のステレオブロック構造の特徴として、下記要件▲３▼〜▲９▼及び（１０）が挙げられる。これらの要件は、いずれも、プロピレン系重合体主鎖中に結晶性の高いブロックと非晶性の高いブロックが共存し、かつ、結晶性の高いブロックがアイソタクチック性に富む構造となっていることと密接に関係している。
▲３▼　２０．３〜２０．５ｐｐｍにピークトップを有するピーク（ｒｒｒｒ）の面積をＳ_３とした際、その面積Ｓ_３の比率（Ｓ_３／Ｓ）が０．２〜３％であること
▲４▼　２０．６〜２０．８ｐｐｍにピークトップを有するピーク（ｒｍｒｍ）の面積をＳ_４とした際、その面積Ｓ_４の比率（Ｓ_４／Ｓ）が０．３〜７％であること
▲５▼　Ｓ_４がＳ_３よりも大きいこと、
▲６▼　Ｓ_１とＳ_２の関係が、２５＞４＋２Ｓ_１　／Ｓ_２＞５を満たすこと
▲７▼　面積Ｓ_１の比率（Ｓ_１／Ｓ）が３０〜５０％であること
▲８▼　面積Ｓ_３の比率（Ｓ_３／Ｓ）が１〜３％であること
▲９▼　面積Ｓ_４の比率（Ｓ_４／Ｓ）が４〜７％であること、
（１０）Ｓ_１とＳ_２の関係が、１０＞４＋２Ｓ_１　／Ｓ_２＞７を満たすこと
【００３１】
プロピレン系重合体主鎖は、要件▲２▼の如く、４＋２Ｓ_１／Ｓ_２＞５という関係を満足することが好ましい。この関係式は、Ｗａｙｍｏｕｔｈらによりアイソタクチックブロックインデックス（ＢＩ）と名づけられた指数（特表平９−５１０７４５号公報参照）と密接な関連がある。ＢＩは、重合体のステレオブロック性を表す指標であり、ＢＩ＝４＋２［ｍｍｍｍ］／［ｍｍｍｒ］で定義される。より具体的には、ＢＩは、４個以上のプロピレン単位を有するアイソタクチックブロックの平均連鎖長を表す（Ｊ．Ｗ．Ｃｏｌｌｅｔｅ　ｅｔａｌ．，Ｍａｃｒｏｍｏｌ．，２２，３８５８（１９８９）；Ｊ．Ｃ．Ｒａｎｄａｌｌ，Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．Ｐｏｌｙｍ．Ｐｈｙｓ．Ｅｄ．，１４，２０８３（１９７６））。統計的に完全なアタクチックポリプロピレンの場合、ＢＩ＝５となる。したがって、ＢＩ＝４＋２［ｍｍｍｍ］／［ｍｍｍｒ］＞５とは、重合体中に含まれるアイソタクチックブロックの平均連鎖長が、アタクチックポリプロピレンのそれよりも長いことを意味する。
【００３２】
要件▲２▼、▲６▼又は（１０）における、４＋２Ｓ_１／Ｓ_２は、上述のＢＩと完全には同一でないものの、おおむね対応していることから、４＋２Ｓ_１／Ｓ_２＞５という要件▲２▼は、本発明の重合体主鎖が、アタクチックポリプロピレンとは異なり、結晶化可能な連鎖長のアイソタクチックブロックを含有することを意味する。また、アタクチックブロックが存在するということは、言い換えれば、立体特異性（ｓｔｅｒｅｏｓｐｅｃｉｆｉｃｉｔｙ）が乱れたシークエンスからなるブロックも同時に主鎖に存在することを意味する。このように、主鎖中に結晶性を有するブロックと非晶性のブロックとが共存し、かつ、結晶性を有するブロックが、比較的長い平均連鎖長を有するアイソタクチックブロックから形成され、アイソタクチック性に富む構造になっているという特異な構造である。
【００３３】
特性（４）　２５℃におけるトルエンに１０重量％の濃度で溶解した際に、その不溶分が１重量％以下であること
室温のトルエン（２５℃）に１０重量％濃度で溶解した場合、特性（２）と同様レベルの溶解性を示すものが好ましい。
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。
トルエン不溶分が１重量％を超えると、溶解性が不足するために、塗膜の肌荒れや平滑性などの塗装性能が低下する傾向があり、さらに塗料として用いた場合の溶液状態の貯蔵安定性が悪化し分離しやすくなる傾向があり塗装工程における作業性が低下するため好ましくない。
【００３４】
特性（５）　ＧＰＣで測定した重量平均分子量Ｍｗが５，０００〜１００万である
ＧＰＣ（Ｇｅｌ　Ｐｅｒｍｅａｔｉｏｎ　Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）で測定した重量平均分子量Ｍｗが５，０００〜２００，０００であることが好ましい。Ｍｗが５，０００より小さい場合には、グラフト共重合により変性した極性基含有プロピレン系重合体を用いて基材上に塗布した後の造膜性が悪化するばかりでなく、べたつきもあり好ましくない。また、Ｍｗが１００万を越える場合には、造膜性やべたつきについては大きな問題はないものの、極性基含有プロピレン系重合体を溶媒に溶解した際の粘度が高くなりすぎ、製造上あるいは該極性基含有プロピレン系重合体溶液のハンドリング上、不都合を生じるために好ましくない。本発明において、好ましい重量平均分子量Ｍｗの範囲は５，０００〜１００万であるが、より好ましくは、１０，０００〜５０万、さらに好ましくは、３０，０００〜２０万である。
【００３５】
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。
なお、ＧＰＣによる分子量の測定は、オルトジクロロベンゼンを溶媒とし、ポリスチレンを標準試料として、市販の装置を用いて従来公知の方法で行うことができる。
分子量分布については、特に制限はないが、過度に広すぎる分子量分布は、低分子量成分の含有量が必然的に多いことを意味するので避けた方が良い。分子量分布の指標として重量平均分子量Ｍｗと数平均分子量Ｍｎとの比Ｍｗ／Ｍｎを用いた場合、好ましくはＭｗ／Ｍｎ＜２０、さらに好ましくはＭｗ／Ｍｎ＜１０、最も好ましくはＭｗ／Ｍｎ＜５のものが好適に使用される。
【００３６】
特性（６）　ＤＳＣで測定した結晶融解熱量が１Ｊ／ｇ以上に相当する明確なピークが存在しないこと
プロピレン系重合体主鎖においては、結晶融解熱が１Ｊ／ｇに相当する明確なピークが存在すると、溶媒への溶解性が低下するので好ましくない。測定方法としては、熱分析システム（ＤＳＣ）を用いて、試料を２００℃で３分間融解後、１０℃／分の速度で３０℃まで降温し、１０℃／分で２００℃まで昇温することにより融解曲線を得る。最後の昇温段階における融解曲線から、５０〜１６０℃の温度域において、１Ｊ／ｇ以上に相当する明確なピークが存在するか否かを評価する。ピークが存在する場合、ピークトップ温度を融点とし、吸熱ピーク面積から結晶融解熱を求めた。
【００３７】
特性（７）　６０℃のオルトジクロロベンゼン（ＯＤＣ）に実質的に全て溶解すること
プロピレン系重合体主鎖は、特性（３）で述べたように、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、重合体をオルトジクロロベンゼン（ＯＤＣ）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。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。
【００３８】
プロピレン系重合体主鎖は、特性（２）（４）（７）で述べたように有機溶媒に対する溶解性に優れる。ヘプタン、トルエン、オルトジクロロベンゼン以外の有機溶媒としては、ベンゼン、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−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、パークロルエチレン、クロル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る。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。
これらの有機溶媒は、プロピレン系重合体主鎖の変性反応の溶媒あるいは変性反応物を溶解する塗料ビヒクルとして好適に用いられる。
【００３９】
次に、極性基含有プロピレン系重合体の極性基について説明する。本発明において、「極性基」とは、カルボキシル基、カルボン酸無水物基又はカルボン酸エステル基の総称であり、極性基含有プロピレン系重合体の側鎖に相当するものである。
プロピレン系重合体主鎖に極性基を導入する方法として、カルボキシル基等を含有する重合性単量体をグラフト共重合させる方法が一般的である。
【００４０】
グラフト共重合させるカルボキシル基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。
【００４１】
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。
【００４２】
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（３−メチル−２−ペンテン−１，５−ジカルボン酸）、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。
【００４３】
本発明の極性基含有プロピレン系重合体を用いて塗膜を形成した場合、塗膜と基材との塗膜密着性の面から、これらのグラフトするカルボキシル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。
【００４４】
本発明で用いられる極性基含有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無水物を、プロピレン系重合体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。
【００４５】
極性基含有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、すなわち変性重合体中の含有量が、プライマーとして成形品に塗布して塗料の付着性が高い塗膜が得られ、また該塗膜と成形品との付着性も良好で、外観が良好となる点で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。
【００４６】
前記プロピレン系重合体にモノオレフィンジカルボン酸、その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、プロピレン系重合体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；プロピレン系重合体を加熱して溶解し、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；プロピレン系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。
【００４７】
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。
【００４８】
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。
【００４９】
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。
【００５０】
本発明の変性プロピレン系重合体も変性前のプロピレン系重合体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。本発明の変性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／ｃｍ^３）^１／２以下の溶媒には溶解性が高いので、このプロピレン系重合体のグラフト変性体を溶解度パラメーターが１１（ｃａｌ／ｃｍ^３）^１／２以下の溶剤に１重量部以上溶解した組成物は塗料組成物として有効である。
【００５１】
溶解度パラメーターが１１（ｃａｌ／ｃｍ^３）^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。
【００５２】
本発明の塗料組成物は、塗料成分（Ａ）と該塗料成分（Ａ）を溶解する有機溶媒を主成分とするが、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。
【００５３】
本発明の極性基含有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に塗布することができる。これらのオレフィン系重合体のうち、プロピレン系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形品、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形品、例えば自動車用バンパー等の成形品、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。
【００５４】
本発明の極性基含有プロピレン系重合体を含有する塗料成分（Ａ）を基材（Ｂ）に塗布した際に形成される塗膜は、基材に対して良好な密着性を示すので、基材に対する塗膜密着性樹脂として使用することができる。なお、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。
【００５５】
本発明の極性基含有プロピレン系重合体を含有する塗料成分（Ａ）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。
【００５６】
極性基含有プロピレン系重合体を含有する塗料成分（Ａ）は、プライマー成分として用いることができる。すなわち、基材（Ｂ）の表面に塗布し、その表面への塗料の付着性や耐水性およ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成分として用いることができる。
具体的には、アクリル樹脂及び／又はポリエステル樹脂並びにポリウレタン変性ポリプロピレン樹脂と該極性基含有プロピレン系重合体とを、基材（Ｂ）へ塗布することができる。このようなプライマーは、塩素のようなハロゲンを含有せず、べたつき性がなく、溶解性にも優れ、かつアクリル樹脂及びポリエステル樹脂に対する相溶性に優れ、基材に対して良好な接着性、塗装性を保持し、耐水性、耐ガソホール性の高い塗膜を形成することが可能となる。
【００５７】
極性基含有プロピレン系重合体を含有する塗料成分（Ａ）は、プライマー成分の塗布が不要なベースカラー成分として用いることができる。すなわち、基材（Ｂ）の表面に塗布するに際し、基材の表面処理や洗浄を必要とせず、プライマー塗布が不要で、一回の塗装により良好な耐水性、耐候性を持つ塗膜が形成できるベースカラー成分として用いることができる。
【００５８】
このようなベースカラーは塩素のようなハロゲンを含有せず、べたつき性がなく、溶解性にも優れ、かつアクリルポリール及びポリエステルポリオールに対する相溶性に優れ、基材としての結晶性プロピレン系重合体等のポリオレフィンに対して良好な接着性、塗装性を保持し、耐久性、耐薬品性の高い塗膜を形成することが可能なであり、プライマー塗装が不要で、一回の塗装により良好な耐水性、耐候性を持つ塗膜が形成することができる。
【００５９】
なお、基材に対しプライマー成分を塗布し、塗膜の密着性をさらに改善することも可能である。
【００６０】
＜ＩＩ＞　基材（Ｂ）
（ＩＩ−１）結晶性ポリプロピレン成分
本発明に用いられる基材（Ｂ）は、結晶性ポリプロピレン及び無機フィラー成分からなる樹脂組成物の成形体である。ここに、結晶性ポリプロピレンとは、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である。
【００６１】
該プロピレン単独重合体、及びプロピレン・エチレンブロック共重合体のＭＦＲは好ましくは２ｇ／１０分以上、より好ましくは１０〜３００ｇ／１０分、特に好ましくは、２５〜２００ｇ／１０分である。
上記プロピレン・エチレンブロック共重合体及びプロピレン単独重合体のＭＦＲが２ｇ／１０分未満であると流れ性が不十分となる傾向がある。逆に著しく高い場合、機械物性に劣るので好ましくない。
上記プロピレン・エチレンブロック共重合体のＭＦＲは、重合時に調整したもの、或いは重合後にジアシルパーオキサイド、ジアルキルパーオキサイド等の有機過酸化物で調整したものであってもよい。
【００６２】
プロピレン・エチレンブロック共重合体は、結晶性ポリプロピレン部（ａ単位部）とエチレン・プロピレンランダム共重合体部（ｂ単位部）とを含有するプロピレン・エチレンブロック共重合体である。
上記ａ単位部は、通常プロピレンの単独重合、場合によってはプロピレンに少量の他のα―オレフィンを共重合することによって得られる。
ａ単位部の、ポリプロピレン単独重合体のＭＦＲは、好ましくは１０ｇ／１０分以上、より好ましくは１５〜５００ｇ／１０分、さらに好ましくは、２０〜４００ｇ／１０、特に好ましくは、４０〜３００ｇ／１０分である。
上記プロピレン・エチレンブロック共重合体のプロピレン単独重合体部（ａ単位部）のＭＦＲが１０ｇ／１０分未満であると流れ性が不十分となる傾向がある。逆にＭＦＲが著しく高い場合、機械物性に劣る傾向がある。
【００６３】
一方、上記ｂ単位部はプロピレンとエチレンとのランダム共重合によって得られるゴム状成分である。
上記プロピレン・エチレン共重合体部（ｂ単位部）のプロピレン含量は、好ましくは３０〜８５重量％、より好ましくは４０〜８０重量％、さらに好ましくは５０〜７５重量％である。共重合体部のプロピレン含量が上記範囲を逸脱した場合、その分散性が悪化したり、ガラス転移温度が上昇するなど、衝撃特性の悪化する傾向がある。
プロピレン・エチレン共重合体部のプロピレン含量は、プロピレン・エチレン共重合体部の重合時にプロピレンとエチレンの濃度比を制御することにより、調整することができる。
【００６４】
また、上記プロピレン・エチレン共重合体部の分子量については、特に制約はないが、分散性や耐衝撃性を考慮し、重量平均分子量（Ｍｗ）は、好ましくは２０万〜３００万、より好ましくは３０万〜２５０万、さらに好ましくは４０万〜２００万である。
【００６５】
ａ単位部、ｂ単位部の量については特に制限はないが、一般にａ単位部は、好ましくは全重合量の９５重量％以下、より好ましくは５０〜９５重量％、さらに好ましくは６０〜９０重量％、ｂ単位部は、好ましくは全重合量の５重量％以上、より好ましくは５〜５０重量％、さらに好ましくは１０〜４０重量％となるように調整される。
ｂ単位部の量が、上記範囲未満であると、ブロック共重合体として期待される耐衝撃特性が不十分となる傾向があり、上記範囲を超えると剛性、強度及び耐熱性が不足する傾向があり好ましくない。
【００６６】
本発明において、この共重合体部の量は、昇温溶出分別法を用いて測定するものとする。すなわちａ単位部は、オルトジクロロベンゼンによる抽出において、１００℃以下で溶出しないが、ｂ単位部は容易に溶出する。従って、製造後の重合体に対して、上記したオルトジクロロベンゼンによる抽出分析によりプロピレン・エチレンブロック共重合体の組成を判定するものとする。
プロピレン・エチレン共重合体部の量は、プロピレン単独重合体部の重合量とプロピレン・エチレン共重合体部の重合量の比率を重合時間などにより制御し、調整することができる。
【００６７】
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の製造法は特に限定されるものではなく、公知の方法、条件の中から適宜に選択される。プロピレンの重合触媒としては、通常、高立体規則性触媒が用いられる。例えば、四塩化チタンを有機アルミニウム化合物で還元し、更に各種の電子供与体及び電子受容体で処理して得られた三塩化チタン組成物と有機アルミニウム化合物及び芳香族カルボン酸エステルを組み合わせた触媒（特開昭５６―１００８０６号、特開昭５６−１２０７１２号、特開昭５８−１０４９０７号の各公報参照）、及び、ハロゲン化マグネシウムに四塩化チタンと各種の電子供与体を接触させた担持型触媒（特開昭５７−６３３１０号、同６３−４３９１５号、同６３−８３１１６号の各公報参照）等を例示することができる。さらに、ＷＯ−９１／０４２５７号公報等に示されるようなメタロセン系触媒が挙げられる。なお、メタロセン系触媒と称せられる触媒は、アルモキサンを含まなくてもよいが、好ましくはメタロセン化合物とアルモキサンとを組み合わせた触媒、いわゆるカミンスキー系触媒のことである。
【００６８】
プロピレン・エチレンブロック共重合体は、上記触媒の存在下、気相重合法、液相塊状重合法、スラリー重合法等の製造プロセスを適用して、プロピレンを単独で重合し、続いてプロピレンとエチレンをランダム重合することにより得られる。上記した溶融特性（ＭＦＲ）等を有するプロピレン・エチレンブロック共重合体を得るためには、スラリー法、気相流動床法にて、多段重合することが好ましい。プロピレンの単独重合を多段で行い、続いてプロピレンとエチレンをランダム重合する方法で得ることもできる。ｂ単位部の多いプロピレン・エチレンブロック共重合体の製造においては、特に気相流動床法が好ましい。
【００６９】
プロピレン単独重合体は、上記触媒の存在下、気相重合法、液相塊状重合法、スラリー重合法等の製造プロセスを適用して、プロピレンを単独で重合することにより得られる。上記した溶融特性（ＭＦＲ）を有するプロピレン単独重合体を得るためには、スラリー法、気相流動床法にて、多段重合することが好ましい。
【００７０】
（ＩＩ−２）エラストマー成分
本発明の基材（Ｂ）を構成するプロピレン系樹脂組成物で用いるエラストマー成分は、エチレン・α−オレフィンランダム共重合ゴム、エチレン・α−オレフィン・非共役ジエン共重合体ゴム、スチレン含有熱可塑性エラストマー等が挙げられる。具体例としては、エチレン・プロピレン共重合体ゴム、エチレン・１−ブテン共重合体ゴム、エチレン・１−ヘキセン共重合体ゴム、エチレン・１−オクテン共重合体ゴム等の、エチレン・α−オレフィン共重合体ゴム、エチレン・プロピレン・エチリデンノルボルネン共重合体ゴム（ＥＰＤＭ）等の、エチレン・α−オレフィン・非共役ジエン共重合体ゴム、スチレン−ブタジエン−スチレントリブロック体の水素添加物（ＳＥＢＳ）、スチレン−イソプレン−スチレントリブロック体の水素添加物（ＳＥＰＳ）等のスチレン含有熱可塑性エラストマーが例示できる。これらのエラストマーは、下記のように製造することができる。
【００７１】
これらのエラストマー成分のメルトフローレート（２３０℃、２．１６ｋｇ荷重）は、本発明の主要用途である自動車外装材を考慮した場合、好ましくは０．５〜１５０ｇ／１０分、より好ましくは０．７〜１００ｇ／１０分、特に好ましくは０．７〜８０ｇ／１０分の範囲のものが好ましい。
上記エラストマー成分は、１種類である必要はなく、２種類以上の混合物であっても良い。
【００７２】
［エチレン・α−オレフィンランダム共重合ゴム］
エチレン・α−オレフィンランダム共重合ゴム中のα−オレフィン単位の含有量は、通常１５〜７０重量％、好ましくは２０〜５５重量％である。α−オレフィン単位の含有量が上記範囲よりも少なすぎると衝撃強度が劣り、一方、多すぎると剛性が低下するばかりでなく、このエラストマーの形状をペレット状に保持しにくくなって樹脂組成物の製造に際しての生産ハンドリングが著しく低下するため、各々不適である。
【００７３】
α−オレフィンとしては、炭素数３〜２０のものが挙げられ、具体的には、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン等を挙げることができる。なかでも、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテンが好ましい。
【００７４】
また、上記エチレン・α−オレフィンランダム共重合ゴムのＭＦＲ（２３０℃、荷重２１．１８Ｎ）は、通常０．０１〜１００ｇ／１０分、特に０．１〜１００ｇ／１０分のものが好ましい。さらに、密度は通常０．８５〜０．９０ｇ／ｃｍ^３、特に０．８６〜０．８９ｇ／ｃｍ^３のものが好ましい。
【００７５】
ＭＦＲが０．０１ｇ／１０分未満のものは、樹脂組成物を形成する際の混練時に十分な分散を得ることができず、衝撃強度の低下を引き起こす。一方、ＭＦＲが１００ｇ／１０分を超えるものは、共重合ゴム自身の靭性が足らず、やはり衝撃強度が低下する。また、密度が０．９０ｇ／ｃｍ^３を超えるものは衝撃強度が劣るようになり、０．８５ｇ／ｃｍ^３未満のものはそれ自体のペレット化が困難となる。また、これらは後述するバナジウム化合物系や、ＷＯ−９１／０４２５７号公報等に示されるようなメタロセン系の触媒を用いて製造されたものが好ましい。
【００７６】
ここで、α−オレフィンの含有量は赤外スペクトル分析法や１３Ｃ−ＮＭＲ法等の常法に従って測定される値である。密度はＪＩＳ−Ｋ７１１２に各々準拠して測定される値である。
【００７７】
エチレン・α−オレフィンランダム共重合ゴムは、その重合法として、例えば気相流動床法、溶液法、スラリー法や高圧重合法などを挙げることができ、また少量の例えばジシクロペンタジエン、エチリデンノルボルネンなどのジエン成分が共重合されていてもよい。
【００７８】
重合触媒としては、ハロゲン化チタンのようなチタン化合物、バナジウム化合物、アルキルアルミニウム−マグネシウム錯体、アルキルアルコキシアルミニウム−マグネシウム錯体のような有機アルミニウム−マグネシウム錯体や、アルキルアルミニウム或いはアルキルアルミニウムクロリドなどの有機金属化合物との組合せによるいわゆるチーグラー型触媒、もしくはＷＯ−９１／０４２５７号公報等に示されるようなメタロセン系触媒が挙げられる。なお、メタロセン系触媒と称せられる触媒は、アルモキサンを含まなくてもよいが、好ましくはメタロセン化合物とアルモキサンとを組み合わせた触媒、いわゆるカミンスキー系触媒のことである。
重合法としては、気相流動床、溶液法、スラリー法等の製造プロセスを適用して重合することができる。
【００７９】
このようなエチレン・α−オレフィンランダム共重合ゴムは、各種市販されている。例えば、エチレン・プロピレンゴムとしてＪＳＲ　ＥＰ０２Ｐ、ＥＰ０７Ｐ、ＥＰ９１２Ｐ、ＥＰ５７Ｐ等（以上、ＪＳＲ社製）、タフマーＰ０１８０、Ｐ０４８０、Ｐ０６８０等（以上、三井化学社製）、エチレン・ブテンゴムとしてＪＳＲ　ＥＢＭ２０４１Ｐ、ＥＢＭ２０１１Ｐ、ＥＢＭ３０２１Ｐ等（以上、ＪＳＲ社製）、タフマーＡ４０８５、Ａ４０９０、Ａ２００９０等（以上、三井化学社製）、その他エチレン・１−オクテンゴムとして、ＥＧ８１５０、ＥＧ８１００、ＥＧ８２００（以上、デュポンダウエラストマー社製、商品名「エンゲージ」）などが市販されている。
【００８０】
［スチレン含有熱可塑性エラストマー］
本発明で用いるスチレン含有熱可塑性エラストマーは、ポリスチレン部を５〜６０重量％、好ましくは１０〜３０重量％含有するものである。ポリスチレンの含有量が上記範囲外のものであると、耐衝撃性が不十分となる。そのＭＦＲ（２３０℃、荷重２１．１８Ｎ）は、０．０１〜１００ｇ／１０分、好ましくは０．１〜５０ｇ／１０分の範囲のものが用いられる。ＭＦＲが上記範囲外の場合は、やはり耐衝撃性が不十分となる。
【００８１】
かかるスチレン含有熱可塑性エラストマーの具体例としては、スチレン・エチレン／ブチレン・スチレンブロック共重合体（ＳＥＢＳ）を挙げることができる。これは、ポリスチレンブロック単位とポリエチレン／ブチレンゴムブロック単位とからなる熱可塑性エラストマーである。このようなＳＥＢＳでは、ハードセグメントであるポリスチレンブロック単位が物理架橋（ドメイン）を形成してゴムブロック単位の橋かけ点として存在しており、このポリスチレンブロック単位間に存在するゴムブロック単位はソフトセグメントであってゴム弾性を有している。
ＳＥＢＳのセグメント割合として、ポリスチレン単位を１０〜４０モル％の量で含有していることが望ましい。なおスチレンから導かれる単位の含有量は、赤外スペクトル分析法、^１３Ｃ−ＮＭＲ法などの常法によって測定される値である。
【００８２】
このＳＥＢＳは、具体的にはたとえば特公昭６０−５７４６３号公報などに記載されている公知の方法によって得られる。
これらのスチレン含有熱可塑性エラストマーは一般的なアニオンリビング重合法で製造することができる。これには、逐次的にスチレン、ブタジエン、スチレンを重合しトリブロック体を製造した後に水添する方法（ＳＥＢＳの製造方法）と、スチレン−ブタジエンのジブロック共重合体をはじめに製造した後、カップリング剤を用いてトリブロック体にした後水添する方法がある。また、ブタジエンの代わりにイソプレンを用いる事によってスチレン−イソプレン−スチレントリブロック体の水素添加物（ＳＥＰＳ）も製造する事ができる。
このようなＳＥＢＳとしては、クレイトン（Ｋｒａｔｏｎ）Ｇ１６５０、Ｇ１６５２、Ｇ１６５７（クレイトンポリマーズ社製）、タフテック（旭化成社製）などの市販品が使用できる。
【００８３】
本発明で用いられるＳＥＢＳは、一般的にスチレン・ブタジエン系ブロック共重合体であるＳＢＳ（スチレン・ブタジエン・スチレンブロック共重合体）の水添物として知られている。本発明では、ＳＥＢＳと共にＳＢＳおよび他のスチレン・共役ジエン系共重合体あるいはこれらの完全又は不完全水素化物を用いてもよい。
【００８４】
このようなスチレン・共役系共重合体としては、具体的には、ＳＢＲ（スチレン・ブタジエンランダム共重合体）、ＳＢＳ、ＰＳ−ポリイソブチレンブロック共重合体、ＳＩＳ（スチレン・イソブチレン・スチレンブロック共重合体）及びＳＩＳ水添物（ＳＥＰＳ）などが挙げられる。より具体的には、クレイトン（Ｋｒａｔｏｎ：クレイトンポリマーズ社製）、キャリブレックスＴＲ（クレイトンポリマーズ社製）、ソルブレン（フィリップスペトロリファム社製）、ユーロブレンＳＯＬＴ（アニッチ社製）、タフブレン（旭化成社製）、ソルブレン−Ｔ（日本エラストマー社製）、ＪＳＲＴＲ（ＪＳＲ社製）、電化ＳＴＲ（電気化学社製）、クインタック（日本ゼオン社製）、クレイトンＧ（クレイトンポリマーズ社製）、タフテック（旭化成社製）などが挙げられる。
【００８５】
本発明では、エラストマー成分として、上述したエチレン・α−オレフィンランダム共重合ゴム及びスチレン含有熱可塑性エラストマーを、各々単独で用いてもよく、またこれらを適宜組み合わせて用いてもよい。
【００８６】
（ＩＩ−３）無機フィラー成分
本発明の無機フィラー成分は、曲げ弾性率、剛性などの機械的性質を向上させる為に使用するものである。
具体的には、タルク、マイカ、モンモリロナイト等の板状フィラー、短繊維ガラス繊維、長繊維ガラス繊維、炭素繊維、アラミド繊維、アルミナ繊維、ボロン繊維、ゾノライト等の繊維状フィラー、チタン酸カリウム、マグネシウムオキシサルフェート、窒化珪素、ホウ酸アルミニウム、塩基性硫酸マグネシウム、酸化亜鉛、ワラストナイト、炭酸カルシウム、炭化珪素等の針状（ウイスカー）フィラー、沈降性炭酸カルシウム、重質炭酸カルシウム、炭酸マグネシウム等の粒状フィラー、ガラスバルーンのようなバルン状フィラーである。
その中でも、物性・コスト面のバランスより、タルク、マイカ、ガラス繊維、ウイスカーが好ましい。以下、タルク、ガラス繊維、マイカ、ウイスカーなど特に好ましいフィラーについて詳述する。
【００８７】
（１）タルク
タルクの平均粒径は、通常１０μｍ以下、好ましくは０．５〜８μｍ、さらに好ましくは１〜７μｍである。
該平均粒径は、レーザー回折法（例えば堀場製作所製ＬＡ９２０Ｗ）や、液層沈降方式光透過法（例えば、島津製作所製ＣＰ型等）によって測定した粒度累積分布曲線から読みとった累積量５０重量％の粒径値より求めることができる。本発明の値は、前者の方法にて測定する平均粒径値である。
これらタルクは、天然に産出されたものを機械的に微粉砕化することにより得られたものを更に精密に分級することによって得られる。また、一度粗分級したものを更に分級してもかまわない。
機械的に粉砕する方法としては、ジョークラシャ−、ハンマークラシャ−、ロールクラシャー、スクリーンミル、ジェット粉砕機、コロイドミル、ローラーミル、振動ミル等の粉砕機を用いる方法があげられる。
これらの粉砕されたタルクは、本発明で示される平均粒径に調節するために、サイクロン、サイクロンエアセパレーター、ミクロセパレーター、サイクロンエアセパレーター、シャープカットセパレター、等の装置で１回又は繰り返し湿式又は乾式分級する。本発明のタルクを製造する際は、特定の粒径に粉砕した後シャープカットセパレターにて分級操作を行うことが好ましい。
これらのタルクは、重合体との接着性或いは分散性を向上させる目的で、各種の有機チタネート系カップリング剤、有機シランカップリング剤、不飽和カルボン酸、又はその無水物をグラフトした変性ポリオレフィン、脂肪酸、脂肪酸金属塩、脂肪酸エステル等によって表面処理したものを用いてもよい。
【００８８】
（２）ガラス繊維
ガラス繊維としては、ガラスチョップドストランドを用いるのが一般的であり、これらチョップドストランドの長さは、通常３〜５０ｍｍ、繊維の径は３〜２５μｍ程度、好ましくは８〜１４μｍのものである。このガラスチョップドストランドはシラン系化合物による表面改質及びポリビニルアルコール、ポリ酢酸ビニル、ポリウレタン、エポキ樹脂若しくはオレフィン系成分等の集束剤等による表面処理を施したものを用いることが好ましい。
上記シラン系化合物としては、例えば、ビニルトリエトキシシラン、ビニル−トリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、β−（２，４−エポキシシクロヘキシル）エトキシメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン等を挙げることができる。
一方、集束剤としてのオレフィン系成分としては、不飽和カルボン酸変性ポリオレフィン、又はポリオレフィン低分子量物等が挙げられる。不飽和カルボン酸は上述のものを挙げることができ、ポリオレフィン低分子量物としてはポリエチレン樹脂、ポリプロピレン樹脂、プロピレン・エチレンブロック共重合体、エチレン・ブチレン共重合体、エチレン・ペンテン共重合体の等低分子量物を挙げることができる。
本発明において、必要に応じて、機械的強度の向上を図るために、不飽和カルボン酸及び／又はその誘導体を、ポリプロピレン樹脂とガラス繊維の界面接着を目的に配合する。本発明におけるガラス繊維の分散性には殆ど寄与しないが、機械的強度をより一層向上させる場合には配合する必要がある。これら、不飽和カルボン酸及び／又はその誘導体としては、例えば、マレイン酸、無水マレイン酸、アクリル酸、メタクリル酸、イタコン酸、無水イタコン酸、クロトン酸、シトラコン酸、アンゲリカ酸、ソルビン酸等や、これら不飽和カルボン酸の金属塩、アミド、イミド、エステル等を挙げることができる。これらは単独で、若しくは、その誘導体によって変性されたポリオレフィン樹脂を用いることが好ましく、特にポリプロピレン樹脂を母体として変性したものが好ましく、変性率が０．１〜１０重量％のものを用いることが好ましい。
【００８９】
（３）マイカ
マイカは、平均粒径が２〜１００μｍで平均アスペクト比が１０以上のものが好ましく、とりわけ平均粒径が２〜８０μｍで平均アスペクト比が１５以上のものが好ましい。マイカの平均粒径が上記範囲より大きいものを用いると、成形品の耐傷性、外観、衝撃強度が劣り、上記範囲より小さい場合には分散がかえって悪化し、成形品の耐傷性、外観や、衝撃強度が低下する。また、該マイカはいわゆる白マイカ、金マイカ、黒マイカ等いずれでも構わないが、中でも金マイカ、白マイカが好ましく、とりわけ白マイカが好ましい。
マイカの製造方法は特に限定されず、先述のタルクに準じた方法で製造されるが、中でも乾式粉砕・湿式分級又は湿式粉砕・湿式分級方式で製造されたものが好ましく、とりわけ湿式粉砕・湿式分級方式が好ましい。これらのフィラーは、界面活性剤、カップリング剤等で表面処理を施したものでもよい。表面処理したフィラーは成形品の強度や耐熱剛性をさらに向上させる効果を有する。
【００９０】
（ＩＩ−４）ポリプロピレン系樹脂組成物の物性
本発明における基材（Ｂ）を構成するポリプロピレン系樹脂組成物の機械的物性は、曲げ弾性率が好ましくは５００ＭＰａ以上　より好ましくは８００〜１００００ＭＰａ、さらに好ましくは１０００〜６０００ＭＰａ、特に好ましくは１２００〜３０００ＭＰａである。前記範囲外であると、著しく剛性感に劣り、構造材料として適さない。
ＩＺＯＤ衝撃強度は好ましくは５ｋＪ／ｍ^２以上、より好ましくは１０〜１００ｋＪ／ｍ^２、さらに好ましくは１５〜８０ｋＪ／ｍ^２、特に好ましくは２０〜６０ｋＪ／ｍ^２の範囲が好ましい。前記範囲未満であると、著しく耐衝撃特性に劣り、構造材料として適さない。
【００９１】
本発明の基材（Ｂ）が、亜鉛華、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、本発明の基材（Ｂ）は、上記以外に、本発明の効果を著しく損なわない範囲で、任意の添加剤や配合成分を含有することができる。
具体的には、着色するための顔料、フェノール系、イオウ系、リン系などの酸化防止剤、帯電防止剤、ヒンダードアミン等光安定剤、紫外線吸収剤、各種造核剤、分散剤、中和剤、発泡剤、銅害防止剤、滑剤、難燃剤、上記プロピレン系ブロック共重合体以外の各種樹脂、ポリブタジエン、ポリイソプレン等各種ゴム成分等の配合材を挙げることができる。
【００９２】
詳しくは、ペンタエリスチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシルフェニル）プロピオネート］、オクタデシル−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、トリス−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−イソシアヌレート、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシルフェニル）プロピオネート］等のフェノール系酸化防止剤、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールジフォスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）４，４’−ビフェニレンジフォスフォナイト等のリン系酸化防止剤、ジミリスチル−３，３’−チオジプロピオネート、ジステアリルチオジプロピオネート、２−（３−ｔ−ブチル−５−メチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール、２−（３，５−ジ−ｔ−ブチル−２−ヒドロキシフェニル）ベンゾトリアゾール、２−ヒドロキシ−４−ｎ−オクチルオキシベンゾフェノン等の紫外線吸収剤、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノー１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］、ビス（１−オクチル−２，２，６，６−テトラメチル−４−ピペリジル）セバケート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）１，２，３，４−ブタンテトラカーボキシレート、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジル）１，２，３，４−ブタンテトラカーボキシレート、２，４−ジ−ｔ−ブチルフェニル−３，５−ジ−ｔ−ブチル−４−ヒドロキシベンゾエート等の耐候安定剤、グリセリルモノステアレート等の帯電防止剤を例示できる。
【００９３】
（ＩＩ−５）ポリプロピレン系樹脂組成物の製法
本発明の基材（Ｂ）を構成するプロピレン系樹脂組成物の製造方法は特に限定されず、従来公知の方法で、必要に応じて、上記配合成分をプロピレン系樹脂へ配合し、混合及び溶融混練することにより製造することができる。
基材（Ｂ）を構成する樹脂組成物の配合は、結晶性ポリプロピレンを、通常５１〜９９重量部、好ましくは５５〜９８重量部、さらに好ましくは６５〜９５重量部、エラストマー成分を、通常１〜４９重量部、好ましくは２〜４５重量部、さらに好ましくは５〜３５重量部である。
結晶性ポリプロピレンの含有量が、上記範囲未満であると引張り伸び、耐衝撃特性、特に低温耐衝撃特性が不足し、上記範囲を超えると、剛性、耐熱性が不足する。エラストマー成分の含有量が、上記範囲未満であると、耐衝撃特性、特に低温耐衝撃特性が不足し、上記範囲を超えると、剛性、耐熱性が不足する。
【００９４】
基材（Ｂ）を構成するプロピレン系樹脂組成物の配合は、結晶性ポリプロピレンとエラストマー成分の合計１００重量部に対し、無機フィラー成分を好ましくは１〜８０重量部、より好ましくは２〜７０重量部、さらに好ましくは３〜６０重量部含有するものである。
無機フィラー成分の含有量が、上記範囲未満であると、剛性、耐熱性が不足し、上記範囲を超えると、引張り伸び、耐衝撃特性、特に低温耐衝撃特性が不足し、比重が高くなるため、成形体の重量が重くなる。
【００９５】
本発明においては、上述した必須成分、すなわち、結晶性ポリプロピレン及びエラストマー成分、並びに必要に応じて用いられる無機フィラー成分や任意成分等を、上記配合割合で配合して、一軸押出機、二軸押出機、バンバリーミキサー、ロールミキサー、ブラベンダープラストグラフ、ニーダー等の通常の混練機を用いて混練・造粒することによって、本発明の基材（Ｂ）を構成するプロピレン系樹脂組成物が得られる。
【００９６】
この場合、各成分の分散を良好にすることができる混練・造粒方法を選択することが好ましく、通常は二軸押出機を用いて行われる。この混練・造粒の際には、上記各成分の配合物を同時に混練してもよく、また性能向上をはかるべく各成分を分割して混練する、すなわち例えば先ずプロピレン系ブロック共重合体の一部又は全部と無機フィラーとを混練し、その後に残りの成分を混練・造粒するといった方法を採用することもできる。
【００９７】
本発明の基材（Ｂ）は、結晶性ポリプロピレン成分及びエラストマー成分からなるプロピレン系樹脂組成物を使用し、公知の各種方法による成形により得ることができる。例えば射出成形（ガス射出成形も含む）、圧縮成形、射出圧縮成形（プレスインジェクション）、押出成形、中空成形、回転成形、カレンダー成形、インフレーション成形、一軸延伸フィルム成形、二軸延伸フィルム成形等にて成形することによって各種成形体を得ることができる。このうち、射出成形、圧縮成形、射出圧縮成形による成形体が好ましい。
【００９８】
本発明のポリプロピレン系塗装成形体は、塩素などのハロゲンを含有しないため環境負荷が少なく、塗膜密着性に優れ、さらに剛性、耐衝撃性に優れた物性バランスを有するものである。
具体的には、各種工業部品分野、特に薄肉化、高機能化、大型化された各種成形品、例えばバンパー、インストルメントパネル、トリム、ガーニッシュ、エアクリーナケース、ヒーターケース、ファンシュラウド、灯体などの自動車部品、テレビケース、洗濯機槽、冷蔵庫部品、エアコン部品、掃除機部品などの家電機器部品、便座、便座蓋、水タンクなどのトイレタリー周りの部品、浴槽、浴室の壁、天井などの部品、排水パンなどの浴室周りの部品などの各種工業部品用成形材料として、実用に十分な性能を有している。
【００９９】
【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。
【０１００】
（１）分子量
クロマト分析装置（ウオーターズ社製ＧＰＣ１５０ＣＶ型）を使用した。溶媒としてオルト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。
【０１０１】
（２）プロピレン単位連鎖部のペンタッド
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。
【０１０２】
（３）結晶化度
広角×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）融点及び結晶融解熱
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）を精秤し専用のアルミパンに入れる。２００℃で３分間融解後、１０℃／分の速度で３０℃まで降温した後に、１０℃／分で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。またそのピークとベースラインで囲まれた面積から算出される熱量を試料の重量で割ったものを結晶融解熱量（Ｊ／ｇ）とする。融解曲線の５０〜１６０℃の温度域において、１Ｊ／ｇ以上に相当する明確なピークが存在しない場合、ｎ．ｄ．として表した。
【０１０３】
（５）オルトジクロロベンゼンによる昇温溶出分別
溶出分別装置（三菱化学社製ＣＦＣ−Ｔ−１０２Ｌ）を用いて、１００％溶出温度として求めた。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
溶剤（ヘプタン又はトルエン）に試料を濃度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、溶液温度を２５℃に調節して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重量％以下
×：不溶分１重量％以上
【０１０４】
（７）ノンタック性
指触タック性試験により下記基準で評価した。
評価基準　○：ノンタック性優れる
△：タック性ややあり
×　：タック性有り
（８）曲げ弾性率
型締め圧１００トンの射出成型機を用いて、金型温度４０℃、シリンダー温度２２０℃にて射出成形により９０ｍｍ×１０ｍｍ×３ｍｍの試験片を成形し、得られた射出成形片について、ＪＩＳ−Ｋ７２０３に準拠して試験速度２ｍｍ／分、２３℃下で測定（単位：Ｍｐａ）した。
（９）アイゾット（ＩＺＯＤ）衝撃強度
同上試験片について、ＪＩＳ−Ｋ７１１０に準拠して２３℃下で測定（単位：ｋＪ／ｍ^２）した。
【０１０５】
（１０）層間密着性試験
日本ポリケム社製ポリプロピレンを、射出成型機（東芝機械社製ＩＳ１７０）を用いて、成形温度２２０℃の設定で、１５０ｍｍ×７０ｍｍ×２ｍｍの試験片を成形した。
後述の方法で塗膜を形成した後、ＪＩＳ−Ｋ５４００に記載されている碁盤目試験の方法に準じて、碁盤目を付けた試験片を作成し、粘着テープ（ニチバン社製、登録商標セロテープ）を、試験片の碁盤目上に張り付けた後、これを速やかに垂直方向に引っ張って剥離させ、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」で表記した。
（１１）耐水性試験
塗料成分（Ａ）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、前記層間密着性試験と同様にして碁盤目試験（ＪＩＳ−Ｋ５４００）に準じた密着性試験を行った。
【０１０６】
（１２）耐ガソホール性試験
塗料成分（Ａ）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。
【０１０７】
［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　配位子の合成
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（３４．０ｍｌ，　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。
【０１０８】
（１）−２　錯体の合成
（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％）。
上記化合物の^１Ｈ−ＮＭＲ測定した結果を以下に示す。
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）：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）。
【０１０９】
（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、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。
【０１１０】
（３）重合
（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、トリイソブチルアルミニウム（東ソー・アクゾ社製）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。
【０１１１】
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。表１中、「ｎ．ｄ．」は非検知（ｎｏｔ　ｄｅｔｅｃｔｅｄ）を表す。
【０１１２】
［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。
【０１１３】
［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。
【０１１４】
［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。
【０１１５】
［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。
【０１１６】
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。
【０１１７】
（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。
【０１１８】
（３）　予備重合
（２）で得られたトルエンスラリー（固形分として９１４．２　ｍｇ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、（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１１．０　ｇ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。
【０１１９】
（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。
【０１２０】
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。
【０１２１】
［製造例６］
内容積５０ｍＬ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（３１．１ｇ）、ヘプタン（１８０ｍｌ）、Ｐｄ／Ｃ（アルドリッチ社：１０重量％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。
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：１５，０００ｇ／１０分；
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％。
【０１２２】
［参考例１］
チーグラー・ナッタ系ポリプロピレン（宇部興産社製、ウベタックＵＴ−２１１５）の物性を同様に測定した。
【０１２３】
以下の実施例において使用した、基材（Ｂ）を構成する各種結晶性ポリプロピレン（ベースＰＰ）のグレード名、物性等を表２に示した。ＰＰ−１〜ＰＰ−５のグレード名はいずれも日本ポリケム社の商品名である。表２中、ペンタッド分率はｍｍｍｍペンタッドを指す。
【０１２４】
また、以下の実施例において、エラストマー成分として使用した市販品の各種エラストマー材料のグレード名、物性等を表３に示した。同様に、無機フィラー成分として使用した市販品の各種充填材のグレード名、物性等を表４に示した
【０１２５】
また、表２に示す結晶性ポリプロピレンに対して、表３に示すエラストマー成分及び表４に示す無機フィラー成分を所定量配合し、各種のＰＰ基材（Ｂ）を製造した。得られたＰＰ基材（Ｂ）の物性を表５に示した。なお、ＰＰ基材（Ｂ）の製造法及び評価の詳細は下記の通りである。
これらの配合成分を、表５に記載された配合割合（重量％）で配合し、フェノール系酸化防止剤（チバスペシャルティケミカルズ社製ＩＲＧＡＮＯＸ１０１０）０．１重量部、リン系酸化防止剤（チバスペシャルティケミカルズ社製ＩＲＧＡＦＯＳ１６８）０．０５重量部、ステアリン酸カルシウム０．２重量部と共に混合した後、２軸押出機（日本製鋼所製ＴＥＸ３０α）を用いて、スクリュー回転数３００ｒｐｍ、押出レート１５ｋｇ／ｈｒで溶融混練し、樹脂組成物のペレットを得た。得られたペレットを用いて、金型温度４０℃、シリンダ温度２３０℃の条件で射出成形し、樹脂組成物の各種試験片とした。得られた試験片を用いて、上述の方法により、各種物性を評価した。
さらに、表５に示した各樹脂組成物を、射出成型機（東芝機械社製ＩＳ１７０）を用いて、成形温度２２０℃の設定で、１５０ｍｍ×７０ｍｍ×２ｍｍの試験片を射出成形し、塗装性評価用の基材とした。
【０１２６】
【表１】

【０１２７】
【表２】

【０１２８】
【表３】

【０１２９】
【表４】

【０１３０】
【表５】

【０１３１】
［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（１０重量％）１６ｇを、定量ポンプを用いて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、白色粉末状の変性樹脂が得られた。この変性樹脂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、グラフト量（無水マレイン酸基の含量）は、３．３重量％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１０重量％溶液を調製した。
【０１３２】
（２）　変性プロピレン重合体の物性評価
表５に示す各種のＰＰ基材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、上記（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塗布量３〜５ｇ／ｍ^２で噴霧塗布した。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（関西ペイント社製：商品名レタンＰＧ８０ＩＩＩ）を、所定量の硬化剤と配合して、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。その結果を以下の実施例と纏めて表６（１）〜表６（２）に示す。
【０１３３】
［実施例２］
トルエン（８０ｇ）、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）のトルエン溶液（１０重量％）１２ｇを用い、１１０℃にて反応した以外は、実施例１と同様の操作にて無水マレイン酸変性を行い、該変性重合体を用いて塗装物を作成し、同様に物性評価試験を行った。
【０１３４】
［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と同様の操作にて無水マレイン酸変性を行い、該変性重合体を用いて塗装物を作成し、同様に物性評価試験を行った。
【０１３５】
［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と同様の操作にて無水マレイン酸変性を行い、該変性重合体を用いて塗装物を作成し、同様に物性評価試験を行った。
【０１３６】
［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と同様の操作にて無水マレイン酸変性を行い、該変性重合体を用いて塗装物を作成し、同様に物性評価試験を行った。
【０１３７】
［実施例６］
無水マレイン酸（４ｇ）の代わりにメタクリル酸（５ｇ）を使用し、ジクミルペルオキシド（ＤＣＰＯ）のクロロベンゼン溶液（１０重量％）の添加量を１６ｇから５ｇへ変えた以外は、実施例１と同様の操作にて変性樹脂が得られた。この変性樹脂の赤外線吸収スペクトル測定を行った結果、グラフト量（メタクリル酸基の含量）は、１．１重量％であった。該変性重合体を用いて塗装物を作成し、同様に物性評価試験を行った。
【０１３８】
［実施例７］
無水マレイン酸（４ｇ）の代わりに２−ヒドロキシエチルメタアクリレート（ＨＥＭＡ、５ｇ）を使用し、ジクミルペルオキシド（ＤＣＰＯ）のクロロベンゼン溶液（１０重量％）の添加量を１６ｇから５ｇへ変えた以外は、実施例１と同様の操作にて変性樹脂が得られた。この変性樹脂の赤外線吸収スペクトル測定を行った結果、グラフト量（２−ヒドロキシエチルメタクリレート基の含量）は、１．０重量％であった。該変性重合体を用いて塗装物を作成し、同様に物性評価試験を行った。
【０１３９】
［実施例８］
無水マレイン酸（４ｇ）の代わりに２−ヒドロキシエチルメタアクリレート（ＨＥＭＡ、５ｇ）およびスチレン（Ｓｔ、５ｇ）を使用し、ジクミルペルオキシド（ＤＣＰＯ）のクロロベンゼン溶液（１０重量％）の添加量を１６ｇから５ｇへ変えた以外は、実施例１と同様の操作にて変性樹脂が得られた。この変性樹脂の赤外線吸収スペクトル測定を行った結果、２−ヒドロキシエチルメタアクリレート基の含量は、２．５重量％であった。該変性重合体を用いて塗装物を作成し、同様に物性評価試験を行った。
【０１４０】
［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と同様の操作にて無水マレイン酸変性を行った。変性プロピレン重合体のグラフト量は３．４重量％であり、溶解性試験を行ったところ、トルエンへの溶解性が悪く９６％以上不溶解物が得られ塗装評価ができなかった。但し、ノンタック性は優れていた。その結果を以下の比較例と纏めて表７（１）〜表７（２）に示す。
【０１４１】
［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と同様の操作にて無水マレイン酸変性を行った。変性プロピレン重合体のグラフト量は３．５重量％であり、溶解性試験を行ったところ、トルエンへの溶解性は良好であったが、べたつきが多く、塗装評価には至らなかった。またタック性にも問題があった。
【０１４２】
［比較例３］
チーグラー・ナッタ触媒系ポリプロピレン（宇部興産社製ウベタックＵＴ−２１１５）を用い、実施例１と同様の操作にて無水マレイン酸変性を行った。変性プロピレン重合体のグラフト量は３．４重量％であり、トルエンの溶解性試験を行ったところ、不溶解物が２９．５重量％と多く、塗装評価ができなかった。またタック性にも問題があった。
【０１４３】
［比較例４］
プロピレン・ブテン−１共重合体（三井化学社製タフマーＸＲ−１１０Ｔ、プロピレン成分：ブテン−１成分＝７６：２４）を用い、実施例１と同様の操作にて無水マレイン酸変性を行った。変性プロピレン重合体のグラフト量は３．０重量％であり、トルエンの溶解性試験を行ったところ、不溶解物が６７．４重量％と多く、塗装評価ができなかった。但し、ノンタック性は優れていた。
【０１４４】
［比較例５］
変性重合体として、無水マレイン酸変性塩素化ポリプロピレン（Ｅａｓｔｍａｎ社、ＣＰ−３４３−１）を用いて、塗装評価を行った。ノンタック性は優れていたが、特に密着性と耐水性に劣るものであった。
【０１４５】
【表６】［表６（１）］

【０１４６】
【表７】［表６（２）］

【０１４７】
【表８】［表７（１）］

【０１４８】
【表９】［表７（２）］

【０１４９】
【発明の効果】
本発明のポリプロピレン系塗装成形体は、塗膜密着性に優れ、さらに剛性、耐衝撃性に優れた物性バランスを有する。又、地球環境に有害なハロゲン類を使用していないため、地球環境保護に役立つばかりでなく、ハロゲンの耐候性等への悪影響が大幅に軽減されるため、塗装成形体が長期安定性に優れ、その結果ライフサイクルの延長をもたらし、ひいては限りある地球資源の節約にも貢献する技術開発であるため、その工業的価値は極めて大きい。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polypropylene-based molded article. More specifically, the present invention relates to a polypropylene-based molded article obtained by coating an elastomer-containing crystalline polypropylene molded article with a paint component containing a polar group-containing propylene-based polymer.
[0002]
[Prior art]
Propylene homopolymer, propylene resin composition containing propylene resin such as propylene / ethylene block copolymer composed of propylene homopolymer part and propylene / ethylene copolymer part and containing elastomer, is only lightweight. It has excellent mechanical properties, moldability and recyclability, and is used for a wide range of industrial parts. However, the propylene-based polymer serving as the base material has a defect that the coating film adhesion is low at the time of coating for enhancing the design, since it has a structure without a so-called polar group. In order to remedy this drawback, the surface of the molded article of the propylene-based resin composition is chemically treated with a chemical or the like, or the surface is oxidized using a technique such as corona discharge treatment, plasma treatment, or flame treatment. Various techniques have been tried. However, these methods not only require special equipment but also cannot be said to be sufficient in terms of the effect of improving paintability and coating film adhesion.
[0003]
On the other hand, paint components containing so-called chlorinated polypropylene have been developed as a device for imparting good coatability and coating film adhesion to a propylene-based resin composition by a relatively simple method. Chlorinated polypropylene is generally soluble in organic solvents such as toluene and xylene, and has relatively good adhesion to a propylene-based resin composition as a base material. Therefore, by applying the hydrocarbon solution of the chlorinated polypropylene to the surface of the propylene-based resin composition as a base material and removing the solvent, the paintability of the propylene-based resin composition and the adhesion of the coating film are relatively simple. It is known to improve the properties. It is known that a modified chlorinated polypropylene obtained by further modifying a chlorinated polypropylene by graft copolymerization of a polar monomer is more excellent in the effect of improving the coating properties and coating film adhesion.
[0004]
However, since the modified product contains a chlorine atom, there is a problem in terms of recycling of the resin and generation of harmful substances due to incineration, and its use becomes a social problem like the vinyl chloride resin. In addition, there are still problems such as a resin containing chlorine having poor weather resistance. Therefore, as for the chlorinated polypropylene, similarly to the vinyl chloride resin, it is strongly desired to develop a substitute resin containing no halogen such as chlorine. Further, a resin containing chlorine has problems such as poor weather resistance. Therefore, there is a strong demand for chlorinated polypropylene, as well as vinyl chloride resin, to develop a substitute resin containing no halogen such as chlorine.
[0005]
As a method for solving such a problem, on the other hand, a resin containing no chlorine has been developed. For example, Japanese Patent Publication No. 44-958 discloses a treating agent obtained by dissolving an amorphous polypropylene polymer modified with a specific ratio of maleic acid or its anhydride in a solvent. As used herein, the term "amorphous polypropylene polymer" refers to an atactic polypropylene and an amorphous polypropylene containing at least about 20 mol% propylene units in a copolymer and comprising at least one copolymerized monomer and a propylene copolymer. It is a polymer. As a similar treating agent, Japanese Patent Application Laid-Open No. 8-217835 discloses an amorphous polypropylene or amorphous propylene / 1-butene copolymer obtained by graft copolymerization of an unsaturated carboxylic acid having 3 to 10 carbon atoms. A polymer is disclosed. When such a graft-modified product is used, although the solubility is improved and the coating property is excellent as compared with a general modified propylene-based resin, the solubility in a solvent at room temperature is still low, the tackiness is high, and the coating property is high. Poor film adhesion. For this reason, the above-mentioned chlorinated polypropylene or modified chlorinated polypropylene is considered to be relatively excellent at present as a surface treatment agent and a paint component.
[0006]
Therefore, a coated molded article obtained by applying a chlorinated polypropylene or a modified chlorinated polypropylene to a molded article based on a propylene-based resin composition has recyclability and environmental problems at the time of incineration. The coated molded product coated with the graft modified product has problems in terms of quality such as handleability (solubility in a solvent) and stickiness, and a product satisfying the required performance has not been obtained.
[0007]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems, and does not contain a halogen such as chlorine, has no stickiness, is excellent in solubility in a solvent, and expresses a good coating adhesion, and applies a novel coating component. The present invention also provides a polypropylene-based painted molded article.
[0008]
[Means for Solving the Problems]
The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention resides in a polypropylene-based molded article obtained by applying the following coating component (A) to a substrate (B).
Coating component (A): a polar group comprising a main chain composed of a propylene polymer having the following characteristics (1) and (2) and a side chain containing a carboxyl group, a carboxylic anhydride group or a carboxylic ester group. A paint component containing a propylene-based polymer.
(1) Manufactured using a single-site catalyst
(2) When dissolved in heptane at 98 ° C. at a concentration of 10% by weight, its insoluble content is 1% by weight or less.
Substrate (B): molded product of a resin composition comprising crystalline polypropylene and an elastomer component.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
<I> Paint component (A)
The polymer constituting the coating component (A) of the present invention is a polar group-containing propylene polymer, which is composed of a propylene polymer having the following characteristics, a carboxyl group, and a carboxylic acid. And a side chain containing an anhydride group or a carboxylic acid ester group (hereinafter, these may be collectively referred to as “polar group”).
Hereinafter, a main chain composed of a propylene-based polymer (hereinafter, may be simply referred to as “main chain”) will be described. The main chain has a number of properties, but important properties are as follows (1) and (2), and characteristics (3) to (7) are further added thereto.
(1) Manufactured using a single-site catalyst
(2) When dissolved in heptane at 98 ° C. at a concentration of 10% by weight, its insoluble content is 1% by weight or less.
[0010]
Characteristics (1) Manufactured with a single-site catalyst
The main chain of the polar group-containing propylene polymer contained in the coating component (A) is obtained by a method of polymerizing with a single-site catalyst. Single-site catalysts are characterized by the ability to control microtacticity through ligand design, the ability to easily produce polymers with relatively low molecular weight, and the sharp distribution of molecular weight and stereoregularity of the polymer. As If the molecular weight distribution or the stereoregularity distribution is irregular, there is a possibility that a difference in solubility occurs, and a partially insoluble one may be formed.
Among the single-site catalysts, metallocene catalysts are preferably used because microtacticity can be precisely controlled. As shown below, the metallocene-based catalyst includes a metallocene compound (component [a]) and a cocatalyst (component [b]) as essential components.
[0011]
Examples of the metallocene compound (component (a)) include C having a transition metal-containing crosslinking group.₁-Symmetric answer metallocene is preferred. Non-bridged metallocenes can also be applied to the production of the propylene polymer of the present invention, but in general, Answer-metallocenes having a crosslinking group are more excellent in thermal stability and the like, and are particularly preferable from an industrial point of view. .
The ans-metallocene having a transition metal-containing bridging group used in the present invention is a compound of a bridged Group 4 transition metal compound having a conjugated 5-membered ring ligand.₁-Metallocenes with symmetry. Such a transition metal compound is known, and it is also known to use it as a catalyst component for α-olefin polymerization.
[0012]
The metallocene compound of the component [a] is represented by the following general formula (1),₁-A compound having symmetry. Further, a plurality of metallocene compounds represented by the general formula may be used as a mixture.
Q (C₅H_4-aR² _a) (C₅H_4-bR³ _b) MXY (1)
In the general formula (1), Q is a bonding group bridging two conjugated 5-membered ring ligands, M is a transition metal of Group 4 of the periodic table, and X and Y are each independently hydrogen, halogen, C 1-20 hydrocarbon group, C 1-20 oxygen-containing hydrocarbon group, C 1-20 nitrogen-containing hydrocarbon group, C 1-20 phosphorus-containing hydrocarbon group or C 1-C 20 silicon-containing hydrocarbon groups represented by R²And R³Each independently represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen, a hydrocarbon group containing 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, or nitrogen. Shows a hydrocarbon group containing boron or a hydrocarbon group containing boron. In addition, two adjacent R²And / or R³May 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.
[0013]
Among the metallocene compounds represented by the above general formula (1), dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium is most preferred, and dichloro [dimethyl] is more preferred. Germylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl)] hafnium and dichloro [dimethylsilylene (2-methyl-1-indenyl) (2,4-dimethyl-4H-1-azulenyl) Hafnium is also a suitable catalyst.
[0014]
As the metallocene compound, a mixture of a plurality of compounds having different structures may be used, or two or more kinds may be used in combination. Further, a known solid catalyst containing titanium trichloride as a main component or a carrier-supported catalyst containing magnesium, titanium, and halogen as essential components can be used as an auxiliary. Further, at the end of the first stage of polymerization or before the start of the second stage of polymerization, the component [a] may be newly added and used.
[0015]
In the present invention, the cocatalyst used as the component [b] includes, as essential components, (1) an organic aluminum oxy compound, and (2) a reaction with the transition metal of the component [a] to convert the component [a] to a cation. Or at least one substance selected from the group consisting of (3) a Lewis acid, and (4) an ion-exchange layered compound or an inorganic silicate excluding silicate.
[0016]
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. Specifically, it is a trialkyl aluminum, a halogen or alkoxy-containing alkyl aluminum, or a hydrogen-containing organic aluminum compound. Of these, particularly preferred are trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum. These optional components may be used in combination of two or more. Further, an optional component [c] may be newly added after the start of the polymerization.
[0017]
The metallocene-based catalyst can be obtained by contacting the component [a], the component [b], and the optional component [c], but the contact 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.
At the time of contact of each component of the catalyst or after the contact, a solid of an inorganic oxide such as a propylene polymer, silica, or alumina may coexist or may be brought into 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. It is preferable to use those solvents which have been subjected to an operation for removing poisonous 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.
[0018]
The amount of each component of the catalyst is not particularly limited, but when an ion-exchange layered compound other than silicate or an inorganic silicate is used as the component [b], the component [a] per 1 g of the component [b] Is 0.0001 to 10 mmol, preferably 0.001 to 5 mmol, and the component [c] is 0 to 10,000 mmol, preferably 0.01 to 100 mmol. The atomic ratio between the transition metal in the component [a] and the aluminum in the component [c] is controlled to be 1: 0 to 1,000,000, preferably 1: 0.1 to 100,000. Is preferable in terms of polymerization activity and the like.
The catalyst thus obtained may be used after being washed with an inert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane, toluene, xylene, or may be used without washing. Good.
At the time of washing, a new component [c] may be used in combination as needed. It is preferable that the amount of the component [c] used at this time is 1: 0 to 10,000 in terms of the atomic ratio of the aluminum in the component [c] to the transition metal in the component [a].
[0019]
A catalyst obtained by preliminarily polymerizing propylene and washing as necessary can be used as the catalyst. 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 and xylene.
The polymerization reaction of propylene is carried out 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-mentioned inert hydrocarbon.
[0020]
Specifically, a propylene polymer is produced in the presence of the components [a] and [b], or the components [a], [b] and [c]. The polymerization temperature, polymerization pressure, and polymerization time are not particularly limited, but usually, optimal settings can be made from the following ranges in consideration of productivity and process capability. That is, the polymerization temperature is usually 0 to 150 ° C, preferably 20 to 100 ° C, and the polymerization pressure is 0.1 to 100 MPa, preferably 0.3 to 10 MPa, more preferably 0.5 to 4 MPa, and the polymerization time. Is selected from the range of 0.1 to 10 hours, preferably 0.3 to 7 hours, and more preferably 0.5 to 6 hours.
[0021]
The main chain composed of a propylene-based polymer is a homopolymer containing propylene as a monomer or a copolymer containing propylene as a main component. The propylene homopolymer means a polymer having a propylene content of substantially 100% by weight. The propylene-based copolymer is a copolymer containing a small amount of another monomer as a copolymer component. In the present invention, the propylene content is usually 95% by weight or more, preferably 99.5% by weight or more, and more preferably 99.9% by weight or more. When the propylene content is less than 95% by weight, it is difficult to grow the isotactic block, and the coating film adhesion to the substrate tends to decrease. The copolymer of propylene is characterized by increased solubility in solvents such as heptane and toluene as compared with the homopolymer.
[0022]
As the copolymerization component, monomers having an olefinic double bond, for example, ethylene, butene, pentene, hexene, octene, decene, butadiene, hexadiene, octadiene, cyclobutene, cyclopentene, cyclohexene, norbornene, norbornadiene, styrene and these Suitable derivatives can be selected from the derivatives. Of these, ethylene, butene, pentene, hexene, and octene are preferred, and ethylene and butene are more preferred.
[0023]
Characteristics (2) When dissolved in heptane at 98 ° C at a concentration of 10% by weight, the insoluble content is 1% by weight or less.
The solubility of the propylene-based polymer main chain produced by using the single-site catalyst described in the property (1) is much superior to that of ordinary high stereoregular isotactic polypropylene, and the 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. Preferably, it is 0.1% by weight or less, and more preferably, there is no insoluble component. When the amount of the insoluble component exceeds 1% by weight, the solubility is insufficient, so that the coating performance such as the roughened surface and the smoothness of the coating film tends to decrease, and the workability in the coating process tends to decrease.
As a measuring method, for example, a solution dissolved at a predetermined temperature and a predetermined concentration is filtered in the vicinity of the temperature (when the temperature is high, filtration under hot conditions) as follows, and the filter paper or SUS wire mesh used at that time (weight in advance is used). Is measured) and the weight of the insoluble matter is measured.
[0024]
Characteristics (3) Having a stereo block structure including both isotactic blocks and amorphous blocks
As described above in (1) and (2), the main chain composed of a propylene-based polymer is one produced with a specific catalyst and having a small amount of heptane-insoluble components. Among them,^ThirteenThose having the property (3) defined by the C-NMR spectrum are preferred. This property (3) is that the highly crystalline block and the highly amorphous block coexist in a good balance in the propylene polymer main chain, and the highly crystalline block has a structure that is rich in isotacticity. To indicate that In other words, if there are too many blocks with high crystallinity in the polymer, the solubility in the solvent will deteriorate, so the balance between blocks with high crystallinity and blocks with high amorphousness is important. As part of^ThirteenThe requirements defined by the C-NMR spectrum apply.
[0025]
In the present invention^ThirteenThe method for measuring the C-NMR spectrum is as follows.
A sample of 350 to 500 mg is completely dissolved in a 10 mmφ sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene is added as a lock solvent to homogenize, and the measurement is performed at 130 ° C. by a complete proton decoupling method. The measurement conditions are flip angle 90 °, pulse interval 5T.₁(T₁Is the longest value of the spin-lattice relaxation times of the methyl group). In the propylene-based polymer, the spin-lattice relaxation time of the methylene group and the methine group is shorter than that of the methyl group, so that the recovery of the magnetization of all carbons is 99% or more under this measurement condition. In order to improve the quantitative accuracy,^ThirteenIt is preferable to use an NMR apparatus having a resonance frequency of C nucleus of 125 MHz or more and perform integration for 20 hours or more.
[0026]
The chemical shift is defined as a methyl branch among ten kinds of pentads (mmmm, mmmr, rmmr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrm, mrrm) of a propylene unit chain composed of a head-to-tail (head-to-tail) bond. Are absolutely the same, that is, the chemical shift of the peak based on the methyl group of the third unit of 5 chains of propylene units represented by mmmm is set to 21.8 ppm, and other carbon peaks are set on the basis of this. Is determined. According to this criterion, for example, in the case of the other five chains of propylene units, the chemical shift of the peak based on the methyl group of the third unit is roughly as follows.

It should be noted that the chemical shifts of the peaks derived from these pentads have some fluctuation depending on the NMR measurement conditions, and that the peaks are not necessarily single peaks (single peaks), but rather complex cleavage patterns ( (split @ pattern) in many cases. In the present invention, the term isotactic block refers to a mmmm pentad, and the term amorphous block refers to all other pentads including at least one r dyad.
[0027]
Important features of the stereo block structure in the present invention are the following requirements (1) and (2).
{Circle around (1)} When the chemical shift of the peak attributable to the pentad represented by mmmm at the peak top is 21.8 ppm, the total of the peaks belonging to the above ten kinds of pentads appearing in the range of 19.8 to 22.2 ppm. Area S of peak having a peak top of 21.8 ppm with respect to area S₁Ratio (S₁/ S) is 10 to 60%
{Circle around (2)} The area of a peak (mmmr) having a peak top at 21.5 to 21.7 ppm is represented by S₂And S₁And S₂Is 4 + 2S₁/ S₂> 5 must be satisfied.
[0028]
S for S₁If the ratio is less than 10%, the crystallinity is too low, sufficient coating film adhesion cannot be obtained, and problems such as stickiness tend to occur. On the other hand, S for S₁If the ratio exceeds 60%, on the other hand, the crystallinity is too high, and the solubility in the solvent is reduced. S for S₁Is preferably 20 to 50%, more preferably 30 to 50%.
[0029]
S₁And S₂Are controlled so as to fall within the range defined by the above requirement (2). And the like. S₁, S₂The temperature dependency and the monomer concentration dependency depend on the catalyst used, and cannot be described unconditionally. Therefore, it is important to control these conditions based on the properties of the catalyst used. In the case where the control is performed by the structure of the polymerization catalyst, the structure of the ligand constituting the transition metal component is important. In particular, when a bridged metallocene is used, the substituent at the α-position is important with the bridgehead of the bridged group as a base point. In general, when there is a somewhat bulky substituent at the α-position, stereoselectivity is likely to be improved. Furthermore, when a bridged metallocene containing a ligand having a condensed ring such as an indenyl group or an azulenyl group is used, the structure of the substituent at the 4-position also has a significant effect on stereoselectivity. Generally, when there is a somewhat bulky substituent at the 4-position, stereoselectivity is likely to be improved. Conversely, by introducing a relatively small steric substituent at the 4-position, it is possible to effectively control the stereoselectivity and control the crystallinity of the resulting polymer.
[0030]
Further, the features of the stereo block structure of the present invention include the following requirements (3) to (9) and (10). All of these requirements are such that a highly crystalline block and a highly amorphous block coexist in the propylene polymer main chain, and the highly crystalline block has a structure that is rich in isotacticity. Is closely related to that.
{Circle around (3)} The area of a peak (rrrr) having a peak top at 20.3 to 20.5 ppm is represented by S₃And the area S₃Ratio (S₃/ S) is 0.2 to 3%
{Circle around (4)} The area of a peak (rmrm) having a peak top at 20.6 to 20.8 ppm is represented by S₄And the area S₄Ratio (S₄/ S) is 0.3 to 7%
▲ 5 ▼ S₄Is S₃Greater than,
▲ 6 ▼ S₁And S₂Is 25> 4 + 2S₁/ S₂Meet> 5
▲ 7 ▼ Area S₁Ratio (S₁/ S) is 30 to 50%
▲ 8 ▼ Area S₃Ratio (S₃/ S) is 1 to 3%
▲ 9 ▼ S₄Ratio (S₄/ S) is 4 to 7%,
(10) S₁And S₂Is 10> 4 + 2S₁/ S₂Satisfying> 7
[0031]
The propylene polymer main chain is 4 + 2S as per requirement (2).₁/ S₂> 5 is preferably satisfied. This relational expression is closely related to an index named Isotactic Block Index (BI) by Waymouth et al. (See Japanese Patent Application Laid-Open No. 9-510745). BI is an index indicating the stereoblock property of the polymer, and is defined as BI = 4 + 2 [mmmm] / [mmmr]. More specifically, BI represents the average chain length of an isotactic block having four or more propylene units (JW Collet et al., Macromol., 22, 3858 (1989); Randall, J. Polym. Sci. Polym. Phys. Ed., 14, 2083 (1976)). For a statistically perfect atactic polypropylene, BI = 5. Therefore, BI = 4 + 2 [mmmm] / [mmmr]> 5 means that the average chain length of the isotactic block contained in the polymer is longer than that of the atactic polypropylene.
[0032]
4 + 2S in requirements (2), (6) or (10)₁/ S₂Is not completely the same as the BI described above, but roughly corresponds to 4 + 2S₁/ S₂The requirement (2) of> 5 means that the polymer main chain of the present invention contains an isotactic block having a crystallizable chain length, unlike atactic polypropylene. Further, the presence of the atactic block means that, in other words, a block composed of a sequence in which stereospecificity is disturbed also exists in the main chain at the same time. As described above, the crystalline block and the amorphous block coexist in the main chain, and the crystalline block is formed from the isotactic block having a relatively long average chain length. This structure is unique in that it has a highly tactic structure.
[0033]
Property (4) When dissolved in toluene at 25 ° C. at a concentration of 10% by weight, the insoluble content is 1% by weight or less.
When dissolved in toluene (25 ° C.) at room temperature at a concentration of 10% by weight, those exhibiting the same level of solubility as the property (2) are preferable.
As a measuring method, for example, a solution dissolved at a predetermined temperature and a predetermined concentration is filtered in the vicinity of the temperature (when the temperature is high, filtration under hot conditions) as follows, and the filter paper or SUS wire mesh used at that time (weight in advance is used). Is measured) and the weight of the insoluble matter is measured.
When the toluene-insoluble content exceeds 1% by weight, the coating performance such as rough surface and smoothness of the coating film tends to decrease due to insufficient solubility, and furthermore, the storage stability of the solution state when used as a coating material. This is not preferable because the workability in the coating process is reduced due to the tendency to deteriorate and the workability in the coating process is reduced.
[0034]
Property (5) The weight average molecular weight Mw measured by GPC is 5,000 to 1,000,000
The weight-average molecular weight Mw measured by GPC (Gel Permeation Chromatography) is preferably 5,000 to 200,000. When Mw is smaller than 5,000, not only the film forming property after coating on a base material using a polar group-containing propylene polymer modified by graft copolymerization is deteriorated, but also stickiness is not preferred. . Further, when Mw exceeds 1,000,000, although there is no major problem with respect to film forming property and stickiness, the viscosity when the polar group-containing propylene-based polymer is dissolved in a solvent becomes too high, so that the production or the polar It is not preferable because handling of the group-containing propylene polymer solution causes inconvenience. In the present invention, the preferable range of the weight average molecular weight Mw is 5,000 to 1,000,000, more preferably 10,000 to 500,000, and further preferably 30,000 to 200,000.
[0035]
A conventionally known method can be used for controlling the molecular weight of the polymer. That is, there are 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. When a chain transfer agent is used, hydrogen is preferred.
The measurement of the molecular weight by GPC can be performed by a conventionally known method using a commercially available device using orthodichlorobenzene as a solvent and polystyrene as a standard sample.
Although there is no particular limitation on the molecular weight distribution, an excessively broad molecular weight distribution means that the content of the low molecular weight component is necessarily large, so it is better to avoid it. 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, it is preferably Mw / Mn <20, more preferably Mw / Mn <10, and most preferably Mw / Mn <5. Are preferably used.
[0036]
Property (6) No clear peak corresponding to a heat of crystal fusion measured by DSC of 1 J / g or more
In the propylene-based polymer main chain, if there is a clear peak corresponding to a heat of crystal fusion of 1 J / g, the solubility in a solvent decreases, which is not preferable. As a measuring method, a sample is melted at 200 ° C. for 3 minutes using a thermal analysis system (DSC), and then cooled at a rate of 10 ° C./min to 30 ° C. and heated at a rate of 10 ° C./min to 200 ° C. To obtain a melting curve. From the melting curve in the final heating step, it is evaluated whether or not a clear peak corresponding to 1 J / g or more exists in a temperature range of 50 to 160 ° C. When a peak is present, the heat of crystal fusion was determined from the endothermic peak area with the peak top temperature as the melting point.
[0037]
Characteristic (7) Almost completely soluble in orthodichlorobenzene (ODC) at 60 ° C
As described in the characteristic (3), the propylene-based polymer main chain has a characteristic that the stereoregularity distribution of the methyl group is moderate, so that the propylene-based polymer has relatively low crystallinity and excellent solubility in a solvent. Specifically, when a polymer is heated and eluted and separated with orthodichlorobenzene (ODC), substantially all components are eluted at 60 ° C. or lower. Components eluted at a temperature higher than 60 ° C. are components having a very 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 a high-potential component becoming an insoluble component and gelation tend to occur. Preferably, substantially all components are eluted at preferably 50 ° C. or lower, more preferably 40 ° C. or lower.
[0038]
The propylene-based polymer main chain has excellent solubility in organic solvents as described in the characteristics (2), (4), and (7). Organic solvents other than heptane, toluene and orthodichlorobenzene include aromatic hydrocarbons such as benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-octane and n-decane; cyclohexane; Cycloaliphatic hydrocarbons such as methylcyclohexane and dimethylcyclohexane, halogenated hydrocarbons such as methylene chloride, carbon tetrachloride, trichloroethylene, perchlorethylene and chlorobenzene, esters such as n-ethyl acetate and n-butyl acetate And ketones such as methyl isobutyl ketone and cyclohexanone, and polar solvents such as tetrahydrofuran and dimethyl sulfoxide. Among these, aromatic hydrocarbons or halogenated hydrocarbons are preferred, and toluene, xylene and chlorobenzene are particularly preferred.
These organic solvents are suitably used as a solvent for the modification reaction of the propylene-based polymer main chain or as a coating vehicle for dissolving the modification reaction product.
[0039]
Next, the polar group of the polar group-containing propylene polymer will be described. In the present invention, the “polar group” is a general term for a carboxyl group, a carboxylic acid anhydride group or a carboxylic acid ester group, and corresponds to a side chain of a propylene-based polymer containing a polar group.
As a method of introducing a polar group into the propylene polymer main chain, a method of graft copolymerizing a polymerizable monomer having a carboxyl group or the like is generally used.
[0040]
Examples of the polymerizable monomer having a carboxyl group to be graft-copolymerized include (meth) acrylic acid and its acid derivative, monoolefin dicarboxylic acid, its anhydride and its monoester, and at least one selected from these. Seeds are used. To be more specific, (meth) acrylic acid and its ester derivative include (meth) acrylic acid; (meth) acrylate monomers having an alkyl group having 1 to 12 carbon atoms, for example, (meth) acrylic acid Methyl, 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 .; an aryl group or arylalkyl having 6 to 12 carbon atoms The a (meth) monomers acrylic acid ester, for example (meth) acrylate, phenyl (meth) toluyl acrylate include benzyl (meth) acrylate and the like.
[0041]
Further, as other (meth) acrylic acid derivatives, monomers of a (meth) acrylate ester having a heteroatom-containing alkyl group having 1 to 20 carbon atoms, for example, hydroxyethyl (meth) acrylate, (meth) acrylic acid Dimethylaminoethyl, diethylaminoethyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, glycidyl (meth) acrylate Adduct of (meth) acrylate ethylene oxide; a monomer of a (meth) acrylate ester having a fluorine atom-containing alkyl group having 1 to 20 carbon atoms, such as trifluoromethylmethyl (meth) acrylate; ) -2-trifluoromethylethyl acrylate, (meth) acrylic acid-2 Perfluoroethyl ethyl, and the like; (meth) acrylamide monomers such as (meth) acrylamide, (meth) acrylic dimethyl amides.
[0042]
Examples of the monoolefin dicarboxylic acid include, for example, maleic acid, chloromaleic acid, citraconic acid, itaconic acid, glutaconic acid, 3-methyl-2-pentene diacid (3-methyl-2-pentene-1,5-dicarboxylic acid) ), 2-methyl-2-pentene diacid, 2-hexene diacid, and the like. Further, examples of the monoalkyl diolefin monocarboxylic acid ester include monoesters of an alkyl alcohol having 1 to 12 carbon atoms and these dicarboxylic acids. Specific examples of the alkyl alcohol include methyl alcohol, ethyl alcohol, and propyl alcohol. Butyl alcohol, pentyl alcohol, octyl alcohol, cyclohexyl alcohol and the like.
[0043]
When a coating film is formed using the polar group-containing propylene-based polymer of the present invention, from the viewpoint of coating film adhesion between the coating film and the substrate, these graftable polymerizable monomers containing a carboxyl group or the like. It is preferable that the solubility parameter is high, that is, an unsaturated carboxylic acid derivative component composed of an unsaturated carboxylic acid having 3 to 10 carbon atoms, an acid anhydride thereof and an ester thereof is preferable. Particularly, maleic anhydride is preferred.
[0044]
Among the polar group-containing propylene polymers used in the present invention, the modified polymer having a monoalkylene dicarboxylic acid monoalkyl ester as a graft copolymer unit is, for example, a monoolefin dicarboxylic acid monoalkyl ester graft-polymerized to a polymer. Polymerization method: It can be obtained by a method in which a monoolefin dicarboxylic acid or its anhydride is graft-copolymerized to a propylene-based polymer, and then one of the carboxylic acid groups is esterified with an alkyl alcohol.
[0045]
The graft amount of at least one type of graft copolymerized unit selected from polymerizable monomers containing a carboxyl group or the like in the polar group-containing propylene-based polymer, that is, the content in the modified polymer is used as a primer in the molded article. When applied, a coating film having a high adhesion of the paint is obtained, and the adhesion between the coating film and the molded article is good, and the appearance is good. Graft copolymerization so as to be about 15% by weight.
[0046]
As a method for graft-polymerizing a polymerizable monomer such as a monoolefin dicarboxylic acid, an anhydride thereof and a monoalkyl dicarboxylic acid monoalkyl ester to the propylene-based polymer, various known methods can be used. For example, a method in which a propylene-based polymer is dissolved in an organic solvent, a graft copolymerization reaction is performed by adding the polymerizable monomer to be grafted and a radical polymerization initiator, and heating and stirring; heating the propylene-based polymer. Graft polymerization by adding a polymerizable monomer and a radical polymerization initiator to be grafted to the melt and stirring the mixture; or stirring and grafting while supplying each component to an extruder. A method in which a propylene polymer powder is impregnated with a solution in which the polymerizable monomer to be grafted and the radical polymerization initiator are dissolved in an organic solvent, and then heated to a temperature at which the powder does not dissolve, and graft copolymerization is performed. And the like.
[0047]
At this time, the usage ratio of the radical polymerization initiator / the polymerizable monomer to be grafted is usually in the range of 1/100 to 3/5, preferably 1/20 to 1/2 in 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.
[0048]
The radical polymerization initiator used for the graft copolymerization can be appropriately selected from ordinary radical initiators and used, and examples thereof include organic peroxides and azonitrile. Examples of the organic peroxide 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 azonitrile include azobisbutyronitrile and azobisisopropylnitrile. Of these, benzoyl peroxide and dicumyl peroxide are preferred.
[0049]
When the graft copolymerization reaction is performed using an organic solvent, specific examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; and aliphatic hydrocarbons such as hexane, heptane, octane, and decane. Hydrocarbons; halogenated hydrocarbons such as trichloroethylene, perchlorethylene, chlorobenzene, o-dichlorobenzene and the like; among them, aromatic hydrocarbons or halogenated hydrocarbons are preferable, and toluene, xylene, chlorobenzene is particularly preferable. Is preferred.
[0050]
The modified propylene polymer of the present invention can also be dissolved in the same solvent as the above-mentioned solvent in which the propylene polymer before modification is soluble. The modified propylene polymer of the present invention has a solubility parameter of particularly 11 (cal / cm) among solvents.³)^1/2Since the following solvents have high solubility, this graft-modified propylene-based polymer has a solubility parameter of 11 (cal / cm).³)^1/2A composition dissolved at least 1 part by weight in the following solvent is effective as a coating composition.
[0051]
The solubility parameter is 11 (cal / cm³)^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 , Methylcyclohexane, cycloaliphatic hydrocarbons such as dimethylcyclohexane, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchlorethylene, chlorobenzene, halogenated hydrocarbons such as o-dichlorobenzene, n-methyl acetate, n-ethyl acetate, esters such as n-butyl acetate, methyl isobutyl ketone, ketones such as cyclohexanone, ethers such as tetrahydrofuran, etc., among these, aromatic hydrocarbons or halogenated hydrocarbons are preferred, Especially toluene, xylene, Rorubenzen is preferable.
[0052]
The coating composition of the present invention contains a coating component (A) and an organic solvent that dissolves the coating component (A) as main components, and various components such as an antioxidant, a weather resistance stabilizer, and a heat resistance inhibitor, if necessary. Stabilizer; may contain a coloring agent such as titanium oxide and organic pigment, and a conductivity-imparting agent such as carbon black and ferrite.
[0053]
Since the polar group-containing propylene polymer of the present invention is soluble in a solvent as described above, it can be applied to a molded article of an olefin polymer having crystallinity. Of these olefin polymers, a propylene polymer is preferably used. Also, molded articles made of polypropylene and synthetic rubber, polyamide resin, unsaturated polyester resin, polybutylene terephthalate resin, molded articles made of polycarbonate resin and the like, for example, molded articles such as bumpers for automobiles, and further for steel plate and electrodeposition treatment It can also be used for surface treatment of steel sheets and the like. Furthermore, a primer, a primer, an adhesive or the like containing polyurethane resin, fatty acid-modified polyester resin, oil-free polyester resin, melamine resin, epoxy resin, or the like as a main component is applied to the surface, and the paint or the like is adhered to the surface. Can be used to form a coating film having excellent sharpness, low-temperature impact resistance and the like.
[0054]
The coating film formed when the coating component (A) containing the polar group-containing propylene polymer of the present invention is applied to the substrate (B) exhibits good adhesion to the substrate, It can be used as a coating film adhesive resin for materials. In order to obtain good adhesion to the substrate, it is preferable to heat after the application. The heating temperature is not particularly limited, but is preferably 50 to 150 ° C., more preferably 60 to 130 ° C. in consideration of practicality. The method of application is not particularly limited, and a conventionally known method such as a method of applying with a spray, a method of applying with a roller, and a method of applying with a brush can be used.
[0055]
The coating material (A) containing the polar group-containing propylene polymer of the present invention is applied, and a coating is formed on the surface of the formed article by a method such as electrostatic coating, spray coating, or brush coating. Can be applied.
The application of the paint may be performed by a method of applying an undercoat and then overcoating. After applying the paint, the coating is cured according to a usual method of heating with electric heat, infrared rays, high frequency, etc., to obtain a molded article having a desired coating on the surface. 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.
[0056]
The coating component (A) containing the polar group-containing propylene polymer can be used as a primer component. That is, it can be applied to the surface of the base material (B) and used as a primer component for improving the coating properties such as the adhesion of the paint to the surface, water resistance and gasoline resistance.
Specifically, an acrylic resin and / or a polyester resin, a polyurethane-modified polypropylene resin, and the polar group-containing propylene-based polymer can be applied to the substrate (B). Such a primer does not contain a halogen such as chlorine, has no stickiness, is excellent in solubility, and has excellent compatibility with an acrylic resin and a polyester resin. It is possible to form a coating film having high water resistance and gasohol resistance while maintaining the property.
[0057]
The coating component (A) containing the polar group-containing propylene polymer can be used as a base color component that does not require application of a primer component. That is, when applied to the surface of the base material (B), no surface treatment or cleaning of the base material is required, no primer coating is required, and a coating film having good water resistance and weather resistance is formed by a single coating. It can be used as a possible base color component.
[0058]
Such a base color does not contain halogen such as chlorine, has no stickiness, is excellent in solubility, and has excellent compatibility with acrylic polyol and polyester polyol, and is a crystalline propylene-based polymer as a base material. It maintains good adhesion and coating properties to polyolefins, etc., and is capable of forming coatings with high durability and chemical resistance. A coating film having water resistance and weather resistance can be formed.
[0059]
In addition, it is also possible to further improve the adhesion of the coating film by applying a primer component to the substrate.
[0060]
<II> Base material (B)
(II-1) Crystalline polypropylene component
The substrate (B) used in the present invention is a molded article of a resin composition comprising crystalline polypropylene and an inorganic filler component. Here, the crystalline polypropylene is a propylene homopolymer and / or a propylene / ethylene block copolymer composed of a propylene homopolymer part and a propylene / ethylene copolymer part.
[0061]
The MFR of the propylene homopolymer and the propylene / ethylene block copolymer is preferably 2 g / 10 min or more, more preferably 10 to 300 g / 10 min, and particularly preferably 25 to 200 g / 10 min.
If the MFR of the propylene / ethylene block copolymer and the propylene homopolymer is less than 2 g / 10 minutes, the flowability tends to be insufficient. On the other hand, when it is extremely high, it is not preferable because the mechanical properties are inferior.
The MFR of the propylene / ethylene block copolymer may be adjusted at the time of polymerization or may be adjusted with an organic peroxide such as diacyl peroxide or dialkyl peroxide after polymerization.
[0062]
The propylene / ethylene block copolymer is a propylene / ethylene block copolymer containing a crystalline polypropylene part (a unit part) and an ethylene / propylene random copolymer part (b unit part).
The a unit is usually obtained by homopolymerization of propylene, or in some cases, by copolymerizing propylene with a small amount of another α-olefin.
The MFR of the polypropylene homopolymer in the unit a is preferably 10 g / 10 min or more, more preferably 15 to 500 g / 10 min, further preferably 20 to 400 g / 10, and particularly preferably 40 to 300 g / 10. Minutes.
If the MFR of the propylene homopolymer part (a unit part) of the propylene / ethylene block copolymer is less than 10 g / 10 minutes, the flowability tends to be insufficient. Conversely, if the MFR is extremely high, the mechanical properties tend to be poor.
[0063]
On the other hand, the b unit is a rubber-like component obtained by random copolymerization of propylene and ethylene.
The propylene content of the propylene / ethylene copolymer part (b unit part) is preferably 30 to 85% by weight, more preferably 40 to 80% by weight, and further preferably 50 to 75% by weight. When the propylene content of the copolymer part is out of the above range, the dispersibility tends to deteriorate and the glass transition temperature increases, and the impact properties tend to deteriorate.
The propylene content of the propylene / ethylene copolymer part can be adjusted by controlling the concentration ratio of propylene and ethylene during the polymerization of the propylene / ethylene copolymer part.
[0064]
The molecular weight of the propylene / ethylene copolymer portion is not particularly limited, but the weight average molecular weight (Mw) is preferably 200,000 to 3,000,000, more preferably, in consideration of dispersibility and impact resistance. It is 300,000 to 2.5 million, more preferably 400,000 to 2,000,000.
[0065]
The amounts of the a unit and the b unit are not particularly limited, but generally the a unit is preferably 95% by weight or less, more preferably 50 to 95% by weight, and still more preferably 60 to 90% by weight of the total polymerization amount. % And the b unit are adjusted so as to be preferably 5% by weight or more, more preferably 5 to 50% by weight, and still more preferably 10 to 40% by weight of the total polymerization amount.
If the amount of the b unit is less than the above range, the impact resistance expected as a block copolymer tends to be insufficient, and if it exceeds the above range, rigidity, strength and heat resistance tend to be insufficient. There is not preferred.
[0066]
In the present invention, the amount of the copolymer part is measured by a temperature-elution fractionation method. That is, the unit a does not elute below 100 ° C. in the extraction with orthodichlorobenzene, but the unit b easily elutes. Therefore, the composition of the propylene / ethylene block copolymer is determined by the above-mentioned extraction analysis using ortho-dichlorobenzene with respect to the polymer after production.
The amount of the propylene / ethylene copolymer part can be adjusted by controlling the ratio of the polymerization amount of the propylene homopolymer part to the polymerization amount of the propylene / ethylene copolymer part by the polymerization time or the like.
[0067]
The method for producing the propylene homopolymer and / or the propylene / ethylene block copolymer composed of the propylene homopolymer part and the propylene / ethylene copolymer part is not particularly limited, and may be any of known methods and conditions. Is selected as appropriate. As a polymerization catalyst for propylene, a highly stereoregular catalyst is usually used. For example, a catalyst obtained by reducing titanium tetrachloride with an organoaluminum compound, and further treating the titanium trichloride composition with various electron donors and electron acceptors, and combining an organoaluminum compound and an aromatic carboxylic acid ester ( JP-A-56-100806, JP-A-56-120712, and JP-A-58-104907), and a support type in which titanium tetrachloride and various electron donors are brought into contact with magnesium halide. Catalysts (see JP-A-57-63310, JP-A-63-43915 and JP-A-63-83116) and the like can be exemplified. Further, metallocene catalysts such as those disclosed in WO-91 / 04257 are exemplified. The catalyst referred to as a metallocene catalyst may not contain alumoxane, but is preferably a catalyst obtained by combining a metallocene compound and alumoxane, that is, a so-called Kaminsky catalyst.
[0068]
Propylene-ethylene block copolymer, in the presence of the above catalyst, by applying a production process such as a gas phase polymerization method, a liquid phase bulk polymerization method, a slurry polymerization method, polymerizes propylene alone, and then propylene and ethylene Can be obtained by random polymerization. In order to obtain a propylene / ethylene block copolymer having the above-mentioned melting characteristics (MFR) and the like, it is preferable to carry out multistage polymerization by a slurry method or a gas phase fluidized bed method. It can also be obtained by a method in which propylene homopolymerization is carried out in multiple stages, followed by random polymerization of propylene and ethylene. In the production of a propylene / ethylene block copolymer having a large number of b units, a gas phase fluidized bed method is particularly preferred.
[0069]
The propylene homopolymer is obtained by polymerizing propylene alone by applying a production process such as a gas phase polymerization method, a liquid phase bulk polymerization method, or a slurry polymerization method in the presence of the above catalyst. In order to obtain a propylene homopolymer having the above-mentioned melting characteristics (MFR), it is preferable to carry out multistage polymerization by a slurry method or a gas phase fluidized bed method.
[0070]
(II-2) Elastomer component
Elastomer components used in the propylene resin composition constituting the base material (B) of the present invention include ethylene / α-olefin random copolymer rubber, ethylene / α-olefin / non-conjugated diene copolymer rubber, and styrene-containing thermoplastic resin. Elastomers and the like. Specific examples include ethylene / α-olefins such as ethylene / propylene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1-hexene copolymer rubber, and ethylene / 1-octene copolymer rubber. Ethylene / α-olefin / non-conjugated diene copolymer rubber such as copolymer rubber, ethylene / propylene / ethylidene norbornene copolymer rubber (EPDM), hydrogenated product of styrene-butadiene-styrene triblock (SEBS) And styrene-containing thermoplastic elastomers such as hydrogenated styrene-isoprene-styrene triblock (SEPS). These elastomers can be manufactured as described below.
[0071]
The melt flow rate (at 230 ° C., 2.16 kg load) of these elastomer components is preferably 0.5 to 150 g / 10 min, more preferably 0.1 to 150 g / 10 minutes in consideration of the automotive exterior material which is the main application of the present invention. Those having a range of 7 to 100 g / 10 minutes, particularly preferably 0.7 to 80 g / 10 minutes, are preferred.
The elastomer component need not be one kind, and may be a mixture of two or more kinds.
[0072]
[Ethylene / α-olefin random copolymer rubber]
The content of the α-olefin unit in the ethylene / α-olefin random copolymer rubber is usually 15 to 70% by weight, preferably 20 to 55% by weight. If the content of the α-olefin unit is less than the above range, the impact strength is inferior.On the other hand, if the content is too large, not only does the rigidity decrease, but also it becomes difficult to maintain the shape of the elastomer in the form of pellets. Each of these is unsuitable because the production handling during production is significantly reduced.
[0073]
Examples of the α-olefin include those having 3 to 20 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1- Decene, 1-undecene, 1-dodecene and the like can be mentioned. Among them, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene are preferred.
[0074]
The ethylene / α-olefin random copolymer rubber preferably has an MFR (230 ° C., load: 21.18 N) of usually 0.01 to 100 g / 10 min, particularly preferably 0.1 to 100 g / 10 min. Further, the density is usually 0.85 to 0.90 g / cm³, Especially 0.86-0.89 g / cm³Are preferred.
[0075]
When the MFR is less than 0.01 g / 10 minutes, sufficient dispersion cannot be obtained at the time of kneading when forming the resin composition, and the impact strength is reduced. On the other hand, when the MFR exceeds 100 g / 10 minutes, the toughness of the copolymer rubber itself is insufficient, and the impact strength is also lowered. The density is 0.90 g / cm³If the value exceeds, the impact strength becomes inferior, and 0.85 g / cm³If it is less, it becomes difficult to pelletize itself. Further, these are preferably manufactured using a vanadium compound-based catalyst described later or a metallocene-based catalyst as described in WO-91 / 04257.
[0076]
Here, the α-olefin content is a value measured according to a conventional method such as an infrared spectrum analysis method or a 13C-NMR method. The density is a value measured according to JIS-K7112.
[0077]
Examples of the ethylene / α-olefin random copolymer rubber include polymerization methods such as a gas-phase fluidized-bed method, a solution method, a slurry method, and a high-pressure polymerization method, and a small amount of, for example, dicyclopentadiene, ethylidene norbornene, or the like. May be copolymerized.
[0078]
Examples of the polymerization catalyst include titanium compounds such as titanium halides, vanadium compounds, organoaluminum-magnesium complexes such as alkylaluminum-magnesium complexes and alkylalkoxyaluminum-magnesium complexes, and organometallic compounds such as alkylaluminum or alkylaluminum chloride. And a metallocene catalyst as disclosed in WO-91 / 04257 and the like. The catalyst referred to as a metallocene catalyst may not contain alumoxane, but is preferably a catalyst obtained by combining a metallocene compound and alumoxane, that is, a so-called Kaminsky catalyst.
As the polymerization method, polymerization can be performed by applying a production process such as a gas-phase fluidized bed, a solution method, and a slurry method.
[0079]
Various ethylene / α-olefin random copolymer rubbers are commercially available. For example, as ethylene / propylene rubber, JSR @ EP02P, EP07P, EP912P, EP57P, etc. (all from JSR), Tuffmer P0180, P0480, P0680, etc. (all from Mitsui Chemicals), and as ethylene / butene rubber, JSR @ EBM2041P, EBM2011P, EBM3021P (Manufactured by JSR Corporation), Toughmer A4085, A4090, A20090 (manufactured by Mitsui Chemicals, Inc.), and other ethylene / 1-octene rubbers such as EG8150, EG8100, EG8200 (manufactured by DuPont Dow Elastomer Co., Ltd., trade name " Engage ”) is commercially available.
[0080]
[Styrene-containing thermoplastic elastomer]
The styrene-containing thermoplastic elastomer used in the present invention contains 5 to 60% by weight, preferably 10 to 30% by weight of a polystyrene part. If the polystyrene content is outside the above range, the impact resistance becomes insufficient. The MFR (at 230 ° C. under a load of 21.18 N) in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min is used. If the MFR is outside the above range, the impact resistance will also be insufficient.
[0081]
Specific examples of such a styrene-containing thermoplastic elastomer include styrene / ethylene / butylene / styrene block copolymer (SEBS). This is a thermoplastic elastomer composed of polystyrene block units and polyethylene / butylene rubber block units. In such SEBS, a polystyrene block unit, which is a hard segment, forms a physical crosslink (domain) and exists as a bridge point of a rubber block unit, and a rubber block unit existing between the polystyrene block units is a soft segment. And has rubber elasticity.
It is desirable that the segment ratio of SEBS contains polystyrene units in an amount of 10 to 40 mol%. The content of units derived from styrene is determined by infrared spectrum analysis,^ThirteenIt is a value measured by a conventional method such as a C-NMR method.
[0082]
This SEBS is specifically obtained by a known method described in, for example, Japanese Patent Publication No. 60-57463.
These styrene-containing thermoplastic elastomers can be produced by a general anionic living polymerization method. These include a method of successively polymerizing styrene, butadiene, and styrene to produce a triblock, followed by hydrogenation (a method of producing SEBS), and a method of first producing a diblock copolymer of styrene-butadiene, followed by a cup. There is a method in which a triblock is formed using a ring agent and then hydrogenated. By using isoprene instead of butadiene, a hydrogenated product of styrene-isoprene-styrene triblock (SEPS) can also be produced.
As such SEBS, commercially available products such as Kraton G1650, G1652, G1657 (manufactured by Clayton Polymers), and Tuftec (manufactured by Asahi Kasei Corporation) can be used.
[0083]
SEBS used in the present invention is generally known as a hydrogenated product of SBS (styrene / butadiene / styrene block copolymer), which is a styrene / butadiene block copolymer. In the present invention, SBS and other styrene / conjugated diene copolymers or completely or incomplete hydrides thereof may be used together with SEBS.
[0084]
Specific examples of such a styrene / conjugated copolymer include SBR (styrene / butadiene random copolymer), SBS, PS-polyisobutylene block copolymer, and SIS (styrene / isobutylene / styrene block copolymer). And SIS hydrogenated product (SEPS). More specifically, Kraton (Kraton: manufactured by Clayton Polymers), Calibrex TR (manufactured by Clayton Polymers), Sorbrene (manufactured by Philippe Petro Rifam), Eurobren SOLT (manufactured by Anich), Toughbren (manufactured by Asahi Kasei Corporation) ), Sorbrene-T (manufactured by Nippon Elastomer Co., Ltd.), JSRTR (manufactured by JSR Corporation), Electrified STR (manufactured by Denki Kagaku), Quintac (manufactured by Zeon Corporation), Clayton G (manufactured by Clayton Polymers), Toughtec (Asahi Kasei Corporation) Manufactured).
[0085]
In the present invention, as the elastomer component, the above-mentioned ethylene / α-olefin random copolymer rubber and styrene-containing thermoplastic elastomer may be used alone or in an appropriate combination.
[0086]
(II-3) Inorganic filler component
The inorganic filler component of the present invention is used for improving mechanical properties such as flexural modulus and rigidity.
Specifically, plate-like filler such as talc, mica, montmorillonite, short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber, zonolite and other fibrous filler, potassium titanate, magnesium Needle-like (whisker) fillers such as oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide, etc., precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. It is a granular filler or a balun-like filler such as a glass balloon.
Among them, talc, mica, glass fiber, and whisker are preferable in terms of balance between physical properties and cost. Hereinafter, particularly preferred fillers such as talc, glass fiber, mica, and whisker will be described in detail.
[0087]
(1) Talc
The average particle size of talc is usually 10 μm or less, preferably 0.5 to 8 μm, and more preferably 1 to 7 μm.
The average particle diameter is calculated by a laser diffraction method (for example, LA920W manufactured by HORIBA, Ltd.) or a liquid layer sedimentation type light transmission method (for example, a CP type manufactured by Shimadzu, etc.). Can be determined from the particle size value of The value of the present invention is an average particle size value measured by the former method.
These talcs can be obtained by further finely classifying those obtained by mechanically pulverizing naturally produced products. Moreover, once the coarse classification is performed, the classification may be further performed.
Examples of the method of mechanical pulverization include a method using a pulverizer such as a jaw crusher, a hammer crusher, a roll crusher, a screen mill, a jet pulverizer, a colloid mill, a roller mill, and a vibration mill.
These pulverized talc may be wet-processed once or repeatedly in a device such as a cyclone, a cyclone air separator, a micro separator, a cyclone air separator, a sharp cut separator, or the like, in order to adjust the average particle size shown in the present invention. Dry classify. When producing the talc of the present invention, it is preferable to perform a classification operation using a sharp cut separator after pulverizing to a specific particle size.
These talc, for the purpose of improving the adhesiveness or dispersibility with the polymer, various organic titanate-based coupling agent, organic silane coupling agent, unsaturated carboxylic acid, or a modified polyolefin grafted with an anhydride thereof, Those surface-treated with fatty acids, fatty acid metal salts, fatty acid esters and the like may be used.
[0088]
(2) Glass fiber
As glass fibers, glass chopped strands are generally used, and the length of these chopped strands is usually 3 to 50 mm, and the fiber diameter is about 3 to 25 μm, preferably 8 to 14 μm. It is preferable to use a glass chopped strand which has been subjected to surface modification with a silane compound and surface treatment with a sizing agent such as polyvinyl alcohol, polyvinyl acetate, polyurethane, epoxy resin or olefin component.
Examples of the silane compound include vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (2,4-epoxycyclohexyl) ethoxymethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, and the like. Can be.
On the other hand, examples of the olefin-based component as the sizing agent include unsaturated carboxylic acid-modified polyolefins and polyolefin low-molecular-weight products. Unsaturated carboxylic acids include those described above. Examples of polyolefin low-molecular weight compounds include polyethylene resins, polypropylene resins, propylene / ethylene block copolymers, ethylene / butylene copolymers, and ethylene / pentene copolymers. Molecular weight substances can be mentioned.
In the present invention, if necessary, an unsaturated carboxylic acid and / or a derivative thereof is blended for the purpose of interfacial adhesion between the polypropylene resin and the glass fiber in order to improve the mechanical strength. Although it hardly contributes to the dispersibility of the glass fiber in the present invention, it is necessary to mix it in order to further improve the mechanical strength. As these unsaturated carboxylic acids and / or derivatives thereof, for example, maleic acid, maleic anhydride, acrylic acid, methacrylic acid, itaconic acid, itaconic anhydride, crotonic acid, citraconic acid, angelic acid, sorbic acid, Examples thereof include metal salts, amides, imides and esters of these unsaturated carboxylic acids. These are preferably used alone or a polyolefin resin modified by a derivative thereof is used. Particularly, a resin modified using a polypropylene resin as a base is preferable, and a resin having a modification ratio of 0.1 to 10% by weight is preferably used. .
[0089]
(3) Mica
Mica preferably has an average particle size of 2 to 100 μm and an average aspect ratio of 10 or more, and particularly preferably has an average particle size of 2 to 80 μm and an average aspect ratio of 15 or more. When the average particle size of mica is larger than the above range, the scratch resistance, appearance and impact strength of the molded product are inferior, and when the size is smaller than the above range, the dispersion is rather deteriorated, and the scratch resistance and appearance of the molded product, Impact strength decreases. Further, the mica may be any of so-called white mica, gold mica, black mica, etc. Among them, gold mica and white mica are preferable, and white mica is particularly preferable.
The method for producing mica is not particularly limited, and it is produced by a method according to the above-described talc. Among them, those produced by dry pulverization / wet classification or wet pulverization / wet classification are preferable, and in particular, wet pulverization / wet classification The system is preferred. These fillers may be surface-treated with a surfactant, a coupling agent or the like. The surface-treated filler has the effect of further improving the strength and heat-resistant rigidity of the molded article.
[0090]
(II-4) Physical properties of polypropylene resin composition
The mechanical properties of the polypropylene resin composition constituting the base material (B) in the present invention are such that the flexural modulus is preferably 500 MPa or more, more preferably 800 to 10000 MPa, still more preferably 1000 to 6000 MPa, and particularly preferably 1200 to 3000 MPa. It is. If it is outside the above range, the feeling of rigidity is remarkably inferior, and it is not suitable as a structural material.
The IZOD impact strength is preferably 5 kJ / m²Above, more preferably 10 to 100 kJ / m²And more preferably 15 to 80 kJ / m.²And particularly preferably 20 to 60 kJ / m.²Is preferable. If it is less than the above range, the impact resistance is remarkably poor, and it is not suitable as a structural material.
[0091]
Even when the base material (B) of the present invention contains zinc white, a pigment and the like, a coating film having particularly good adhesion can be formed.
In addition, the base material (B) of the present invention can contain, in addition to the above, any additive or compounding component as long as the effects of the present invention are not significantly impaired.
Specifically, pigments for coloring, phenol-based, sulfur-based, phosphorus-based antioxidants, antistatic agents, light stabilizers such as hindered amines, ultraviolet absorbers, various nucleating agents, dispersants, and neutralizing agents And a compounding material such as a foaming agent, a copper damage inhibitor, a lubricant, a flame retardant, various resins other than the propylene-based block copolymer, and various rubber components such as polybutadiene and polyisoprene.
[0092]
Specifically, pentaerythyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxylphenyl) propionate] Phenolic antioxidants, such as tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-diphenyl) Phosphorus-based antioxidants such as -t-butylphenyl) 4,4'-biphenylenediphosphonite, dimyristyl-3, '-Thiodipropionate, distearylthiodipropionate, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t- UV absorbers such as butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-n-octyloxybenzophenone, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} (2,2,6,6-tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}], bis ( -Octyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate , Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 2,4-di-t-butylphenyl-3,5-di- Examples include weather stabilizers such as t-butyl-4-hydroxybenzoate and antistatic agents such as glyceryl monostearate.
[0093]
(II-5) Method for producing polypropylene-based resin composition
The method for producing the propylene-based resin composition constituting the base material (B) of the present invention is not particularly limited, and if necessary, the above components are blended into the propylene-based resin by a conventionally known method, and then mixed and melted. It can be manufactured by kneading.
The compounding of the resin composition constituting the base material (B) is usually 51 to 99 parts by weight, preferably 55 to 98 parts by weight, more preferably 65 to 95 parts by weight of the crystalline polypropylene, and usually 1 to 95 parts by weight of the elastomer component. ４９49 parts by weight, preferably 2-45 parts by weight, more preferably 5-35 parts by weight.
If the content of the crystalline polypropylene is less than the above range, tensile elongation and impact resistance, particularly low-temperature impact resistance, will be insufficient, and if it exceeds the above range, rigidity and heat resistance will be insufficient. If the content of the elastomer component is less than the above range, impact resistance, particularly low-temperature impact resistance, will be insufficient, and if it exceeds the above range, rigidity and heat resistance will be insufficient.
[0094]
The blending of the propylene resin composition constituting the base material (B) is such that the inorganic filler component is preferably 1 to 80 parts by weight, more preferably 2 to 70 parts by weight, based on 100 parts by weight of the total of the crystalline polypropylene and the elastomer component. Parts, more preferably 3 to 60 parts by weight.
If the content of the inorganic filler component is less than the above range, rigidity and heat resistance are insufficient, and if it exceeds the above range, tensile elongation, impact resistance, particularly low-temperature impact resistance is insufficient, and specific gravity increases. As a result, the weight of the molded body increases.
[0095]
In the present invention, the essential components described above, that is, the crystalline polypropylene and the elastomer component, and the inorganic filler component and optional components used as needed are blended in the above blending ratio, and a single-screw extruder, a twin-screw extruder. Kneading and granulating using an ordinary kneading machine such as a kneader, a Banbury mixer, a roll mixer, a Brabender plastograph, a kneader, etc., to obtain a propylene-based resin composition constituting the base material (B) of the present invention. .
[0096]
In this case, it is preferable to select a kneading / granulating method capable of improving the dispersion of each component, and usually, a twin-screw extruder is used. In the kneading / granulation, the compound of each of the above components may be kneaded at the same time, or the components are divided and kneaded in order to improve the performance, that is, for example, first, one part of the propylene-based block copolymer is kneaded. It is also possible to employ a method in which part or all of the mixture and the inorganic filler are kneaded, and then the remaining components are kneaded and granulated.
[0097]
The substrate (B) of the present invention can be obtained by molding using a propylene-based resin composition comprising a crystalline polypropylene component and an elastomer component by various known methods. For example, injection molding (including gas injection molding), compression molding, injection compression molding (press injection), extrusion molding, hollow molding, rotational molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, etc. Various molded articles can be obtained by molding. Among these, a molded article obtained by injection molding, compression molding, or injection compression molding is preferable.
[0098]
Since the polypropylene-based molded article of the present invention does not contain halogen such as chlorine, it has a low environmental load, is excellent in coating film adhesion, and has a balance of physical properties excellent in rigidity and impact resistance.
Specifically, in the field of various industrial parts, especially thinned, highly functional, large-sized various molded products, such as bumpers, instrument panels, trims, garnishes, air cleaner cases, heater cases, fan shrouds, lamps, etc. Home appliance parts such as automobile parts, TV cases, washing machine tubs, refrigerator parts, air conditioner parts, vacuum cleaner parts, toilet seat parts such as toilet seats, toilet seat lids, water tanks, bathtubs, bathroom walls and ceiling parts, It has sufficient performance for practical use as a molding material for various industrial parts such as parts around the bathroom such as drain pans.
[0099]
【Example】
Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited by these Examples unless departing from the gist thereof.
In the following Examples and Comparative Examples, physical properties and performances of polymers were measured as follows. In each example, the catalyst synthesis step and the polymerization step were all performed under a purified nitrogen atmosphere, and the solvent was dehydrated with a molecular sieve (MS-4A) and then deaerated by bubbling with purified nitrogen before use.
[0100]
(1) Molecular weight
A chromatographic analyzer (GPC150CV, manufactured by Waters) was used. Ortho-dichlorobenzene was used as a solvent, and the measurement temperature was 135 ° C. For molecular weight calculation, commercially available monodisperse polystyrene was used as a standard sample, and a calibration curve relating to retention time and molecular weight was created from the viscosity formula of the polystyrene standard sample and polypropylene to calculate the molecular weight.
[0101]
(2) Pentad of propylene unit chain
A sample of 350 to 500 mg is completely dissolved in a 10 mmφ sample tube for NMR using about 2.2 ml of orthodichlorobenzene. Next, about 0.2 ml of deuterated benzene is added as a lock solvent to homogenize, and the measurement is performed at 130 ° C. by a complete proton decoupling method. The measurement conditions are a flip angle of 90 ° and a pulse interval of 5T1 or more (T1 is the longest value of the spin-lattice relaxation time of the methyl group). In the propylene polymer, the spin-lattice relaxation time of the methylene group and the methine group is shorter than that of the methyl group, so that under these measurement conditions, the recovery of the magnetization of all carbons is 99% or more. In order to improve the quantitative accuracy,^ThirteenIt is preferable to use an NMR apparatus having a resonance frequency of C nucleus of 125 MHz or more and perform integration for 20 hours or more.
[0102]
(3) Crystallinity
It was measured by wide-angle x-ray crystal diffraction and determined by the multiple peak separation method (symmetric transmission method (2θ / θ = 5 to 60 °, 0.1 ° / step)).
(4) Melting point and heat of crystal fusion
The melting point Tm and heat of crystal fusion were determined by the following method using a thermal analysis system TA2000 manufactured by DuPont.
A sample (about 5 to 10 mg) is precisely weighed and placed in a dedicated aluminum pan. After melting 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 a rate of 10 ° C./min to obtain a melting curve. Was determined as the melting point. The calorific value calculated from the area surrounded by the peak and the baseline divided by the weight of the sample is defined as the heat of crystal fusion (J / g). When there is no clear peak corresponding to 1 J / g or more in the temperature range of 50 to 160 ° C. in the melting curve, n. d. Expressed as
[0103]
(5) Elevated temperature elution fractionation with orthodichlorobenzene
Using an elution fractionation apparatus (CFC-T-102L manufactured by Mitsubishi Chemical Corporation), it was determined as a 100% elution temperature. Elution fractionation was started at 5 ° C., and the temperature was measured at 4 to 5 ° C. increments.
(6) Solubility test
A sample is charged into a solvent (heptane or toluene) at a concentration of 10% by weight in a separable flask equipped with stirring blades, and heptane is dissolved at an external temperature of 110 ° C and toluene is heated to an external temperature of 120 ° C. After the internal temperature becomes constant, stirring is continued for 2 hours. Heptane is quickly cooled to the temperature at the time of boiling, and toluene is naturally cooled to 30 ° C., and then the solution temperature is adjusted to 25 ° C., and the solution is allowed to stand for 1 hour. What was left in the wire net was made into an insoluble matter, and what passed as a solution was made into a soluble matter. Weigh and calculate the fraction of insolubles.
Evaluation criteria: Insoluble content 1% by weight or less
×: 1% by weight or more of insoluble matter
[0104]
(7) Non-tack property
The evaluation was made according to the following criteria by a finger tackiness test.
Evaluation criteria: excellent non-tack property
△: slightly tacky
×: With tackiness
(8) Flexural modulus
Using an injection molding machine with a mold clamping pressure of 100 tons, a test piece of 90 mm × 10 mm × 3 mm was molded by injection molding at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C., and the obtained injection molded piece was subjected to JIS- It was measured at 23 ° C. (unit: Mpa) at a test speed of 2 mm / min in accordance with K7203.
(9) Izod (IZOD) impact strength
The test piece was measured at 23 ° C in accordance with JIS-K7110 (unit: kJ / m).²)did.
[0105]
(10) Interlayer adhesion test
Test pieces of 150 mm × 70 mm × 2 mm were molded from polypropylene manufactured by Nippon Polychem Co., Ltd. using an injection molding machine (IS170 manufactured by Toshiba Machine Co., Ltd.) at a setting temperature of 220 ° C.
After forming a coating film by the method described below, a cross-cut test piece was prepared according to the cross-cut test method described in JIS-K5400, and an adhesive tape (Nichiban Co., Ltd., Cellotape) Is stuck on the grid of the test piece, and then quickly pulled in the vertical direction to be peeled off, and the number of grids that were not peeled out of the 100 grids was counted, and the “number of remaining grids / 100 grids” ".
(11) Water resistance test
A coating film is formed on a substrate using the coating component (A) or another polymer as a primer, and a base coat is applied and baked on the coating film. Immerse in it for 10 days. Thereafter, after the surface moisture was dried, an adhesion test according to a grid test (JIS-K5400) was performed in the same manner as the interlayer adhesion test.
[0106]
(12) Gasohol resistance test
A coating film is formed on a substrate using the coating component (A) or another polymer as a primer, and a base coat is applied over the coating film and baked. It was immersed in a gasoline: ethanol = 9: 1 mixed solution and the time required for significant peeling of the coating film was measured.
[0107]
[Production Example 1]
(1) Synthesis of dichloro [dimethylsilylene (cyclopentadienyl) (2,4-dimethyl-4H-1-azulenyl) hafnium
(1) Synthesis of -1 ligand
After dissolving 2-methylazulene (4.01 g) in tetrahydrofuran (56 ml) and cooling to 0 ° C. in an ice bath, 24.8 ml of a diethyl ether solution of methyllithium (1.14 mol / l) is added dropwise at the same temperature. did. After the addition, the ice bath was removed and the mixture was stirred for 2 hours. This solution was slowly added dropwise to a solution of dimethylsilyl dichloride (34.0 ml, @ 0.280 mol) in tetrahydrofuran (140 ml) cooled to 0 ° C in an ice bath. After completion of the dropwise addition, the mixture was stirred for 3 hours with the ice bath removed, 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 the addition was completed, the mixture was stirred at room temperature for 12 hours. After completion of the stirring, water was added, and the desired compound was extracted with diethyl ether. The extract solution was dehydrated with magnesium sulfate and then dried to obtain a crude product of the target ligand. The crude product was purified by silica gel column chromatography using n-hexane as an eluting solvent to obtain the desired ligand (6.29 g) in a yield of 79%.
[0108]
(1) Synthesis of 2 complex
The ligand (6.29 g) obtained in (1) -1 was dissolved in tetrahydrofuran (100 ml) and cooled to 0 ° C in 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 the dropwise addition, the ice bath was removed and the mixture was stirred for 3 hours, and the solvent was distilled off under reduced pressure. After toluene (60 ml) was added to the residue obtained after the distillation, the mixture was cooled to -78 ° C. To this, a suspension of hafnium tetrachloride (7.17 g) in toluene (140 ml) cooled to -78 ° C was slowly added. 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. From the brown powder, the target complex was extracted with hot n-hexane (180 ml × 3 times). After the extract solution is dried, the obtained solid is 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%).
Of the above compound¹The result of the H-NMR measurement is shown below.
¹H-NMR (CDCl₃): Δ 0.85 (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).
[0109]
(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 under stirring. 16.7 g of granulated montmorillonite (Benclay SL manufactured by Mizusawa Chemical Co., Ltd.) was dispersed in this solution, the temperature was raised to 100 ° C. over 2 hours, and the mixture was stirred at 100 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature over 1 hour, and the obtained slurry was filtered to collect a wet cake. The collected cake was again slurried in deionized water (500 ml) in a 1,000-ml round bottom flask, and filtered. This operation was repeated twice. The cake finally obtained was dried overnight at 110 ° C. under a nitrogen atmosphere to obtain chemically treated montmorillonite (13.3 g).
[0110]
(3) polymerization
Toluene solution of triethylaluminum (0.4 mmol / ml, 2.0 ml) was added to the chemically treated montmorillonite (0.44 g) obtained in (2), 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).
0.114 mmol of triisobutylaluminum (manufactured by Tosoh Akzo) was collected in another flask, and the clay slurry (3.8 ml) obtained here and the complex (6) obtained in Production Example 1 (1) -2 were collected. 0.02 mg (11.4 μmol) in toluene was added and stirred at room temperature for 10 minutes to obtain a catalyst slurry.
[0111]
Next, toluene (750 ml), triisobutylaluminum (1.9 mmol) and liquid propylene (180 ml) were introduced into an induction stirring type autoclave having an internal volume of 2 liters. At room temperature, the whole amount of the catalyst slurry was introduced, the temperature was raised to 60 ° C., and stirring was continued at the same temperature for 1 hour while maintaining the total pressure during polymerization at 0.7 MPa. After completion of the stirring, unreacted propylene was purged to terminate the polymerization. The autoclave was opened to collect the entire amount of the toluene solution of the polymer, and the solvent and the clay residue were removed. As a result, 23.2 g of a propylene polymer was obtained. Table 1 summarizes the results of the analysis of the obtained polymer. In Table 1, "nd" represents non-detection (not @ detected).
[0112]
[Production Example 2]
As a clay slurry material, 17.8 mg (34.2 mmol) of a complex, triisobutylaluminum (0.342 mmol), and a clay slurry (11.4 ml) were used, and toluene (1100 ml) and triisobutylaluminum (0.5 mmol) were used. , Liquid propylene (264 ml), the temperature during the polymerization 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. Table 1 summarizes the results of the analysis of the obtained polymer.
[0113]
[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 temperature during polymerization 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. Table 1 summarizes the results of the analysis of the obtained polymer.
[0114]
[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. Table 1 summarizes the results of the analysis of the obtained polymer.
[0115]
[Production Example 5]
(1) Synthesis of racemic dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azulenyl]} 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) was dissolved. (0.6 mmol, 1.54N) at -78 ° C. After stirring at −10 ° C. for 2 hours, 2-ethylazulene (3.55 g, 22.8 mmol) was added to the 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. To the obtained yellow precipitate, n-hexane (30 ml) and tetrahydrofuran (40 ml) were added at 0 ° C. Next, N-methylimidazole (50 ml) and dimethyldichlorosilane (1.4 ml, 11.4 mmol) were added, and the mixture was heated to room temperature and stirred at room temperature for 1 hour. Thereafter, dilute hydrochloric acid was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -1. , 4-dihydroazulene) (8.3 g).
[0116]
Next, the crude product obtained above was dissolved in diethyl ether (30 ml), and an n-hexane solution of n-butyllithium (14.9 ml, 22.8 mmol, 1.53 N) was added dropwise at −70 ° C. The temperature was gradually raised, and the mixture was stirred at room temperature overnight. Further, toluene (200 ml) was added, 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. Most of the solvent was distilled off from the obtained slurry under reduced pressure, diethyl ether (50 ml) was added, and the obtained slurry was filtered. After washing with diethyl ether (5 ml × 2), ethanol (15 ml × 2), and n-hexane (10 ml × 2), dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4) [Biphenylyl) -4H-azulenyl] {hafnium racemic / meso mixture (4.53 g, 42% yield) was obtained. The resulting racemic-meso mixture¹As a result of analysis by 1 H-NMR, it was found that the mixture was a mixture of racemic 76.6% and meso 23.4%.
The obtained racemic-meso mixture (4.5 g) 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, and toluene (25 ml) and dichloromethane (11 ml) were added to the obtained solid, followed by heating to 60 ° C. to obtain a homogeneous solution. Dichloromethane was distilled off under reduced pressure to precipitate crystals. The obtained crystals were filtered, washed twice with hexane (5 ml), and dried under reduced pressure to obtain a racemic form (1.79 g).
[0117]
(2) Chemical treatment of clay minerals
55.85 g of demineralized water, 32.70 g of sulfuric acid, and 8.01 g of lithium hydroxide were added to a 500-ml round bottom flask, and stirred. Then, 51.65 g of montmorillonite (Mizusawa Chemical: Mizusawa Smectite) was added, and the mixture was heated. Treated at reflux for 140 minutes. After adding 300 ml of demineralized water and performing suction filtration, the solid components were dispersed in 600 ml of demineralized water and suction filtered. This operation was repeated once more. The residue obtained by filtration was dried at 100 ° C. to obtain montmorillonite treated with acid and metal salt. 1.05 g of the obtained montmorillonite treated with an acid and a metal salt was collected in a 100-ml round bottom flask, and dried by heating at 200 ° C. under reduced pressure for 2 hours. To this was added 4.0 ml of a toluene solution of triethylaluminum (0.5 mmol / ml) under purified nitrogen, reacted at room temperature for 30 minutes, washed twice with 30 ml of toluene, and contained chemically treated montmorillonite. A toluene slurry was obtained.
[0118]
(3) Preliminary polymerization
Toluene was extracted from the toluene slurry (containing 914.2 mg as a solid content) obtained in (2), and the amount of residual toluene was adjusted to 1.0 ml. To this slurry was added a toluene solution of triisobutylaluminum (0.5 mmol / ml, 0.5 ml), and the dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- ( 2-Fluoro-4-biphenylyl) -4H-azulenyl] {a racemic solution of hafnium in toluene (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 entire amount of the catalyst slurry were introduced under purified nitrogen. 11.0 g of propylene was introduced under stirring, and prepolymerization was carried out at 30 ° C. for 2 hours and then at 50 ° C. for 0.5 hour. After the prepolymerization, unreacted propylene was purged, and the pressure was replaced by 0.5 MPa with purified nitrogen twice, and then the prepolymerized catalyst was taken out. It contained 9.7 g of polymer per gram of chemically treated montmorillonite component.
[0119]
(4) Polymerization
A 2-liter induction-stirring autoclave having a built-in anchor-type stirring blade was replaced with purified nitrogen, and then 750 g of liquefied propylene was charged at 25 ° C. After a toluene solution of triisobutylaluminum (0.1 mmol / ml, 5.0 ml) was injected at the same temperature, the temperature was raised to 70 ° C. After hydrogen was added so that the concentration of hydrogen in the gas phase became 0.2 mol%, 30.0 mg of the prepolymerized catalyst obtained in the above (3) was added at 70 ° C. to initiate polymerization. One hour later, unreacted propylene was purged to terminate the polymerization. The amount of the obtained propylene polymer was 384 g.
[0120]
The results of analyzing the obtained polymer are summarized in Table 1.
In addition,^ThirteenA peak derived from a carbon atom of a methyl group in a propylene unit chain portion composed of a head-to-tail bond by C-NMR: [mmmm]> 99.9 (%), and a peak derived from another pentad is hardly observed. Was.
[0121]
[Production Example 6]
High stereospecific isotactic polypropylene (31.1 g), heptane (180 ml), Pd / C (Aldrich: 10% by weight Pd / C) (7.87 g) in an induction stirring type micro autoclave having an internal volume of 50 mL. Was added, the system was closed, and the atmosphere was 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, the reaction was stopped by purging with hydrogen. The autoclave was opened to collect the entire heptane solution of the polymer, and the solvent and the Pd / C residue were removed. As a result, 30.6 g of a propylene polymer was obtained.
The physical properties of the high stereospecific isotactic polypropylene used are as follows.
MFR: 15,000 g / 10 minutes;
Tm: 154.9 ° C;
Mw: 37,000; Mn: 18,000; Mw / Mn: 2.1;
[Mmmm]: 98.4%; [mmmmr]: 0.0%; [rmrm]: 0.1%; [rrrr]: 0.2%.
[0122]
[Reference Example 1]
The physical properties of Ziegler-Natta polypropylene (Ube Tack UT-2115, manufactured by Ube Industries, Ltd.) were measured in the same manner.
[0123]
Table 2 shows grade names, physical properties, and the like of various crystalline polypropylenes (base PP) constituting the base material (B) used in the following examples. All grade names of PP-1 to PP-5 are trade names of Nippon Polychem. In Table 2, the pentad fraction indicates mmmm pentads.
[0124]
Table 3 shows grade names, physical properties, and the like of various commercially available elastomer materials used as the elastomer components in the following examples. Similarly, Table 4 shows grade names, physical properties, and the like of various commercially available fillers used as the inorganic filler components.
[0125]
Further, predetermined amounts of the elastomer components shown in Table 3 and the inorganic filler components shown in Table 4 were mixed with the crystalline polypropylene shown in Table 2 to produce various PP base materials (B). Table 5 shows the physical properties of the obtained PP substrate (B). The details of the production method and evaluation of the PP base material (B) are as follows.
These components were blended at the blending ratio (% by weight) shown in Table 5, 0.1 part by weight of a phenolic antioxidant (IRGANOX1010 manufactured by Ciba Specialty Chemicals), and a phosphorus-based antioxidant (Ciba Specialty Chemicals). 0.05 parts by weight of IRGAFOS168) and 0.2 parts by weight of calcium stearate, and then melt-kneaded using a twin-screw extruder (TEX30α manufactured by Nippon Steel Works) at a screw rotation speed of 300 rpm and an extrusion rate of 15 kg / hr. Then, pellets of the resin composition were obtained. Using the obtained pellets, injection molding was performed under the conditions of a mold temperature of 40 ° C. and a cylinder temperature of 230 ° C. to obtain various test pieces of the resin composition. Using the obtained test pieces, various physical properties were evaluated by the methods described above.
Further, a test piece of 150 mm × 70 mm × 2 mm was injection molded from each of the resin compositions shown in Table 5 using an injection molding machine (IS170 manufactured by Toshiba Machine Co., Ltd.) at a molding temperature of 220 ° C. It was used as a substrate for evaluation.
[0126]
[Table 1]

[0127]
[Table 2]

[0128]
[Table 3]

[0129]
[Table 4]

[0130]
[Table 5]

[0131]
[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) were added to a stainless steel pressure-resistant reaction vessel equipped with a thermometer and a stirrer. And the temperature was raised to 132 ° C. After the temperature was raised, 16 g of a chlorobenzene solution (10% by weight) of dicumyl peroxide (DCPO) was supplied in 5 hours using a metering pump, and then the mixture was stirred at the same temperature for 3 hours to carry out a reaction. After completion of the reaction, the system was cooled to around room temperature, acetone was added, and the precipitated polymer was separated by filtration. Further, precipitation and filtration were repeated with acetone, and the finally obtained polymer was washed with acetone. The polymer obtained after the washing was dried under reduced pressure, whereby a white powdery modified resin was obtained. As a result of infrared ray absorption spectrum measurement, neutralization titration and the like of this modified resin, the graft amount (maleic anhydride group content) was 3.3% by weight.
To 15 g of the maleic anhydride-modified propylene polymer obtained above, 135 g of toluene was added, and the mixture was heated to 100 ° C. and dissolved for 1 hour. After cooling the obtained solution to around room temperature, a 10% by weight solution of a maleic anhydride-modified propylene polymer was prepared through a SUS wire mesh of # 400.
[0132]
(2) Evaluation of physical properties of modified propylene polymer
A coating amount of the toluene solution of the maleic anhydride-modified propylene polymer obtained in the above (1) was applied to an injection-molded test piece (the surface of which was wiped with isopropyl alcohol) made of various PP base materials shown in Table 5. 3-5 g / m²Was spray applied. Next, the molded test piece was allowed to stand at 25 ° C. for 1 hour, and then dried at 80 ° C. for 30 minutes in a Safeven dryer. Next, the dried product was allowed to stand at 25 ° C. for 1 hour, and then an acrylic polyol urethane paint (manufactured by Kansai Paint Co., Ltd., trade name: Retan PG80III) was blended with a predetermined amount of a curing agent from the top of the coating film. After adjusting the viscosity with a special thinner at Ford Cup No. 4 and adjusting the viscosity to be 12 to 13 seconds, spray-coating is performed so that the dry coating amount is 50 to 60 g. At 100 ° C. for 30 minutes. Furthermore, it was left standing at 25 ° C. for 10 days for curing. An interlayer adhesion test was performed on the obtained coated article. In addition, a water resistance test and a gasohol resistance test were also performed. The results are summarized in the following Examples and shown in Tables 6 (1) and 6 (2).
[0133]
[Example 2]
Using toluene (80 g), a propylene polymer (20 g) synthesized in Production Example 2, 10 g of maleic anhydride, and 12 g of a toluene solution of dicumyl peroxide (DCPO) (10 wt%) at 110 ° C. Was modified with maleic anhydride in the same manner as in Example 1, a coated article was prepared using the modified polymer, and a physical property evaluation test was conducted in the same manner.
[0134]
[Example 3]
A maleic anhydride modification was performed in the same manner as in Example 1 except that the propylene polymer synthesized in Production Example 2 was used, and a coated product was prepared using the modified polymer. went.
[0135]
[Example 4]
A maleic anhydride modification was performed in the same manner as in Example 1 except that the propylene polymer synthesized in Production Example 3 was used, and a coated product was prepared using the modified polymer. went.
[0136]
[Example 5]
A maleic anhydride modification was performed in the same manner as in Example 1 except that the propylene polymer synthesized in Production Example 4 was used, and a coated product was prepared using the modified polymer. went.
[0137]
[Example 6]
Same as Example 1 except that methacrylic acid (5 g) was used in place of maleic anhydride (4 g) and the amount of dicumyl peroxide (DCPO) in chlorobenzene (10% by weight) was changed from 16 g to 5 g. The modified resin was obtained by the above operation. As a result of measuring the infrared absorption spectrum of this modified resin, the graft amount (content of methacrylic acid group) was 1.1% by weight. A coated article was prepared using the modified polymer, and a physical property evaluation test was similarly performed.
[0138]
[Example 7]
2-hydroxyethyl methacrylate (HEMA, 5 g) was used instead of maleic anhydride (4 g), and the addition amount of a dicumyl peroxide (DCPO) chlorobenzene solution (10% by weight) was changed from 16 g to 5 g. The modified resin was obtained in the same manner as in Example 1. As a result of measuring the infrared absorption spectrum of this modified resin, the graft amount (content of 2-hydroxyethyl methacrylate group) was 1.0% by weight. A coated article was prepared using the modified polymer, and a physical property evaluation test was similarly performed.
[0139]
Example 8
Instead of maleic anhydride (4 g), 2-hydroxyethyl methacrylate (HEMA, 5 g) and styrene (St, 5 g) were used, and the added amount of dicumyl peroxide (DCPO) in chlorobenzene (10% by weight) was 16 g. The modified resin was obtained in the same manner as in Example 1 except that the amount was changed from 5 g to 5 g. As a result of measuring the infrared absorption spectrum of this modified resin, the content of 2-hydroxyethyl methacrylate group was 2.5% by weight. A coated article was prepared using the modified polymer, and a physical property evaluation test was similarly performed.
[0140]
[Comparative Example 1]
A maleic anhydride modification was performed in the same manner as in Example 1 except that the propylene polymer synthesized in Production Example 5 was used. The grafting amount of the modified propylene polymer was 3.4% by weight, and a solubility test was performed. As a result, the solubility in toluene was poor, and 96% or more insolubles were obtained. However, the non-tack property was excellent. The results are shown together with the following comparative examples in Tables 7 (1) and 7 (2).
[0141]
[Comparative Example 2]
A maleic anhydride modification was performed in the same manner as in Example 1 except that the propylene polymer synthesized in Production Example 6 was used. The graft amount of the modified propylene polymer was 3.5% by weight, and a solubility test was performed. As a result, the solubility in toluene was good, but the stickiness was large and the coating was not evaluated. There was also a problem in tackiness.
[0142]
[Comparative Example 3]
Using a Ziegler-Natta catalyst type polypropylene (Ube Tack UT-2115 manufactured by Ube Industries, Ltd.), maleic anhydride modification was performed in the same operation as in Example 1. The graft amount of the modified propylene polymer was 3.4% by weight, and a solubility test of toluene was performed. As a result, the insoluble matter was as large as 29.5% by weight, and coating evaluation could not be performed. There was also a problem in tackiness.
[0143]
[Comparative Example 4]
Using a propylene / butene-1 copolymer (Tuffmer XR-110T manufactured by Mitsui Chemicals, Inc., propylene component: butene-1 component = 76: 24), maleic anhydride modification was performed in the same manner as in Example 1. The graft amount of the modified propylene polymer was 3.0% by weight, and a solubility test of toluene was performed. As a result, the insoluble matter was as large as 67.4% by weight, and coating evaluation could not be performed. However, the non-tack property was excellent.
[0144]
[Comparative Example 5]
The coating evaluation was performed using maleic anhydride-modified chlorinated polypropylene (Eastman, CP-343-1) as the modified polymer. Although the non-tack property was excellent, it was particularly poor in adhesion and water resistance.
[0145]
[Table 6] [Table 6 (1)]

[0146]
[Table 7] [Table 6 (2)]

[0147]
[Table 8] [Table 7 (1)]

[0148]
[Table 9] [Table 7 (2)]

[0149]
【The invention's effect】
ADVANTAGE OF THE INVENTION The polypropylene coating molded article of this invention is excellent in coating-film adhesion, and also has the physical property balance excellent in rigidity and impact resistance. In addition, the use of halogens that are harmful to the global environment not only helps protect the global environment, but also greatly reduces the adverse effects of halogens on weather resistance, etc. However, its industrial value is extremely large because it is a technology development that results in an extension of the life cycle and, consequently, a saving of limited earth resources.

Claims (14)

A polypropylene-based molded article, characterized in that the following coating component (A) is applied to a substrate (B).
Coating component (A): a polar group comprising a main chain comprising a propylene polymer having the following characteristics (1) and (2) and a side chain comprising a carboxyl group, a carboxylic anhydride group or a carboxylic ester group. A paint component containing a propylene-based polymer.
(1) Produced by a single-site catalyst (2) When dissolved in heptane at 98 ° C. at a concentration of 10% by weight, its insoluble content is 1% by weight or less Base material (B): crystalline polypropylene And a molded article of a resin composition comprising an elastomer component. The polypropylene-based molded article according to claim 1, wherein the base material (B) further contains an inorganic filler component. The polypropylene-based molded article according to claim 1 or 2, wherein the main chain comprising the propylene-based polymer has the following property (3).
(3) Having a stereo block structure including both isotactic blocks and amorphous blocks 4. The molded article according to claim 3, wherein the stereo block structure satisfies the following requirements (1) and (2).
{Circle around (1)} When the chemical shift of the peak attributable to the pentad represented by mmmm is 21.8 ppm, the total area of the peaks belonging to ten kinds of pentads appearing in the range of 19.8 to 22.2 ppm. The ratio (S ₁ / S) of the peak area S ₁ having a peak top at 21.8 ppm to S is 10 to 60%. (2) A peak having a peak top at 21.5 to 21.7 ppm (mmmr when the area of) was _{S 2,} the relationship of _{S 1} and _{S 2 are, 4 + 2S 1 / S 2} > 5 be satisfied. The polypropylene-based molded article according to any one of claims 1 to 4, wherein the main chain composed of a propylene-based polymer has the following property (4).
(4) When dissolved in toluene at 25 ° C. at a concentration of 10% by weight, the insoluble content is 1% by weight or less. The polypropylene-based molded article according to any one of claims 1 to 5, wherein the main chain composed of a propylene-based polymer has the following property (5).
(5) The weight average molecular weight Mw measured by GPC is 5,000 to 1,000,000. The polypropylene coating according to any one of claims 1 to 6, wherein the crystalline polypropylene is a propylene homopolymer or a propylene / ethylene block copolymer comprising a propylene homopolymer portion and a propylene / ethylene copolymer portion. Molded body. The elastomer component is at least one selected from the group consisting of an ethylene / α-olefin copolymer, an ethylene / α-olefin / diene terpolymer, and a styrene copolymer rubber. Or a polypropylene-based molded article according to item 1. The polypropylene-based molded article according to any one of claims 2 to 8, wherein the inorganic filler component is at least one selected from the group consisting of talc, mica, glass fiber, and whisker. The polypropylene-based coating molding according to any one of claims 1 to 9, wherein the substrate (B) is a molded article of a resin composition comprising 51 to 99% by weight of a crystalline polypropylene and 1 to 49% by weight of an elastomer component. body. The base material (B) is a molded article of a resin composition comprising 1 to 80 parts by weight of an inorganic filler component based on 100 parts by weight of a total amount of a crystalline polypropylene and an elastomer component. Item 7. A polypropylene-based molded article according to the above item. The polypropylene-based molded article according to claim 7, wherein the propylene homopolymer has an MFR of 2 to 300 g / 10 minutes. The propylene homopolymer part of the propylene / ethylene block copolymer is 50 to 95% by weight, the propylene / ethylene copolymer part is 5 to 50% by weight, and the MFR of the propylene homopolymer part is 10 to 500 g / The polypropylene-based molded article according to claim 7, which is 10 minutes. The propylene homopolymer portion of the propylene / ethylene block copolymer is 60 to 90% by weight, the propylene / ethylene copolymer portion is 10 to 40% by weight, and the MFR of the propylene homopolymer portion is 10 to 500 g / 10 min. 14. The molded article according to claim 13, wherein the density of the elastomer component is 0.889 g / cm ³ or less.