JP2004059817A - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent qualities in impact resistance, heat resistance, moldability/processability, appearance in molding, and resistance to chemicals by improving the compatibility between a polyphenylene ether resin and a polyester resin. <P>SOLUTION: There is used a thermoplastic resin composition which contains, per 100 pts.wt. of a resin mixture composed of 10-90 wt.% of a polyphenylene ether resin (A), 90-10 wt.% of a polyester resin (B), and 0-50 wt.% of a polyolefin resin (C) (wherein (A)+(B)+(C)=100 wt.%), 1-50 pts.wt. of a hydrogenated polymer of a block copolymer (D) having at least one polymer block mainly consisting of an aromatic vinyl compound and at least one polymer block mainly consisting of a conjugated diene compound and besides containing an amino group. <P>COPYRIGHT: (C)2004,JPO

Description

【００１０】
（上記一般式（３）中、Ｒ^１２、Ｒ^１３は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、フェニル基、アミノアルキル基、ハロゲン原子を表わす。Ｒ^１４、Ｒ^１５は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、フェニル基を表わす。）
このポリフェニレンエーテル系樹脂の具体的な例としては、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−エチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）等が挙げられ、さらに、２，６−ジメチルフェノールと他のフェノール類（例えば、２，３，６−トリメチルフェノールや２−メチル−６−ブチルフェノール）との共重合体のようなポリフェニレンエーテル共重合体も挙げられる。中でもポリ（２，６−ジメチル−１，４−フェニレンエーテル）、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体が好ましく、さらにポリ（２，６−ジメチル−１，４−フェニレンエーテル）が好ましい。
本発明のポリフェニレンエーテル系樹脂の分子量は特に限定されないが、クロロホルム中で測定した３０℃の固有粘度が０．２〜０．８ｄｌ／ｇであるものが好ましい。更に好ましくは、固有粘度が０．３〜０．６ｄｌ／ｇのものである。
【００１１】
２．ポリエステル系樹脂
本発明に用いられるポリエステル系樹脂（以下「（Ｂ）成分」という場合がある）は、熱可塑性の飽和ポリエステル樹脂が好ましく、芳香族ジカルボン酸あるいはそのエステル形成性誘導体と、ジオールあるいはそのエステル誘導体とを主成分とする縮合反応により得られる重合体ないし共重合体、あるいはラクトンの開環重合体等が挙げられ、これらは単独又は２種以上組み合わせて用いられる。
【００１２】
上記「芳香族ジカルボン酸」としては、テレフタル酸、イソフタル酸、フタル酸、２，６−ナフタレンジカルボン酸、ビス（ｐ−カルボキシフェニル）メタン、アントラセンジカルボン酸、４，４’−ジフェニルカルボン酸、４，４’−ジフェニルエーテルジカルボン酸、あるいはそれらのエステル形成性誘導体等が挙げられ、これらは単独又は２種以上組み合わせて用いられる。
上記「ジオール」成分としては炭素数２〜１０の脂肪族ジオール、即ち、エチレングリコール、１，３−プロパンジオール、２−メチルプロパンジオール、１，４−ブタンジオール、ネオペンチルグリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、シクロヘキサンジオール等、あるいは分子量４００〜６０００の長鎖グリコール、即ち、ポリエチレングリコール、ポリ−１，３−ポリプロピレングリコール、ポリテトラメチレングリコール等が挙げられ、これらは単独又は２種以上組み合わせて用いられる。
【００１３】
更に、本発明のポリエステル系樹脂は、全構造単位に基づいて１モル％以下であれば、例えば、グリセリン、トリメチロールプロパン、ペンタエリスリトール、トリメリット酸、ピロメリット酸などの３官能以上のモノマーから誘導される構造単位を有してもよい。
本発明のポリエステル系樹脂は、具体的には、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチレンテレフタレート、ポリヘキサメチレンテレフタレート、ポリエチレン−２，６−ナフタレート、ポリエチレン−１，２−ビス（フェノキシ）エタン４，４’−ジカルボキシレート、ポリカプロラクトン系樹脂、ポリアリレート系樹脂等が挙げられ、これらは単独又は２種以上組み合わせて用いられる。中でも、機械特性、耐熱性、成形性の点から、ポリブチレンテレフタレート、ポリエチレンテレフタレート又はこれらの混合物が好ましい。
本発明のポリエステル系樹脂の分子量は特に限定されないが、フェノール／テトラクロロエタン（重量比＝１／１）混合溶媒中で測定した時の極限粘度が０．５〜１．５の範囲にあるものが機械的強度、耐熱性の点で好ましい。
【００１４】
３．ポリオレフィン系樹脂
本発明に用いられるポリオレフィン系樹脂（以下「（Ｃ）成分」という場合がある）は、１種又は２種以上のモノオレフィンを高圧法又は低圧法のいずれかによる重合から得られる結晶性のポリオレフィン樹脂（重合体）であり、中でも、ポリエチレン、ポリプロピレン、ポリブテン−１が好ましい。このポリオレフィン樹脂は単独重合体であってもよく、他のモノマーと共重合してなる共重合体であってもよい。
【００１５】
共重合可能な他のモノマーとしては、例えば、エチレン（主たる重合体がポリエチレンの場合は除く）、プロピレン（主たる重合体がポリプロピレンの場合は除く）、ブテン−１（主たる重合体がポリブテン−１である場合は除く）、ペンテン−１、ヘキセン−１、ヘプテン−１、オクテン−１等の直鎖状α−オレフィン；４−メチルペンテン−１、２−メチルプロペン−１、３−メチルペンテン−１、５−メチルヘキセン−１、４−メチルヘキセン−１、４，４−ジメチルペンテン−１等の分岐状α−オレフィン；並びに、前記α−オレフィンと共重合することができるモノマーを挙げることができる。これら共重合可能なモノマー成分の配合量としては、２０重量％以下、好ましくは１５重量％以下である。これらを共重合した場合の共重合体の様式については結晶性を有する限り特に制限はなく、例えば、ランダム型、ブロック型、グラフト型、これらの混合型等のいずれであってもよい。
【００１６】
本発明の熱可塑性樹脂組成物における（Ａ）成分の割合は、（Ａ）、（Ｂ）及び（Ｃ）成分の合計量を１００重量％とした場合、１０〜９０重量％であり、好ましくは３０〜７０重量％である。１０重量％未満では耐熱性が低下し、９０重量％を越えると成形加工性、耐薬品性が低下する。
（Ｂ）成分の配合割合は、９０〜１０重量％、好ましくは７０〜３０重量％である。１０重量％未満では耐薬品性が劣り、９０重量％を越えると耐熱性を低下させるおそれがある。
（Ｃ）成分の配合割合は、０〜５０重量％、好ましくは５〜３０重量％である。（Ｃ）成分を配合することにより耐衝撃性が向上するが、５０重量％を越えると耐熱性が低下する。
【００１７】
４．水添重合体
本発明に用いられる水添重合体（以下「（Ｄ）成分」という場合がある）は、芳香族ビニル化合物を主体とする重合体ブロックを少なくとも一つと、共役ジエン化合物を主体とする重合体ブロックを少なくとも一つを有し、かつアミノ基を含有するブロック共重合体（以下「本発明のブロック共重合体」という）の水添重合体（以下「本発明の水添重合体」という）で、不活性有機溶媒中、芳香族ビニル化合物と共役ジエン化合物を、有機アルカリ金属化合物を重合開始剤としてアミノ基含有ブロック共重合体とし、その後、該共重合体を水素添加することにより容易に得ることができる。
【００１８】
具体的には、例えば以下に示す（ａ）〜（ｃ）の方法により得ることができる。
（ａ）芳香族ビニル化合物と共役ジエン化合物を、アミノ基を有する有機アルカリ金属化合物の存在下でブロック共重合し、その後、該重合体を水素添加することにより製造される。
（ｂ）芳香族ビニル化合物と共役ジエン化合物を有機アルカリ金属化合物の存在下でブロック共重合し、得られた重合体の活性点に、下記一般式（１）及び／又は下記一般式（２）で表される化合物を反応させた重合体とし、その後、該重合体を水素添加することにより製造される。
Ｒ^１Ｒ^２Ｃ＝Ｎ−Ｙ　　　　　　　　　　（１）
［上記一般式（１）中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基又は炭素数１〜１００のオルガノシロキシ基である。また、Ｙは水素原子、炭素数３〜１８のトリアルキルシリル基、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基又は炭素数１〜１００のオルガノシロキシ基である。］。
Ｒ^３ _{（４−ｍ−ｎ）}Ｓｉ（ＯＲ^４）_ｍＸ_ｎ　　　　（２）
［上記一般式（２）中、Ｒ^３は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基又は炭素数１〜１００のオルガノシロキシ基であり、Ｒ^３が複数ある場合は、各Ｒ^３は同じ基でも異なる基でもよい。Ｒ^４は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基であり、Ｒ^４が複数ある場合は、各Ｒ^４は同じ基でも異なる基でもよい。ＸはＮ原子を含む極性基を有する置換基であり、Ｘが複数ある場合は、各Ｘは同じ基でも異なる基でもよく、また、各Ｘは独立の置換基でも環状構造を形成していてもよい。ｍは１、２又は３であり、ｎは１、２又は３の整数を示す。ｍとｎの和は１〜４である。］
（ｃ）芳香族ビニル化合物と共役ジエン化合物とアミノ基を有する不飽和単量体とを有機アルカリ金属化合物の存在下でブロック共重合し、その後、該重合体を水素添加することにより製造される。
このうち（ａ）または（ｂ）により製造した共重合体を用いた場合、本発明の組成物の耐熱性、耐衝撃性がより改善されためより好ましい。
【００１９】
上記「芳香族ビニル化合物」としては、スチレン、ｔｅｒｔ−ブチルスチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−エチルスチレン、ジビニルベンゼン、１，１−ジフェニルスチレン、ビニルナフタレン、ビニルアントラセン、Ｎ，Ｎ−ジエチル−ｐ−アミノエチルスチレン、ビニルピリジン等が挙げられる。この中で、スチレン及びｔｅｒｔ−ブチルスチレンが好ましい。
上記「共役ジエン化合物」としては、例えば、１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−オクタジエン、１，３−ヘキサジエン、１，３−シクロヘキサジエン、４，５−ジエチル−１，３−オクタジエン、３−ブチル−１，３−オクタジエン、ミルセン、クロロプレン等が挙げられる。この中で、１，３−ブタジエン、イソプレンが好ましい。
【００２０】
（ａ）の方法で使用するアミノ基を有する有機アルカリ金属化合物としては、下記一般式（４）又は（５）が挙げられる。
【００２１】
【化２】

【００２２】
【化３】

【００２３】
［上記一般式（４）中、Ｒ^５及びＲ^６は両方とも炭素数３〜１８のトリアルキルシリル基であるか、又はどちらか一方が上記トリアルキルシリル基であり、他方が炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基若しくは炭素数１〜１００のオルガノシロキシ基である。また、上記一般式（４）及び（５）中のＲ^７は、炭素数１〜２０のアルキレン基又はアルキリデン基である。更に、上記一般式（５）中のＲ^８は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基又は炭素数１〜１００のオルガノシロキシ基である。］
上記一般式（４）又は（５）で表される有機アルカリ金属化合物の具体例としては、３−リチオ−１−［Ｎ，Ｎ−ビス（トリメチルシリル）］アミノプロパン（ＣＡＳ　Ｎｏ．２８９７１９−９８−８）、２−リチオ−１−［Ｎ，Ｎ−ビス（トリメチルシリル）］アミノエタン、３−リチオ−２，２−ジメチル−１−［Ｎ，Ｎ−ビス（トリメチルシリル）］アミノプロパン、２，２，５，５−テトラメチル−１−（３−リチオプロピル）−１−アザ−２，５−ジシラシクロペンタン、２，２，５，５−テトラメチル−１−（３−リチオ−２，２−ジメチル−プロピル）−１−アザ−２，５−ジシラシクロペンタン、２，２，５，５−テトラメチル−１−（２−リチオエチル）−１−アザ−２，５−ジシラシクロペンタン、３−リチオ−１−［Ｎ−（ｔｅｒｔ−ブチル−ジメチルシリル）−Ｎ−トリメチルシリル］アミノプロパン、３−リチオ−１−（Ｎ−メチル−Ｎ−トリメチルシリル）アミノプロパン、３−リチオ−１−（Ｎ−エチル−Ｎ−トリメチルシリル）アミノプロパンなどが挙げられる。
（ａ）の方法で使用するアミノ基を有する有機アルカリ金属化合物の使用量については特に限定はなく、必要に応じて種々の量を使用できるが、通常はモノマー１００重量％あたり０．０２〜１５重量％の量で、好ましくは０．０３〜５重量％の量で用いられる。
【００２４】
（ｂ）及び（ｃ）の方法で使用する有機アルカリ金属化合物としては、有機リチウム化合物、有機ナトリウム化合物等が挙げられ、特にｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム等の有機リチウム化合物が好ましい。
その使用量については特に限定はなく、必要に応じて種々の量を使用できるが、通常はモノマー１００重量％あたり０．０２〜１５重量％の量で、好ましくは０．０３〜５重量％の量で用いられる。
【００２５】
（ｂ）の方法で使用する上記一般式（１）の化合物の具体例としては、Ｎ−ベンジリデンメチルアミン、Ｎ−ベンジリデンエチルアミン、Ｎ−ベンジリデンブチルアミン、Ｎ−ベンジリデンアニリンなどが挙げられる。
【００２６】
また、（ｂ）の方法で使用する上記一般式（２）で表されるアルコキシシラン化合物の具体例としては、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルジメチルエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルジメチルメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルトリメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルトリエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルジメチルエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルジメチルメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルジエトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルジメトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルトリメトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルトリエトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルジメチルエトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルジメチルメトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルメチルジエトキシシラン、Ｎ−メチル−Ｎ−トリメチルシリルアミノプロピルメチルジメトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルトリメトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルトリエトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルジメチルエトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルジメチルメトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルメチルジエトキシシラン、Ｎ，Ｎ−ジメチルアミノプロピルメチルジメトキシシラン、Ｎ−（１，３−ジメチルブチリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（トリエトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（トリメトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（メチルジメトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（メチルジエトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（ジメチルメトキシシリル）−１−プロパンアミン、Ｎ−（１，３−ジメチルブチリデン）−３−（ジメチルエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルエチリデン）−３−（ジメチルエトキシシリル）−１−プロパンアミン、Ｎ−エチリデン−３−（ジメチルエトキシシリル）−１−プロパンアミン、Ｎ−（１−メチルプロピリデン）−３−（ジメチルエトキシシリル）−１−プロパンアミン、Ｎ−（４−Ｎ，Ｎ−ジメチルアミノベンジリデン）−３−（ジメチルエトキシシリル）−１−プロパンアミンなどが挙げられる。
【００２７】
上記一般式（１）及び／又は一般式（２）で表される化合物を、上記芳香族ビニル化合物と共役ジエン化合物とのブロック共重合体と反応させて変性する場合の使用量は特に限定がないが、通常、有機アルカリ金属化合物由来の活性点のモル数に対し０．２〜３倍モル、好ましくは０．３〜１．５倍モル、更に好ましくは０．４〜１．３倍モルの割合で用いられる。
【００２８】
（ｃ）の方法で使用するアミノ基を有する不飽和単量体としては、下記一般式（６）又は（７）である。
【００２９】
【化４】

【００３０】
【化５】

【００３１】
［上記一般式（６）及び（７）中、Ｒ^９及びＲ^１０は、両方とも炭素数３〜１８のトリアルキルシリル基であるか、又はどちらか一方が上記トリアルキルシリル基であり、他方が炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基若しくは炭素数１〜１００のオルガノシロキシ基である。また、上記一般式（７）中、Ｒ^１１は、炭素数１〜２０のアルキレン基又はアルキリデン基である。更に、上記一般式（６）及び（７）中のｎは１〜３である。］
【００３２】
上記一般式（６）又は（７）で表される不飽和単量体の具体例としては、ｐ−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノ］スチレン、ｐ−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノメチル］スチレン、ｐ−｛２−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノ］エチル｝スチレン、ｍ−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノ］スチレン、ｐ−（Ｎ−メチル−Ｎ−トリメチルシリルアミノ）スチレン、ｐ−（Ｎ−メチル−Ｎ−トリメチルシリルアミノメチル）スチレンなどが挙げられる。
一般式（６）又は（７）で表される不飽和単量体の使用量は、有機アルカリ金属由来の活性点のモル数に対して０．０１〜１００倍モル、好ましくは０．０１〜１０倍モル、特に好ましくは１．０〜３．０倍モルの割合で添加する。更に、該不飽和単量体は、重合の開始時、重合途中、重合終了前、重合終了後等の任意の時に添加することができる。
【００３３】
本発明のブロック共重合体中のアミノ基の含有量は、通常、０．５〜３００ｍｍｏｌ／ｋｇ・重合体、好ましくは、１〜１００ｍｍｏ１／ｋｇ・重合体、さらに好ましくは、３〜５０ｍｍｏ１／ｋｇ・重合体である。なお、アミノ基の位置は特に限定はなく、重合体鎖末端に存在してもよく、側鎖に存在してもよいが、重合体鎖末端に存在するのが好ましい。重合体鎖末端に存在するブロック共重合体は、上記（ａ）又は（ｂ）により製造され、該共重合体を用いた場合、本発明の組成物の耐熱性、耐衝撃性がより改善されためより好ましい。
また、アミノ基は第１級アミノ基及び／又は第２級アミノ基が好ましい。
【００３４】
また、本発明のブロック共重合体における芳香族ビニル化合物の重合単位と共役ジエン化合物の重合単位との含有量の割合は、重量比で２０／８０〜８０／２０、好ましくは３０／７０〜６０／４０の範囲である。
【００３５】
本発明のブロック共重合体は、「少なくとも一つの芳香族ビニル化合物を主体とする重合体ブロックと、少なくとも一つの共役ジエン化合物を主体とする重合体ブロックを有する共重合体」で、以下の（Ａ）の重合体ブロックと（Ｂ）及び／又は（Ｃ）の重合体ブロックとの共重合体、さらにはこれらと（Ｄ）の重合体ブロックとの共重合体も含む。
（Ａ）芳香族ビニル化合物が８０重量％以上である芳香族ビニル化合物重合体ブロック
（Ｂ）ビニル結合含量が２５重量％未満の共役ジエン重合体ブロック
（Ｃ）ビニル結合含量が２５重量％以上９０重量％以下の共役ジエン重合体ブロック
（Ｄ）芳香族ビニル化合物と共役ジエンのランダム共重合体ブロック又は芳香族ビニル化合物含量が連続的に一分子中で変化するいわゆるテーパーブロック
【００３６】
上記「少なくとも一つの芳香族ビニル化合物を主体とする重合体ブロックと、少なくとも一つの共役ジエン化合物を主体とする重合体ブロックを有する共重合体」の具体例としては、（Ａ）−（Ｂ）、（Ａ）−（Ｃ）、［（Ａ）−（Ｂ）］ｘ―Ｙ、［（Ａ）−（Ｃ）］ｘ―Ｙ、（Ａ）−（Ｂ）−（Ｃ）、（Ａ）−（Ｂ）−（Ｄ）、（Ａ）−（Ｂ）−（Ａ）、（Ａ）−（Ｃ）−（Ａ）、（Ａ）−（Ｄ）−（Ｃ）、（Ａ）−（Ｃ）−（Ｂ）、［（Ａ）−（Ｂ）−（Ｃ）］ｘ―Ｙ、［（Ａ）−（Ｂ）−（Ａ）］ｘ―Ｙ、［（Ａ）−（Ｃ）−（Ａ）］ｘ―Ｙ、［（Ａ）−（Ｄ）−（Ｃ）］ｘ―Ｙ、（Ａ）−（Ｂ）−（Ａ）−（Ｂ）、（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、（Ａ）−（Ｃ）−（Ａ）−（Ｃ）、（Ｃ）−（Ａ）−（Ｃ）−（Ａ）、［（Ａ）−（Ｂ）−（Ａ）−（Ｂ）］ｘ―Ｙ、（Ａ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、［（Ａ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）］ｘ―Ｙ、［（Ｂ）−（Ａ）］ｘ―Ｙ、［（Ｃ）−（Ａ）］ｘ―Ｙ、（Ｂ）−（Ａ）−（Ｂ）−（Ｃ）、（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、（Ｂ）−（Ａ）−（Ｃ）−（Ａ）、（Ｃ）−（Ａ）−（Ｄ）−（Ａ）、（Ｃ）−（Ａ）−（Ｄ）−（Ｃ）、［（Ｃ）−（Ａ）−（Ｂ）−（Ｃ）］ｘ―Ｙ、［（Ｄ）−（Ａ）−（Ｂ）−（Ａ）］ｘ―Ｙ、［（Ｄ）−（Ａ）−（Ｃ）−（Ａ）］ｘ―Ｙ、［（Ｄ）−（Ａ）−（Ｄ）−（Ｃ）］ｘ―Ｙ、（Ｄ）−（Ａ）−（Ｂ）−（Ａ）−（Ｂ）、（Ｄ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、（Ｄ）−（Ａ）−（Ｃ）−（Ａ）−（Ｃ）、（Ｄ）−（Ｃ）−（Ａ）−（Ｃ）−（Ａ）、［（Ｄ）−（Ａ）−（Ｂ）−（Ａ）−（Ｂ）］ｘ―Ｙ、（Ｄ）−（Ａ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）、［（Ｄ）−（Ａ）−（Ｂ）−（Ａ）−（Ｂ）−（Ａ）］ｘ―Ｙ等が挙げられる（但し、ｘは２〜８の整数であり、Ｙはカップリング剤の残基である。）。
【００３７】
上記カップリング剤としては、例えば、ハロゲン化合物、エポキシ化合物、カルボニル化合物、ポリビニル化合物等が挙げられ、具体的には、例えばメチルジクロロシラン、メチルトリクロロシラン、ブチルトリクロロシラン、テトラクロロシラン、ジブロモエタン、エポキシ化大豆油、ジビニルベンゼン、テトラクロロ錫、ブチルトリクロロ錫、テトラクロロゲルマニウム、ビス（トリクロロシリル）エタン、アジピン酸ジエチル、アジピン酸ジメチル、ジメチルテレフタル酸、ジエチルテレフタル酸、ポリイソシアネート等が挙げられる。
【００３８】
本発明の水添重合体は、上記のようにして得られたアミノ基を含有するブロック共重合体に部分的あるいは選択的に水添を行う。この水添の方法、反応条件については特に限定はなく、通常は、２０〜１５０℃、０．１〜１０ＭＰａの水素加圧下、水添触媒の存在下に水添する事によって行われる。この場合、水添率は、水添触媒の量、水添反応時の水素圧力、又は反応時間等を変えることにより任意に選定することができる。水添率は、不飽和部である共役ジエンに由来する二重結合の５０％以上、好ましくは８０％以上、特に好ましくは９５％以上である。なお、二重結合として主鎖、側鎖のいずれかに存在するがランダムに水添されていてもよく、側鎖が優先されて水添されていてもよく、主鎖が優先されて水添されていても良い。上記水添触媒として通常は、元素周期表Ｉｂ、ＩＶｂ、Ｖｂ、ＶＩｂ、ＶＩＩｂ、ＶＩＩＩ族金属のいずれかを含む化合物、例えば、Ｔｉ、Ｖ、Ｃｏ、Ｎｉ、Ｚｒ、Ｒｕ、Ｒｈ、Ｐｄ、Ｈｆ、Ｒｅ、Ｐｔ原子を含む化合物を用いることができる。上記水添触媒として具体的には、例えば、Ｔｉ、Ｚｒ、Ｈｆ、Ｃｏ、Ｎｉ、Ｐｄ、Ｐｔ、Ｒｕ、Ｒｈ、Ｒｅ等のメタロセン系化合物、Ｐｄ、Ｎｉ、Ｐｔ、Ｒｈ、Ｒｕ等の金属をカーボン、シリカ、アルミナ、ケイソウ土等の担体に担持させた担持型不均一系触媒、Ｎｉ、Ｃｏ等の金属元素の有機塩又はアセチルアセトン塩と有機アルミニウム等の還元剤とを組み合わせた均一系チーグラー型触媒、Ｒｕ、Ｒｈ等の有機金属化合物又は錯体、及び水素を吸蔵させたフラーレンやカーボンナノチューブ等が挙げられる。この中で、Ｔｉ、Ｚｒ、Ｈｆ、Ｃｏ、Ｎｉのいずれかを含むメタロセン化合物は、不活性有機溶媒中、均一系で水添反応できる点で好ましい。更に、Ｔｉ，Ｚｒ，Ｈｆのいずれかを含むメタロセン化合物が好ましい。特にチタノセン化合物とアルキルリチウムとを反応させた水添触媒は安価で工業的に特に有用な触媒であるので好ましい。具体的な例として、例えば、特開平１−２７５６０５号公報、特開平５−２７１３２６号公報、特開平５−２７１３２５号公報、特開平５−２２２１１５号公報、特開平１１−２９２９２４号公報、特開２０００−３７６３２号公報、特開昭５９−１３３２０３号公報、特開昭６３−５４０１号公報、特開昭６２−２１８４０３号公報、特開平７−９００１７号公報、特公昭４３−１９９６０号公報、特公昭４７−４０４７３号公報に記載の水添触媒が挙げられる。尚、上記水添触媒は１種のみ用いてもよく、又は２種以上を併用することもできる。本発明では、水添後、必要に応じて触媒の残渣を除去し、又はフェノール系又はアミン系の老化防止剤を添加し、その後、水添重合体溶液から水添重合体を単離する。水添重合体の単離は、例えば、水添重合体溶液にアセトン又はアルコール等を加えて沈殿させる方法、水添重合体溶液を熱湯中に撹拌下投入し、溶媒を蒸留除去する方法等により行うことができる。
本発明の水添重合体の分子量は特に限定されないが、ＧＰＣ法におけるポリスチレン換算による重量平均分子量で３万〜２００万、好ましくは４万〜１００万、更に好ましくは５万〜５０万である。
【００３９】
本発明の熱可塑性樹脂組成物における（Ｄ）成分の配合量は、（Ａ）成分１０〜９０重量％、（Ｂ）成分９０〜１０重量％、及び（Ｃ）成分０〜５０重量％（但し、（Ａ）＋（Ｂ）＋（Ｃ）＝１００重量％）とからなる樹脂混合物１００重量部に対して、１〜５０重量部配合する。好ましくは５〜３０重量部である。１重量部未満では相溶化効果がなく衝撃強度が低下し、成形品に層状剥離が生じたり外観を悪化させる場合がある。その一方、５０重量部を超えると組成物の剛性や耐熱性が低下するので好ましくない。
【００４０】
さらに本発明の熱可塑性樹脂組成物には、上記（Ａ）〜（Ｄ）成分以外に、本発明の効果を損なうことのない範囲で、無機充填剤、有機充填剤、エラストマーおよび他の添加剤、例えば滑剤、可塑剤、離型剤、酸化防止剤、耐候（光）剤、紫外線吸収剤、帯電防止剤、熱硬化性樹脂、難燃剤、着色剤などを配合できる。
【００４１】
無機充填剤を配合する場合、その配合量は、（Ａ）〜（Ｄ）の成分からなる熱可塑性樹脂混合物１００重量部に対し、０〜１５０重量部を配合することができ、特に好ましくは１〜１００重量部である。１５０重量部を越えると樹脂の含浸がうまくいかないことがある。
【００４２】
無機充填剤の例として、タルク、マイカ、合成マイカ、合成ハイドロタルサイト、炭酸カルシウム、クレー、カオリナイト、酸化チタン、酸化亜鉛、珪藻土、シリカ、ガラスビーズ、ガラス中空球、ガラスフレーク、ガラスファイバー、炭化ケイ素ウイスカー、窒化ケイ素ウイスカー、酸化亜鉛ウイスカー、炭酸カルシウムウイスカー、硫酸バリウム、硫酸カルシウム、ウォラストナイト、チタン酸カリウム、セピオライト、ゾノトライト、ホウ酸アルミニウム、スメクタイト、カオリン、バーミキュライト、金属粉末、金属繊維、金属箔、カーボンファイバー、カーボンブラック等をあげることができる。
これらの無機充填剤は、そのままで又はシランカップリング剤等で表面処理して添加することが出来る。好ましいシランカップリング剤はアミノアルキルシランで、例えば、δ−アミノプロピルメチルエトキシシラン、δ−（Ｎ−アミノエチル）アミノブチルトリエトキシシラン、δ−（Ｎ−メチルエチル（Ｎ−アミノエチル）アミノイミノブチルトリエトキシシラン、ビスγ−Ｎ−プロピルジエチルアミノプロピルジメトキシシラン、ビスβ−（Ｎ−アミノエチル）ジエトキシシラン、β−Ｎ−エチルアミノエチルトリメトキシシラン、γ−プロピル（Ｎ−アミノエチル）アミノトリメトキシシラン及びβ−Ｎ−エチルアミンエチルトリβ−メトキシエトキシシラン等が挙げられる。
【００４３】
本発明の熱可塑性樹脂組成物の製造は、特定の方法に限定されないが、好ましくは溶融混練によるものである。これについて、熱可塑性樹脂について一般に実用されている混練方法が適用できる。例えば、（Ａ）〜（Ｄ）の各成分を、必要であれば、前述の付加的成分の項に記載の添加物等と共に、ヘンシェルミキサー、リボンブレンダー、Ｖ型ブレンダー等により均一に混合した後、一軸または多軸混練押出機、ロール、バンバリーミキサー、ラボプラストミル（ブラベンダー）等で混練することができる。前述した付加的成分を含め各成分は混練機に一括でフィードしても、順次フィードしても良い。また、前述した付加的成分から選ばれた２種以上の成分を予め混合したものを用いても良い。
【００４４】
混練温度と混練時間は望まれる熱可塑性樹脂組成物や混練機の種類等の条件により任意に選ぶことができるが、混練温度は１５０〜３５０℃、混練時間は２０分以下が好ましい。混練温度が３５０℃又は混練時間が２０分を越えると亜リン酸トリエステル、ＰＰＥ、又はポリエステル系樹脂の熱劣化が問題となり、成形品の物性の低下や外観の悪化が生じることがある。
【００４５】
本発明の熱可塑性樹脂組成物の成形加工法は、特に限定されるものではなく、一般に使用される熱可塑性樹脂成形機で成形することが可能であって、例えば、射出成形、押出成形、ブロー成形、カレンダー成形などの各種成形方法が適用可能である。
本発明の熱可塑性樹脂組成物およびその成形品は、自動車の内外装部品、電気機器外装部品、電線、ならびにオフィスオートメーション機器、あるいは薬品ビンなどの部品用途に適しており、特に自動車部品では、ボンネット、エアースポイラー、バンパー、フェンダー、サイドプロテクター、燃料タンク、オイルタンク、ラジエーター、ダクトホース、ハーネスチューブ、シート、リアシェルフ、インパネ、ホイールカバー、フロントパネル、外板等の用途に適している。
【００４６】
【実施例】
以下、実施例によって本発明をさらに具体的に説明するが、本発明はこれらの実施例によって何ら制限を受けるものではない。
なお、実施例、比較例中の部及び％は、特に断らない限り重量基準である。また、実施例、比較例中の各種測定は、下記の方法に拠った。
【００４７】
（１）水添重合体の製造
以下に記載の１）〜６）の方法により、水添重合体を製造した。尚、重合体の特性は以下の方法で測定した。
▲１▼ビニル結合（１，２結合及び３，４結合）含量
赤外吸収スペクトル法（モレロ法）によって求めた。
▲２▼結合スチレン含量
赤外吸収スペクトル法により、検量線を作成し求めた。
▲３▼重量平均分子量
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によりポリスチレン換算で求めた。装置は東ソー社製のＨＬＣ−８１２０を使用した。
▲４▼アミノ基含量（ｍｍｏｌ／ｋｇ・重合体）
Ａｎａｌｙ．Ｃｈｅｍ．５６４頁（１９５２）記載のアミン滴定法による定量により求めた。即ち、水添変性重合体を精製後、有機溶剤に溶解し、指示薬としてメチルバイオレットを用い、溶液の色が紫から水色に変化するまでＨＣｌＯ_４／ＣＨ_３ＣＯＯＨを滴定することにより求めた。
▲５▼共役ジエンの水添率
四塩化炭素を溶媒に、２７０ＭＨｚ、^１Ｈ−ＮＭＲスペクトルから算出した。
【００４８】
１）水添重合体（Ｄ−１）〜（Ｄ−３）および重合体（Ｒ−１）の製造
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、スチレン２００ｇ、テトラヒドロフラン１５０ｇ、及びｎ−ブチルリチウム０．９ｇを加え、重合開始温度５０℃にて１段目重合し、反応完結後、温度を２０℃として１，３−ブタジエン６９０ｇを添加して断熱にて２段目重合した。３０分後、スチレン１００ｇを添加し３段目重合し、反応完結後、１，３−ブタジエン１０ｇを添加してさらに４段目重合を行った。一部取り出したこのブロック重合体はビニル結合を８０％含有し、ＧＰＣで測定した重量平均分子量は約１１万であった。そして、この系内にＮ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリエトキシシラン３．９３ｇを加え、３０分反応させた。反応後、反応溶液を７０℃にし、ビス（η^５−シクロペンタジエニル）チタニウム（テトラヒドロフルフリルオキシ）クロライド０．４ｇ及びｎ−ブチルリチウム０．１５ｇを加え、水素圧１．０ＭＰａで６０分反応させた。反応後、反応液を常温、常圧に戻して反応容器より抜き出し、水中に撹拌投入して溶媒を水蒸気蒸留除去することによって重合体（Ｄ−１）を得た。得られた重合体（Ｄ−１）の水添率は９５％、重量平均分子量は約１２万、アミノ基含量は８ｍｍｏｌ／ｋｇ・重合体であった。
重合体（Ｄ−１）に準じて、表１に示すようなアミノ基を有する水添重合体になるように変性剤種類、単量体量などを変化させて重合体（Ｄ−２）〜（Ｄ−３）を得た。
また、重合体（Ｒ−１）は、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリエトキシシランを使用しない以外は重合体（Ｄ−１）に準じて重合して得た未変性水添共役ジエン重合体である。
【００４９】
２）水添重合体（Ｄ−４）の製造
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、テトラヒドロフラン１５０ｇ、スチレン４００ｇ、及び３−リチオ−１−Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロパン２．８８ｇを加え、重合開始温度５０℃にて重合した。反応完結後、温度を２０℃として１，３−ブタジエン５００ｇを添加して断熱重合した。３０分後、スチレン１００ｇを添加し、さらに重合を行った。そして、反応溶液を８０℃以上にして系内に水素を導入した。次いで、ビス（η^５−シクロペンタジエニル）チタニウム（テトラヒドロフルフリルオキシ）クロライド０．３２ｇ、テトラクロロシラン０．３９ｇを加え、水素圧１．０ＭＰａを保つようにして１時間反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より抜き出し、次いで、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、重合体（Ｄ−４）を得た。得られた重合体（Ｄ−４）の水添率は９８％、重量平均分子量は約１０万、アミノ基含量は９．５ｍｍｏｌ／ｋｇ・重合体であった。
【００５０】
３）水添重合体（Ｄ−５）の製造
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、テトラヒドロフラン１５０ｇ、スチレン５００ｇ、及び２，２，５，５−テトラメチル−１−（３−リチオプロピル）−１−アザ−２，５−ジシラシクロペンタンを２．８９ｇを加え、重合開始温度５０℃にて重合した。反応完結後、温度を２０℃として１，３−ブタジエン４００ｇを添加して断熱重合した。３０分後、スチレン１００ｇを添加し、さらに重合を行った。そして、反応溶液を８０℃以上にして系内に水素を導入した。次いで、ビス（η^５−シクロペンタジエニル）チタニウム（フルフリルオキシ）クロライド０．５５ｇ及びテトラクロロシラン０．３９ｇを加え、水素圧１．０ＭＰａを保つようにして１時間反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より抜き出し、次いで、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、重合体（Ｄ−５）を得た。得られた重合体（Ｄ−５）の水添率は９７％、重量平均分子量は約１２万、アミノ基含量は８．３ｍｍｏｌ／ｋｇ・重合体であった。
【００５１】
４）水添重合体（Ｄ−６）の製造
重合開始剤にｎ−ＢｕＬｉを用いて、表１の（Ｄ−６）に示す水添前共重合体構造になるように重合開始剤の量、単量体種類、単量体量、重合温度、重合時間等を変化させて、上記１）の製法に準じ重合体を得た。そして、該重合体の活性点にＰ−｛２−［Ｎ，Ｎ−ビス（トリメチルシリル）アミノ］エチル｝スチレン７．４ｇを加え、３０分反応させた。そして、反応溶液を８０℃以上にして系内に水素を導入した。次いで、ジクロロトリス（トリフェニルホスフィン）ルテニウム２．９７ｇを加え、水素圧２．０ＭＰａを保つようにして１時間反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より抜き出し、次いで、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、重合体（Ｄ−６）を得た。得られた重合体（Ｄ−６）の水添率は９９％、重量平均分子量は約１２万、アミノ基含量は４５ｍｍｏｌ／ｋｇ・重合体であった。
【００５２】
５）水添重合体（Ｄ−７）の製造
重合開始剤にｎ−ＢｕＬｉを用いて、表１の（Ｄ−７）に示す水添前共重合体構造になるように重合開始剤の量、単量体種類、単量体量、重合温度、重合時間等を変化させて、上記１）の製法に準じ重合体を得た。次いで、該重合体の活性点にＮ−ベンジリデンエチルアミン１．５６ｇを加え、３０分反応させた。そして、反応溶液を８０℃以上にして系内に水素を導入した。次いで、Ｐｄ−ＢａＳＯ_４２．６０ｇを加え、水素圧２．０ＭＰａを保つようにして１時間反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より抜き出し、次いで、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、重合体（Ｄ−７）を得た。得られた重合体（Ｄ−７）の水添率は９８％、重量平均分子量は約１３万、アミノ基含量は７ｍｍｏｌ／ｋｇ・重合体であった。
【００５３】
６）水添重合体（Ｄ−８）および重合体（Ｒ−２）の製造
窒素置換された内容積１０リットルの反応容器に、シクロヘキサン５０００ｇ、ブタジエン２００ｇ、テトラヒドロフラン０．２５ｇ、及びｎ−ブチルリチウム０．８０ｇを加え、重合開始温度７０℃にて１段目重合し反応完結後、一部取り出したこのブロック重合体のビニル結合は１０％であった温度を２０℃としてテトラヒドロフラン２５ｇ添加後、１，３−ブタジエン２９０ｇを添加して断熱にて２段目重合した。３０分後、スチレン５００ｇを添加し３段目重合し、反応完結後、１，３−ブタジエン１０ｇを添加してさらに４段目重合を行った。一部取り出したこのブロック重合体はビニル結合を６５％含有し、ＧＰＣで測定した重量平均分子量は約１２万であった。そして、この系内にＮ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリエトキシシラン３．４９ｇを加え、３０分反応させた。反応後、反応溶液を７０℃にし、ビス（η^５−シクロペンタジエニル）チタニウム（テトラヒドロフルフリルオキシ）クロライド０．４ｇ及びｎ−ブチルリチウム０．１５ｇを加え、水素圧１．０ＭＰａで６０分反応させた。反応後、反応液を常温、常圧に戻して反応容器より抜き出し、水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、重合体（Ｄ−８）を得た。得られた重合体（Ｄ−８）の水添率は９８％、重量平均分子量は約１５万、アミノ基含量は６．５ｍｍｏｌ／ｋｇであった。また、重合体（Ｒ−２）は、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリエトキシシランを使用しない以外は重合体（Ｄ−８）に準じて重合して得た未水添重合体である。
尚、表１に記載する重合体の構造Ａは「スチレン重合体ブロック」、Ｂは「ビニル結合含量が２５重量％未満のブタジエン重合体ブロック」、Ｃは「ビニル結合含量が２５重量％以上９０重量％以下のブタジエン重合体ブロック」を示す。
【００５４】
【表１】

【００５５】
（２）実施例及び比較例の各成分
（Ａ−１）ポリフェニレンエーテル樹脂（日本ジーイープラスチックス社製、商品名：ノリル７３１Ｊ）
（Ｂ−１）ポリブチレンテレフタレート樹脂（東レ社製、商品名：１４０１−Ｘ０６）
（Ｃ−１）ポリプロピレン（チッソ社製、商品名：Ｋ８０１７）
（Ｄ）水添重合体
表１に示す構造を有する水添重合体（Ｄ−１）〜（Ｄ−８）及び（Ｒ−１）〜（Ｒ−２）
尚、（Ｒ−３）は無水マレイン酸変性スチレン−エチレン・ブチレン−スチレンブロック共重合体（旭化成社製、商品名「タフテックＭ−１９１３」、スチレン含量４０重量％）
【００５６】
（３）物性評価
▲１▼メルトフローレート（ＭＦＲ）：ＪＩＳ　Ｋ　７２１０に準拠。ただし、温度は２８０℃，荷重は５ｋｇで測定した。数値が高いほど成形加工性が良い。
▲２▼耐熱性：荷重１８．６ｋｇ／ｃｍ２での荷重たわみ温度（℃）で表示した。
▲３▼アイゾット衝撃強度（単位：ｋｇ・ｃｍ／ｃｍ）：ノッチ付きのアイゾット衝撃強度を尺度とし、厚み１／４インチの試験片で評価した。
▲４▼成形外観：試験片の表面を目視で観察した。評価は、「表面が滑らか」を「○」、「表面がざらついて層状剥離している」を「×」とした。
▲５▼耐薬品性：試験片を室温下でトルエンに３０日間浸漬し、その前後での変化を目視にて観察した。表面の荒れなどの変化がみられたものを「×」、際立った変化がみられなかったものを「○」として判断した。
【００５７】
実施例１
（Ａ）成分であるＰＰＥ（Ａ−１）を６０部、（Ｂ）成分であるポリブチレンテレフタレート樹脂（Ｂ−１）を４０部、及び（Ｄ）成分であるアミノ基を含有する水添重合体（Ｄ−１）を１０部、とを二軸押出機（日本製鋼所社製ＴＥＸ４４）を用いて温度３００℃で溶融混練し、熱可塑性樹脂組成物を得た。次いで、この熱可塑性樹脂組成物を射出成形機（東芝機械社製ＩＳ−９０Ｂ型）を用い、シリンダー温度２６０℃、金型冷却温度８０℃にて射出成形を行い、試験片を作成した。上記記載の方法により物性評価を行った。結果を表２に示す。
【００５８】
実施例２〜１１
表２に示す配合を用い実施例１と同様にして試験片を作成し、物性評価を行った。結果を表２に示す。
【００５９】
【表２】

【００６０】
比較例１〜６
表３に示す配合を用い実施例１と同様にして試験片を作成し、物性評価を行った。結果を表３に示す。
【００６１】
【表３】

【００６２】
表２及び表３より、本発明の樹脂組成物は、成形加工性、耐衝撃性、耐熱性、成形外観及び耐薬品性に優れることが分かる。これに対し、（Ａ）成分と（Ｂ）成分の組成物（比較例１）では、成形加工性、耐衝撃性、耐熱性、成形外観及び耐薬品性のいずれもが劣り、（Ａ）成分が９０重量％を超えた比較例２では、成形加工性、耐衝撃性及び耐薬品性が劣る。一方、（Ｂ）成分が９０重量％を超えた比較例３では、耐熱性が劣る。未変性の水添重合体を用いた比較例４〜５では、耐熱性、耐衝撃性、成形外観に劣る。また、無水マレイン酸変性水添重合体を用いた比較例６では、成形加工性が極端に低下し、成形外観、耐衝撃性にも劣ることが分かる。
【００６３】
【発明の効果】
本発明の熱可塑性樹脂組成物は、アミノ基を含有するブロック共重合体の水添重合体を配合することにより、ポリフェニレンエーテル系樹脂及びポリエステル系樹脂との相溶性が向上し、各樹脂が有する特性を十分に奏することができる熱可塑性樹脂組成物が提供される。本発明の熱可塑性樹脂組成物は、耐熱性、耐衝撃性、成形加工性、成形外観及び耐薬品性などに優れ、電気電子用から自動車用まで様々な用途に使用できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a thermoplastic resin composition. More specifically, a thermoplastic resin composition having excellent moldability, impact resistance, heat resistance, and molded appearance, having chemical resistance, and which can be used in a wide range of fields such as electric and electronic parts, mechanical parts, and automobile parts. It relates to a product and a molded product thereof.
[0002]
[Prior art]
Polyphenylene ether-based resins (hereinafter sometimes referred to as “PPE”) are used as engineering plastics having excellent heat resistance, dimensional stability, non-hygroscopicity, electrical properties, and the like. However, it is unsuitable to use it alone for producing injection-molded products or extruded / hollow-molded products because of poor molding processability and chemical resistance.
On the other hand, a polyester resin represented by polyethylene terephthalate has a high melting point or a high glass transition temperature, has a low melt viscosity, and has good chemical resistance. As an engineering plastic with excellent strength, it is widely used in automobile parts and electric / electronic device parts. However, since a polyester-based resin has a low melt tension, it is difficult to obtain a single large hollow molded article.
[0003]
For this reason, if a resin composition having both the good properties of PPE and a polyester-based resin and complementing the undesired properties can be obtained, it will be possible to provide an excellent resin material having a wide range of applications, and its industrial meaning is It can be said that it is very large. Therefore, compositions in which both resins are simply melt-mixed are described in, for example, JP-B-51-21664, JP-A-49-75662 and JP-A-59-159847. However, the compatibility between PPE and the polyester resin is poor, and the composition is unlikely to be uniform and fine in such a simple blend system. As a result, the obtained molded article does not show a satisfactory improvement effect on the impact resistance, heat resistance and chemical resistance that is equivalent to the composition, and the appearance of the molded article is rather deteriorated.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to improve the compatibility between PPE and a polyester resin to provide a thermoplastic resin composition having excellent moldability, impact resistance, heat resistance, and molded appearance, and having chemical resistance. And
[0005]
[Means for Solving the Invention]
The present inventors have conducted intensive studies to achieve the above object, and as a result, a polyphenylene ether resin and a polyester resin can be made compatible with each other by blending a hydrogenated polymer of a block copolymer containing an amino group, As a result, they have found that a thermoplastic resin composition having both impact resistance, heat resistance, moldability, mold appearance, and chemical resistance can be obtained, and have completed the present invention.
[0006]
That is, the present invention provides the following thermoplastic resin composition and a molded article using the same.
[1] (A) 10 to 90% by weight of polyphenylene ether-based resin, (B) 90 to 10% by weight of polyester-based resin, and (C) 0 to 50% by weight of polyolefin-based resin (however, (A) + (B) + (C) = 100% by weight) with respect to 100 parts by weight of the resin mixture consisting of (D) at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound. A thermoplastic resin composition having at least one and containing 1 to 50 parts by weight of a hydrogenated polymer of a block copolymer containing an amino group.
[2] The thermoplastic resin composition according to the above [1], wherein the content of the amino group in the hydrogenated polymer is 0.5 to 300 mmol / kg · polymer.
[3] The thermoplastic resin composition according to any of [1] or [2], wherein at least 50% of the double bonds derived from the conjugated diene of the hydrogenated polymer are saturated.
[4] The thermoplastic resin according to any one of [1] to [3], wherein the hydrogenated polymer is a polymer produced by the following method (a) or (b). Resin composition.
(A) A polymer produced by block copolymerizing an aromatic vinyl compound and a conjugated diene compound in the presence of an organic alkali metal compound having an amino group, and then hydrogenating the polymer.
(B) An aromatic vinyl compound and a conjugated diene compound are block-copolymerized in the presence of an organic alkali metal compound, and the active site of the obtained polymer is subjected to the following general formula (1) and / or the following general formula (2) A polymer produced by reacting a compound represented by the formula (1) with a polymer, and then hydrogenating the polymer.
R¹R²C = N−Y (1)
[In the above general formula (1), R¹And R²Is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 100 carbon atoms. Is an organosiloxy group. ]
R³ _(4-mn)Si (OR⁴)_mX_n(2)
[In the above general formula (2), R³Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms;³When there are a plurality of³May be the same or different groups. R⁴Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms;⁴When there are a plurality of⁴May be the same or different groups. X is a substituent having a polar group containing an N atom. When there are a plurality of Xs, each X may be the same or different, and each X may be an independent substituent forming a cyclic structure. Is also good. m is 1, 2 or 3, and n is an integer of 1, 2 or 3. The sum of m and n is 1-4. ]
(C) produced by subjecting an aromatic vinyl compound, a conjugated diene compound and an unsaturated monomer having an amino group to block copolymerization in the presence of an organic alkali metal compound, and thereafter hydrogenating the polymer. .
[5] A molded article comprising the thermoplastic resin composition according to any one of the above [1] to [4].
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the thermoplastic resin composition of the present invention will be specifically described.
The thermoplastic resin composition of the present invention comprises (A) 10 to 90% by weight of a polyphenylene ether-based resin, (B) 90 to 10% by weight of a polyester-based resin, and (C) 0 to 50% by weight of a polyolefin-based resin (however, (D) at least one polymer block mainly composed of an aromatic vinyl compound and 100 parts by weight of a resin mixture composed of (A) + (B) + (C) = 100% by weight, and a conjugated diene compound. It is characterized by having 1 to 50 parts by weight of a hydrogenated polymer of a block copolymer having at least one polymer block as a main component and containing an amino group.
Hereinafter, each component will be described more specifically.
[0008]
1. Polyphenylene ether resin
The polyphenylene ether-based resin (hereinafter sometimes referred to as “component (A)”) used in the present invention is a polymer and / or copolymer having a repeating unit structure represented by the following general formula (3).
[0009]
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[0010]
(In the above general formula (3), R¹², R¹³Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, an aminoalkyl group, or a halogen atom. R¹⁴, R^FifteenEach independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. )
Specific examples of the polyphenylene ether-based resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2 -Methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like. Further, 2,6-dimethylphenol and other phenols (for example, , 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1) is more preferable. , 4-phenylene ether) are preferred.
The molecular weight of the polyphenylene ether-based resin of the present invention is not particularly limited, but preferably has an intrinsic viscosity of 0.2 to 0.8 dl / g at 30 ° C. measured in chloroform. More preferably, it has an intrinsic viscosity of 0.3 to 0.6 dl / g.
[0011]
2. Polyester resin
The polyester-based resin (hereinafter sometimes referred to as “component (B)”) used in the present invention is preferably a thermoplastic saturated polyester resin, and is composed of an aromatic dicarboxylic acid or an ester-forming derivative thereof, and a diol or an ester derivative thereof. Or a ring-opened polymer of lactone, etc., obtained by a condensation reaction containing as a main component, and these are used alone or in combination of two or more.
[0012]
Examples of the “aromatic dicarboxylic acid” include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4′-diphenylcarboxylic acid, , 4'-diphenyletherdicarboxylic acid, or ester-forming derivatives thereof, and the like, and these are used alone or in combination of two or more.
The "diol" component is an aliphatic diol having 2 to 10 carbon atoms, that is, ethylene glycol, 1,3-propanediol, 2-methylpropanediol, 1,4-butanediol, neopentyl glycol, 1,5- Pentanediol, 1,6-hexanediol, 1,8-octanediol, cyclohexanediol or the like, or a long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-polypropylene glycol, polytetramethylene glycol, or the like And these may be used alone or in combination of two or more.
[0013]
Furthermore, the polyester-based resin of the present invention may be, for example, a tri- or higher-functional monomer such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, or pyromellitic acid if it is 1 mol% or less based on all structural units. It may have derived structural units.
Specifically, the polyester resin of the present invention includes polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polyethylene-2,6-naphthalate, polyethylene-1,2-bis (phenoxy) ethane 4,4. '-Dicarboxylate, polycaprolactone-based resin, polyarylate-based resin, etc., and these can be used alone or in combination of two or more. Among them, polybutylene terephthalate, polyethylene terephthalate or a mixture thereof is preferable from the viewpoint of mechanical properties, heat resistance, and moldability.
Although the molecular weight of the polyester resin of the present invention is not particularly limited, those having an intrinsic viscosity of 0.5 to 1.5 when measured in a phenol / tetrachloroethane (weight ratio = 1/1) mixed solvent are preferred. It is preferable in terms of mechanical strength and heat resistance.
[0014]
3. Polyolefin resin
The polyolefin resin (hereinafter sometimes referred to as “component (C)”) used in the present invention is a crystalline polyolefin obtained by polymerizing one or more monoolefins by either a high-pressure method or a low-pressure method. It is a resin (polymer), and among them, polyethylene, polypropylene and polybutene-1 are preferable. The polyolefin resin may be a homopolymer or a copolymer obtained by copolymerizing with another monomer.
[0015]
Other copolymerizable monomers include, for example, ethylene (excluding the case where the main polymer is polyethylene), propylene (excluding the case where the main polymer is polypropylene), and butene-1 (where the main polymer is polybutene-1). Linear α-olefins such as pentene-1, hexene-1, heptene-1, and octene-1; 4-methylpentene-1, 2-methylpropene-1, and 3-methylpentene-1 And α-olefins such as 5-methylhexene-1, 4-methylhexene-1, and 4,4-dimethylpentene-1; and monomers copolymerizable with the α-olefin. . The compounding amount of these copolymerizable monomer components is 20% by weight or less, preferably 15% by weight or less. There is no particular limitation on the form of the copolymer when these are copolymerized, as long as they have crystallinity. For example, they may be any of a random type, a block type, a graft type, and a mixed type thereof.
[0016]
The proportion of the component (A) in the thermoplastic resin composition of the present invention is 10 to 90% by weight when the total amount of the components (A), (B) and (C) is 100% by weight, and is preferably. 30 to 70% by weight. If it is less than 10% by weight, the heat resistance decreases, and if it exceeds 90% by weight, the moldability and the chemical resistance decrease.
The compounding ratio of the component (B) is 90 to 10% by weight, preferably 70 to 30% by weight. If it is less than 10% by weight, the chemical resistance is poor, and if it exceeds 90% by weight, the heat resistance may be reduced.
The compounding ratio of the component (C) is 0 to 50% by weight, preferably 5 to 30% by weight. By blending the component (C), the impact resistance is improved, but if it exceeds 50% by weight, the heat resistance is reduced.
[0017]
4. Hydrogenated polymer
The hydrogenated polymer (hereinafter sometimes referred to as “component (D)”) used in the present invention comprises at least one polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound. And a hydrogenated polymer (hereinafter, referred to as "hydrogenated polymer of the present invention") of a block copolymer having at least one and containing an amino group (hereinafter, referred to as "the block copolymer of the present invention"). In an inert organic solvent, an aromatic vinyl compound and a conjugated diene compound can be easily obtained by forming an amino group-containing block copolymer using an organic alkali metal compound as a polymerization initiator and thereafter hydrogenating the copolymer. be able to.
[0018]
Specifically, it can be obtained, for example, by the following methods (a) to (c).
(A) It is produced by block copolymerizing an aromatic vinyl compound and a conjugated diene compound in the presence of an organic alkali metal compound having an amino group, and then hydrogenating the polymer.
(B) An aromatic vinyl compound and a conjugated diene compound are block-copolymerized in the presence of an organic alkali metal compound, and the active site of the obtained polymer is subjected to the following general formula (1) and / or the following general formula (2) Is produced by reacting a compound represented by the following formula with a polymer, and then hydrogenating the polymer.
R¹R²C = N−Y (1)
[In the above general formula (1), R¹And R²Is each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 100 carbon atoms. Is an organosiloxy group. ].
R³ _(4-mn)Si (OR⁴)_mX_n(2)
[In the above general formula (2), R³Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms;³When there are a plurality of³May be the same or different groups. R⁴Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms;⁴When there are a plurality of⁴May be the same or different groups. X is a substituent having a polar group containing an N atom. When there are a plurality of Xs, each X may be the same or different, and each X may be an independent substituent forming a cyclic structure. Is also good. m is 1, 2 or 3, and n is an integer of 1, 2 or 3. The sum of m and n is 1-4. ]
(C) produced by subjecting an aromatic vinyl compound, a conjugated diene compound and an unsaturated monomer having an amino group to block copolymerization in the presence of an organic alkali metal compound, and thereafter hydrogenating the polymer. .
Of these, the use of the copolymer produced by (a) or (b) is more preferable because the composition of the present invention has improved heat resistance and impact resistance.
[0019]
Examples of the “aromatic vinyl compound” include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned. Of these, styrene and tert-butylstyrene are preferred.
Examples of the “conjugated diene compound” include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadiene, 1,3 -Hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, chloroprene and the like. Of these, 1,3-butadiene and isoprene are preferred.
[0020]
Examples of the organic alkali metal compound having an amino group used in the method (a) include the following general formulas (4) and (5).
[0021]
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[0022]
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[0023]
[In the above general formula (4), R⁵And R⁶Are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, and the other is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It is an aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms. Further, R in the above general formulas (4) and (5)⁷Is an alkylene group or an alkylidene group having 1 to 20 carbon atoms. Further, R in the above general formula (5)⁸Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. ]
Specific examples of the organic alkali metal compound represented by the general formula (4) or (5) include 3-lithio-1- [N, N-bis (trimethylsilyl)] aminopropane (CAS No. 289719-98-). 8), 2-lithio-1- [N, N-bis (trimethylsilyl)] aminoethane, 3-lithio-2,2-dimethyl-1- [N, N-bis (trimethylsilyl)] aminopropane, 2,2, 5,5-tetramethyl-1- (3-lithiopropyl) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (3-lithio-2,2 -Dimethyl-propyl) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (2-lithioethyl) -1-aza-2,5-disilacyclopentane , 3-Lithio-1- [ -(Tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminopropane, 3-lithio-1- (N-methyl-N-trimethylsilyl) aminopropane, 3-lithio-1- (N-ethyl-N-trimethylsilyl) Aminopropane and the like.
The amount of the organic alkali metal compound having an amino group to be used in the method (a) is not particularly limited, and various amounts can be used as needed. %, Preferably used in an amount of 0.03 to 5% by weight.
[0024]
Examples of the organic alkali metal compound used in the methods (b) and (c) include an organic lithium compound and an organic sodium compound, and an organic lithium compound such as n-butyllithium and sec-butyllithium is particularly preferable.
The amount used is not particularly limited, and various amounts can be used as necessary. Usually, the amount is 0.02 to 15% by weight, preferably 0.03 to 5% by weight, per 100% by weight of the monomer. Used in quantity.
[0025]
Specific examples of the compound of the general formula (1) used in the method (b) include N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutylamine, N-benzylideneaniline and the like.
[0026]
Specific examples of the alkoxysilane compound represented by the general formula (2) used in the method (b) include N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane and N, N-bis (trimethylsilyl). ) Aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropyldimethylethoxysilane, N, N-bis (trimethylsilyl) aminopropyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) Minoethyldimethylethoxysilane, N, N-bis (trimethylsilyl) aminoethyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N -Methyl-N-trimethylsilylaminopropyltrimethoxysilane, N-methyl-N-trimethylsilylaminopropyltriethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylmethoxysilane , N-methyl-N-trimethylsilylaminopropylmethyldiethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldimethoxysilane, N, N-dimethyl Aminopropyltrimethoxysilane, N, N-dimethylaminopropyltriethoxysilane, N, N-dimethylaminopropyldimethylethoxysilane, N, N-dimethylaminopropyldimethylmethoxysilane, N, N-dimethylaminopropylmethyldiethoxysilane N, N-dimethylaminopropylmethyldimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (tri Ethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N -(4-N, N-dimethylaminobenzylidene) -3- (trier Toxisilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (trimethoxysilyl)- 1-propanamine, N-ethylidene-3- (trimethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (trimethoxysilyl) -1-propanamine, N- (4- N, N-dimethylaminobenzylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- ( 1-methylethylidene) -3- (methyldimethoxysilyl) -1-propanamine, N-ethylidene-3- (methyldimethoxysilyl) -1-propa Amine, N- (1-methylpropylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (methyldimethoxysilyl) -1-propane Amine, N- (1,3-dimethylbutylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (methyldiethoxysilyl) -1-propanamine N-ethylidene-3- (methyldiethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (dimethyl Toxisilyl) -1-propanamine, N- (1-methylethylidene) -3- (dimethylmethoxysilyl) -1-propanamine, N-ethylidene-3- (dimethylmethoxysilyl) -1-propanamine, N- ( 1-methylpropylidene) -3- (dimethylmethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (dimethylmethoxysilyl) -1-propanamine, N- ( 1,3-dimethylbutylidene) -3- (dimethylethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (dimethylethoxysilyl) -1-propanamine, N-ethylidene-3- (Dimethylethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (dimethylethoxysilyl) L) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (dimethylethoxysilyl) -1-propanamine and the like.
[0027]
The amount used when the compound represented by the general formula (1) and / or the general formula (2) is modified by reacting with the block copolymer of the aromatic vinyl compound and the conjugated diene compound is not particularly limited. However, usually, it is 0.2 to 3 moles, preferably 0.3 to 1.5 moles, more preferably 0.4 to 1.3 moles, per mole of the active site derived from the organic alkali metal compound. Used in the ratio of
[0028]
The unsaturated monomer having an amino group used in the method (c) is represented by the following general formula (6) or (7).
[0029]
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[0030]
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[0031]
[In the above general formulas (6) and (7), R⁹And R¹⁰Are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, and the other is an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms And an aralkyl group having 7 to 20 carbon atoms or an organosiloxy group having 1 to 100 carbon atoms. Further, in the general formula (7), R¹¹Is an alkylene group or an alkylidene group having 1 to 20 carbon atoms. Further, n in the general formulas (6) and (7) is 1 to 3. ]
[0032]
Specific examples of the unsaturated monomer represented by the general formula (6) or (7) include p- [N, N-bis (trimethylsilyl) amino] styrene and p- [N, N-bis (trimethylsilyl) ) Aminomethyl] styrene, p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene, m- [N, N-bis (trimethylsilyl) amino] styrene, p- (N-methyl-N- Trimethylsilylamino) styrene, p- (N-methyl-N-trimethylsilylaminomethyl) styrene and the like.
The amount of the unsaturated monomer represented by the general formula (6) or (7) is 0.01 to 100 times, preferably 0.01 to 100 times, the number of moles of the active site derived from the organic alkali metal. It is added in a molar ratio of 10 times, particularly preferably 1.0 to 3.0 times. Further, the unsaturated monomer can be added at any time such as at the start of polymerization, during polymerization, before polymerization, or after polymerization.
[0033]
The content of the amino group in the block copolymer of the present invention is usually 0.5 to 300 mmol / kg · polymer, preferably 1 to 100 mmol / kg · polymer, more preferably 3 to 50 mmol / kg. -It is a polymer. The position of the amino group is not particularly limited, and may be present at the polymer chain terminal or at the side chain, but is preferably present at the polymer chain terminal. The block copolymer present at the polymer chain end is produced according to the above (a) or (b), and when the copolymer is used, the heat resistance and impact resistance of the composition of the present invention are further improved. Therefore, it is more preferable.
Further, the amino group is preferably a primary amino group and / or a secondary amino group.
[0034]
In the block copolymer of the present invention, the content ratio of the polymerized unit of the aromatic vinyl compound to the polymerized unit of the conjugated diene compound is 20/80 to 80/20 by weight, preferably 30/70 to 60. / 40 range.
[0035]
The block copolymer of the present invention is a “copolymer having at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound”, and has the following ( Copolymers of the polymer block of A) with the polymer blocks of (B) and / or (C), and also copolymers of these with the polymer block of (D) are included.
(A) Aromatic vinyl compound polymer block containing 80% by weight or more of an aromatic vinyl compound
(B) a conjugated diene polymer block having a vinyl bond content of less than 25% by weight
(C) a conjugated diene polymer block having a vinyl bond content of 25% by weight or more and 90% by weight or less
(D) a random copolymer block of an aromatic vinyl compound and a conjugated diene or a so-called taper block in which the content of the aromatic vinyl compound changes continuously in one molecule
[0036]
Specific examples of the above “copolymer having at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound” include (A)-(B) , (A)-(C), [(A)-(B)] x-Y, [(A)-(C)] x-Y, (A)-(B)-(C), (A) -(B)-(D), (A)-(B)-(A), (A)-(C)-(A), (A)-(D)-(C), (A)-( C)-(B), [(A)-(B)-(C)] x-Y, [(A)-(B)-(A)] x-Y, [(A)-(C)- (A)] XY, [(A)-(D)-(C)] xy, (A)-(B)-(A)-(B), (B)-(A)-( B)-(A), (A)-(C)-(A)-(C), (C)-(A)-(C)-(A), [(A)- B)-(A)-(B)] x-Y, (A)-(B)-(A)-(B)-(A), [(A)-(B)-(A)-(B) )-(A)] x-Y, [(B)-(A)] x-Y, [(C)-(A)] x-Y, (B)-(A)-(B)-(C ), (B)-(A)-(B)-(A), (B)-(A)-(C)-(A), (C)-(A)-(D)-(A), (C)-(A)-(D)-(C), [(C)-(A)-(B)-(C)] x-Y, [(D)-(A)-(B)- (A)] xy, [(D)-(A)-(C)-(A)] xy, [(D)-(A)-(D)-(C)] xy, (D)-(A)-(B)-(A)-(B), (D)-(B)-(A)-(B)-(A), (D)-(A)-(C )-(A)-(C), (D)-(C)-(A)-(C)-(A), [( )-(A)-(B)-(A)-(B)] x-Y, (D)-(A)-(B)-(A)-(B)-(A), [(D) -(A)-(B)-(A)-(B)-(A)] xY (where x is an integer of 2 to 8, and Y is a residue of a coupling agent) is there.).
[0037]
Examples of the coupling agent include a halogen compound, an epoxy compound, a carbonyl compound, and a polyvinyl compound.Specifically, for example, methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, dibromoethane, epoxy For example, petroleum soybean oil, divinylbenzene, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis (trichlorosilyl) ethane, diethyl adipate, dimethyl adipate, dimethyl terephthalic acid, diethyl terephthalic acid, polyisocyanate and the like can be mentioned.
[0038]
The hydrogenated polymer of the present invention partially or selectively hydrogenates the amino-containing block copolymer obtained as described above. The hydrogenation method and reaction conditions are not particularly limited, and the hydrogenation is usually carried out by hydrogenation at 20 to 150 ° C. and under a hydrogen pressure of 0.1 to 10 MPa in the presence of a hydrogenation catalyst. In this case, the hydrogenation rate can be arbitrarily selected by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, or the reaction time. The degree of hydrogenation is at least 50%, preferably at least 80%, particularly preferably at least 95% of the double bond derived from the conjugated diene which is an unsaturated part. The double bond is present in either the main chain or the side chain, but may be randomly hydrogenated, the side chain may be preferentially hydrogenated, or the main chain may be preferentially hydrogenated. It may be. The hydrogenation catalyst is generally a compound containing any one of metals from the group Ib, IVb, Vb, VIb, VIIb, and VIII of the periodic table, such as Ti, V, Co, Ni, Zr, Ru, Rh, Pd, and Hf. , Re, and a compound containing a Pt atom can be used. Specific examples of the hydrogenation catalyst include metallocene compounds such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, and Re, and metals such as Pd, Ni, Pt, Rh, and Ru. A supported heterogeneous catalyst supported on a carrier such as carbon, silica, alumina, or diatomaceous earth; a homogeneous Ziegler type in which an organic salt or acetylacetone salt of a metal element such as Ni or Co is combined with a reducing agent such as organic aluminum. Examples include catalysts, organometallic compounds or complexes such as Ru and Rh, and fullerenes and carbon nanotubes that have absorbed hydrogen. Among them, a metallocene compound containing any of Ti, Zr, Hf, Co, and Ni is preferable in that a hydrogenation reaction can be performed uniformly in an inert organic solvent. Further, a metallocene compound containing any of Ti, Zr, and Hf is preferable. Particularly, a hydrogenation catalyst obtained by reacting a titanocene compound with alkyllithium is preferable because it is an inexpensive and industrially particularly useful catalyst. As specific examples, for example, JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, JP-A-11-292924, 2000-37632, JP-A-59-133203, JP-A-63-5401, JP-A-62-218403, JP-A-7-90017, JP-B-43-19960, The hydrogenation catalyst described in JP-B-47-40473 is exemplified. The above hydrogenation catalyst may be used alone or in combination of two or more. In the present invention, after hydrogenation, the residue of the catalyst is removed as necessary, or a phenolic or amine-based antioxidant is added, and then the hydrogenated polymer is isolated from the hydrogenated polymer solution. Isolation of the hydrogenated polymer is performed, for example, by a method of adding acetone or alcohol to the hydrogenated polymer solution to cause precipitation, a method of throwing the hydrogenated polymer solution into boiling water with stirring, and removing the solvent by distillation. It can be carried out.
Although the molecular weight of the hydrogenated polymer of the present invention is not particularly limited, it is 30,000 to 2,000,000, preferably 40,000 to 1,000,000, and more preferably 50,000 to 500,000 as a weight average molecular weight in terms of polystyrene by the GPC method.
[0039]
In the thermoplastic resin composition of the present invention, the compounding amount of the component (D) is 10 to 90% by weight of the component (A), 90 to 10% by weight of the component (B), and 0 to 50% by weight of the component (C). , (A) + (B) + (C) = 100% by weight) with respect to 100 parts by weight of the resin mixture. Preferably it is 5 to 30 parts by weight. If the amount is less than 1 part by weight, there is no compatibilizing effect, the impact strength is reduced, and the molded product may be delaminated or deteriorate the appearance. On the other hand, if it exceeds 50 parts by weight, the rigidity and heat resistance of the composition decrease, which is not preferable.
[0040]
Furthermore, in addition to the above components (A) to (D), the thermoplastic resin composition of the present invention may contain an inorganic filler, an organic filler, an elastomer, and other additives within a range that does not impair the effects of the present invention. For example, a lubricant, a plasticizer, a release agent, an antioxidant, a weather (light) agent, an ultraviolet absorber, an antistatic agent, a thermosetting resin, a flame retardant, a colorant, and the like can be blended.
[0041]
When the inorganic filler is compounded, the compounding amount can be 0 to 150 parts by weight, particularly preferably 1 to 100 parts by weight of the thermoplastic resin mixture composed of the components (A) to (D). １００100 parts by weight. If it exceeds 150 parts by weight, impregnation of the resin may not be successful.
[0042]
Examples of inorganic fillers include talc, mica, synthetic mica, synthetic hydrotalcite, calcium carbonate, clay, kaolinite, titanium oxide, zinc oxide, diatomaceous earth, silica, glass beads, glass hollow spheres, glass flakes, glass fiber, Silicon carbide whiskers, silicon nitride whiskers, zinc oxide whiskers, calcium carbonate whiskers, barium sulfate, calcium sulfate, wollastonite, potassium titanate, sepiolite, zonotolite, aluminum borate, smectite, kaolin, vermiculite, metal powder, metal fibers, Examples include metal foil, carbon fiber, carbon black, and the like.
These inorganic fillers can be added as they are or after surface treatment with a silane coupling agent or the like. Preferred silane coupling agents are aminoalkylsilanes, for example, δ-aminopropylmethylethoxysilane, δ- (N-aminoethyl) aminobutyltriethoxysilane, δ- (N-methylethyl (N-aminoethyl) aminoimino Butyltriethoxysilane, bis-γ-N-propyldiethylaminopropyldimethoxysilane, bisβ- (N-aminoethyl) diethoxysilane, β-N-ethylaminoethyltrimethoxysilane, γ-propyl (N-aminoethyl) amino And trimethoxysilane and β-N-ethylamineethyltriβ-methoxyethoxysilane.
[0043]
The production of the thermoplastic resin composition of the present invention is not limited to a specific method, but is preferably by melt kneading. In this regard, kneading methods generally used for thermoplastic resins can be applied. For example, after each of the components (A) to (D) is uniformly mixed with the additives described in the above-mentioned additional components, if necessary, using a Henschel mixer, a ribbon blender, a V-type blender, or the like. Can be kneaded with a single-screw or multi-screw kneading extruder, roll, Banbury mixer, Labo Plast mill (Bradbender) or the like. Each component including the above-mentioned additional components may be fed to the kneader at once or may be fed sequentially. Further, a mixture of two or more components selected from the above-mentioned additional components in advance may be used.
[0044]
The kneading temperature and the kneading time can be arbitrarily selected depending on the desired conditions such as the type of the thermoplastic resin composition and the kneading machine, but the kneading temperature is preferably 150 to 350 ° C., and the kneading time is preferably 20 minutes or less. When the kneading temperature is 350 ° C. or the kneading time exceeds 20 minutes, thermal degradation of the phosphite triester, PPE, or polyester resin becomes a problem, and the physical properties and appearance of the molded product may deteriorate.
[0045]
The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and can be molded by a commonly used thermoplastic resin molding machine, for example, injection molding, extrusion molding, blow molding. Various molding methods such as molding and calendering can be applied.
The thermoplastic resin composition of the present invention and the molded product thereof are suitable for interior and exterior parts of automobiles, exterior parts of electric equipment, electric wires, and office automation equipment, or parts such as chemical bottles. Suitable for applications such as air spoilers, bumpers, fenders, side protectors, fuel tanks, oil tanks, radiators, duct hoses, harness tubes, seats, rear shelves, instrument panels, wheel covers, front panels, and outer panels.
[0046]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited by these Examples.
Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified. Various measurements in the examples and comparative examples were based on the following methods.
[0047]
(1) Production of hydrogenated polymer
A hydrogenated polymer was produced by the methods 1) to 6) described below. The properties of the polymer were measured by the following methods.
(1) Content of vinyl bond (1,2 bond and 3,4 bond)
It was determined by an infrared absorption spectrum method (Morello method).
(2) Bound styrene content
A calibration curve was created and determined by infrared absorption spectroscopy.
(3) Weight average molecular weight
It was determined in terms of polystyrene by gel permeation chromatography (GPC). The apparatus used was HLC-8120 manufactured by Tosoh Corporation.
(4) Amino group content (mmol / kg polymer)
Analy. Chem. Quantitative determination by the amine titration method described on page 564 (1952). That is, after the hydrogenated modified polymer is purified, it is dissolved in an organic solvent, methyl violet is used as an indicator, and HClO is used until the color of the solution changes from purple to light blue.₄/ CH₃COOH was determined by titration.
(5) Hydrogenation rate of conjugated diene
270MHz, using carbon tetrachloride as a solvent¹It was calculated from the 1 H-NMR spectrum.
[0048]
1) Production of hydrogenated polymers (D-1) to (D-3) and polymer (R-1)
To a nitrogen-replaced reaction vessel having an internal volume of 10 liters, 5000 g of cyclohexane, 200 g of styrene, 150 g of tetrahydrofuran, and 0.9 g of n-butyllithium were added, and the first-stage polymerization was carried out at a polymerization initiation temperature of 50 ° C., and the reaction was completed. The temperature was set to 20 ° C., and 690 g of 1,3-butadiene was added, and the second-stage polymerization was performed with heat insulation. Thirty minutes later, 100 g of styrene was added to perform third-stage polymerization, and after completion of the reaction, 10 g of 1,3-butadiene was added to perform fourth-stage polymerization. The partially removed block polymer contained 80% of vinyl bonds and had a weight average molecular weight of about 110,000 as measured by GPC. Then, to this system, 3.93 g of N, N-bis (trimethylsilyl) aminopropyltriethoxysilane was added and reacted for 30 minutes. After the reaction, the reaction solution was heated to 70 ° C., and bis (η⁵-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride (0.4 g) and n-butyllithium (0.15 g) were added and reacted at a hydrogen pressure of 1.0 MPa for 60 minutes. After the reaction, the reaction solution was returned to normal temperature and normal pressure, withdrawn from the reaction vessel, stirred and poured into water, and the solvent was distilled off by steam to obtain a polymer (D-1). The hydrogenation ratio of the obtained polymer (D-1) was 95%, the weight average molecular weight was about 120,000, and the amino group content was 8 mmol / kg · polymer.
According to the polymer (D-1), the type of the modifier, the amount of the monomer, and the like are changed so as to obtain a hydrogenated polymer having an amino group as shown in Table 1 and the polymer (D-2) to (D-3) was obtained.
The polymer (R-1) is an unmodified hydrogenated conjugated diene obtained by polymerization according to the polymer (D-1) except that N, N-bis (trimethylsilyl) aminopropyltriethoxysilane is not used. It is a polymer.
[0049]
2) Production of hydrogenated polymer (D-4)
5000 g of cyclohexane, 150 g of tetrahydrofuran, 400 g of styrene and 2.88 g of 3-lithio-1-N, N-bis (trimethylsilyl) aminopropane were added to a nitrogen-replaced reaction vessel having an internal volume of 10 liters, and a polymerization initiation temperature of 50 ° C. Was polymerized. After the reaction was completed, the temperature was set to 20 ° C., and 500 g of 1,3-butadiene was added to perform adiabatic polymerization. After 30 minutes, 100 g of styrene was added, and polymerization was further performed. Then, the temperature of the reaction solution was raised to 80 ° C. or higher, and hydrogen was introduced into the system. Then, screw (η⁵-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride (0.32 g) and tetrachlorosilane (0.39 g) were added, and the mixture was reacted for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure and withdrawn from the reaction vessel, and then the reaction solution was stirred into water to remove the solvent by steam distillation to obtain a polymer (D-4). The hydrogenation ratio of the obtained polymer (D-4) was 98%, the weight average molecular weight was about 100,000, and the amino group content was 9.5 mmol / kg · polymer.
[0050]
3) Production of hydrogenated polymer (D-5)
In a 10-liter reaction vessel purged with nitrogen, 5000 g of cyclohexane, 150 g of tetrahydrofuran, 500 g of styrene, and 2,2,5,5-tetramethyl-1- (3-lithiopropyl) -1-aza-2,5 2.89 g of disilacyclopentane was added, and the mixture was polymerized at a polymerization initiation temperature of 50 ° C. After completion of the reaction, the temperature was set to 20 ° C., and 400 g of 1,3-butadiene was added to carry out adiabatic polymerization. After 30 minutes, 100 g of styrene was added, and polymerization was further performed. Then, the temperature of the reaction solution was raised to 80 ° C. or higher, and hydrogen was introduced into the system. Then, screw (η⁵0.55 g of (cyclopentadienyl) titanium (furfuryloxy) chloride and 0.39 g of tetrachlorosilane were added, and the mixture was reacted for 1 hour while maintaining a hydrogen pressure of 1.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution was stirred into water, and the solvent was distilled off by steam to obtain a polymer (D-5). The hydrogenation ratio of the obtained polymer (D-5) was 97%, the weight average molecular weight was about 120,000, and the amino group content was 8.3 mmol / kg · polymer.
[0051]
4) Production of hydrogenated polymer (D-6)
Using n-BuLi as the polymerization initiator, the amount of the polymerization initiator, the type of the monomer, the amount of the monomer, and the polymerization temperature so that the copolymer structure before hydrogenation shown in (D-6) of Table 1 is obtained. By changing the polymerization time and the like, a polymer was obtained according to the production method of 1) above. Then, 7.4 g of P- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene was added to the active site of the polymer and reacted for 30 minutes. Then, the temperature of the reaction solution was raised to 80 ° C. or higher, and hydrogen was introduced into the system. Next, 2.97 g of dichlorotris (triphenylphosphine) ruthenium was added, and the mixture was reacted for 1 hour while maintaining the hydrogen pressure at 2.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure and withdrawn from the reaction vessel. Then, the reaction solution was stirred into water, and the solvent was distilled off by steam to obtain a polymer (D-6). The hydrogenation rate of the obtained polymer (D-6) was 99%, the weight average molecular weight was about 120,000, and the amino group content was 45 mmol / kg · polymer.
[0052]
5) Production of hydrogenated polymer (D-7)
Using n-BuLi as the polymerization initiator, the amount of the polymerization initiator, the type of the monomer, the amount of the monomer, and the polymerization temperature so that the copolymer structure before hydrogenation shown in (D-7) of Table 1 is obtained. By changing the polymerization time and the like, a polymer was obtained according to the production method of 1) above. Next, 1.56 g of N-benzylideneethylamine was added to the active site of the polymer and reacted for 30 minutes. Then, the temperature of the reaction solution was raised to 80 ° C. or higher, and hydrogen was introduced into the system. Then, Pd-BaSO₄2.60 g was added, and the mixture was reacted for 1 hour while maintaining a hydrogen pressure of 2.0 MPa. After the reaction, the reaction solution was returned to normal temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution was stirred into water and the solvent was distilled off by steam to obtain a polymer (D-7). The hydrogenation ratio of the obtained polymer (D-7) was 98%, the weight average molecular weight was about 130,000, and the amino group content was 7 mmol / kg · polymer.
[0053]
6) Production of hydrogenated polymer (D-8) and polymer (R-2)
To a 10-liter reaction vessel purged with nitrogen, 5,000 g of cyclohexane, 200 g of butadiene, 0.25 g of tetrahydrofuran, and 0.80 g of n-butyllithium were added, and the first-stage polymerization was performed at a polymerization initiation temperature of 70 ° C., and the reaction was completed. The temperature of the block polymer, which was partially removed, was 10%, the temperature was set to 20 ° C., 25 g of tetrahydrofuran was added, 290 g of 1,3-butadiene was added, and the second-stage polymerization was performed with heat insulation. Thirty minutes later, 500 g of styrene was added to perform third-stage polymerization, and after completion of the reaction, 10 g of 1,3-butadiene was added to perform fourth-stage polymerization. The partially removed block polymer contained 65% of vinyl bonds and had a weight average molecular weight of about 120,000 as measured by GPC. Then, 3.49 g of N, N-bis (trimethylsilyl) aminopropyltriethoxysilane was added to the system and reacted for 30 minutes. After the reaction, the reaction solution was heated to 70 ° C., and bis (η⁵-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride (0.4 g) and n-butyllithium (0.15 g) were added and reacted at a hydrogen pressure of 1.0 MPa for 60 minutes. After the reaction, the reaction solution was returned to normal temperature and normal pressure, extracted from the reaction vessel, stirred and poured into water, and the solvent was distilled off by steam to obtain a polymer (D-8). The hydrogenation rate of the obtained polymer (D-8) was 98%, the weight average molecular weight was about 150,000, and the amino group content was 6.5 mmol / kg. The polymer (R-2) is an unhydrogenated polymer obtained by polymerization according to the polymer (D-8) except that N, N-bis (trimethylsilyl) aminopropyltriethoxysilane is not used. is there.
In Table 1, the structure A of the polymer is a “styrene polymer block”, the polymer B is a “butadiene polymer block having a vinyl bond content of less than 25% by weight”, and the polymer C is a polymer having a vinyl bond content of 25% by weight to 90%. % By weight or less of a butadiene polymer block. "
[0054]
[Table 1]

[0055]
(2) Each component of Examples and Comparative Examples
(A-1) Polyphenylene ether resin (manufactured by Nippon GE Plastics Co., Ltd., trade name: Noryl 731J)
(B-1) Polybutylene terephthalate resin (trade name: 1401-X06, manufactured by Toray Industries, Inc.)
(C-1) Polypropylene (manufactured by Chisso Corporation, trade name: K8017)
(D) hydrogenated polymer
Hydrogenated polymers (D-1) to (D-8) and (R-1) to (R-2) having the structures shown in Table 1
In addition, (R-3) is a maleic anhydride-modified styrene-ethylene / butylene-styrene block copolymer (trade name “TUFTEC M-1913”, manufactured by Asahi Kasei Corporation, styrene content 40% by weight).
[0056]
(3) Physical property evaluation
{Circle around (1)} Melt flow rate (MFR): based on JIS K7210. However, the temperature was measured at 280 ° C. and the load was measured at 5 kg. The higher the value, the better the moldability.
{Circle around (2)} Heat resistance: Degree of load deflection (° C.) at a load of 18.6 kg / cm 2.
{Circle around (3)} Izod impact strength (unit: kg · cm / cm): Using a notched Izod impact strength as a scale, evaluation was made on a 1/4 inch thick test piece.
{Circle around (4)} Molded appearance: The surface of the test piece was visually observed. In the evaluation, "o" indicates "smooth surface" and "x" indicates "surface is rough and delaminated."
(5) Chemical resistance: The test piece was immersed in toluene at room temperature for 30 days, and changes before and after the test were visually observed. A sample in which a change such as surface roughness was observed was evaluated as "x", and a sample in which no significant change was observed was evaluated as "o".
[0057]
Example 1
Hydrogenation weight containing 60 parts of PPE (A-1) as the component (A), 40 parts of the polybutylene terephthalate resin (B-1) as the component (B), and an amino group as the component (D) 10 parts of the combined product (D-1) were melt-kneaded at a temperature of 300 ° C. using a twin-screw extruder (TEX44, manufactured by Nippon Steel Works Ltd.) to obtain a thermoplastic resin composition. Next, this thermoplastic resin composition was subjected to injection molding using an injection molding machine (Model IS-90B manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 260 ° C. and a mold cooling temperature of 80 ° C. to prepare a test piece. Physical properties were evaluated by the methods described above. Table 2 shows the results.
[0058]
Examples 2 to 11
Test pieces were prepared using the formulations shown in Table 2 in the same manner as in Example 1, and physical properties were evaluated. Table 2 shows the results.
[0059]
[Table 2]

[0060]
Comparative Examples 1 to 6
Test pieces were prepared in the same manner as in Example 1 using the formulations shown in Table 3, and physical properties were evaluated. Table 3 shows the results.
[0061]
[Table 3]

[0062]
Tables 2 and 3 show that the resin composition of the present invention is excellent in moldability, impact resistance, heat resistance, molded appearance, and chemical resistance. On the other hand, the composition of the component (A) and the component (B) (Comparative Example 1) is inferior in molding workability, impact resistance, heat resistance, molded appearance and chemical resistance, and the component (A) In Comparative Example 2 in which the content exceeds 90% by weight, moldability, impact resistance and chemical resistance are poor. On the other hand, in Comparative Example 3 in which the component (B) exceeds 90% by weight, heat resistance is poor. Comparative Examples 4 and 5 using an unmodified hydrogenated polymer are inferior in heat resistance, impact resistance and molded appearance. Further, in Comparative Example 6 using the maleic anhydride-modified hydrogenated polymer, it can be seen that the molding processability was extremely reduced, and the molding appearance and impact resistance were also inferior.
[0063]
【The invention's effect】
The thermoplastic resin composition of the present invention has improved compatibility with the polyphenylene ether-based resin and the polyester-based resin by blending a hydrogenated polymer of a block copolymer containing an amino group, and each resin has Provided is a thermoplastic resin composition capable of sufficiently exhibiting characteristics. The thermoplastic resin composition of the present invention is excellent in heat resistance, impact resistance, molding workability, molding appearance, chemical resistance, and the like, and can be used for various applications from electric and electronic to automotive.

Claims (5)

(A) 10 to 90% by weight of a polyphenylene ether-based resin, (B) 90 to 10% by weight of a polyester-based resin, and (C) 0 to 50% by weight of a polyolefin-based resin (provided that (A) + (B) + (C) ) = 100% by weight) with respect to 100 parts by weight of the resin mixture consisting of (D) at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound. And a hydrogenated polymer of an amino group-containing block copolymer in an amount of 1 to 50 parts by weight. The thermoplastic resin composition according to claim 1, wherein the content of the amino group in the hydrogenated polymer is 0.5 to 300 mmol / kg · polymer. 3. The thermoplastic resin composition according to claim 1, wherein 50% or more of the double bond derived from the conjugated diene of the hydrogenated polymer is saturated. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the hydrogenated polymer is a polymer produced by the following methods (a) to (c).
(A) A polymer produced by block copolymerizing an aromatic vinyl compound and a conjugated diene compound in the presence of an organic alkali metal compound having an amino group, and then hydrogenating the polymer.
(B) An aromatic vinyl compound and a conjugated diene compound are block-copolymerized in the presence of an organic alkali metal compound, and the active site of the obtained polymer is subjected to the following general formula (1) and / or the following general formula (2) A polymer produced by reacting a compound represented by the formula (1) with a polymer, and then hydrogenating the polymer.
R ¹ R ² C = N−Y (1)
[In the above general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a carbon number. 1 to 100 organosiloxy groups. Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 100 carbon atoms. Is an organosiloxy group. ]
R ³ _(4-mn) Si (OR ⁴ ) _m X _n (2)
[In the above general formula (2), R ³ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. , R ³ , each R ³ may be the same or different. R ⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, ^{if R 4} have more than one purpose, each ^{R 4} is different even in the same group group Good. X is a substituent having a polar group containing an N atom. When there are a plurality of Xs, each X may be the same or different, and each X may be an independent substituent forming a cyclic structure. Is also good. m is 1, 2 or 3, and n is an integer of 1, 2 or 3. The sum of m and n is 1-4. ]
(C) produced by subjecting an aromatic vinyl compound, a conjugated diene compound and an unsaturated monomer having an amino group to block copolymerization in the presence of an organic alkali metal compound, and thereafter hydrogenating the polymer. . A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 4.