JP3630490B2 - Method for producing resin composition - Google Patents

Description

【００１２】
式中、Ｒ１，Ｒ２，Ｒ３，およびＲ４はそれぞれ、水素、ハロゲン、炭素数１〜７までの第一級または第二級低級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基または少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択されるものであり、互いに同一でも異なっていてもよい。
【００１３】
本発明におけるＰＰＥは、還元粘度（０．５ｇ／ｄｌ，クロロホルム溶液，３０℃測定）が、０．１５〜０．７０の範囲、より好ましくは０．２０〜０．６０の範囲にあるホモ重合体および／または共重合体である。
このＰＰＥの具体例としては、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）との共重合体のごとき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。
【００１４】
本発明におけるＰＰＥの製造方法は、例えば、米国特許第３３０６８７４号記載のＨａｙによる第一銅塩とアミンのコンプレックスを触媒として用い、例えば２，６−キシレノールを酸化重合することにより容易に製造でき、その他、米国特許第３３０６８７５号、同第３２５７３５７号および同第３２５７３５８号、特公昭５２−１７８８０号および特開昭５０−５１１９７号および同６３−１５２６２８号等に記載された方法が挙げられる。
【００１５】
また、本発明で用いるＰＰＥは、上記したＰＰＥの他に、ＰＰＥとスチレン系モノマーおよび／もしくはα，β−不飽和カルボン酸またはその誘導体とをラジカル発生剤の存在下、非存在下で溶融状態、溶液状態、スラリー状態で８０〜３５０℃の温度下で反応させることによって得られる変性（該スチレン系モノマーおよび／もしくはα，β−不飽和カルボン酸またはその誘導体が０．０１〜１０重量％グラフトまたは付加）ＰＰＥであってもよく、さらに上記したＰＰＥと該変性ＰＰＥの任意の割合の混合物であってもかまわない。
【００１６】
また、本発明で用いるＰＰＥは上記したＰＰＥの他に、これらＰＰＥ１００重量部に対してポリスチレンまたはハイインパクトポリスチレンを４００重量部を超えない範囲で加えたものも好適に用いることができる。
本発明で用いる（ｃ）成分として用いるポリプロピレン系樹脂は、結晶性プロピレンホモポリマーおよび、重合の第一工程で得られる結晶性プロピレンホモポリマー部分と重合の第二工程以降でプロピレン、エチレンおよび／または少なくとも１つの他のα−オレフィン（例えば、ブテン−１、ヘキセン−１等）を共重合して得られるプロピレン系ランダム共重合体部分を有する結晶性プロピレン系ブロック共重合体であり、さらにこれら結晶性プロピレンホモポリマーと結晶性プロピレン−エチレンブロック共重合体の混合物であってもかまわない。
【００１７】
かかるポリプロピレン系樹脂は、通常、三塩化チタン触媒または塩化マグネシウムなどの担体に担持したハロゲン化チタン触媒等とアルキルアルミニウム化合物の存在下に、重合温度０〜１００℃の範囲で、重合圧力３〜１００気圧の範囲で重合して得られる。この際、重合体の分子量を調製するために水素等の連鎖移動剤を添加することも可能であり、また重合方法としてバッチ式、連続式いずれの方法でも可能で、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン等の溶媒下での溶液重合、スラリー重合等の方法も選択でき、さらには無溶媒下モノマー中での塊状重合、ガス状モノマー中での気相重合方法などが適用できる。
【００１８】
また、さらには、上記した重合触媒の他に得られるポリプロピレンのアイソタクティシティおよび重合活性を高めるため、第三成分として電子供与性化合物を内部ドナー成分または外部ドナー成分として用いることができる。
これらの電子供与性化合物としては、例えば、ε−カプロラクトン、メタクリル酸メチル、安息香酸エチル、トルイル酸メチルなどのエステル化合物、亜リン酸トリフェニル、亜リン酸トリブチルなどの亜リン酸エステル、ヘキサメチルホスホリックトリアミドなどのリン酸誘導体など、アルコキシエステル化合物、芳香族モノカルボン酸エステル、芳香族アルキルアルコキシシラン、脂肪族炭化水素アルコキシシラン、各種エーテル化合物、各種アルコール類、各種フェノール類などが挙げられる。
【００１９】
このポリプロピレン系樹脂のメルトフローレート（ＭＦＲ）（２３０℃、荷重２．１６ｋｇ）は、０．０１〜３００ｇ／１０分であり、好ましくは０．１〜１００ｇ／１０分、より好ましくは０．３〜５０ｇ／１０分の範囲である。
本発明で供するポリプロピレン系樹脂は上記した方法で得られるものであれば、いかなる結晶性や融点を有するものでも単独あるいは併用して用いることができる。
【００２０】
本発明で用いる（ｂ）成分として、ビニル芳香族化合物−共役ジエン化合物の水素添加物（以下、水添ブロック共重合体と略す）は、共役ジエン化合物の１，２−ビニル結合もしくは３，４−ビニル結合量が３２〜５５％、好ましくは３５〜５５％である共役ジエン化合物重合体ブロックが少なくとも１個、ビニル芳香族化合物重合体ブロックＡが少なくとも１個からなるブロック共重合体を５０％以上水素添加してなる水添ブロック共重合体である。
【００２１】
ブロック共重合体としては、Ａ−Ｂ、Ａ−Ｂ−Ａ、Ｂ−Ａ−Ｂ−Ａ、（Ａ−Ｂ−）_４−Ｓｉ、Ａ−Ｂ−Ａ−Ｂ−Ａ等の構造を有するビニル芳香族化合物−共役ジエン化合物ブロック共重合体の水素添加物である。この（ｂ）成分の水添ブロック共重合体は、その水素添加する前のブロック共重合体が結合したビニル芳香族化合物を２０〜９５重量％、好ましくは３０〜８０重量％、さらに好ましくは４０〜７０重量％である。
【００２２】
また共役ジエン化合物重合体ブロックＢは、共役ジエン化合物のホモ重合体ブロックまたは、共役ジエン化合物を５０重量％を超え好ましくは７０重量％以上含有する共役ジエン化合物であり、ビニル芳香族化合物共重合体ブロックＡは、ビニル芳香族化合物のホモ重合体ブロックまたは、ビニル芳香族化合物を５０重量％を超え好ましくは７０重量％以上含有するビニル芳香族化合物共重合体ブロックである。
【００２３】
また、これらの共役ジエン化合物重合体ブロックＢ、ビニル芳香族化合物重合体ブロックＡは、それぞれの重合体ブロックにおける分子鎖中のビニル芳香族化合物または共役ジエン化合物の分布がランダム、テーパード（分子鎖に沿ってモノマー成分が増加または減少するもの）、一部ブロック状またはこれらの任意の組み合わせで成っていてもよく、該共役ジエン化合物重合体ブロックＢおよび該ビニル芳香族化合物重合体ブロックＡがそれぞれ２個以上ある場合は、各重合体ブロックはそれぞれ同一構造であってもよく、異なる構造であってもよい。
【００２４】
このブロック共重合体を構成する共役ジエン化合物としては、例えば、ブタジエン、イソプレン、１，３−ペンタジエン、２，３−ジメチル−１，３−ブタジエン等のうちから１種または２種以上が選ばれ、中でもブタジエン、イソプレンおよびこれらの組み合わせが好ましい。そして共役ジエン化合物を主体とする重合体ブロックは、そのブロックにおけるミクロ構造（共役ジエン化合物の結合形態）を任意に選ぶことができ、例えばブタジエンを主体とする重合体ブロックにおいては１，２−ビニル結合が３０超え〜５５％である。また、イソプレンを主体とする重合体ブロックにおいては、３，４−ビニル結合が３０超え〜５５％である。これらの共役ジエン化合物の結合形態は通常、赤外分光光度計やＮＭＲ等で知ることができる。
【００２５】
また、ビニル芳香族化合物としては、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−ｔｅｒｔ−ブチルスチレン、ジフェニルエチレン等のうちから１種または２種以上が選択でき、中でもスチレンが好ましい。
また、上記の構造を有するブロック共重合体の数平均分子量は５，０００〜１，０００，０００、好ましくは１０，０００〜８００，０００、さらに好ましくは３０，０００〜５００，０００の範囲であり、分子量分布〔ゲルパーミエーションクロマトグラフィーで測定した重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比〕は１０以下である。さらに、このブロック共重合体の分子構造は、直鎖状、分岐状、放射状あるいはこれらの任意の組み合わせのいずれでもよい。
【００２６】
このような構造を持つブロック共重合体は、上記したブロック共重合体の共役ジエン化合物重合体ブロックＢの脂肪族系二重結合を水素添加した水添ブロック共重合体は、脂肪族系二重結合の水素添加率は５０％以上、好ましくは８０％以上、より好ましくは９０％以上である。この水素添加率は通常、赤外分光光度計やＮＭＲ等によって知ることができる。
【００２７】
これらの上記した（ｂ）成分の水添ブロック共重合体の製造方法としては、特開昭４７−１１４８６号公報、特開昭４９−６６７４３号公報、特開昭５０−７５６５１号公報、特開昭５４−１２６２５５号公報、特開昭５６−１０５４２号公報、特開昭５６−６２８４７号公報、特開昭５６−１００８４０号公報、英国特許第１１３０７７０号、米国特許第３２８１３８３号、同第３６３９５１７号、英国特許第１０２０７２０号、米国特許第３３３３０２４号および同第４５０１８５７号に記載された方法がある。
【００２８】
なお本発明において、供する水添ブロック共重合体は、共役ジエン化合物の１，２−ビニル結合もしくは３，４−ビニル結合が３０％以下であるとポリプロピレン系樹脂中にポリフェニレンエーテル系樹脂が良好に乳化分散しないので好ましくない。一方、共役ジエン化合物の１，２−ビニル結合もしくは３，４−ビニル結合が５５％を超えてくると水添ブロック共重合体が単独でポリプロピレン中に分散し得られる組成物の耐熱性、剛性を著しく悪化させ好ましくない。
【００２９】
本発明の製造方法は、上記した（ａ）、（ｂ）、（ｃ）成分を下記に示す方法で行う。すなわち（ａ）成分と（ｂ）成分の溶融混練状態に、（ｃ）成分を追加添加し一緒に溶融混練する方法であり、種々の混練押出機を用いて製造することができる。これらの方法を行う溶融混錬機として例えば、単軸押出機、二軸押出機を含む多軸押出機、ロール、ニーダー、ブラベンダープラストグラフ、バンバリーミキサー等による加熱溶融混練機が挙げられるが、中でも二軸押出機を用いた溶融混練方法が最も好ましい。具体的には、ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製のＺＳＫシリーズ、東芝機械（株）製のＴＥＭシリーズ、日本製鋼所（株）製のＴＥＸシリーズなどが挙げられる。
【００３０】
押出機を用いた本発明の好ましい態様を以下に述べる。押出機のＬ／Ｄ（バレル有効長／バレル内径）は２０以上６０以下の範囲であり、好ましくは３０以上５０以下の範囲である。押出機は原料の流れ方向に対し上流側に第１原料供給口、これより下流に第１真空ベント、その下流に第２原料供給口を設け、さらにその下流に第２真空ベントを設けたものが好ましい。なかでも、第１真空ベントの上流にニーディングセクションを設け、第１真空ベントと第２原料供給口の間にニーディングセクションを設け、また第２原料供給口と第２真空ベントの間にニーディングセクションを設けたものがより好ましい。第２供給口への原材料供給方法は、特に限定されるものでは無いが、押出機第２供給口開放口よりの単なる添加供給よりも、押出機サイド開放口から強制サイドフィーダーを用いて供給する方が安定で好ましい。特に、粉体、フィラー等が含まれる場合は、押出機サイドから供給する強制サイドフィーダーの方がより好ましく、押出機第２供給口の上部開放口は同搬する空気を抜くため開放とすることもできる。この際の溶融混練温度、スクリュー回転数は特に限定されるものではないが、通常溶融混練温度２００〜３７０℃、スクリュー回転数１００〜１２００ｒｐｍの中から任意に選ぶことができる。
【００３１】
本発明では、（ａ）成分及び（ｃ）成分の合計１００重量部に対して（ｂ）成分を合計量で５〜３０重量部添加する。
第１原料供給口より（ａ）成分５５〜１０重量％、（ｂ）成分１．５〜２１重量部を供給し溶融混練を行い、第２原料供給口より（ｃ）成分４５〜９０重量％及び残り（ｂ）成分を供給し、溶融混練状態の組成物に加え、さらに溶融混練を続けて行うことにより、成分（ａ）はポリプロピレン系樹脂マトリックスに中に分散相を形成し、該分散相の平均粒径は１．５μｍ以下に微分散する。かかる（ａ）成分の分散形態を知るには、本発明で得たペレットの切断面と平行方向の面をルテニウム酸染色法により染め、ウルトラミクロトーム（ライヘルト社製 ウルトラカットＥ）により超薄切片を作成、それを透過型電子顕微鏡（日本電子製１２００ＥＸ）により容易に観察出来る。具体的には得られた透過型電子顕微鏡写真をもとに画像解析装置（旭化成製 ＩＰ１０００）を用いて分散相の周囲長から円相当径を求め平均化することで、分散粒径を求めることができる。
【００３２】
この微分散化により、得られる樹脂組成物は混和性が改良され、層剥離が改良される他に、耐熱耐久性（耐熱クリープ）が大幅に改良される。一方、本発明の製造方法において、▲１▼（ｂ）成分を、（ａ）成分と一緒に第１供給口より供給したり、▲２▼（ｂ）成分を、（ｃ）成分と一緒に第２原料供給口より供給する方法で得られる樹脂組成物は、該（ａ）成分が（ｃ）成分のポリプロピレン系樹脂中に微分散されず、混和性に劣り、層剥離が発現されたり、耐熱耐久性（耐熱クリープ）に劣り、好ましくない。また、本発明の方法と異なる方法の一つである、（ａ）、（ｂ）、（ｃ）各成文を、第１原料供給口より一括して供給する方法で得られる樹脂組成物も同様に、混和性、及び耐熱耐久性（耐熱クリープ）に劣り、
好ましくない。
【００３３】
本発明では、上記した成分を用い、上記した方法で本発明の樹脂組成物を製造するが、本発明の特徴及び効果を損なわない範囲で必要に応じて他の付加的成分、例えば、酸化防止剤、金属不活性化剤、難燃剤（有機リン酸エステル系化合物、無機リン系化合物、芳香族ハロゲン系難燃剤、シリコーン系難燃剤など）、フッ素系ポリマー、可塑剤（オイル、低分子量ポリエチレン、エポキシ化大豆油、ポリエチレングリコール、脂肪酸エステル類等）、三酸化アンチモン等の難燃助剤、耐候（光）性改良剤、ポリオレフィン用造核剤、スリップ剤、無機または有機の充填材や強化材（ガラス繊維、カーボン繊維、ポリアクリロニトリル繊維、ウィスカー、マイカ、タルク、カーボンブラック、酸化チタン、炭酸カルシウム、チタン酸カリウム、ワラストナイト、導電性金属繊維、導電性カーボンブラック等）、各種着色剤、離型剤等を添加してもかまわない。
【００３４】
このようにして得られる本発明の樹脂組成物は、例えば、射出成形、押出成形、押出異形成形、中空成形により各種部品の成形体として成形できる。これら各種部品としては、自動車部品が挙げられ、具体的には、バンパー、フェンダー、ドアーパネル、各種モール、エンブレム、エンジンフード、ホイールキャップ、ルーフ、スポイラー、各種エアロパーツ等の外装品や、インストゥルメントパネル、コンソールボックス、トリム等の内装部品等に適している。さらに、電気機器の内外装部品としても好適に使用でき、具体的には各種コンピューターおよびその周辺機器、その他のＯＡ機器、テレビ、ビデオ、各種ディスクプレーヤー等のキャビネット、冷蔵庫等の部品用途に適している。
【００３５】
【発明の実施の形態】
＜（ａ）成分のＰＰＥの調整＞
ａ−１：２，６−キシレノールを酸化重合して得た還元粘度０．４３のポリフェニレンエーテル
＜（ｃ）成分の高結晶ポリプロピレンの調整＞
ｃ−１：ホモ−ポリプロピレン、融点＝１５９℃、ＭＦＲ＝０．３
ポリプロピレンのＭＦＲ（メルトフローレート）はＡＳＴＭ Ｄ１２３８に準拠し、２３０℃、２．１６Ｋｇの荷重で測定した。
＜（ｂ）成分の水添ブロック共重合体の調整＞
ポリスチレン−水素添加されたポリブタジエン−ポリスチレンの構造を有し、結合スチレン量６０％、数平均分子量８５，０００、分子量分布１．０８、水素添加前のポリブタジエンの１，２−ビニル結合量が３６％、ポリブタジエン部の水素添加率が９９．９％の選択水添ブロック共重合体を合成し、このポリマーを（ｂ−１）とした。
【００３６】
ポリスチレン−水素添加されたポリブタジエン−ポリスチレンの構造を有し、結合スチレン量６０％、数平均分子量８３，０００、分子量分布１．０５、水素添加前のポリブタジエンの１，２−ビニル結合量が７１％、ポリブタジエン部の水素添加率が９９．９％の選択水添ブロック共重合体を合成し、このポリマーを（ｂ−２）とした。
【００３７】
ポリスチレン−水素添加されたポリブタジエン−ポリスチレンの構造を有し、結合スチレン量４７％、数平均分子量１２０，０００、分子量分布１．０４、水素添加前のポリブタジエンの１，２−ビニル結合量が５０％、ポリブタジエン部の水素添加率が９９．９％の選択水添ブロック共重合体を合成し、このポリマーを（ｂ−３）とした。
【００３８】
ポリスチレン−水素添加されたポリブタジエン−ポリスチレンの構造を有し、結合スチレン量５０％、数平均分子量１０８，０００、分子量分布１．０６、水素添加前のポリブタジエンの１，２−ビニル結合量が６０％、ポリブタジエン部の水素添加率が９９．９％の選択水添ブロック共重合体を合成し、このポリマーを（ｂ−４）とした。
【００３９】
【実施例１〜８および比較例１〜３】
ポリプロピレン、ポリフェニレンエーテル、混和剤を表１に示した組成で配合し、樹脂流れ方向に対し上流に第１原料フィード口及び下流に第２原料フィード口を有し、第２フィード口の上流及び第２フィード口とダイとの間に真空ベント口を設けた二軸押出機ＺＳＫ−４０（ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製）を用いて押出温度２９０℃、スクリュー回転数３００ｒｐｍ、吐出量６０ｋｇ／時間の条件にて溶融混練しペレットとして得た。
【００４０】
このペレットを用いて２４０〜２８０℃に設定したスクリューインライン型射出成形機に供給し、金型温度６０℃の条件で、曲げ弾性率測定試験用テストピース、アイゾット衝撃試験用テストピースおよび熱変形温度測定用テストピースを射出成形した。つぎに、これらのテストピースを用いて曲げ弾性率（ＡＳＴＭ Ｄ−７９０：２３℃）、アイゾット（ノッチ付き）衝撃強度（ＡＳＴＭ Ｄ−２５６：２３℃）および熱変形温度（ＡＳＴＭ Ｄ−６４８）、なお、混和性の効果を確認するため、ペレットの断面を、透過型電子顕微鏡（日本電子製 １２００ＥＸ）を用い、さらに画像解析装置を用いて、樹脂組成物中に分散する（ａ）成分の平均粒径を測定した。本発明の製造方法で得た組成物の耐熱耐久性（耐熱クリープ）を確認するため、レオバイブロン（オリエンテック株式会社製 ＤＤＶ−０１／２５ＦＰ型）を用いて、１ｍｍ×１ｍｍ×３０ｍｍの棒状サンプル、応力１３０ｋｇ／ｃｍ^２ｆ相当の荷重、温度６５℃の条件で、耐熱クリープテストを行い、破断までの時間を測定した。結果を表１に示す。
【００４１】
表１から明らかなように、第１供給口から成分（ａ）及び、（ｂ）成分を供給し、この溶融混練状態の組成物中に、成分（ｃ）及び、（ｂ）成分の残量を第２供給口より加え、さらに溶融混練を行うことにより、比較例に比べて、プロピレン系樹脂マトリックスに対し、ポリフェニレンエーテル系樹脂が、１．５μｍ以下の分散相を形成するため、混和性が改良され、耐熱耐久性（耐熱クリープ）が著しく改良される。
【００４２】
一方、本発明の（ｂ）成分を用いないものは、耐熱耐久性（耐熱クリープ）が劣る。
【００４３】
【表１】

【００４４】
【発明の効果】
本発明の製造方法により得られた樹脂組成物は、ポリフェニレンエーテル系樹脂が、１．５μｍ以下で分散するため、得られた組成物の耐熱クリープ性能が著しく改良される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition excellent in oil resistance, chemical resistance, heat resistance, impact resistance and rigidity, which can be used in the electric / electronic field, automobile field, and other various industrial material fields. The present invention relates to a method for producing a resin composition having excellent durability (heat-resistant creep).
[0002]
[Prior art]
Polyphenylene ether has mechanical properties, electrical properties, heat resistance, low temperature properties, low water absorption and excellent dimensional stability, but has the disadvantage of poor moldability and impact resistance, so it blends with polystyrene and high impact polystyrene. Thus, these problems are improved and widely used as resin compositions for, for example, electric / electronic parts, office equipment housings, automobile parts, precision parts, various industrial parts and the like.
[0003]
However, this polyphenylene ether resin composition comprising polyphenylene ether and high impact polystyrene (disclosed in US Pat. No. 3,383,435) has the disadvantage of poor chemical resistance, although the impact resistance is improved. ing.
For this reason, for example, US Pat. No. 3,361,851 proposes to improve solvent resistance and impact resistance by blending polyphenylene ether with polyolefin, and US Pat. No. 3,994,856 discloses polyphenylene ether. There is a description of improvement in impact resistance and solvent resistance by blending an ether and a styrenic resin with a hydrogenated block copolymer. US Pat. No. 4,145,377 discloses a polyphenylene ether and a styrenic resin as polyolefin / Hydrogenated block copolymer = 20 to 80 parts by weight / 80 to 20 parts by weight A premix and a description about improvement of impact resistance and solvent resistance by blending with hydrogenated block copolymer Japanese Patent No. 4166055 and US Pat. No. 42396. The 3 Pat, improvement of impact resistance by blending a hydrogenated block copolymer and polyolefin polyphenylene ethers. In U.S. Pat. No. 4,383,082 and European Patent No. 115712, it is described that impact resistance is improved by blending polyphenylene ether with polyolefin and hydrogenated block copolymer.
[0004]
JP-A-63-113058, JP-A-63-225642, U.S. Pat. No. 4,863,997, JP-A-3-72512, JP-A-4-183748, JP-A-5-320471. Has proposed a resin composition excellent in chemical resistance and workability by blending a specific hydrogenated block copolymer for modification of a resin composition comprising a polyolefin resin and a polyphenylene ether resin.
[0005]
In addition, the applicant of the present application is disclosed in Japanese Patent Application Laid-Open Nos. 62-20551, 62-25149, 62-48757, 62-48758, and 62-199637. And U.S. Pat. No. 4,772,657 propose a rubber composition excellent in rubber elasticity composed of polyphenylene ether, polyolefin and hydrogenated block copolymer, and JP-A-2-225563 and JP-A-3-185050. JP-A-5-70679, JP-A-5-295184, JP-A-6-9828, JP-A-6-16924, JP-A-6-57130, JP-A-6-136202. Has excellent compatibility, rigidity and heat resistance composed of polyphenylene ether, polyolefin and specific hydrogenated block copolymer, It proposed a resin composition excellent in resistance. JP-A-4-28739 and JP-A-4-28740 are excellent in mechanical properties, particularly in balance between impact strength and rigidity, comprising polyphenylene ether, polyolefin and hydrogenated block copolymer or rubber-like polymer. A method for producing a resin composition has been proposed. Japanese Laid-Open Patent Publication No. 7-166026 proposes a method for producing a resin composition having good compatibility between a polyphenylene ether resin and a polyolefin and having excellent mechanical properties, particularly impact resistance.
[0006]
The prior art disclosed here provides a resin composition having drastically improved solvent resistance compared to a polyphenylene ether resin composition or an elastomer composition having excellent heat resistance. In addition, such advancement of the prior art surely improves remarkably from the viewpoint of the miscibility (whether or not the composition is delaminated when both components are mixed) when mixing the polyolefin resin and polyphenylene ether. However, it has been revealed that it does not necessarily have sufficient miscibility when used in complex molding processes accompanying recent advances in molding technology.
[0007]
In other words, the resin composition obtained by the above-described conventional technology is not currently selected as an effective admixture even in the admixture, and further, these components (polyolefin resin, polyphenylene ether resin) At present, no method for producing a polymer alloy having a good dispersion form with an admixture has been proposed.
[0008]
[Problems to be solved by the invention]
A good dispersion of a hydrogenated block copolymer resin composition of a block copolymer comprising a polyphenylene ether resin, a polypropylene resin, and a conjugated diene compound polymer block B and a vinyl aromatic compound polymer block A The present invention proposes a method for producing a polymer alloy having excellent durability (heat-resistant creep).
[0009]
[Means for Solving the Problems]
That is, the present invention relates to (b) a total of 100 parts by weight of (a) polyphenylene ether resin 55 to 10% by weight and (c) polypropylene resin 45 to 90% by weight of (a) and (c) components. ) At least one conjugated diene compound polymer block B and at least one vinyl aromatic compound polymer block A in which the amount of 1,2-vinyl bond or 3,4-vinyl bond of the conjugated diene compound is 32 to 55%. In a method for producing a resin composition containing a total of 5 to 30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising: (a) component and (b) component 1. A method for producing a resin composition, comprising adding 5 to 21 parts by weight of a melt-kneaded product and adding the remaining amount of the component (c) and the component (b), followed by melt-kneading.
[0010]
In the present invention, the polyphenylene ether of component (a) (hereinafter abbreviated as PPE) is an essential component for imparting heat resistance and flame retardancy to the resin composition of the present invention. It consists of general.
[0011]
[Chemical 1]

[0012]
In the formula, R1, R2, R3 and R4 are each hydrogen, halogen, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group, hydrocarbonoxy group. Or, at least two carbon atoms are selected from the group consisting of a halohydrocarbonoxy group separating a halogen atom and an oxygen atom, and may be the same or different from each other.
[0013]
The PPE in the present invention has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 to 0.70, more preferably in the range of 0.20 to 0.60. It is a combination and / or copolymer.
Specific examples of this PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6- 6). Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2, 3, 6). Also included are polyphenylene ether copolymers such as copolymers with -trimethylphenol and 2-methyl-6-butylphenol). Of these, 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 , 4-phenylene ether).
[0014]
The method for producing PPE in the present invention can be easily produced by, for example, oxidative polymerization of 2,6-xylenol using, for example, a complex of Hay cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. In addition, the methods described in U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628 are exemplified.
[0015]
In addition to the above-mentioned PPE, the PPE used in the present invention is a molten state of PPE and a styrene monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof in the presence or absence of a radical generator. , A modification obtained by reacting at a temperature of 80 to 350 ° C. in a solution state or a slurry state (the styrene monomer and / or α, β-unsaturated carboxylic acid or derivative thereof is 0.01 to 10% by weight graft) Or addition) PPE, or a mixture of the above-mentioned PPE and the modified PPE in an arbitrary ratio.
[0016]
Further, as the PPE used in the present invention, in addition to the above-mentioned PPE, those obtained by adding polystyrene or high-impact polystyrene in an amount not exceeding 400 parts by weight to 100 parts by weight of these PPEs can be suitably used.
The polypropylene resin used as the component (c) used in the present invention is composed of a crystalline propylene homopolymer and a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene, ethylene and / or in the second and subsequent steps of polymerization. A crystalline propylene-based block copolymer having a propylene-based random copolymer portion obtained by copolymerizing at least one other α-olefin (for example, butene-1, hexene-1, etc.), and these crystals A mixture of a propylene homopolymer and a crystalline propylene-ethylene block copolymer may be used.
[0017]
Such a polypropylene resin is usually used in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of 3 to 100. Obtained by polymerization in the range of atmospheric pressure. At this time, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer, and the polymerization method can be either a batch type or a continuous type, butane, pentane, hexane, heptane. Further, methods such as solution polymerization in a solvent such as octane and slurry polymerization can also be selected. Furthermore, bulk polymerization in a monomer in the absence of a solvent, gas phase polymerization method in a gaseous monomer, and the like can be applied.
[0018]
Furthermore, in addition to the polymerization catalyst described above, an electron donating compound can be used as an internal donor component or an external donor component as a third component in order to increase the isotacticity and polymerization activity of the polypropylene obtained.
Examples of these electron-donating compounds include ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate and methyl toluate, phosphites such as triphenyl phosphite and tributyl phosphite, and hexamethyl. Examples include phosphoric acid derivatives such as phosphoric triamide, alkoxy ester compounds, aromatic monocarboxylic acid esters, aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols, and various phenols. .
[0019]
The melt flow rate (MFR) (230 ° C., load 2.16 kg) of this polypropylene resin is 0.01 to 300 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes, more preferably 0.3. It is in the range of ˜50 g / 10 minutes.
As long as the polypropylene resin used in the present invention is obtained by the above-described method, any resin having any crystallinity or melting point can be used alone or in combination.
[0020]
As the component (b) used in the present invention, a hydrogenated vinyl aromatic compound-conjugated diene compound (hereinafter abbreviated as hydrogenated block copolymer) is a 1,2-vinyl bond or 3,4 of the conjugated diene compound. -50% of a block copolymer comprising at least one conjugated diene compound polymer block and at least one vinyl aromatic compound polymer block A having a vinyl bond content of 32 to 55%, preferably 35 to 55%. This is a hydrogenated block copolymer obtained by hydrogenation.
[0021]
Block copolymers include A-B, A-B-A, B-A-B-A, and (A-B-). ₄ It is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as -Si or ABABABA. The hydrogenated block copolymer of component (b) is 20 to 95% by weight, preferably 30 to 80% by weight, more preferably 40% by weight of the vinyl aromatic compound to which the block copolymer before hydrogenation is bonded. ~ 70 wt%.
[0022]
The conjugated diene compound polymer block B is a homopolymer block of a conjugated diene compound or a conjugated diene compound containing more than 50% by weight of a conjugated diene compound, preferably 70% by weight or more, and is a vinyl aromatic compound copolymer. The block A is a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound copolymer block containing a vinyl aromatic compound in an amount of more than 50% by weight, preferably 70% by weight or more.
[0023]
Further, these conjugated diene compound polymer block B and vinyl aromatic compound polymer block A have a random, tapered (molecular chain) distribution of the vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block. Along which the monomer component increases or decreases), may be partially block-like or any combination thereof, and each of the conjugated diene compound polymer block B and the vinyl aromatic compound polymer block A may be 2 When there are more than one, each polymer block may have the same structure or a different structure.
[0024]
As the conjugated diene compound constituting this block copolymer, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. Of these, butadiene, isoprene and combinations thereof are preferred. For the polymer block mainly composed of a conjugated diene compound, the microstructure (bonded form of the conjugated diene compound) in the block can be arbitrarily selected. For example, in a polymer block mainly composed of butadiene, 1,2-vinyl is used. The bond is more than 30 to 55%. In the polymer block mainly composed of isoprene, the 3,4-vinyl bond is more than 30 to 55%. The bonding form of these conjugated diene compounds can be usually known by an infrared spectrophotometer, NMR or the like.
[0025]
Moreover, as a vinyl aromatic compound, 1 type (s) or 2 or more types can be selected from styrene, (alpha) -methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, etc. Among these, styrene is preferable.
The number average molecular weight of the block copolymer having the above structure is in the range of 5,000 to 1,000,000, preferably 10,000 to 800,000, more preferably 30,000 to 500,000. The molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography] is 10 or less. Further, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.
[0026]
The block copolymer having such a structure is a hydrogenated block copolymer obtained by hydrogenating the aliphatic double bond of the conjugated diene compound polymer block B of the block copolymer described above. The hydrogenation rate of the bond is 50% or more, preferably 80% or more, more preferably 90% or more. This hydrogenation rate can usually be known by an infrared spectrophotometer, NMR or the like.
[0027]
As methods for producing these hydrogenated block copolymers of component (b) described above, JP-A Nos. 47-11486, 49-66743, 50-75651, and JP-A-50-75651 are disclosed. JP 54-126255, JP 56-10542, JP 56-62847, JP 56-1000084, British Patent 1130770, US Pat. No. 3,281,383, US 3639517 , British Patent No. 1020720, US Pat. Nos. 3,333,024 and 4,501,857.
[0028]
In the present invention, when the hydrogenated block copolymer to be provided has a 1,2-vinyl bond or 3,4-vinyl bond of the conjugated diene compound of 30% or less, the polyphenylene ether resin is excellent in the polypropylene resin. Since it is not emulsified and dispersed, it is not preferable. On the other hand, when the 1,2-vinyl bond or 3,4-vinyl bond of the conjugated diene compound exceeds 55%, the heat resistance and rigidity of the composition in which the hydrogenated block copolymer can be dispersed in polypropylene alone. This is not preferable because it significantly deteriorates
[0029]
In the production method of the present invention, the above-described components (a), (b) and (c) are carried out by the method shown below. That is, this is a method in which the component (c) is additionally added to the melt-kneaded state of the component (a) and the component (b) and melt-kneaded together, and can be produced using various kneading extruders. Examples of the melt kneader for performing these methods include a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, kneader, Brabender plastograph, and a heat-melt kneader using a Banbury mixer, Among them, the melt kneading method using a twin screw extruder is most preferable. Specific examples include the ZSK series manufactured by WERNER & PFLIDEERER, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Nippon Steel Works.
[0030]
A preferred embodiment of the present invention using an extruder will be described below. The L / D (barrel effective length / barrel inner diameter) of the extruder is in the range of 20 to 60, preferably in the range of 30 to 50. The extruder has a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent on the downstream side, a second raw material supply port on the downstream side, and a second vacuum vent on the downstream side. Is preferred. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and a knee section is provided between the second raw material supply port and the second vacuum vent. It is more preferable to provide a sectioning section. Although the raw material supply method to a 2nd supply port is not specifically limited, it supplies using a forced side feeder from an extruder side open port rather than the mere addition supply from an extruder 2nd supply port open port. Is more stable and preferred. In particular, when powder, filler, etc. are included, the forced side feeder supplied from the extruder side is more preferable, and the upper opening of the second supply port of the extruder should be opened in order to remove the carried air. You can also. The melt-kneading temperature and screw rotation speed at this time are not particularly limited, but can normally be arbitrarily selected from a melt-kneading temperature of 200 to 370 ° C. and a screw rotation speed of 100 to 1200 rpm.
[0031]
In this invention, 5-30 weight part of (b) component is added with the total amount with respect to a total of 100 weight part of (a) component and (c) component.
Component (a) 55 to 10% by weight and component (b) 1.5 to 21 parts by weight are supplied from the first raw material supply port and melt kneaded, and component (c) 45 to 90% by weight from the second raw material supply port. In addition, the component (a) forms a dispersed phase in the polypropylene resin matrix by supplying the remaining component (b), adding to the composition in the melt-kneaded state, and further performing melt-kneading. The average particle size of is finely dispersed to 1.5 μm or less. In order to know the dispersion form of the component (a), the surface parallel to the cut surface of the pellet obtained in the present invention is dyed by a ruthenic acid staining method, and an ultrathin section is obtained by an ultramicrotome (Ultracut E manufactured by Reichert). It can be easily observed with a transmission electron microscope (JEOL 1200EX). Specifically, based on the obtained transmission electron micrograph, an equivalent particle diameter is obtained from the perimeter of the dispersed phase using an image analyzer (Asahi Kasei IP1000), and the dispersed particle diameter is obtained. Can do.
[0032]
By this fine dispersion, the resulting resin composition has improved miscibility and improved delamination, as well as greatly improved heat durability (heat resistant creep). On the other hand, in the production method of the present invention, the component (1) (b) is supplied from the first supply port together with the component (a), or the component (2) (b) is combined with the component (c). In the resin composition obtained by the method of supplying from the second raw material supply port, the component (a) is not finely dispersed in the polypropylene resin of the component (c), is inferior in miscibility, and exhibits delamination, It is inferior in heat resistance (heat resistance creep) and is not preferable. The same applies to the resin composition obtained by the method of supplying each component (a), (b), (c) from the first raw material supply port, which is one of the methods different from the method of the present invention. In addition, it is inferior in miscibility and heat resistance (heat creep),
It is not preferable.
[0033]
In the present invention, the above-described components are used to produce the resin composition of the present invention by the above-described method. However, other additional components, for example, antioxidants, may be used as long as the characteristics and effects of the present invention are not impaired. Agent, metal deactivator, flame retardant (organic phosphate ester compound, inorganic phosphorus compound, aromatic halogen flame retardant, silicone flame retardant, etc.), fluorine polymer, plasticizer (oil, low molecular weight polyethylene, Epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weather resistance (light) improvers, polyolefin nucleating agents, slip agents, inorganic or organic fillers and reinforcing materials (Glass fiber, carbon fiber, polyacrylonitrile fiber, whisker, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate, Wollastonite, conductive metal fibers, conductive carbon black, etc.), various colorants, may be added such as mold release agents.
[0034]
The resin composition of the present invention thus obtained can be molded as molded parts of various parts by, for example, injection molding, extrusion molding, extrusion profile forming, and hollow molding. These various parts include automotive parts. Specifically, bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts and other exterior parts, and instruments. It is suitable for interior parts such as a maintenance panel, console box and trim. Furthermore, it can also be used suitably as an interior / exterior part of electrical equipment. Specifically, it is suitable for parts such as various computers and peripheral equipment, other OA equipment, television, video, various disk player cabinets, refrigerators, etc. Yes.
[0035]
DETAILED DESCRIPTION OF THE INVENTION
<Adjustment of PPE of component (a)>
a-1: Polyphenylene ether having a reduced viscosity of 0.43 obtained by oxidative polymerization of 2,6-xylenol
<Preparation of High Crystalline Polypropylene (c)>
c-1: Homo-polypropylene, melting point = 159 ° C., MFR = 0.3
The MFR (melt flow rate) of polypropylene was measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238.
<Preparation of hydrogenated block copolymer of component (b)>
Polystyrene-hydrogenated polybutadiene-polystyrene structure, bonded styrene content 60%, number average molecular weight 85,000, molecular weight distribution 1.08, polybutadiene before hydrogenation 36% 1,2-vinyl bond content A selective hydrogenated block copolymer having a polybutadiene part hydrogenation rate of 99.9% was synthesized, and this polymer was designated as (b-1).
[0036]
Polystyrene-hydrogenated polybutadiene-polystyrene structure, 60% bonded styrene, number average molecular weight 83,000, molecular weight distribution 1.05, 71% 1,2-vinyl bond of polybutadiene before hydrogenation A selective hydrogenated block copolymer having a polybutadiene part hydrogenation rate of 99.9% was synthesized, and this polymer was designated as (b-2).
[0037]
Polystyrene-hydrogenated polybutadiene-polystyrene structure, bonded styrene content 47%, number average molecular weight 120,000, molecular weight distribution 1.04, polybutadiene before hydrogenation 1,2-vinyl bond content 50% A selective hydrogenated block copolymer having a polybutadiene part hydrogenation rate of 99.9% was synthesized, and this polymer was designated as (b-3).
[0038]
Polystyrene-hydrogenated polybutadiene-polystyrene structure, bonded styrene content 50%, number average molecular weight 108,000, molecular weight distribution 1.06, 1,2-vinyl bond content of polybutadiene before hydrogenation 60% Then, a selective hydrogenated block copolymer having a polybutadiene part hydrogenation rate of 99.9% was synthesized, and this polymer was designated as (b-4).
[0039]
Examples 1-8 and Comparative Examples 1-3
Polypropylene, polyphenylene ether and an admixture are blended in the composition shown in Table 1, and have a first raw material feed port upstream and a second raw material feed port downstream with respect to the resin flow direction, and upstream and second of the second feed port. Using a twin screw extruder ZSK-40 (manufactured by WERNER & PFLEIDERER) with a vacuum vent port between the two feed ports and the die, melted under conditions of extrusion temperature of 290 ° C, screw rotation speed of 300rpm, discharge rate of 60kg / hour Kneaded to obtain pellets.
[0040]
Using this pellet, it is supplied to a screw inline type injection molding machine set at 240 to 280 ° C., and under the condition of a mold temperature of 60 ° C., a test piece for bending elastic modulus measurement test, a test piece for Izod impact test, and a heat distortion temperature. A test piece for measurement was injection molded. Next, using these test pieces, flexural modulus (ASTM D-790: 23 ° C.), Izod (notched) impact strength (ASTM D-256: 23 ° C.) and heat distortion temperature (ASTM D-648), In order to confirm the effect of miscibility, the average cross-section of the component (a) dispersed in the resin composition using a transmission electron microscope (JEOL 1200EX) and further using an image analyzer is used for the cross section of the pellet. The particle size was measured. In order to confirm the heat durability (heat resistant creep) of the composition obtained by the production method of the present invention, a rod-shaped sample of 1 mm × 1 mm × 30 mm using Leo Vibron (DDV-01 / 25FP type manufactured by Orientec Co., Ltd.), Stress 130kg / cm ² A heat-resistant creep test was performed under the conditions of a load corresponding to f and a temperature of 65 ° C., and the time until fracture was measured. The results are shown in Table 1.
[0041]
As apparent from Table 1, the components (a) and (b) are supplied from the first supply port, and the remaining amount of the components (c) and (b) in the melt-kneaded composition. Is added from the second supply port and further melt kneaded, so that the polyphenylene ether resin forms a dispersed phase of 1.5 μm or less relative to the propylene resin matrix as compared with the comparative example. It is improved and heat durability (heat resistant creep) is remarkably improved.
[0042]
On the other hand, those not using the component (b) of the present invention are inferior in heat resistance (heat resistance creep).
[0043]
[Table 1]

[0044]
【The invention's effect】
In the resin composition obtained by the production method of the present invention, since the polyphenylene ether resin is dispersed at 1.5 μm or less, the heat resistant creep performance of the obtained composition is remarkably improved.

Claims (1)

(B) 1 of the conjugated diene compound with respect to a total of 100 parts by weight of the (a) and (c) components of 55 to 10% by weight of the polyphenylene ether resin and 45 to 90% by weight of the (c) polypropylene resin. Block copolymer consisting of at least one conjugated diene compound polymer block B and at least one vinyl aromatic compound polymer block A having an amount of 1,2-vinyl bond or 3,4-vinyl bond of 32 to 55% In the method for producing a resin composition containing a total amount of 5 to 30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the coalescence, (a) component and (b) 1.5 to 21 parts by weight of component A method for producing a resin composition, comprising adding the remaining amount of component (c) and component (b) to a melt-kneaded product and further melt-kneading.