JP3761291B2 - Resin composition and process for producing the same - Google Patents

Description

【００１４】
（ここで、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）からなり、還元粘度（０．５ｇ／ｄｌ，クロロホルム溶液，３０℃測定）が、０．１５〜２．５０の範囲、好ましくは０．３０〜２．００、より好ましくは０．３５〜２．００の範囲にあるホモ重合体および／または共重合体である。
【００１５】
このポリフェニレンエーテルの具体的な例としては、例えばポリ（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。
【００１６】
かかるポリフェニレンエーテルの製造方法は公知の方法で得られるものであれば特に限定されるものではなく、例えば、米国特許第３３０６８７４号明細書記載の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、そのほかにも米国特許第３３０６８７５号明細書、同第３２５７３５７号明細書および同第３２５７３５８号明細書、特公昭５２−１７８８０号公報および特開昭５０−５１１９７号公報および同６３−１５２６２８号公報等に記載された方法で容易に製造できる。
【００１７】
また、本発明で用いるポリフェニレンエーテル系樹脂は上記したポリフェニレンエーテルのほかに、これらポリフェニレンエーテル１００重量部に対してポリスチレン（シンジオタクチックポリスチレンも含む）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。
【００１８】
つぎに、本発明で用いる（ｃ）ビニル芳香族化合物を主体とする重合体ブロック−共役ジエン化合物を主体とする重合体ブロックからなるブロック共重合体を水素添加反応して得られる水添ブロック共重合体（以下、水添ブロック共重合体と略記する）は、（ａ）ポリプロピレン系樹脂と（ｂ）ポリフェニレンエーテル系樹脂を溶融混合した際に、（ｂ）ポリフェニレンエーテル系樹脂を（ａ）ポリプロピレン系樹脂中に好適に分散させる能力を有する水添ブロック共重合体である。すなわち、本発明では、少なくとも１個のビニル芳香族化合物を主体とする重合体ブロックＡと、共役ジエン化合物のビニル結合量が４５％以上である少なくとも１個の共役ジエン化合物を主体とするブロックＢとからなる水添ブロック共重合体において、該水添ブロック共重合体のヨウ素価が４０以下である水添ブロック共重合体である。これらの水添ブロック共重合体の構造は、例えば、Ａ−Ｂ、Ａ−Ｂ−Ａ、Ａ−Ｂ−Ａ−Ｂ、（Ａ−Ｂ−）４−Ｓｉ、Ａ−Ｂ−Ａ−Ｂ−Ａ等の構造を有する水添ブロック共重合体である。
【００１９】
このブロック共重合体を構成するビニル芳香族化合物としては、例えば、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、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の１，２−および３，４−ビニル結合量の合計量（以下ビニル結合量と略記する）は４５％以上であり、好ましくは、ブタジエンを主体とする重合体ブロックにおいては、ビニル結合量が６５〜９０％、より好ましくは７０〜８５％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、好ましくはビニル結合量が４８％以上、より好ましくは４８〜９０％である。また、ブタジエンとイソプレンの組み合わせよりなるランダム，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），ブロック共重合体等の共役ジエン化合物から成る重合体ブロックにおいては、好ましくはビニル結合量が４８％以上、より好ましくは４８〜９０％である。このビニル結合量が４５重量％未満であるとポリプロピレン系樹脂と変性ポリフェニレンエーテル系樹脂の混和性が低下し、耐衝撃性、引張伸度が低下し好ましくない。また、かかるビニル結合量が９０％を超えても、混和性の改良効果は顕著でない。そしてこれらのビニル結合量は通常、赤外分光光度計やＮＭＲ等で知ることができる。
【００２０】
また、該水添ブロック共重合体のヨウ素価は４０以下であり、好ましくは３７以下、より好ましくは３５以下である。この水添ブロック共重合体のヨウ素価が４０を超えると、樹脂組成物を加熱溶融混練により製造する際、および樹脂組成物が高温下に置かれたときの水添ブロック共重合体の熱劣化の度合いが大きく、衝撃強度や引張伸度が低下し好ましくない。この水添ブロック共重合体のヨウ素価は通常、ヨウ素滴定法によって定量し、消費されたヨウ素量を水添ブロック共重合体重量に対する百分率で表わした数値である。
【００２１】
また、上記の構造を有する水添ブロック共重合体の数平均分子量は４００００〜５０００００、好ましくは５００００〜３０００００、さらに好ましくは６００００〜２０００００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、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あってもよい。
【００２２】
これらの上記した（ｃ）水添ブロック共重合体は、上記した構造を有するものであればどのような製造方法で得られるものであってもかまわない。公知の製造方法の例としては、例えば、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、特開平２−３００２１８号公報、英国特許第１１３０７７０号明細書および米国特許第３２８１３８３号明細書および同第３６３９５１７号明細書に記載された方法や英国特許第１０２０７２０号明細書および米国特許第３３３３０２４号明細書および同第４５０１８５７号明細書に記載された方法がある。
【００２３】
また、本発明で用いる（ｃ）水添ブロック共重合体は、上記した水添ブロック共重合体のほかに、該水添ブロック共重合体と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公知の変性（該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）水添ブロック共重合体であってもよく、さらに上記した水添ブロック共重合体と該変性水添ブロック共重合体の任意の割合の混合物であってもかまわない。
【００２４】
つぎに本発明で用いる（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体は、モルフォロジー変化を抑制するために必須の成分であり、少なくとも分散相を形成するポリフェニレンエーテル中に存在することが必要である。
【００２５】
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。共役ジエン化合物とビニル芳香族化合物との共重合体としては、これら共役ジエン化合物とビニル芳香族化合物とからなるブロック，ランダム，テーパード，グラフト等の結合様式をなす共重合体である。この共役ジエン化合物とビニル芳香族化合物との共重合体を構成する共重合成分のビニル芳香族化合物としては、例えば、スチレン、ビニルトルエン、α−メチルスチレン等のうちから１種または２種以上が選択できるが、中でもスチレンが好ましい。また、該共役ジエン化合物とビニル芳香族化合物との共重合体中には、共役ジエンに由来する二重結合を有しており、部分的に架橋構造を含むものであってもよい。
【００２６】
この共役ジエン化合物とビニル芳香族化合物との共重合体は、そのミクロ構造（共役ジエン化合物の結合形態）を任意に選ぶことができ、ビニル結合量（１，２−および３，４−ビニル結合量の合計量）は１〜９０％、好ましくは５〜８５％であり、より好ましくは１０〜６０％、さらに好ましくは１０〜５０％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。そして、共役ジエン化合物とビニル芳香族化合物との共重合体におけるビニル芳香族化合物の含有量は、０〜８０重量％、好ましくは０〜７０重量％、より好ましくは１５〜６５重量％である。また、上記の構造を有する共役ジエン化合物とビニル芳香族化合物との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の範囲である。
【００２７】
これらの上記した（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体は、上記した構造を有するものであればどのような製造方法で得られるものであってもかまわない。公知の製造方法の例としては、例えば、特公昭４０−２３７９８号公報、米国特許第３５９５９４２号明細書および同第４０９０９９６号明細書等に記載された方法がある。
【００２８】
また、本発明で用いる（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体は、上記した重合体のほかに、該重合体と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公知の変性（該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）重合体であってもよく、さらに上記した重合体と該変性重合体の任意の割合の混合物であってもかまわない。
【００２９】
これらの共役ジエン化合物とビニル芳香族化合物との共重合体共役ジエン化合物から成る重合体は、各々単独で用いても良いし２種以上を組み合わせて用いても良い。
【００３０】
本発明の樹脂組成物は、上記した（ａ）〜（ｄ）成分を基本成分として構成される。
【００３１】
本発明において、（ａ）ポリプロピレン系樹脂の配合量は、４５〜９５重量％であり、好ましくは４５〜８５重量％である。かかる配合量が４５重量％未満では、得られる樹脂組成物の耐熱性は優れるものの、成形加工性、耐溶剤性が劣り好ましくない。また、９５重量％を超える場合は成形加工性、耐溶剤性は良好なものの、耐熱性が劣り耐熱性材料として利用できない。
【００３２】
本発明において、（ｂ）ポリフェニレンエーテル系樹脂の配合量は５５〜５重量％、好ましくは５５〜１５重量％である。かかる配合量が５５重量％を超える場合、得られる樹脂組成物の耐熱性は極度に優れるものの、成形加工性、耐溶剤性が劣り好ましくない。また、５重量％未満では成形加工性、耐溶剤性に優れるものの、耐熱性が劣り耐熱材料として利用できない。
【００３３】
本発明において、（ｃ）水添ブロック共重合体の配合量は、上記（ａ）、（ｂ）成分の合計１００重量部に対して、１〜３０重量部である。かかる配合量が１重量部未満では混和剤としての効果が見られず好ましくない。また、かかる配合量が３０重量部を超える場合は、（ａ）、（ｂ）成分が示す作用効果の耐熱性、耐溶剤性、剛性および機械的強度の低下が顕著であり好ましくない。
【００３４】
本発明において、（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体の配合量は、上記（ａ）、（ｂ）成分の合計１００重量部に対して、１〜３０重量部である。かかる配合量が１重量部未満ではモルフォロジー変化の抑制効果が見られず好ましくない。また、かかる配合量が３０重量部を超える場合は、（ｂ）成分が示す作用効果の耐熱性、剛性の低下が顕著であり好ましくない。
【００３５】
本発明では、上記の成分の他に、本発明の特徴および効果を損なわない範囲で必要に応じて他の附加的成分、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、ガラスフレーク、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。
【００３６】
本発明では、特定の加熱溶融混練方法を取ることにより、優れた乳化分散形態を容易に得ることができる。すなわち、（ｂ）ポリフェニレンエーテル系樹脂と（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体の溶融混練状態に（ｃ）水添ブロック共重合体と（ａ）ポリプロピレン系樹脂を追加添加し一緒に溶融混練する方法や、（ｂ）ポリフェニレンエーテル系樹脂と（ｄ）共役ジエン化合物からなる重合体および（ｃ）水添ブロック共重合体の溶融混練状態に（ａ）ポリプロピレン系樹脂を追加添加し一緒に溶融混練する方法や、（ｃ）水添ブロック共重合体の一部と（ｂ）ポリフェニレンエーテル系樹脂と（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体の溶融混練状態に（ａ）ポリプロピレン系樹脂と（ｃ）水添ブロック共重合体を追加添加し一緒に溶融混練する方法や、（ａ）ポリプロピレン系樹脂の一部と（ｂ）ポリフェニレンエーテル系樹脂と（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体の溶融混練状態に（ｃ）水添ブロック共重合体と（ａ）ポリプロピレン系樹脂を追加添加し一緒に溶融混練する方法や、（ａ）ポリプロピレン系樹脂の一部と（ｂ）ポリフェニレンエーテル系樹脂と（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体および（ｃ）水添ブロック共重合体の溶融混練状態に（ａ）ポリプロピレン系樹脂を追加添加し一緒に溶融混練する方法や、（ａ）ポリプロピレン系樹脂の一部と（ｃ）水添ブロック共重合体の一部および（ｂ）ポリフェニレンエーテル系樹脂と（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体の溶融混練状態に（ａ）ポリプロピレン系樹脂と（ｃ）水添ブロック共重合体を追加添加し一緒に溶融混練する方法が好ましい方法として挙げることができる。
【００３７】
一方、（ｂ）ポリフェニレンエーテル系樹脂の溶融物に、（ａ）ポリプロピレン系樹脂、（ｃ）水添ブロック共重合体および（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体とを追加供給する混練方法は、得られる樹脂組成物のモルフォロジー変化の抑制において不十分である。これらの方法を行う溶融混練機として例えば、単軸押出機、二軸押出機、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方法が挙げられるが、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。
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。
【００３８】
本発明では、第１原料供給口より（ａ）ポリプロピレン系樹脂０〜３０重量％、好ましくは１〜３０重量％と（ｂ）ポリフェニレンエーテル系樹脂５５〜５重量％と、（ａ）（ｂ）成分の合計（下記（ａ）成分も含む）１００重量部に対して、（ｃ）水添ブロック共重合体０〜３０重量部および（ｄ）共役ジエン化合物から成る重合体１〜３０重量部を供給し溶融混練を行い、第２原料供給口より（ｃ）水添ブロック共重合体をその全配合量１〜３０重量部の残部に対応する０〜３０重量部と（ａ）ポリプロピレン系樹脂をその全配合量４５〜９５重量％の残部に対応する１５〜９５重量％を供給し（ａ）ポリプロピレン系樹脂と（ｂ）ポリフェニレンエーテル系樹脂、（ｃ）水添ブロック共重合体および（ｄ）共役ジエン化合物から成る重合体の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、（ｂ）ポリフェニレンエーテル系樹脂、（ｃ）水添ブロック共重合体および（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体は（ａ）ポリプロピレン系樹脂マトリックス中に分散相を形成し、かつ優れた乳化分散形態を容易に与える。このような製法を取ることは、乳化分散能力および衝撃強度、引張伸度を向上させる上で重要な方法である。
【００３９】
このようにして得られる本発明の樹脂組成物は、従来より公知の種々の方法、例えば、射出成形、押出成形、中空成形により各種部品の成形体として成形でき、更にホットランナーを設けた成形機を用いた場合や、成形機内に樹脂を滞留させた場合、大型成形品や超薄肉成形品での使用が可能である。これら各種部品としては、例えば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。
【００４０】
【発明の実施の形態】
以下、実施例によって本発明の実施の形態を説明するが、本発明はこれらの実施例により限定されるものではない。
【００４１】
実施例に用いた（ａ）ポリプロピレン系樹脂（ａ−１）：ホモ−ポリプロピレンＭＦＲ＝６．５ｇ／１０分ポリプロピレンのＭＦＲ（メルトフローレート）はＡＳＴＭＤ１２３８に準拠し、２３０℃、２．１６Ｋｇの荷重で測定した。
【００４２】
実施例に用いた（ｂ）ポリフェニレンエーテル系樹脂（ｂ−１）：２、６−キシレノールを酸化重合して得た還元粘度０．３５のポリフェニレンエーテル（ｂ−２）：２、６−キシレノールを酸化重合して得た還元粘度０．９０のポリフェニレンエーテル実施例に用いた（ｃ）水添ブロック共重合体（ｃ−１）：ポリスチレン（１）−水添ポリイソプレン−ポリスチレン（２）の構造を有し、ヨウ素価３３．９、数平均分子量８６，３００、分子量分布１．１０、水素添加前のポリイソプレンのビニル結合量が５４％、ポリスチレン（１）の数平均分子量２０，２００、ポリスチレン（２）の数平均分子量２０，０００の水添ブロック共重合体を合成し、このポリマーを（ｃ−１）とした。
【００４３】
（ｃ−２）：ポリスチレン（１）−水添ポリブタジエン−ポリスチレン（２）の構造を有し、ヨウ素価３．９、数平均分子量８２，０００、分子量分布１．１０、水素添加前のポリブタジエンのビニル結合量が７５％、ポリスチレン（１）の数平均分子量１９，８００、ポリスチレン（２）の数平均分子量１９，８００の水添ブロック共重合体を合成し、このポリマーを（ｃ−２）とした。
【００４４】
（ｃ−３）：ポリスチレン（１）−ビニル結合量６９％の水添ポリブタジエン−ビニル結合量５１％の水添ポリイソプレン−ポリスチレン（２）の構造を有し、水添ポリブタジエン／水添ポリイソプレン＝５０／５０（重量比）、ヨウ素価１２．９、数平均分子量８３，０００、分子量分布１．１０、ポリスチレン（１）の数平均分子量２０，１００、ポリスチレン（２）の数平均分子量２０，１００の水添ブロック共重合体を合成し、このポリマーを（ｃ−３）とした。
【００４５】
（ｃ−４）：ポリスチレン（１）−水添ポリイソプレン−ポリスチレン（２）の構造を有し、ヨウ素価２９．９、数平均分子量８３，０００、分子量分布１．１０、水素添加前のポリイソプレンのビニル結合量が４２％、ポリスチレン（１）の数平均分子量２０，１００、ポリスチレン（２）の数平均分子量２０，１００の水添ブロック共重合体を合成し、このポリマーを（ｃ−４）とした。
【００４６】
（ｃ−５）：ポリスチレン（１）−水添ポリイソプレン−ポリスチレン（２）の構造を有し、ヨウ素価４３．３、数平均分子量８９，０００、分子量分布１．１０、水素添加前のポリイソプレンのビニル結合量が４８％、ポリスチレン（１）の数平均分子量１８，９００、ポリスチレン（２）の数平均分子量１８，９００の水添ブロック共重合体を合成し、このポリマーを（ｃ−５）とした。
【００４７】
実施例に用いた（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体（ｄ−１）：ポリスチレン（１）−ポリブタジエン−ポリスチレン（２）の構造を有し、結合スチレン量４８％、ブロックスチレン量４０％、数平均分子量９５，０００、ポリブタジエンのビニル結合量が１２％の共重合体を合成し、このポリマーを（ｄ−１）とした。
【００４８】
（ｄ−２）：ポリスチレン（１）−ポリイソプレン−ポリスチレン（２）の構造を有し、結合スチレン量３０％、ブロックスチレン量３０％、数平均分子量８２，０００、ポリイソプレンのビニル結合量が３５％の共重合体を合成し、このポリマーを（ｄ−２）とした。
【００４９】
（ｄ−３）：ポリスチレン（１）−ポリブタジエン−ポリスチレン（２）の構造を有し、結合スチレン量２５％、ブロックスチレン量１８％、数平均分子量１７０，０００、ポリブタジエンのビニル結合量が１６％の共重合体を合成し、このポリマーを（ｄ−３）とした。
【００５０】
樹脂組成物の溶融混練方法（Ａ）：２軸押出機を用い、第１原料供給口より（ｂ）ポリフェニレンエーテル系樹脂と（ｃ）水添ブロック共重合体、（ｄ）共役ジエン化合物とビニル芳香族化合物との共重合体を供給し、第２原料供給口より（ａ）ポリプロピレン系樹脂を供給する溶融混練方法を（Ａ）とした。
【００５１】
（Ｂ）：２軸押出機を用い、第１原料供給口より（ｂ）ポリフェニレンエーテル系樹脂と（ｄ）共役ジエン化合物から成る重合体を供給し、第２原料供給口より（ａ）ポリプロピレン系樹脂と（ｃ）水添ブロック共重合体を供給する溶融混練方法を（Ｂ）とした。
【００５２】
（Ｃ）：２軸押出機を用い、第１原料供給口より（ｂ）ポリフェニレンエーテル系樹脂と（ｄ）共役ジエン化合物から成る重合体、および（ａ）ポリプロピレン系樹脂の一部を供給し、第２原料供給口より（ｃ）水添ブロック共重合体と残りの（ａ）ポリプロピレン系樹脂とを供給する溶融混練方法を（Ｃ）とした。
【００５３】
溶融混練温度は（Ａ）、（Ｂ）、（Ｃ）ともに第１原料供給口から第２原料供給口までのバレル設定温度を３３０℃、第２原料供給口より下流のバレル設定温度を２９０℃とし、スクリュー回転数を３５０ｒｐｍに設定し溶融混練を実施した。
【００５４】
なお、物性の評価は次の通りに行った。
【００５５】
（１）熱履歴処理ギアーオーブンを用い８０℃の環境下に４８時間放置した。
【００５６】
（２）引張伸度試験ＡＳＴＭ Ｄ−６３８に準じ、２３℃で破断伸びを測定した。
【００５７】
（３）アイゾット（ノッチ付き）衝撃強度ＡＳＴＭ Ｄ−２５６に準じ、２３℃で測定した。
【００５８】
（４）樹脂組成物のモルフォロジー安定性確認キャピログラフ１Ｃ（東洋精機（株）製）を用いて、樹脂組成物に一定の押出速度を掛け、押出速度によるモルフォロジーの変形具合いを確認した。キャピログラフ１Ｃのバレル温度を２８０℃に設定し、径が２．０ｍｍ，長さが２０ｍｍのキャピラリーを用いて、押出速度を１ｍｍ／ｓｅｃと１００ｍｍ／ｓｅｃで押出し、キャピラリーから流出した溶融樹脂を液体窒素に浸け、サンプルとした。得られたサンプルの流動方向と平行面を、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）を用いて超薄切片を作成しルテニウム酸により染色し、それを透過型電子顕微鏡（日本電子（株）製 １２００ＥＸ）を用いて観察、写真撮影した。この写真をもとに画像解析装置（旭化成（株）製ＩＰ１０００）を用いて、分散相の長径（Ｌ）と短径（Ｄ）を求め、平均Ｌ／Ｄを求めた。
【００５９】
また、２４０〜２８０℃に設定したスクリューインライン型射出成形機に樹脂組成物を供給し、５分間成形機内に樹脂を滞留させた後、金型温度６０℃の条件で箱型成形品（１５ｃｍ（幅）×１５ｃｍ（奥行）×８ｃｍ（高さ），厚み２ｍｍ，２ｍｍΦピンゲート）を射出成形した。本成形品側面（８ｃｍ×１５ｃｍ）の中央部の流動方向と平行面を、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）を用いて超薄切片を作成しルテニウム酸により染色し、それを透過型電子顕微鏡（日本電子（株）製 １２００ＥＸ）を用いて観察、写真撮影した。この写真をもとに画像解析装置（旭化成（株）製ＩＰ１０００）を用いて、分散相の長径（Ｌ）と短径（Ｄ）を求め、平均Ｌ／Ｄを求めた。
【００６０】
【実施例１】
表１に示した組成および溶融混練方法でポリプロピレン系樹脂、ポリフェニレンエーテル系樹脂、水添ブロック共重合体、共役ジエン化合物から成る重合体を配合、溶融混練しペレットとして得た。溶融混練は２９０〜３３０℃に設定したベントポート付き二軸押出機（ＺＳＫ−２５；ＷＥＲＮＥＲ＆ＰＦＬＥＩＤＥＲＥＲ社製、ドイツ国）を用いて行った。
【００６１】
このペレットを用いて樹脂組成物の分散形態を確認し、さらに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℃の条件で引張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。これらのテストピースの物性を測定し、その結果を併せて表１に載せた。
【００６２】
本発明の範囲内の実施例１は、共役ジエンから成る重合体を用いない比較例１、水添ブロック共重合体が本発明の範囲外である比較例２および３、共役ジエン化合物とビニル芳香族化合物との共重合体の添加量が本発明の範囲外である比較例４に比し、破断伸び、Ｉｚｏｄ衝撃強度および分散形態に優れることが明らかである。
【００６３】
【実施例２】
組成と溶融混練方法は表１に従い、その他は実施例１と同様にして実施例２を得た。
【００６４】
ポリプロピレン系樹脂の添加を二段階に分けた溶融混練方法Ｂによる実施例２は物性および分散形態に優れることが理解される。
【００６５】
【実施例３】
組成と溶融混練方法は表１に従い、その他は実施例１と同様にして実施例３を得た。共役ジエン化合物とビニル芳香族化合物との共重合体の種類と量の異なる例である。
【００６６】
【実施例４】
組成と溶融混練方法は表１に従い、その他は実施例１と同様にして実施例４を得た。高粘度のポリフェニレンエーテル系樹脂を用いた例である。
【００６７】
【実施例５】
組成と溶融混練方法は表１に従い、その他は実施例１と同様にして実施例５を得た。
【００６８】
高粘度のポリフェニレンエーテル系樹脂を用い、水添ブロック共重合体を第１供給口から添加した本発明の範囲内の実施例５は、共役ジエン化合物とビニル芳香族化合物との共重合体の溶融混練方法が本発明の範囲内であれば、期待通りの物性と分散形態を示すことが判る。
【００６９】
これらの結果より、少なくとも１個のビニル芳香族化合物を主体とする重合体ブロックＡと、共役ジエン化合物のビニル結合量が４５％以上である少なくとも１個の共役ジエン化合物を主体とする重合体ブロックＢとからなり、該水添ブロック共重合体のヨウ素価が４０以下である水添ブロック共重合体を用い、さらに加熱溶融混練手段を制御することにより、ポリフェニレンエーテル系樹脂および共役ジエン化合物とビニル芳香族化合物との共重合体がポリプロピレン系樹脂マトリックス中に微分散化した分散相を形成させることにより、ポリプロピレン系樹脂とポリフェニレンエーテル系樹脂とのモルフォロジー安定性の向上した優れた樹脂組成物が得られる。
【００７０】
【表１】

【００７１】
【発明の効果】
本発明の樹脂組成物は、ポリプロピレン系樹脂とポリフェニレンエーテル系樹脂、水添ブロック共重合体および共役ジエン化合物とビニル芳香族化合物との共重合体からなり、水添ブロック共重合体として特定の構造を有する水添ブロック共重合体を用い、かつ特定の加熱溶融混練手段をとったため、従来技術では困難であったポリプロピレン系樹脂とポリフェニレンエーテル系樹脂を含む樹脂組成物のモルフォロジー安定性に優れ、耐薬品性、耐熱性、耐衝撃性、引張伸びに優れた樹脂組成物をもたらす。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition comprising a polypropylene resin and a polyphenylene ether resin. More specifically, the present invention relates to a resin composition that can be suitably used as a molding material for various molded products, and to a method for producing the same that suppresses a change in morphology.
[0002]
[Prior art]
Many attempts have been made to improve solvent resistance, heat resistance, and impact resistance by blending polyphenylene ether with polyolefin. For example, in US Pat. No. 3,361,851, polyphenylene ether is blended with polyolefin. Thus, a proposal for improving solvent resistance and impact resistance has been made, and in US Pat. No. 3,994,856, polyphenylene ether or polyphenylene ether and a styrenic resin are blended with a hydrogenated block copolymer. There is a description regarding improvement of impact resistance and solvent resistance. US Pat. No. 4,145,377 discloses polyphenylene ether or polyphenylene ether and a styrene resin as polyolefin / hydrogenated block copolymer = 20 to 80 parts by weight / 80 to 20 parts by weight In addition, US Pat. No. 4,166,055 and US Pat. No. 4,239,673 describe polyphenylenes and blends with a premix and a hydrogenated block copolymer. Improved impact resistance is described by blending ether with a hydrogenated block copolymer and a polyolefin. U.S. Pat. No. 4,383,082 and European published patent No. 115712 describe that impact resistance is improved by blending polyphenylene ether with a polyolefin and a hydrogenated block copolymer.
[0003]
Further, JP-A-63-113050, JP-A-63-113058, JP-A-62-222542, US Pat. No. 4,863,997, JP-A-2-247240, and JP-A-2- 248447, JP-A-2-305814, JP-A-3-72512, JP-A-4-183748, JP-A-5-320471, and JP-A-7-165998 disclose polyolefin resins and polyphenylenes. A resin composition excellent in compatibility, chemical resistance, and processability has been proposed by blending a specific hydrogenated block copolymer in the modification of a resin composition comprising an ether resin.
[0004]
[Problems to be solved by the invention]
A resin composition obtained by blending polyphenylene ether and polyolefin gives a resin composition having drastically improved solvent resistance.
[0005]
However, when a molding machine equipped with a hot runner is used, or when the resin is retained in the molding machine, the morphology changes, or the morphological deformation occurs in large molded products or ultra-thin molded parts. It can become a big factor which reduces the characteristic which has. Therefore, it has been a problem to provide a resin composition that suppresses morphological changes.
[0006]
[Means for Solving the Problems]
In view of the current situation, the present inventors have given the structure of a hydrogenated block copolymer that can be used as an admixture and a polyphenylene ether-based resin that can be used as a dispersed phase, and a resin composition, in order to impart excellent morphological stability during molding processing. As a result of intensive studies on the manufacturing method of products, hydrogenated block copolymers having a specific structure andCopolymer of conjugated diene compound and vinyl aromatic compoundThe emulsification and dispersibility is improved by melting and kneading the resin composition under a specific production method, and the structure of the dispersed phase component is controlled to suppress the morphological change and deformation during molding. Has been found to result in a resin composition.
[0007]
  That is, the present invention
(1) In the resin composition,
(A) 45 to 95% by weight of polypropylene resin
(B) polyphenylene ether resin 55 to 5% by weight of resin, and
For a total of 100 parts by weight of the components (a) and (b),
(C) The polymer block A mainly composed of at least one vinyl aromatic compound and the vinyl bond amount (total amount of 1,2- and 3,4-vinyl bonds) of the conjugated diene compound is 45% or more. A hydrogenated block copolymer comprising a polymer block B mainly composed of at least one conjugated diene compound, wherein the iodine value of the hydrogenated block copolymer is 40 or less. 30 parts by weight
(D)Copolymer of conjugated diene compound and vinyl aromatic compoundIt is characterized by blending 1 to 30 parts by weightTreeFat composition,
(2)The major axis (L) / minor axis (D) of the dispersed phase obtained from a transmission electron micrograph of the resin extruded with a capillograph (280 ° C., extrusion speed 100 mm / sec, diameter 2.0 mm, length 20 mm using a capillary) The resin composition according to claim 1, wherein the ratio of
(3)(A) 0 to 30% by weight of a polypropylene resin, (b) 55 to 5% by weight of a polyphenylene ether resin,
(C) 0 to 30 parts by weight of a hydrogenated block copolymer, and (d) with respect to 100 parts by weight of the total of the components (a) and (b) (including the component (a) below)Copolymer of conjugated diene compound and vinyl aromatic compound1 to 30 parts by weight of the melt-kneaded product, (a) 15 to 95% by weight of the polypropylene resin corresponding to the balance of 45 to 95% by weight of the total blended amount, and (c) the hydrogenated block copolymer 2 to 30 parts by weight corresponding to the balance of 1 to 30 parts by weight, and further melt-kneading.Or 2A process for producing the resin composition according to claim 1,
Is to provide.
[0008]
The present invention will be described in detail below. The (a) polypropylene resin used in the present invention is composed of a crystalline propylene homopolymer, a crystalline propylene homopolymer portion obtained in the first step of polymerization and propylene, ethylene and / or at least one of the second and subsequent steps of polymerization. A crystalline propylene-ethylene block copolymer having a propylene-ethylene random copolymer portion obtained by copolymerizing another α-olefin (for example, butene-1, hexene-1, etc.), and further, these crystalline It may be a mixture of a propylene homopolymer and a crystalline propylene-ethylene block copolymer.
[0009]
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.
[0010]
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.
[0011]
As these electron-donating compounds, known compounds can be used, for example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, methyl toluate, triphenyl phosphite, tributyl phosphite and the like. Phosphoric acid derivatives such as phosphate esters and hexamethylphosphoric triamide, alkoxy ester compounds, aromatic monocarboxylic acid esters and / or aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols And / or various phenols.
[0012]
The polypropylene resin used in the present invention may be any resin having any crystallinity, melting point, and molecular weight as long as it is obtained by the above-described method. In addition, several types of polypropylene having different crystallinity, melting point, and molecular weight may be used together. It can also be used.
Next, the (b) polyphenylene ether resin used in the present invention is a polyphenylene ether having the following structure. Polyphenylene ether is a compound known per se. Binding unit:
[0013]
[Chemical 1]

[0014]
(Where R₁, R₂, R_Three, And R_FourAre each a hydrogen atom, a halogen atom, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group or at least two carbon atoms as a halogen atom. It is selected from the group consisting of halohydrocarbonoxy groups separating oxygen atoms and may be the same or different from each other, and reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) Is a homopolymer and / or copolymer in the range of 0.15 to 2.50, preferably 0.30 to 2.00, more preferably 0.35 to 2.00.
[0015]
Specific examples of the polyphenylene ether 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, and 2,6-dimethylphenol and other phenols (for example, 2). , 3,6-trimethylphenol and 2-methyl-6-butylphenol) and other polyphenylene ether copolymers. 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).
[0016]
The method for producing such polyphenylene ether is not particularly limited as long as it can be obtained by a known method. For example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst. For example, it can be easily produced by oxidative polymerization of 2,6-xylenol. In addition, US Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, and Japanese Patent Publication No. 52-17880 are disclosed. And can be easily produced by the methods described in JP-A Nos. 50-51197 and 63-152628.
[0017]
In addition to the polyphenylene ether described above, the polyphenylene ether resin used in the present invention is not limited to exceed 400 parts by weight of polystyrene (including syndiotactic polystyrene) or high impact polystyrene with respect to 100 parts by weight of these polyphenylene ethers. What was added can also be used suitably.
[0018]
Next, a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising (c) a polymer block mainly composed of a vinyl aromatic compound and a polymer block mainly composed of a conjugated diene compound used in the present invention. When the polymer (hereinafter abbreviated as hydrogenated block copolymer) is melt-mixed with (a) polypropylene resin and (b) polyphenylene ether resin, (b) polyphenylene ether resin is converted into (a) polypropylene. It is a hydrogenated block copolymer having an ability to be suitably dispersed in a resin. That is, in the present invention, the polymer block A mainly composed of at least one vinyl aromatic compound and the block B mainly composed of at least one conjugated diene compound having a vinyl bond content of 45% or more of the conjugated diene compound. The hydrogenated block copolymer is a hydrogenated block copolymer having an iodine value of 40 or less. The structure of these hydrogenated block copolymers is, for example, AB, ABA, ABAB, (AB) 4-Si, ABBA- A hydrogenated block copolymer having a structure such as A.
[0019]
As the vinyl aromatic compound constituting the block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. Of these, styrene is preferred. Further, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred. The total amount of 1,2- and 3,4-vinyl bonds (hereinafter abbreviated as vinyl bond) of the polymer block mainly composed of a conjugated diene compound is 45% or more, preferably butadiene is mainly composed. In the polymer block, the vinyl bond content is 65 to 90%, more preferably 70 to 85%. In the polymer block mainly composed of isoprene, the vinyl bond content is preferably 48% or more, more preferably 48 to 90%. In addition, a polymer block made of a conjugated diene compound such as a random, tapered (a monomer component increases or decreases along the molecular chain), block copolymer or the like, which is a combination of butadiene and isoprene, preferably has a vinyl bond content. Is 48% or more, more preferably 48 to 90%. If the vinyl bond content is less than 45% by weight, the miscibility between the polypropylene resin and the modified polyphenylene ether resin is lowered, and the impact resistance and tensile elongation are lowered, which is not preferable. Even if the vinyl bond content exceeds 90%, the effect of improving the miscibility is not remarkable. These vinyl bond amounts can usually be known by an infrared spectrophotometer or NMR.
[0020]
The hydrogenated block copolymer has an iodine value of 40 or less, preferably 37 or less, more preferably 35 or less. When the iodine value of the hydrogenated block copolymer exceeds 40, when the resin composition is produced by hot melt kneading, and when the resin composition is placed at a high temperature, the hydrogenated block copolymer is thermally deteriorated. Is unfavorable since the impact strength and tensile elongation are lowered. The iodine value of the hydrogenated block copolymer is usually determined by iodine titration, and is a numerical value representing the amount of iodine consumed as a percentage of the weight of the hydrogenated block copolymer.
[0021]
The number average molecular weight of the hydrogenated block copolymer having the above structure is in the range of 40,000 to 500,000, preferably 50,000 to 300,000, more preferably 60000 to 200,000, and the molecular weight distribution (measured by gel permeation chromatography). The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 10 or less. Furthermore, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.
[0022]
These (c) hydrogenated block copolymers described above may be obtained by any production method as long as they have the structure described above. Examples of known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-54-126255. No. 56-10542, Japanese Patent Laid-Open No. 56-62847, Japanese Patent Laid-Open No. 56-100900, Japanese Patent Laid-Open No. 2-300218, British Patent No. 1130770, US Pat. No. 3,281,383 and the like. And the methods described in British Patent No. 1020720 and US Pat. Nos. 3,330,024 and 4,501,857.
[0023]
The (c) hydrogenated block copolymer used in the present invention includes, in addition to the hydrogenated block copolymer described above, the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or a derivative thereof. A known modification (the α, β-unsaturated carboxylic acid or derivative thereof) obtained by reacting in the presence of a radical generator in the presence or absence of a molten state, solution state, or slurry state at a temperature of 80 to 350 ° C. 0.01-10 wt% grafted or added) hydrogenated block copolymer, or a mixture of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer in an arbitrary ratio. It doesn't matter.
[0024]
Next used in the present invention (d)Copolymer of conjugated diene compound and vinyl aromatic compoundIs an essential component for suppressing morphological change and needs to be present in at least the polyphenylene ether forming the dispersed phase.
[0025]
As the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and these A combination is preferred.Copolymer of conjugated diene compound and vinyl aromatic compoundasThisThese are copolymers composed of a conjugated diene compound and a vinyl aromatic compound and having a bonding mode such as block, random, tapered, or graft. thisCopolymer of conjugated diene compound and vinyl aromatic compoundAs the vinyl aromatic compound of the copolymerization component that constitutes, for example, one or two or more types can be selected from styrene, vinyltoluene, α-methylstyrene, etc., among which styrene is preferable. Also, theCopolymer of conjugated diene compound and vinyl aromatic compoundSome have a double bond derived from a conjugated diene and may partially contain a crosslinked structure.
[0026]
thisCopolymer of conjugated diene compound and vinyl aromatic compoundCan arbitrarily select the microstructure (bonded form of the conjugated diene compound), and the vinyl bond amount (total amount of 1,2- and 3,4-vinyl bonds) is 1 to 90%, preferably 5 It is -85%, More preferably, it is 10-60%, More preferably, it is 10-50%. The bonding form of these conjugated diene compounds can be usually known by an infrared spectrophotometer, NMR or the like. AndCopolymer of conjugated diene compound and vinyl aromatic compoundThe content of the vinyl aromatic compound in is 0 to 80% by weight, preferably 0 to 70% by weight, more preferably 15 to 65% by weight. Also has the above structureCopolymer of conjugated diene compound and vinyl aromatic compoundThe number average molecular weight of is in the range of 5,000 to 1,000,000, preferably 10,000 to 800,000, more preferably 30,000 to 500,000.
[0027]
These (d) aboveCopolymer of conjugated diene compound and vinyl aromatic compoundMay be obtained by any manufacturing method as long as it has the structure described above. Examples of known production methods include those described in, for example, Japanese Patent Publication No. 40-23798, US Pat. Nos. 3,595,942 and 4,090,996.
[0028]
Also, used in the present invention (d)Copolymer of conjugated diene compound and vinyl aromatic compoundIn addition to the above-mentioned polymer, the polymer and the α, β-unsaturated carboxylic acid or derivative thereof in the presence of a radical generator in the absence, in the molten state, in the solution state, or in the slurry state are 80 to 350. It may be a known modified polymer (0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or derivative thereof is grafted or added) obtained by reacting at a temperature of 0 ° C. It may be a mixture of a polymer and the modified polymer in an arbitrary ratio.
[0029]
theseCopolymer of conjugated diene compound and vinyl aromatic compoundThe polymers composed of conjugated diene compounds may be used alone or in combination of two or more.
[0030]
The resin composition of the present invention comprises the above-described components (a) to (d) as basic components.
[0031]
In this invention, the compounding quantity of (a) polypropylene resin is 45 to 95 weight%, Preferably it is 45 to 85 weight%. If the blending amount is less than 45% by weight, the resulting resin composition is excellent in heat resistance but unfavorably inferior in moldability and solvent resistance. On the other hand, if it exceeds 95% by weight, the moldability and solvent resistance are good, but the heat resistance is poor and it cannot be used as a heat resistant material.
[0032]
In this invention, the compounding quantity of (b) polyphenylene ether-type resin is 55 to 5 weight%, Preferably it is 55 to 15 weight%. When the blending amount exceeds 55% by weight, the resulting resin composition has extremely excellent heat resistance, but is inferior in molding processability and solvent resistance. On the other hand, if it is less than 5% by weight, the moldability and solvent resistance are excellent, but the heat resistance is inferior and cannot be used as a heat resistant material.
[0033]
In this invention, the compounding quantity of (c) hydrogenated block copolymer is 1-30 weight part with respect to a total of 100 weight part of said (a), (b) component. If the blending amount is less than 1 part by weight, the effect as an admixture is not seen, which is not preferable. Moreover, when this compounding quantity exceeds 30 weight part, the fall of the heat resistance of the effect which the (a) and (b) component shows, solvent resistance, rigidity, and mechanical strength is remarkable, and is unpreferable.
[0034]
In the present invention, (d)Copolymer of conjugated diene compound and vinyl aromatic compoundThe blending amount is 1 to 30 parts by weight with respect to 100 parts by weight of the total of the components (a) and (b). If the blending amount is less than 1 part by weight, the effect of suppressing morphological change is not seen, which is not preferable. Moreover, when this compounding quantity exceeds 30 weight part, the heat resistance of the effect which the (b) component shows, and the fall of rigidity are remarkable and are unpreferable.
[0035]
In the present invention, in addition to the above-described components, other additional components such as an antioxidant, a metal deactivator, a flame retardant (organophosphoric acid (organic phosphoric acid) are used as long as the characteristics and effects of the present invention are not impaired. Ester compounds, inorganic phosphorus compounds, aromatic halogen flame retardants, silicone flame retardants, etc.), fluorine polymers, plasticizers (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 fibers, glass flakes, carbon fibers, polyacrylonitrile fibers, Whisker, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, conductive metal fiber Conductive carbon black, etc.), various colorants, may be added such as mold release agents.
[0036]
In the present invention, an excellent emulsified dispersion form can be easily obtained by taking a specific heat-melt kneading method. That is, (b) polyphenylene ether resin and (d)Copolymer of conjugated diene compound and vinyl aromatic compound(C) a hydrogenated block copolymer and (a) a polypropylene resin are additionally added to the melt kneaded state and melt kneaded together, and (b) a polyphenylene ether resin and (d) a conjugated diene compound. (C) a method in which a polypropylene resin is additionally added and melt-kneaded together in the melt-kneaded state of the coalescence and (c) hydrogenated block copolymer, and (c) a part of the hydrogenated block copolymer and (b) Polyphenylene ether resin and (d)Copolymer of conjugated diene compound and vinyl aromatic compound(A) a polypropylene resin and (c) a hydrogenated block copolymer are additionally added to the melt kneaded state and melt kneaded together, or (a) a part of the polypropylene resin and (b) a polyphenylene ether resin And (d)Copolymer of conjugated diene compound and vinyl aromatic compound(C) A hydrogenated block copolymer and (a) a polypropylene resin are additionally added to the melt kneaded state and melt kneaded together, or (a) a part of the polypropylene resin and (b) a polyphenylene ether resin And (d)Copolymer of conjugated diene compound and vinyl aromatic compoundAnd (c) a method in which (a) a polypropylene resin is additionally added to the melt-kneaded state of the hydrogenated block copolymer and melt-kneaded together, or (a) a part of the polypropylene resin and (c) a hydrogenated block copolymer Part of the polymer and (b) a polyphenylene ether resin and (d)Copolymer of conjugated diene compound and vinyl aromatic compoundAs a preferable method, (a) polypropylene resin and (c) hydrogenated block copolymer are additionally added to the melt-kneaded state of the above and melt-kneaded together.
[0037]
On the other hand, (b) a melt of polyphenylene ether resin, (a) polypropylene resin, (c) hydrogenated block copolymer, and (d)Copolymer of conjugated diene compound and vinyl aromatic compoundIs not sufficient in suppressing the change in the morphology of the resulting resin composition. Examples of the melt kneader for performing these methods include a heat melt kneading method using a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc., among which a twin screw extruder is used. The melt kneading method used 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.
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 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.
[0038]
In the present invention, (a) 0 to 30% by weight, preferably 1 to 30% by weight of polypropylene resin, (b) 55 to 5% by weight of polyphenylene ether resin, and (a) and (b) from the first raw material supply port. (C) 0-30 parts by weight of a hydrogenated block copolymer and (d) 1-30 parts by weight of a polymer comprising a conjugated diene compound with respect to 100 parts by weight of the total of the components (including the component (a) below) Supply and melt-knead, (c) hydrogenated block copolymer from the second raw material supply port 0 to 30 parts by weight corresponding to the remainder of the total amount of 1 to 30 parts by weight and (a) polypropylene resin (A) polypropylene resin, (b) polyphenylene ether resin, (c) hydrogenated block copolymer, and (d) Heavy consisting of conjugated diene compounds In addition to the composition of the melt-kneading condition of the body, by performing continued further melt kneading, (b) a polyphenylene ether resin, (c) hydrogenated block copolymer and (d)Copolymer of conjugated diene compound and vinyl aromatic compound(A) A dispersed phase is formed in a polypropylene resin matrix, and an excellent emulsified dispersion form is easily provided. Taking such a manufacturing method is an important method for improving the emulsifying and dispersing ability, impact strength, and tensile elongation.
[0039]
The resin composition of the present invention thus obtained can be molded as a molded body of various parts by various conventionally known methods such as injection molding, extrusion molding, and hollow molding, and further provided with a hot runner When the resin is used or when the resin is retained in the molding machine, it can be used in large-sized molded products and ultra-thin molded products. Examples of these various parts include automobile parts. Specifically, bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, and other exterior parts, Suitable for interior parts such as instrument panels, console boxes and trims. 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.
[0040]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, although an example explains an embodiment of the present invention, the present invention is not limited by these examples.
[0041]
(A) Polypropylene resin (a-1) used in the examples: Homo-polypropylene MFR = 6.5 g / 10 min MFR (melt flow rate) of polypropylene conforms to ASTM D1238, 230 ° C., 2.16 kg load Measured with
[0042]
(B) Polyphenylene ether resin (b-1) used in Examples: Polyphenylene ether (b-2): 2,6-xylenol having a reduced viscosity of 0.35 obtained by oxidative polymerization of 2,6-xylenol The structure of (c) hydrogenated block copolymer (c-1): polystyrene (1) -hydrogenated polyisoprene-polystyrene (2) used in the polyphenylene ether examples having a reduced viscosity of 0.90 obtained by oxidative polymerization Having an iodine number of 33.9, a number average molecular weight of 86,300, a molecular weight distribution of 1.10, a vinyl bond amount of polyisoprene before hydrogenation of 54%, a number average molecular weight of polystyrene (1) of 20,200, polystyrene A hydrogenated block copolymer having a number average molecular weight of 20,000 (2) was synthesized, and this polymer was designated as (c-1).
[0043]
(C-2): Polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) structure, iodine value 3.9, number average molecular weight 82,000, molecular weight distribution 1.10, polybutadiene before hydrogenation A hydrogenated block copolymer having a vinyl bond amount of 75%, a polystyrene (1) number average molecular weight of 19,800, and a polystyrene (2) number average molecular weight of 19,800 was synthesized, and this polymer was synthesized as (c-2). did.
[0044]
(C-3): Polystyrene (1) -hydrogenated polybutadiene having a vinyl bond content of 69% -hydrogenated polyisoprene having a vinyl bond content of 51% -polystyrene (2), hydrogenated polybutadiene / hydrogenated polyisoprene = 50/50 (weight ratio), iodine value 12.9, number average molecular weight 83,000, molecular weight distribution 1.10, number average molecular weight 20,100 of polystyrene (1), number average molecular weight 20, of polystyrene (2), 100 hydrogenated block copolymers were synthesized, and this polymer was designated as (c-3).
[0045]
(C-4): Polystyrene (1) -hydrogenated polyisoprene-polystyrene (2) structure, iodine value 29.9, number average molecular weight 83,000, molecular weight distribution 1.10, poly before hydrogenation A hydrogenated block copolymer having a vinyl bond content of isoprene of 42%, a polystyrene (1) number average molecular weight of 20,100 and a polystyrene (2) number average molecular weight of 20,100 was synthesized, and this polymer was synthesized (c-4 ).
[0046]
(C-5): Polystyrene (1) -hydrogenated polyisoprene-polystyrene (2) structure, iodine value 43.3, number average molecular weight 89,000, molecular weight distribution 1.10, poly before hydrogenation A hydrogenated block copolymer having a vinyl bond amount of isoprene of 48%, a polystyrene (1) number average molecular weight of 18,900, and a polystyrene (2) number average molecular weight of 18,900 was synthesized, and this polymer was synthesized (c-5). ).
[0047]
(D) used in the examplesCopolymer of conjugated diene compound and vinyl aromatic compound(D-1): Polystyrene (1) -polybutadiene-polystyrene (2) structure, bonded styrene content 48%, block styrene content 40%, number average molecular weight 95,000, polybutadiene vinyl bond content 12% The copolymer was synthesized and this polymer was designated as (d-1).
[0048]
(D-2): Polystyrene (1) -polyisoprene-polystyrene (2) structure, bound styrene content 30%, block styrene content 30%, number average molecular weight 82,000, polyisoprene vinyl bond content A 35% copolymer was synthesized, and this polymer was designated as (d-2).
[0049]
(D-3): Polystyrene (1) -polybutadiene-polystyrene (2) structure, 25% bonded styrene, 18% block styrene, 170,000 number average molecular weight, 16% vinyl bond of polybutadiene The copolymer was synthesized and this polymer was designated as (d-3).
[0050]
Melt-kneading method of resin composition (A): (b) polyphenylene ether resin and (c) hydrogenated block copolymer from the first raw material supply port using a twin-screw extruder, (d)Copolymer of conjugated diene compound and vinyl aromatic compoundThe melt kneading method for supplying (a) polypropylene resin from the second raw material supply port was defined as (A).
[0051]
(B): Using a twin screw extruder, a polymer comprising (b) a polyphenylene ether resin and (d) a conjugated diene compound is supplied from the first raw material supply port, and (a) a polypropylene type is supplied from the second raw material supply port. The melt kneading method for supplying the resin and (c) hydrogenated block copolymer was defined as (B).
[0052]
(C): Using a twin screw extruder, (b) a polymer composed of a polyphenylene ether resin and (d) a conjugated diene compound, and (a) a part of a polypropylene resin are supplied from the first raw material supply port. The melt kneading method for supplying (c) the hydrogenated block copolymer and the remaining (a) polypropylene resin from the second raw material supply port was defined as (C).
[0053]
As for the melt kneading temperature (A), (B), and (C), the barrel set temperature from the first material supply port to the second material supply port is 330 ° C., and the barrel set temperature downstream from the second material supply port is 290 ° C. Then, melt kneading was performed with the screw speed set to 350 rpm.
[0054]
The physical properties were evaluated as follows.
[0055]
(1) Thermal history treatment A gear oven was used and left in an environment of 80 ° C. for 48 hours.
[0056]
(2) Tensile elongation test Elongation at break was measured at 23 ° C according to ASTM D-638.
[0057]
(3) Izod (notched) impact strength Measured at 23 ° C. according to ASTM D-256.
[0058]
(4) Morphological stability confirmation of resin composition Using Capillograph 1C (manufactured by Toyo Seiki Co., Ltd.), a constant extrusion speed was applied to the resin composition, and the deformation of the morphology due to the extrusion speed was confirmed. Capillograph 1C barrel temperature was set to 280 ° C., using a capillary with a diameter of 2.0 mm and a length of 20 mm, and extrusion speeds of 1 mm / sec and 100 mm / sec were extruded. Soaked in a sample. The surface parallel to the flow direction of the obtained sample was made with an ultra-thin section using an ultramicrotome (Ultracut E manufactured by Reihert) and stained with ruthenic acid, which was then transmitted through an electron microscope (manufactured by JEOL Ltd.). 1200EX) and observed and photographed. Based on this photograph, the major axis (L) and minor axis (D) of the dispersed phase were determined using an image analyzer (IP1000 manufactured by Asahi Kasei Corporation), and the average L / D was determined.
[0059]
Moreover, after supplying a resin composition to the screw in-line type injection molding machine set to 240-280 degreeC, and making resin retain in a molding machine for 5 minutes, a box-shaped molded article (15cm ( (Width) × 15 cm (depth) × 8 cm (height), thickness 2 mm, 2 mmΦ pin gate) was injection molded. An ultra-thin section is made using an ultramicrotome (Ultracut E, manufactured by Reihert), and the surface parallel to the flow direction in the center of the side surface (8cm x 15cm) of this molded product is stained with ruthenic acid, and the transmission electron Observation and photography were performed using a microscope (1200EX manufactured by JEOL Ltd.). Based on this photograph, the major axis (L) and minor axis (D) of the dispersed phase were determined using an image analyzer (IP1000 manufactured by Asahi Kasei Corporation), and the average L / D was determined.
[0060]
[Example 1]
Polymers comprising a polypropylene resin, a polyphenylene ether resin, a hydrogenated block copolymer, and a conjugated diene compound were blended by the composition and melt kneading method shown in Table 1, and melt kneaded to obtain pellets. Melt kneading was performed using a twin-screw extruder with a vent port (ZSK-25; manufactured by WERNER & PFLIDEERER, Germany) set at 290 to 330 ° C.
[0061]
Using this pellet, the dispersion form of the resin composition is confirmed, and further supplied to a screw in-line type injection molding machine set at 240 to 280 ° C., and the test piece for tensile test and Izod impact test are performed at a mold temperature of 60 ° C. A test piece for heat treatment and a test piece for measuring heat distortion temperature were injection molded. The physical properties of these test pieces were measured and the results are shown in Table 1.
[0062]
Example 1 within the scope of the present invention is Comparative Example 1 in which a polymer comprising a conjugated diene is not used, Comparative Examples 2 and 3 in which the hydrogenated block copolymer is outside the scope of the present invention,Copolymer of conjugated diene compound and vinyl aromatic compoundAs compared with Comparative Example 4 in which the amount of addition is outside the range of the present invention, it is clear that the elongation at break, the Izod impact strength and the dispersion form are excellent.
[0063]
[Example 2]
Example 2 was obtained in the same manner as in Example 1 except for the composition and the melt-kneading method according to Table 1.
[0064]
It is understood that Example 2 by the melt kneading method B in which the addition of the polypropylene resin is divided into two stages is excellent in physical properties and dispersion form.
[0065]
[Example 3]
Example 3 was obtained in the same manner as in Example 1 except for the composition and melt-kneading method according to Table 1.Copolymer of conjugated diene compound and vinyl aromatic compoundThis is an example of different types and amounts.
[0066]
[Example 4]
Example 4 was obtained in the same manner as in Example 1 except for the composition and melt kneading method according to Table 1. This is an example using a high-viscosity polyphenylene ether resin.
[0067]
[Example 5]
Example 5 was obtained in the same manner as in Example 1 except for the composition and the melt-kneading method according to Table 1.
[0068]
Example 5 within the scope of the present invention, in which a high-viscosity polyphenylene ether resin was used and a hydrogenated block copolymer was added from the first supply port,Copolymer of conjugated diene compound and vinyl aromatic compoundIf the melt kneading method is within the scope of the present invention, it can be seen that the expected physical properties and dispersion form are exhibited.
[0069]
From these results, a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block mainly composed of at least one conjugated diene compound in which the vinyl bond amount of the conjugated diene compound is 45% or more. A hydrogenated block copolymer comprising the hydrogenated block copolymer having an iodine value of 40 or less, and further controlling the heat-melt kneading means to obtain a polyphenylene ether resin andCopolymer of conjugated diene compound and vinyl aromatic compoundBy forming a dispersed phase finely dispersed in a polypropylene resin matrix, an excellent resin composition having improved morphology stability between the polypropylene resin and the polyphenylene ether resin can be obtained.
[0070]
[Table 1]

[0071]
【The invention's effect】
The resin composition of the present invention comprises a polypropylene resin and a polyphenylene ether resin, a hydrogenated block copolymer, andCopolymer of conjugated diene compound and vinyl aromatic compoundPolypropylene resin and polyphenylene ether resin, which were difficult in the prior art because of using a hydrogenated block copolymer having a specific structure as a hydrogenated block copolymer and taking a specific heat-melt kneading means The resin composition having excellent morphological stability and chemical resistance, heat resistance, impact resistance, and tensile elongation is obtained.

Claims (3)

In the resin composition,
(A) 45 to 95% by weight of polypropylene-based resin, (b) 55% to 5% by weight of polyphenylene ether-based resin, and a total of 100 parts by weight of the components (a) and (b) above,
(C) The polymer block A mainly composed of at least one vinyl aromatic compound and the vinyl bond amount (total amount of 1,2- and 3,4-vinyl bonds) of the conjugated diene compound is 45% or more. A hydrogenated block copolymer comprising a polymer block B mainly composed of at least one conjugated diene compound, wherein the hydrogenated block copolymer has an iodine value of 40 or less. 30 parts by weight (d) conjugated diene compound and a vinyl aromatic compound and a copolymer of 1 to 30 parts by weight wood fat composition characterized by blending the. The major axis (L) / minor axis (D) of the dispersed phase obtained from a transmission electron micrograph of the resin extruded with a capillograph (280 ° C, extrusion speed 100 mm / sec, diameter 2.0 mm, length 20 mm using a capillary) The resin composition according to claim 1, wherein the ratio is from 1.3 to 2.0. (A) 0 to 30% by weight of a polypropylene resin, (b) 55 to 5% by weight of a polyphenylene ether resin,
(C) 0 to 30 parts by weight of a hydrogenated block copolymer, and (d) a conjugated diene compound and vinyl with respect to 100 parts by weight of the total of the components (a) and (b) (including the component (a) below) the melt-kneaded product of a copolymer of 1 to 30 parts by weight of an aromatic compound, (a) a polypropylene resin, the entire amount 45 to 95 wt% of the corresponding to the remainder 15 to 95% by weight and (c) water The resin composition according to claim 1 or 2, wherein the additive block copolymer is added in an amount of 0 to 30 parts by weight corresponding to the remainder of the total amount of 1 to 30 parts by weight, and further melt kneaded. Production method.