JP4042195B2 - Polyphenylene ether resin composition and method for producing the same - Google Patents

Description

【００１０】
上記一般式におけるＲ₁、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅の具体例としては、水素、塩素、臭素、フッ素、ヨウ素、メチル、エチル、ｎ−又はｉｓｏ−プロピル、ｐｒｉ−、ｓｅｃ−又はｔ−ブチル、クロロエチル、ヒドロキシエチル、フェニルエチル、ベンジル、ヒドロキシメチル、カルボキシエチル、メトキシカルボニルエチル、シアノエチル、フェニル、クロロフェニル、メチルフェニル、ジメチルフェニル、エチルフェニル、アリルなどがあげられる。上記一般式の具体例としては、フェノール、ｏ−、ｍ−又はｐ−クレゾール、２，６−、２，５−、２，４−又は３，５−ジメチルフェノール、２−メチル−６−フェニルフェノール、２，６−ジフェニルフェノール、２，６−ジエチルフェノール、２−メチル−６−エチルフェノール、２，３，５−、２，３，６−又は２，４，６−トリメチルフェノール、３−メチル−６−ｔ−ブチルフェノール、チモール、２−メチル−６−アリルフェノールなどがあげられる。更に、上記一般式以外のフェノール化合物、たとえば、ビスフェノール−Ａ、テトラブロモビスフェノール−Ａ、レゾルシン、ハイドロキノン、ノボラック樹脂のような多価ヒドロキシ芳香族化合物と、上記一般式で示されるフェノール化合物とを共重合体の原料としてもよい。これらの化合物の中では、２，６−ジメチルフェノール、２，６−ジフェニルフェノール、３−メチル−６−ｔ−ブチルフェノール及び２，３，６−トリメチルフェノールが好ましい。
【００１１】
フェノール化合物を酸化重合せしめる際に用いる酸化カップリング触媒は、特に限定されるものではなく、重合能を有する如何なる触媒でも使用できる。
【００１２】
ポリフェニレンエーテル系樹脂の製造法は、たとえば米国特許第３３０６８７４号公報、同第３３０６８７５号公報及び同第３２５７３５７号公報、特公昭５２−１７８８０号公報、特開昭５０−５１１９７号公報、特開平１−３０４１１９号公報等に記載されている。
【００１３】
ポリフェニレンエーテル系樹脂の具体例としては、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２，６−ジエチル−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−プロピル−１，４−フェニレンエーテル）、ポリ（２，６−ジプロピル−１，４−フェニレンエーテル）、ポリ（２−エチル−６−プロピル−１，４−フェニレンエーテル）、ポリ（２，６−ブチル−１，４−フェニレンエーテル）、ポリ（２，６−ジプロペニル−１，４−フェニレンエーテル）、ポリ（２，６−ジラウリル−１，４−フェニレンエーテル）、ポリ（２，６−ジフェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジメトキシ−１，４−フェニレンエーテル）、ポリ（２，６−ジエトキシ−１，４−フェニレンエーテル）、ポリ（２−メトキシ−６−エトキシ−１，４−フェニレンエーテル）、ポリ（２−エチル−６−ステアリルオキシ−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−メチル−１，４−フェニレンエーテル）、ポリ（２−エトキシ−１，４−フェニレンエーテル）、ポリ（２−クロロ−１，４−フェニレンエーテル）、ポリ（３−メチル−６−ｔ−ブチル−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）、ポリ（２，５−ジブロモ−１，４−フェニレンエーテル）、ポリ（２，６−ジベンジル−１，４−フェニレンエーテル）及びこれらの重合体を構成する繰り返し単位の複数種を含む各種共重合体をあげることができる。共重合体の中には２，３，６−トリメチルフェノール、２，３，５，６−テトラメチルフェノール等の多置換フェノールと２，６−ジメチルフェノールとの共重合体等も含む。これらポリフェニレンエーテル系樹脂のうちで好ましいものはポリ（２，６−ジメチル−１，４−フェニレンエーテル）及び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である。
【００１４】
本発明に使用することができるポリフェニレンエーテル系樹脂の分子量は、目的によってその好適な範囲が異なるために一概にその範囲は定められないが、一般に３０℃のクロロホルム中で測定した極限粘度で表わして通常０．１〜０．７ｄｌ／ｇ、好ましくは、０．３〜０．６ｄｌ／ｇである。
【００１５】
本発明の(Ｂ)成分は、シンジオタクチック構造を有するアルケニル芳香族系樹脂である。
【００１６】
上記のシンジオタクチック構造とは、立体構造がシンジオタクチック構造、すなわち炭素−炭素結合から形成される主鎖に対して側鎖であるフェニル基や置換フェニル基が交互に反対方向に位置する立体構造を有するものであり、そのタクティシティーは同位体炭素による核磁気共鳴法（¹³Ｃ−ＮＭＲ法）により定量される。¹³Ｃ−ＮＭＲ法により測定されるタクティシティーは、連続する複数個の構成単位の存在割合、たとえば２個の場合はダイアッド、３個の場合はトリアッド、５個の場合はペンタッドによって示すことができるが、本発明に言うシンジオタクチック構造を有するスチレン系重合体とは、通常はラセミダイアッドで７５％以上、好ましくは８５％以上、若しくはラセミペンタッドで３０％以上、好ましくは５０％以上のシンジオタクティシティーを有するポリスチレン、ポリ（アルキルスチレン)、ポリ（ハロゲン化スチレン）、ポリ（ハロゲン化アルキルスチレン）、ポリ（アルコキシスチレン）、ポリ（ビニル安息香酸エステル）、これらの水素化重合体及びこれらの混合物、あるいはこれらを主成分とする共重合体を指称する。なお、ここでポリ（アルキルスチレン）としては、ポリ（メチルスチレン）、ポリ（エチルスチレン）、ポリ（イソプロピルスチレン）、ポリ（ターシャリ−ブチルスチレン）、ポリ（フェニルスチレン）、ポリ（ビニルナフタレン）、ポリ（ビニルスチレン）などがあり、ポリ（ハロゲン化スチレン）としては、ポリ（クロロスチレン）、ポリ（ブロモスチレン）、ポリ（フルオロスチレン) などがある。また、ポリ（ハロゲン化アルキルスチレン）としては、ポリ（クロロメチルスチレン) など、また、ポリ（アルコキシスチレン）としては、ポリ（メトキシスチレン）、ポリ（エトキシスチレン）などがある。
【００１７】
(Ｂ)成分のアルケニル芳香族系樹脂として特に好ましいものとしては、ポリスチレン、ポリ（ｐ−メチルスチレン）、ポリ（ｍ−メチルスチレン）、ポリ（ｐ−ターシャリーブチルスチレン）、ポリ（ｐ−クロロスチレン）、ポリ（ｍ−クロロスチレン）、ポリ（ｐ−フルオロスチレン)及びこれらの構造単位を含む共重合体があげられる。なお、上記スチレン系重合体は、一種のみを単独で、又は二種以上を組み合わせて用いることができる。
【００１８】
（Ｂ）成分は、たとえば特開昭６２−１８７７０８号公報に記載のように、不活性炭化水素溶媒中、又は溶媒の不存在下に、チタン化合物及び水とトリアルキルアルミニウムの縮合生成物を触媒として、アルケニル芳香族系単量体を重合することにより製造できる。
【００１９】
本発明の（Ｃ）成分は、シンジオタクチック構造を有さないアルケニル芳香族系樹脂である。
【００２０】
シンジオタクチック構造を有さないアルケニル芳香族系樹脂とは、通常のラジカル重合等にて製造されるアルケニル芳香族化合物の単独重合物あるいはアルケニル芳香族化合物と共重合可能な単量体を含有したものがあげられる。前記アルケニル芳香族化合物の例としては、スチレン、α−メチルスチレン、α−エチルスチレン、α−メチルスチレン−ｐ−メチルスチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレンなどの核アルキル置換スチレン、ｏ−クロルスチレン、ｍ−クロルスチレン、ｐ−クロルスチレン、ｐ−ブロモスチレン、ジクロルスチレン、ジブロモスチレン、トリクロルスチレン、トリブロモスチレンなどの核ハロゲン化スチレンなどがあげられるが、この中でスチレン、α−メチルスチレンが好ましい。
【００２１】
また、ビニル芳香族化合物と共重合可能な単量体の例としては、たとえばアクリロニトリル、メタクリロニトリル、フマロニトリル、マレオニトリルなどの
シアン化ビニルや、メタクリル酸メチル、アクリル酸メチル、メタクリル酸、アクリル酸、無水マレイン酸などがあげられるが、この中でもアクリロニトリルが好ましい。
【００２２】
本発明のポリフェニレンエーテル系樹脂組成物は、上記（Ａ）成分１０〜９８重量％、（Ｂ）成分１〜８９重量％及び（Ｃ）成分１〜８９重量％を含有するものであり、好ましくは（Ａ）成分１０〜９０重量％及び（Ｂ）成分５〜８５重量％及び（Ｃ）成分５〜８５重量％、更に好ましくは、（Ａ）成分１５〜８５重量％、（Ｂ）成分７〜７７重量％及び（Ｃ）成分８〜７８重量％を含有するものである。（Ａ）成分が過少であると耐熱性及び耐衝撃性に劣り、一方（Ａ）成分が過多であると溶融時の粘度が高くなり成形性に劣る。（Ｂ）成分が過少であると耐熱性及び耐溶剤性の改良効果が不十分となり、一方（Ｂ）成分が過多であると耐衝撃性の低下を招く。（Ｃ）成分が過少であると（Ｂ）成分の結晶化度が高くならず、一方（Ｃ）成分が過多であると耐溶剤性、耐熱性及び耐衝撃性が低くなる。
【００２３】
本発明のポリフェニレンエーテル系樹脂組成物は、第一の工程において、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分のうち２成分のそれぞれの実質的な量を溶融混練することにより溶融混練組成物を得、次いで第二の工程において、第一の工程で得られた該溶融混練組成物と第一の工程で使用する以外の成分の実質的な量とを溶融混練することによって製造される。ここでいう実質的な量とは、本発明の目的であるシンジオタクチック構造を有するアルケニル芳香族系樹脂の結晶化度を増大することを達成しうる量であり、第一の工程において溶融混練される２成分並びに第二の工程において第一の工程で得られた該溶融混練物と溶融混練される第一の工程で使用する以外の成分の量が、最終的な組成物中のそれぞれの成分の量の５０％より多い量であり、好ましくは６０重量％より多い量、更に好ましくは８０重量％よりも多い量である。このような特定の順序による工程を採用することにより、ポリフェニレンエーテル系樹脂組成物の耐熱性及び耐溶剤性を特に優れた水準とすることができる。
【００２４】
溶融混練の方法としては、第一の工程において、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分のうち２成分を溶融混練し、一旦冷却固化により混練物を得た後、次いで同じ混練機又は別の混練機における第二工程にて第一の工程で得られた該混練物と第一の工程で使用する以外の成分とを溶融混練してもよく、また、第一工程において（Ａ）成分、（Ｂ）成分及び（Ｃ）成分のうち２成分を溶融混練し、冷却固化工程無しに、連続的に第一の工程で使用する以外の成分を添加し、第二工程を実施してもよいが、生産性等の経済的観点から、冷却固化工程なしに、第一工程と第二工程を連続的に行うことが望ましい。
【００２５】
第一工程と第二工程とを溶融固化工程無しに連続的に行う方法としては、たとえば、複数の投入口を有する一軸、二軸、又は、多軸の押出混練機を用い、その第１投入口より、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分のうち２成分の実質的な量を投入し溶融混練した後に、第一投入口よりも下流側にある第二投入口以降の投入口より第一の工程で使用する以外の成分の実質的な量を加え、溶融混練を行う方法があげられる。
【００２６】
混練機としては、一軸、二軸、多軸の押出し機の他に、バンバリーミキサー、ブラベンダー、プラストミル等のバッチ式の混練機を使用することができる。
【００２７】
更に、第一の工程において製造された（Ａ）成分、（Ｂ）成分及び（Ｃ）成分のうちの２成分からなる溶融混練物と、第一の工程で使用する以外の成分の溶融混練工程である第二の工程は、射出成形、押出し成形、ブロー成形等の成形加工工程に使用する成形機内で行う事もできる。
【００２８】
混練時における混練機内の樹脂の温度はシンジオタクチック構造を有するアルケニル芳香族系樹脂の融点以上であればよいが、好ましくは２８０〜３８０℃、より好ましくは２８０〜３４０℃の範囲である。
【００２９】
スクリューの形状は特に限定されるものではなく、搬送部材、混練部材及び／又は混合部材が存在していてもよい。更に、混練機中で、滞留時間及び混練特性を制御するために部分的にせき止め部材や返送部材を用いることは可能であり、かつ好ましい。せき止め部材や返送部材は、第一の工程と第二の工程の間にあることが望ましい。また、平行する２軸のスクリューを有する押出し機は、自己洗浄性及び滞留時間分布のより好ましい状態を実現する上で有利に使用される。
【００３０】
本発明では、必須成分である（Ａ）成分〜（Ｃ）成分に加えて、本発明の特徴及び効果を損わない範囲で必要に応じて他の付加的成分を添加しても構わない。たとえば、耐衝撃改良材として、スチレン系エラストマーやポリオレフィンが用いられる。ここで、スチレン系エラストマーは公知のものを用いることがでる。たとえばポリスチレン及びポリブタジエンセグメントをそれぞれ１以上有するスチレン−ブタジエンブロック共重合体、ポリスチレン及びポリイソプレンセグメントをそれぞれ１以上有するスチレン−イソプレン共重合体、ポリスチレン及びイソプレン−ブタジエンの共重合体をそれぞれ１つずつ以上有するブロック共重合体、又はこれらのイソプレン部やブタジエン部の不飽和部分が選択的に水素添加されたブロック共重合体、エチレン、プロピレン、ブテン、ジエン成分を共重合したポリオレフィンエラストマーにスチレンをグラフト重合したものである。
【００３１】
これらスチレンエラストマー中のポリスチレンセグメントの分子鎖の長さは重量平均分子量で１万以上が好ましい。ポリスチレンセグメントが短過ぎると、ＰＰＥ系樹脂組成物との相溶性が低下し、射出成形時に層状剥離を生じたり、十分な耐衝撃性が得らず好ましくない。ポリオレフィンとしては、たとえばポリエチレン、ポリプロピレン、ポリブテン、ポリペンテン、更にはエチレン−酢酸ビニル共重合体、エチレン−ビニルアルコール共重合体、塩素化ポリエチレン、エチレン−プロピレンゴム（ＥＰＲ）、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）などがあげられる。このなかで好ましい耐衝撃改良材はイソプレン部やブタジエン部の不飽和部分が選択的に水素添加されたスチレン系のブロック共重合体と、エチレン、プロピレン、ブテン、ジエン成分を共重合したポリオレフィンエラストマーにスチレンをグラフト重合したものである。
【００３２】
また、強化用、機能付与あるいは増量（コストダウン）等を目的に充填剤を添加して用いることができる。充填剤としては、ガラス繊維、カーボン繊維、アラミド繊維、アルミニウムやステンレスなどの強化用繊維及び金属のウィスカー、シリカ、アルミナ、炭酸カルシウム、タルク、マイカ、クレー、カオリン、硫酸マグネシウム、カーボンブラック、酸化チタン、酸化亜鉛、三酸化アンチモン、の様な無機充填剤を用いることができる。更に、酸化防止剤、耐候性改良剤、ポリオレフィン用造核剤、スリップ剤、難燃剤、難燃助剤、可塑剤、各種着色剤、帯電防止剤、離型剤等を添加することができる。
【００３３】
本発明の樹脂組成物の成形方法は射出成形、押出成形、圧縮成形、中空成形など、一般に行われている成形方法であれば特に問題はなく、得られる樹脂組成物の形状は何等限定されるものではなく、成形方法による制約を受けることはない。
【００３４】
また、得られた成形品は、耐溶剤性が要求される用途、たとえば、フライバックトランス、偏向ヨーク等の電気・電子部品用途、ポンプ、タンク、ダクト等の給排水・給排気部品用途、バッテリーケース等の電槽用途、水道量水器、現像タンク、ファン及びファンハウジング等に使用することが出来る。また、耐熱性が要求される用途、たとえば、ランプリフレクター等の自動車用途、コネクター、リレーのハウジング、コイルボビン等の電気・電子部品用途、耐熱ＩＣトレー等のＩＣ搬送用用途、プリント基板等に使用することができる。更に、インストルメンタルパネル、ホイールカバー、ヒューズホルダー、ラジエーターグリル、イグニッションコイル、サイドマッドガード、バンパー等の自動車用途、ＯＡ機器のハウジング、ＯＡ機器のシャーシ、トレ−等の機構部品用途、ＩＣキャリヤテープ等のＩＣ搬送用用途、自動販売機のコインメカシャーシ等に使用することができる。
【００３５】
【実施例】
以下、実施例に基づいて本発明を更に詳しく説明するが、本発明はこれら実施例に限定されるものではない。
【００３６】
以下に実施例及び比較例で使用した略号の意味を示す。
ＰＰＥ：（Ａ）ポリフェニレンエーテル系樹脂
クロロホルム溶媒中、３０℃で測定した固有粘度が０.４６ｄｌ／ｇのポリ（２．６−ジメチル−１，４−フェニレンエーテル）
ＳＰＳ：（Ｂ）シンジオタクチック構造を有するアルケニル芳香族系樹脂
窒素で置換した内容積５００ｍｌの攪拌機付きガラス容器に脱水トルエン１３０ｍｌとメチルアルミノキサンのトルエン溶液（東ソー・アクゾ（株）製ＭＭＡＯ、タイプ３Ａ、Ａｌ＝６．０ｗｔ％）８．３ｍｌを加え、次いでこれにペンタメチルシクロペンタジエニルチタニウムクロリド１５μｍｏｌをトルエン４．３ｍｌに溶解したものを加えた。続いて、２０℃においてスチレン５７ｍｌを加え１時間重合反応を行ったあと、メタノールを注入して反応を停止した。次に、塩酸とメタノールの混合液を加えて触媒成分を分解したところ４５．５ｇの重合体を得た。
この重合体は、¹³Ｃ−ＮＭＲにてシンジオタクチック構造に起因する１４５．３５ｐｐｍに吸収が認められることより、シンジオタクチック構造を有するポリスチレンと確認された。そのピーク面積から、算出したラセミペンダットでのシンジオタクチシティーは、９５％以上であった。示査走査型熱量計にて昇温速度１０℃／ｍｉｎにて測定した際の融点は、２７０．５℃、融解熱は、２１．５ｍＪ／ｍｇ、ガラス転移温度は、１００℃であった。
ＡＰＳ：（Ｃ）シンジオタクチック構造を有さないアルケニル芳香族系樹脂
スミブライト Ｅ１６３Ｋ（住友化学工業（株）製）（シンジオタクチック構造を有さないスチレン樹脂）
【００３７】
物性値等の評価方法を以下に示す。
ＳＰＳの結晶化分率の測定
示差走査型熱量計にて、昇温速度１０℃／ｍｉｎにて融解熱を測定した。ＳＰＳの結晶化の容易さを示す指標として下記式に従い結晶化分率を求めた。結晶化分率が高いほどブレンド物中のシンジオタクチック構造を有するアルケニル芳香族系樹脂の結晶化が起こり易い。
結晶化分率＝（ブレンド物中のＳＰＳ単位質量あたりの融解熱）／（ＳＰＳ単品のＳＰＳ単位質量あたりの融解熱）
耐熱性の測定
動的粘弾性測定により、昇温速度３℃／ｍｉｎ、周波数１０Ｈｚの条件にて１３０℃における貯蔵弾性率を測定した。貯蔵弾性率の値が大きいほど、耐熱性が高いといえる。
耐溶剤性
プレス成形（３００℃）にて作製した５０ｍｍ×５ｍｍ×０．３ｍｍの試験片を半径７０ｍｍの曲率を有する冶具に取り付け、ＴｎＢＰ（トリノルマルブチルフォスフェート）に浸したガーゼをサンプル中央にのせた。サンプルとガーゼの接触面積は１５×５ｍｍであった。雰囲気温度２３℃にて、３０分放置した後にガーゼを剥がし、目視によりクラック数を数えた。耐薬品性が悪いほど、クラック数が多くなる。
【００３８】
実施例１
ＰＰＥ ６６．７重量％とＡＰＳ ３３．３重量％とをＭＡＸ ＭＩＸ ＥＸＴＲＵＤＥＲ Ｍｏｄｅｌ ＣＳ１９４Ａ（Ｃｕｓｔｏｍ Ｓｃｉｅｎｔｉｆｉｃ Ｉｎｓｔｒｕｍｅｎｔｓ，Ｉｎｃ．製）にて、３００℃、２４０ｒｐｍの混練条件にて混練し、ＰＰＥとＡＰＳの混練物を得た。次にこの混練物６０重量％とＳＰＳ４０重量％をＭＩＮＩＭＡＸにて、３００℃、２４０ｒｐｍの混練条件で混練し組成物１を得た。
組成物１の融解熱を示差走査型熱量計にて測定し、ＳＰＳの結晶化分率を求めたところ、１４５％であった。
１３０℃における貯蔵弾性率は、１．５６×１０¹⁰ｄｙｎ／ｃｍ²であった。
耐溶剤性試験におけるクラック数は、２本であった。
【００３９】
実施例２
ＰＰＥ ５０重量％とＳＰＳ ５０重量％とをＭＡＸ ＭＩＸ ＥＸＴＲＵＤＥＲ Ｍｏｄｅｌ ＣＳ１９４Ａにて、３００℃、２４０ｒｐｍの混練条件にて混練し、ＰＰＥとＳＰＳの混練物を得た。次にこの混練物８０重量％とＡＰＳ２０重量％をＭＩＮＩＭＡＸにて、３００℃、２４０ｒｐｍの混練条件で混練し、組成物２を得た。組成物２の融解熱を示差走査型熱量計にて測定し、ＳＰＳの結晶化分率を求めたところ、５０％であった。１３０℃における貯蔵弾性率は、１．８×１０１０ｄｙｎ／ｃｍ２であった。耐溶剤性試験におけるクラック数は、４本であった。
【００４０】
実施例３
ＳＰＳ ６６．７重量％とＡＰＳ ３３．３重量％とをＭＡＸ ＭＩＸ ＥＸＴＲＵＤＥＲ Ｍｏｄｅｌ ＣＳ１９４Ａにて、３００℃、２４０ｒｐｍの混練条件にて混練し、ＳＰＳとＡＰＳの混練物を得た。次にこの混練物６０重量％とＰＰＥ４０重量％をＭＩＮＩＭＡＸにて、３００℃、２４０ｒｐｍの混練条件で混練し組成物３を得た。組成物３の融解熱を示差走査型熱量計にて測定し、ＳＰＳの結晶化分率を求めたところ、１１５％であった。１３０℃における貯蔵弾性率は、１．７６×１０¹⁰ｄｙｎ／ｃｍ²であった。耐溶剤性試験におけるクラック数は、２本であった。
【００４１】
比較例１
ＰＰＥ ４０重量％とＡＰＳ ２０重量％とＳＰＳ ４０重量％をＭＡＸ ＭＩＸ ＥＸＴＲＵＤＥＲ Ｍｏｄｅｌ ＣＳ１９４Ａにて、３００℃、２４０ｒｐｍの混練条件にて混練し、組成物４を得た。
組成物４の融解熱を示差走査型熱量計にて測定し、ＳＰＳの結晶化分率を求めたところ、７％であった。
１３０℃における貯蔵弾性率は、３．０×１０⁹ｄｙｎ／ｃｍ²であった。
耐溶剤性試験におけるクラック数は、１６本であった。
【００４２】
【発明の効果】
以上説明したとおり、本発明により、シンジオタクチック構造を有するアルケニル芳香族系樹脂の結晶化度を高くし、耐衝撃性及び剛性に優れ、かつ耐熱性及び耐溶剤性に特に優れたポリフェニレンエーテル系樹脂組成物及びその製造方法を提供することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyphenylene ether resin composition and a method for producing the same. More specifically, the present invention relates to a polyphenylene ether-based resin composition having a high crystallinity of an alkenyl aromatic resin having a syndiotactic structure and particularly excellent in heat resistance and solvent resistance, and a method for producing the same. is there.
[0002]
[Prior art]
Polyphenylene ether resin has excellent mechanical properties, electrical properties, heat resistance, low water absorption and excellent dimensional stability, but has the disadvantage of poor molding processability and impact resistance. By blending with, it improves the problem of molding processability and impact resistance, and is widely used as resin moldings for industrial parts, electrical / electronic parts, office equipment housings, automobile parts, precision parts, etc. Yes. However, the polyphenylene ether resin composition composed of this polyphenylene ether and high impact polystyrene has insufficient solvent resistance, and is unsuitable for applications requiring solvent resistance. Also, blending high impact polystyrene with polyphenylene ether improves moldability and impact resistance, but results in a decrease in heat resistance.
[0003]
In order to improve the above drawbacks, Japanese Patent Application Laid-Open No. 02-64140 discloses a technique of adding an alkenyl aromatic resin having a syndiotactic structure to a polyphenylene ether resin. However, even if an alkenyl aromatic resin having a syndiotactic structure is simply added to a polyphenylene ether resin, the alkenyl aromatic resin having a syndiotactic structure is difficult to crystallize, and the improvement in solvent resistance and heat resistance is I can't figure it out. As a method for solving such problems, there is a method for improving solvent resistance and heat resistance by applying a technique for increasing the degree of crystallinity such as annealing. However, this method is economically disadvantageous in that a separate process is required in addition to the normal molding process.
[0004]
In addition, JP-A-8-509008 discloses a method of adding a nucleating agent to a mixture of polyphenylene ether resin and syndiotactic polystyrene, but the crystallinity can be sufficiently increased. The effect of improving solvent resistance and heat resistance is small.
[0005]
[Problems to be solved by the invention]
In view of this situation, the problem to be solved by the present invention is to increase the crystallinity of an alkenyl aromatic resin having a syndiotactic structure, to have excellent impact resistance and rigidity, and to heat resistance and solvent resistance. The present invention resides in providing a particularly excellent polyphenylene ether-based resin composition and a method for producing the same.
[0006]
[Means for Solving the Problems]
That is, one invention among the present invention is a polyphenylene ether-based resin composition containing the following (A) 10 to 98% by weight, (B) 1 to 89% by weight, and (C) 1 to 89% by weight. In the first step, a melt-kneaded composition is obtained by melt-kneading a substantial amount of each of the two components (A), (B) and (C), and then the second step. A polyphenylene ether-based resin composition produced by melt-kneading the melt-kneaded composition obtained in the first step and a substantial amount of components other than those used in the first step It is.
(A): Polyphenylene ether resin
(B): an alkenyl aromatic resin having a syndiotactic structure
(C): an alkenyl aromatic resin having no syndiotactic structure
[0007]
Moreover, other invention among this invention is the manufacturing method of the polyphenylene ether-type resin composition containing the following (A) 10-98 weight%, (B) 1-89 weight%, and (C) 1-89 weight%. In the first step, a melt-kneaded composition is obtained by melt-kneading a substantial amount of each of the two components (A), (B) and (C), In the second step, the melt-kneaded composition obtained in the first step and a substantial amount of components other than those used in the first step are related to a method for producing a polyphenylene ether resin composition, Is.
(A): Polyphenylene ether resin
(B): an alkenyl aromatic resin having a syndiotactic structure
(C): an alkenyl aromatic resin having no syndiotactic structure
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The component (A) of the present invention is a polyphenylene ether resin.
[0009]
As polyphenylene ether resin, the following general formula (in the formula, R₁, R₂, R_Three, R_FourAnd R_FiveAre each selected from a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, of which one is necessarily a hydrogen atom. ) Is a (co) polymer obtained by oxidative polymerization of one or more of the phenolic compounds represented by (2) with oxygen or an oxygen-containing gas using an oxidative coupling catalyst.

[0010]
R in the above general formula₁, R₂, R_Three, R_FourAnd R_FiveSpecific examples of hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, Examples thereof include carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl and the like. Specific examples of the general formula include phenol, o-, m- or p-cresol, 2,6-, 2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenyl. Phenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3,6- or 2,4,6-trimethylphenol, 3- Examples thereof include methyl-6-tert-butylphenol, thymol, 2-methyl-6-allylphenol. Further, a phenol compound other than the above general formula, for example, a polyvalent hydroxyaromatic compound such as bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone, or novolak resin, and a phenol compound represented by the above general formula are used together. It is good also as a raw material of a polymer. Among these compounds, 2,6-dimethylphenol, 2,6-diphenylphenol, 3-methyl-6-tert-butylphenol and 2,3,6-trimethylphenol are preferable.
[0011]
The oxidative coupling catalyst used for oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having polymerization ability can be used.
[0012]
For example, U.S. Pat. Nos. 3,306,874, 3,306,875 and 3,257,357, JP-B-52-17880, JP-A-50-51197, JP-A-1-51,197 are used as methods for producing polyphenylene ether resins. No. 304119.
[0013]
Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), and poly (2-methyl-6- 6). Ethyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether), poly (2-ethyl-) 6-propyl-1,4-phenylene ether), poly (2,6-butyl-1,4-phenylene ether), poly (2,6-dipropenyl-1,4-phenylene ether), poly (2,6- Dilauryl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2,6-dimethoxy-1,4-phenylene ether) ), Poly (2,6-diethoxy-1,4-phenylene ether), poly (2-methoxy-6-ethoxy-1,4-phenylene ether), poly (2-ethyl-6-stearyloxy-1,4) -Phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2-methyl-1,4-phenylene ether), poly (2-ethoxy-1,4-phenylene ether) , Poly (2-chloro-1,4-phenylene ether), poly (3-methyl-6-tert-butyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) , Poly (2,5-dibromo-1,4-phenylene ether), poly (2,6-dibenzyl-1,4-phenylene ether) and repeats constituting these polymers It can be mentioned various copolymers containing position of plural kinds. The copolymer includes a copolymer of a polysubstituted phenol such as 2,3,6-trimethylphenol and 2,3,5,6-tetramethylphenol and 2,6-dimethylphenol. Among these polyphenylene ether resins, preferred are poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol.
[0014]
The molecular weight of the polyphenylene ether-based resin that can be used in the present invention is not generally determined because the preferred range varies depending on the purpose, but it is generally expressed by the intrinsic viscosity measured in chloroform at 30 ° C. Usually, it is 0.1-0.7 dl / g, Preferably, it is 0.3-0.6 dl / g.
[0015]
The component (B) of the present invention is an alkenyl aromatic resin having a syndiotactic structure.
[0016]
The above-mentioned syndiotactic structure is a three-dimensional structure in which a three-dimensional structure in which phenyl groups and substituted phenyl groups that are side chains with respect to the main chain formed from carbon-carbon bonds are alternately positioned in the opposite direction. It has a structure, and its tacticity is an isotope carbon nuclear magnetic resonance method (¹³C-NMR method).¹³The tacticity measured by the C-NMR method can be indicated by the abundance ratio of a plurality of consecutive structural units, for example, a dyad for two, a triad for three, a pentad for five. The styrenic polymer having a syndiotactic structure referred to in the present invention is usually 75% or more of racemic dyad, preferably 85% or more, or 30% or more, preferably 50% or more of racemic pentad. Tacticity polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoate), their hydrogenated polymers and these Or a copolymer containing these as a main component. Here, as poly (alkyl styrene), poly (methyl styrene), poly (ethyl styrene), poly (isopropyl styrene), poly (tertiary-butyl styrene), poly (phenyl styrene), poly (vinyl naphthalene), Examples of the poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
[0017]
As the alkenyl aromatic resin as the component (B), polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tertiarybutylstyrene), poly (p-chloro) are particularly preferable. Styrene), poly (m-chlorostyrene), poly (p-fluorostyrene) and copolymers containing these structural units. In addition, the said styrene-type polymer can be used individually by 1 type or in combination of 2 or more types.
[0018]
As the component (B), for example, as described in JP-A-62-187708, a titanium compound and a condensation product of water and trialkylaluminum in an inert hydrocarbon solvent or in the absence of the solvent are used as a catalyst. Can be produced by polymerizing an alkenyl aromatic monomer.
[0019]
The component (C) of the present invention is an alkenyl aromatic resin not having a syndiotactic structure.
[0020]
An alkenyl aromatic resin having no syndiotactic structure contains a homopolymer of an alkenyl aromatic compound produced by ordinary radical polymerization or the like or a monomer copolymerizable with an alkenyl aromatic compound. Things can be raised. Examples of the alkenyl aromatic compound include nuclei such as styrene, α-methylstyrene, α-ethylstyrene, α-methylstyrene-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene. Examples thereof include substituted styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, and trihalostyrene nucleohalogenated styrene. And styrene and α-methylstyrene are preferred.
[0021]
Examples of monomers copolymerizable with vinyl aromatic compounds include acrylonitrile, methacrylonitrile, fumaronitrile, and maleonitrile.
Examples include vinyl cyanide, methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, maleic anhydride, and among them, acrylonitrile is preferable.
[0022]
The polyphenylene ether-based resin composition of the present invention contains the component (A) 10 to 98% by weight, the component (B) 1 to 89% by weight, and the component (C) 1 to 89% by weight, preferably (A) Component 10 to 90% by weight and (B) Component 5 to 85% by weight and (C) Component 5 to 85% by weight, more preferably (A) Component 15 to 85% by weight, (B) Component 7 to It contains 77% by weight and (C) component 8 to 78% by weight. When the component (A) is too small, the heat resistance and the impact resistance are poor. On the other hand, when the component (A) is excessive, the viscosity at the time of melting becomes high and the moldability is poor. When the component (B) is too small, the effect of improving the heat resistance and the solvent resistance becomes insufficient. On the other hand, when the component (B) is excessive, the impact resistance is lowered. If the component (C) is too small, the crystallinity of the component (B) will not be high, while if the component (C) is excessive, the solvent resistance, heat resistance and impact resistance will be low.
[0023]
In the first step, the polyphenylene ether-based resin composition of the present invention is melt-kneaded by melt-kneading the substantial amounts of the two components (A), (B) and (C). In the second step, a composition is obtained, and then the melt-kneaded composition obtained in the first step and a substantial amount of components other than those used in the first step are melt-kneaded. The The substantial amount here is an amount that can achieve an increase in crystallinity of the alkenyl aromatic resin having a syndiotactic structure, which is the object of the present invention, and is melt-kneaded in the first step. The amount of components other than those used in the first step to be melt-kneaded with the melt-kneaded product obtained in the first step and the two components to be used in the second step in each of the final compositions The amount is more than 50% of the amount of the component, preferably more than 60% by weight, more preferably more than 80% by weight. By adopting such a process based on a specific order, the heat resistance and solvent resistance of the polyphenylene ether-based resin composition can be made particularly excellent.
[0024]
As a method of melt kneading, in the first step, two of the components (A), (B) and (C) are melt-kneaded, and once kneaded by cooling and solidification, the same kneading is performed. The kneaded product obtained in the first step and the components other than those used in the first step may be melt-kneaded in the second step in a machine or another kneader. 2) Among components A), (B) and (C) are melted and kneaded, and components other than those used continuously in the first step are added without performing the cooling and solidification step, and the second step is performed. However, from the economic viewpoint such as productivity, it is desirable to perform the first step and the second step continuously without the cooling and solidification step.
[0025]
As a method of continuously performing the first step and the second step without the melting and solidifying step, for example, using a uniaxial, biaxial, or multiaxial extrusion kneader having a plurality of input ports, the first input is performed. After a substantial amount of two of the components (A), (B) and (C) is charged and melted and kneaded from the mouth, the second and subsequent inlets on the downstream side of the first inlet There is a method in which a substantial amount of components other than those used in the first step is added from the charging port and melt kneading is performed.
[0026]
As a kneading machine, batch type kneading machines such as a Banbury mixer, a Brabender, and a plast mill can be used in addition to a single-screw, twin-screw, and multi-screw extruder.
[0027]
Further, a melt-kneaded process of the components other than those used in the first step, and a melt-kneaded product composed of two of the components (A), (B) and (C) produced in the first step The second step can also be performed in a molding machine used for molding processes such as injection molding, extrusion molding, blow molding and the like.
[0028]
The temperature of the resin in the kneader at the time of kneading may be equal to or higher than the melting point of the alkenyl aromatic resin having a syndiotactic structure, but is preferably in the range of 280 to 380 ° C, more preferably 280 to 340 ° C.
[0029]
The shape of the screw is not particularly limited, and a conveying member, a kneading member and / or a mixing member may exist. Furthermore, it is possible and preferable to partially use a dampening member or a return member in order to control the residence time and kneading characteristics in the kneader. It is desirable that the damming member and the return member are between the first step and the second step. Further, an extruder having parallel twin screw is advantageously used to realize a more preferable state of self-cleaning property and residence time distribution.
[0030]
In the present invention, in addition to the essential components (A) to (C), other additional components may be added as necessary within the range not impairing the characteristics and effects of the present invention. For example, a styrene elastomer or polyolefin is used as an impact resistance improving material. Here, a known styrene elastomer can be used. For example, one or more styrene-butadiene block copolymers each having one or more polystyrene and polybutadiene segments, one or more styrene-isoprene copolymers each having one or more polystyrene and polyisoprene segments, and one copolymer of polystyrene and isoprene-butadiene. Styrene is graft-polymerized to block copolymers that have these, or block copolymers in which unsaturated parts of these isoprene and butadiene parts are selectively hydrogenated, and polyolefin elastomers that are copolymerized with ethylene, propylene, butene, and diene components It is a thing.
[0031]
The molecular chain length of the polystyrene segment in these styrene elastomers is preferably 10,000 or more in terms of weight average molecular weight. If the polystyrene segment is too short, the compatibility with the PPE resin composition is lowered, and delamination occurs during injection molding, or sufficient impact resistance is not obtained. Examples of the polyolefin include polyethylene, polypropylene, polybutene, polypentene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyethylene, ethylene-propylene rubber (EPR), and ethylene-propylene-diene rubber (EPDM). ) Etc. Among these, preferable impact modifiers are styrene block copolymers in which unsaturated parts of isoprene and butadiene are selectively hydrogenated, and polyolefin elastomers obtained by copolymerizing ethylene, propylene, butene and diene components. Styrene is graft polymerized.
[0032]
Moreover, a filler can be added and used for the purpose of strengthening, imparting a function or increasing the amount (cost reduction). Fillers include glass fibers, carbon fibers, aramid fibers, reinforcing fibers such as aluminum and stainless steel and metal whiskers, silica, alumina, calcium carbonate, talc, mica, clay, kaolin, magnesium sulfate, carbon black, titanium oxide Inorganic fillers such as zinc oxide and antimony trioxide can be used. Furthermore, antioxidants, weather resistance improvers, polyolefin nucleating agents, slip agents, flame retardants, flame retardant aids, plasticizers, various colorants, antistatic agents, mold release agents, and the like can be added.
[0033]
The molding method of the resin composition of the present invention is not particularly limited as long as it is a commonly used molding method such as injection molding, extrusion molding, compression molding, and hollow molding, and the shape of the resulting resin composition is not limited in any way. They are not intended to be restricted by the molding method.
[0034]
The obtained molded products are used in applications that require solvent resistance, for example, electrical / electronic parts applications such as flyback transformers and deflection yokes, water supply / drainage supply / exhaust parts applications such as pumps, tanks, ducts, etc., battery cases It can be used for battery cases such as water tanks, water tanks, development tanks, fans and fan housings. Also used in applications that require heat resistance, such as automotive applications such as lamp reflectors, connectors and relay housings, electrical and electronic parts such as coil bobbins, IC transport applications such as heat-resistant IC trays, and printed circuit boards. be able to. In addition, automotive panels such as instrument panels, wheel covers, fuse holders, radiator grills, ignition coils, side mudguards, and bumpers, housings for OA equipment, chassis for OA equipment, mechanical parts such as trains, IC carrier tapes It can be used for IC transportation applications, coin mechanism chassis of vending machines, and the like.
[0035]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to these Examples.
[0036]
The meanings of the abbreviations used in Examples and Comparative Examples are shown below.
PPE: (A) Polyphenylene ether resin
Poly (2.6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.46 dl / g measured at 30 ° C. in a chloroform solvent
SPS: (B) Alkenyl aromatic resin having a syndiotactic structure
To a glass container with a stirrer having an internal volume of 500 ml substituted with nitrogen, add 130 ml of dehydrated toluene and 8.3 ml of a toluene solution of methylaluminoxane (MMAO manufactured by Tosoh Akzo Co., Ltd., Type 3A, Al = 6.0 wt%), A solution prepared by dissolving 15 μmol of pentamethylcyclopentadienyl titanium chloride in 4.3 ml of toluene was added. Subsequently, 57 ml of styrene was added at 20 ° C. to conduct a polymerization reaction for 1 hour, and then methanol was injected to stop the reaction. Next, when a mixed solution of hydrochloric acid and methanol was added to decompose the catalyst component, 45.5 g of a polymer was obtained.
This polymer is¹³Absorption was observed at 145.35 ppm due to the syndiotactic structure in C-NMR, which confirmed that the polystyrene had a syndiotactic structure. From the peak area, the calculated syndiotacticity with racemic pendant was 95% or more. The melting point was 270.5 ° C., the heat of fusion was 21.5 mJ / mg, and the glass transition temperature was 100 ° C. when measured at a heating rate of 10 ° C./min with a scanning scanning calorimeter.
APS: (C) Alkenyl aromatic resin having no syndiotactic structure
Sumibright E163K (manufactured by Sumitomo Chemical Co., Ltd.) (styrene resin without syndiotactic structure)
[0037]
Evaluation methods for physical properties and the like are shown below.
Measurement of crystallization fraction of SPS
The heat of fusion was measured with a differential scanning calorimeter at a heating rate of 10 ° C./min. The crystallization fraction was determined according to the following formula as an index indicating the ease of crystallization of SPS. The higher the crystallization fraction, the easier the crystallization of the alkenyl aromatic resin having a syndiotactic structure in the blend.
Crystallization fraction = (heat of fusion per unit mass of SPS in blend) / (heat of fusion per unit mass of SPS of SPS)
Measurement of heat resistance
The storage elastic modulus at 130 ° C. was measured by dynamic viscoelasticity measurement under conditions of a temperature rising rate of 3 ° C./min and a frequency of 10 Hz. It can be said that heat resistance is so high that the value of a storage elastic modulus is large.
Solvent resistance
A 50 mm × 5 mm × 0.3 mm test piece prepared by press molding (300 ° C.) was attached to a jig having a radius of 70 mm, and gauze dipped in TnBP (tri-normal butyl phosphate) was placed on the center of the sample. The contact area between the sample and the gauze was 15 × 5 mm. After leaving at an ambient temperature of 23 ° C. for 30 minutes, the gauze was peeled off, and the number of cracks was counted visually. The worse the chemical resistance, the greater the number of cracks.
[0038]
Example 1
PPE 66.7% by weight and APS 33.3% by weight were kneaded with MAX MIX EXTRUDER Model CS194A (manufactured by Custom Scientific Instruments, Inc.) at 300 ° C. and 240 rpm, and the mixture of PPE and APS. Got. Next, 60% by weight of this kneaded product and 40% by weight of SPS were kneaded with MINIMAX under the kneading conditions of 300 ° C. and 240 rpm to obtain composition 1.
The heat of fusion of Composition 1 was measured with a differential scanning calorimeter and the crystallization fraction of SPS was determined to be 145%.
The storage elastic modulus at 130 ° C. is 1.56 × 10^Tendyn / cm²Met.
The number of cracks in the solvent resistance test was two.
[0039]
Example 2
  50% by weight of PPE and 50% by weight of SPS were kneaded in a MAX MIX EXTRUDER Model CS194A under kneading conditions of 300 ° C. and 240 rpm.SPSA kneaded product was obtained. Next, 80% by weight of this kneaded product and 20% by weight of APS were kneaded by MINIMAX under the kneading conditions of 300 ° C. and 240 rpm to obtain composition 2. The heat of fusion of composition 2 was measured with a differential scanning calorimeter, and the SPS crystallization fraction was determined to be 50%. The storage elastic modulus at 130 ° C. was 1.8 × 10 10 dyn / cm 2. The number of cracks in the solvent resistance test was 4.
[0040]
Example 3
  SPS 66.7% by weight and APS 33.3% by weight were kneaded in a MAX MIX EXTRUDER Model CS194A under kneading conditions of 300 ° C. and 240 rpm,SPSAnd APS kneaded material was obtained. Next, 60% by weight of this kneaded product and 40% by weight of PPE were kneaded by MINIMAX under the kneading conditions of 300 ° C. and 240 rpm to obtain composition 3. The heat of fusion of composition 3 was measured with a differential scanning calorimeter and the crystallization fraction of SPS was determined to be 115%. The storage elastic modulus at 130 ° C. is 1.76 × 10^Tendyn / cm²Met. The number of cracks in the solvent resistance test was two.
[0041]
Comparative Example 1
40% by weight of PPE, 20% by weight of APS and 40% by weight of SPS were kneaded in a MAX MIX EXTRUDER Model CS194A under the kneading conditions of 300 ° C. and 240 rpm to obtain composition 4.
The heat of fusion of composition 4 was measured with a differential scanning calorimeter, and the crystallization fraction of SPS was determined to be 7%.
The storage elastic modulus at 130 ° C. is 3.0 × 10⁹dyn / cm²Met.
The number of cracks in the solvent resistance test was 16.
[0042]
【The invention's effect】
As described above, according to the present invention, the polyphenylene ether type having a high crystallinity of an alkenyl aromatic resin having a syndiotactic structure, excellent impact resistance and rigidity, and particularly excellent heat resistance and solvent resistance. The resin composition and the manufacturing method thereof could be provided.

Claims (10)

A method for producing a polyphenylene ether-based resin composition containing 10 to 98% by weight of the following (A) component, 1 to 89% by weight of the following (B) component and 1 to 89% by weight of the following (C) component,
A first step of obtaining a melt-kneaded composition by melt-kneading a substantial amount of each of the two components among the component (A), the component (B) and the component (C);
A method for producing a polyphenylene ether-based resin composition, comprising melt-kneading the melt-kneaded composition obtained in the first step and a substantial amount of components other than those used in the first step.
(A): polyphenylene ether resin (B): alkenyl aromatic resin having a syndiotactic structure (C): alkenyl aromatic resin having no syndiotactic structure   The components used in the first step are two components (A) and (C), and the component kneaded with the melt-kneaded product in the second step is the component (B). The manufacturing method of the polyphenylene ether-type resin composition of Claim 1.   The components used in the first step are two components (A) and (B), and the component kneaded with the melt-kneaded product in the second step is the component (C). The manufacturing method of the polyphenylene ether-type resin composition of Claim 1.   The components used in the first step are two components (B) and (C), and the component to be kneaded with the melt-kneaded product in the second step is the component (A). The manufacturing method of the polyphenylene ether-type resin composition of Claim 1.   The amount of the two components melt-kneaded in the first step and the components other than those used in the first step melt-kneaded with the melt-kneaded product in the second step are the final composition. The method for producing a polyphenylene ether-based resin composition according to any one of claims 1 to 4, wherein the amount is larger than 60% of the amount of each component.   The amount of the two components melt-kneaded in the first step and the components other than those used in the first step melt-kneaded with the melt-kneaded product in the second step are the final composition. The method for producing a polyphenylene ether-based resin composition according to any one of claims 1 to 4, wherein the amount is greater than 80% of the amount of each component.   The production of the polyphenylene ether-based resin composition according to any one of claims 1 to 6, wherein the first step and the second step are performed continuously using an extruder having a plurality of inlets. Method.   The extruder has a screw provided with a damming member and / or a return member, and the damming member and / or the return member are an inlet used in the first step and an input used in the second step. The method for producing a polyphenylene ether-based resin composition according to claim 7, which is provided between the mouth and the mouth.   The printed circuit board formed from the polyphenylene ether-type resin composition obtained by the manufacturing method of the polyphenylene ether-type resin composition of any one of Claim 1 to 8.   A heat-resistant IC tray formed from a polyphenylene ether-based resin composition obtained by the method for producing a polyphenylene ether-based resin composition according to any one of claims 1 to 8.