JP4248764B2 - Resin composition - Google Patents

Description

【００１９】
〔Ｒ₁、Ｒ₄は、それぞれ独立して、水素、ハロゲン、第一級もしくは第二級の低級アルキル、フェニル、ハロアルキル、アミノアルキル、炭化水素オキシ、又はハロ炭化水素オキシ（但し、少なくとも２個の炭素原子がハロゲン原子と酸素原子を隔てている）を表わし、Ｒ₂、Ｒ₃は、それぞれ独立して、水素、ハロゲン、第一級もしくは第二級の低級アルキル、フェニル、ハロアルキル、炭化水素オキシ、又はハロ炭化水素オキシ（但し、少なくとも２個の炭素原子がハロゲン原子と酸素原子を隔てている）を表わす。〕
【００２０】
本発明の（Ｂ）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。
【００２１】
本発明で用いる（Ｂ）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号明細書記載されているように第一塩化銅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−ジメチルフェ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号明細書及び同第３２５７３５８号明細書、特公昭５２−１７８８０号公報及び特開昭５０−５１１９７号公報及び同６３−１５２６２８号公報等に記載された方法で容易に製造できる。
【００２２】
本発明で使用することのできる（Ｂ）ポリフェニレンエーテルの還元粘度（０．５ｇ／ｄｌ、クロロホルム溶液、３０℃測定）は、０．１５〜０．７０ｄｌ／ｇの範囲であることが好ましく、さらに好ましくは０．２０〜０．６０ｄｌ／ｇの範囲、より好ましくは０．４０〜０．５５ｄｌ／ｇの範囲である。
これらは、２種以上の還元粘度の異なるポリフェニレンエーテルをブレンドしたものであっても、何ら問題なく使用することができる。例えば、還元粘度０．４５ｄｌ／ｇ以下のポリフェニレンエーテルと還元粘度０．５０ｄｌ／ｇ以上のポリフェニレンエーテルの混合物、還元粘度０．４０ｄｌ／ｇ以下の低分子量ポリフェニレンエーテルと還元粘度０．５０ｄｌ／ｇ以上のポリフェニレンエーテルの混合物等が挙げられるが、もちろん、これらに限定されることはない。
【００２３】
ポリフェニレンエーテルは活性末端基として、フェノール性ＯＨ基を有しているが、本発明において使用するポリフェニレンエーテルの末端ＯＨ基濃度［ＯＨ］は２０〜８０ミリ等量／ｋｇの範囲内にある必要がある。また、末端基濃度の異なる複数のポリフェニレンエーテルを用いた場合の末端基濃度は、その平均をもって表す。
末端ＯＨ基濃度が２０ミリ当量／ｋｇ未満では、ポリアミドとの相溶性が低下するという問題点が生じる。また、８０ミリ当量／ｋｇを上回ると、リワーク後の耐衝撃性が低下するという問題点が生じる。
【００２４】
これら末端ＯＨ基濃度の調整方法は当業者には明らかであるような公知の方法を用いればよい。例えば、ポリフェニレンエーテルの重合時の副生成物であるジフェノキノン等のキノン類の共存下での加熱処理、ビスフェノール化合物の共存下に酸化カップリング重合を行うこと等が挙げられる。
また、本発明に使用できる（Ｂ）ポリフェニレンエーテルは、重合溶媒に起因する有機溶剤が、ポリフェニレンエーテル１００重量部に対して５重量％未満の量で残存していても構わない。これら重合溶媒に起因する有機溶剤は、重合後の乾燥工程で完全に除去するのは困難であり、通常数百ｐｐｍから数％の範囲で残存しているものである。ここでいう重合溶媒に起因する有機溶媒としては、トルエン、キシレンの各異性体、エチルベンゼン、炭素数１〜５アルコール類、クロロホルム、ジクロルメタン、クロルベンゼン、ジクロルベンゼン等の１種以上が挙げられる。
【００２５】
また、本発明で使用できる（Ｂ）ポリフェニレンエーテルは、全部又は一部が変性されたポリフェニレンエーテルであっても構わない。
ここでいう変性されたポリフェニレンエーテルとは、分子構造内に少なくとも１個の炭素−炭素二重結合または、三重結合及び少なくとも１個のカルボン酸基、酸無水物基、アミノ基、水酸基、又はグリシジル基を有する、少なくとも１種の変性化合物で変性されたポリフェニレンエーテルを指す。
【００２６】
該変性されたポリフェニレンエーテルの製法としては、（１）ラジカル開始剤の存在下、非存在下で１００℃以上、ポリフェニレンエーテルのガラス転移温度未満の範囲の温度でポリフェニレンエーテルを溶融させることなく変性化合物と反応させる方法、（２）ラジカル開始剤の存在下、非存在下でポリフェニレンエーテルのガラス転移温度以上３６０℃以下の範囲の温度で変性化合物と溶融混練し反応させる方法、（３）ラジカル開始剤の存在下、非存在下でポリフェニレンエーテルのガラス転移温度未満の温度で、ポリフェニレンエーテルと変性化合物を溶液中で反応させる方法等が挙げられ、これらいずれの方法でも構わないが、（１）及び、（２）の方法が好ましい。
【００２７】
次に分子構造内に少なくとも１個の炭素−炭素二重結合または、三重結合及び少なくとも１個のカルボン酸基、酸無水物基、アミノ基、水酸基、又はグリシジル基を有する少なくとも１種の変性化合物について具体的に説明する。
分子内に炭素−炭素二重結合とカルボン酸基、酸無水物基を同時に有する変性化合物としては、マレイン酸、フマル酸、クロロマレイン酸、シス−４−シクロヘキセン−１，２−ジカルボン酸及びこれらの酸無水物などが挙げられる。特にフマル酸、マレイン酸、無水マレイン酸が良好で、フマル酸、無水マレイン酸が特に好ましい。
【００２８】
また、これら不飽和ジカルボン酸のカルボキシル基の、１個または２個のカルボキシル基がエステルになっているものも使用可能である。
分子内に炭素−炭素二重結合とグリシジル基を同時に有する変性化合物としては、アリルグリシジルエーテル、グリシジルアクリレート、グリシジルメタアクリレート、エポキシ化天然油脂等が挙げられる。これらの中でグリシジルアクリレート、グリシジルメタアクリレートが特に好ましい。
【００２９】
分子内に炭素−炭素二重結合と水酸基を同時に有する変性化合物としては、アリルアルコール、４−ペンテン−１−オール、１，４−ペンタジエン−３−オールなどの一般式Ｃ_nＨ_2n-3ＯＨ（ｎは正の整数）の不飽和アルコール、一般式Ｃ_nＨ_2n-5ＯＨ、Ｃ_nＨ_2n-7ＯＨ（ｎは正の整数）等の不飽和アルコ−ル等が挙げられる。上述した変性化合物は、それぞれ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】
変性されたポリフェニレンエーテルを製造する際の変性化合物の添加量は、ポリフェニレンエーテル１００重量部に対して０．１〜１０重量部が好ましく、更に好ましくは０．３〜５重量部である。
ラジカル開始剤を用いて変性されたポリフェニレンエーテルを製造する際の好ましいラジカル開始剤の量は、ポリフェニレンエーテル１００重量部に対して０．００１〜１重量部である。
【００３１】
また、変性されたポリフェニレンエーテル中の変性化合物の付加率は、０．０１〜５重量％が好ましい。より好ましくは０．１〜３重量％である。
該変性されたポリフェニレンエーテル中には、未反応の変性化合物及び／または、変性化合物の重合体が残存していても構わない。
変性されたポリフェニレンエーテル中に残存する変性化合物及び／または、変性化合物の重合体の量を減少させるために、該変性されたポリフェニレンエーテルを製造する際に、必要に応じてアミド結合及び／またはアミノ基を有する化合物を添加しても構わない。
【００３２】
ここでいうアミド結合を有する化合物とは、分子構造中にアミド結合｛−ＮＨ−Ｃ（＝Ｏ）−｝構造を有する化合物であり、アミノ基を有する化合物とは末端に｛−ＮＨ₂｝構造を有する化合物である。これら化合物の具体例としては、オクチルアミン、ノニルアミン、テトラメチレンジアミン、ヘキサメチレンジアミン等の脂肪族アミン類、アニリン、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン等の芳香族アミン類、上記アミン類とカルボン酸、ジカルボン酸等との反応物、ε−カプロラクタム等のラクタム類及び、ポリアミド樹脂等が挙げられるが、これらに限定されるものではない。
【００３３】
これらアミド結合またはアミノ基を有する化合物を添加する際の好ましい添加量は、ポリフェニレンエーテル１００重量部に対し０．００１〜５重量部である。好ましくは０．０１〜１重量部、より好ましくは０．０１〜０．１重量部である。
また、本発明では、スチレン系熱可塑性樹脂を（Ａ）ポリアミドと（Ｂ）ポリフェニレンエーテルの合計１００重量部に対し、５０重量部未満の量であれば配合しても構わない。
【００３４】
本発明でいうスチレン系熱可塑性樹脂とは、ホモポリスチレン、ゴム変性ポリスチレン（ＨＩＰＳ）、スチレン−アクリロニトリル共重合体（ＡＳ樹脂）、スチレン−ゴム質重合体−アクリロニトリル共重合体（ＡＢＳ樹脂）、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、スチレン−エチレンブチレン共重合体、スチレン−エチレンプロピレン共重合体等が挙げられる。
更に、ポリフェニレンエーテルに添加しても良いとされている公知の添加剤等もポリフェニレンエーテル１００重量部に対して１０重量部未満の量で添加しても構わない。
【００３５】
本発明において、（Ａ）ポリアミドの末端アミノ基濃度と（Ｂ）ポリフェニレンエーテルの末端ＯＨ基濃度の濃度比が下式を満足する事が重要である。
［ＮＨ₂］／［ＯＨ］＝０．３〜２．０
［上式で、［ＯＨ］は（Ｂ）ポリフェニレンエーテルの末端ＯＨ基濃度（単位：ミリ等量／ｋｇ）、［ＮＨ₂］は（Ａ）ポリアミドの末端アミノ基濃度（単位：ミリ等量／ｋｇ）を表す。］
この［ＮＨ₂］／［ＯＨ］濃度比が規定の範囲を外れると、アニール後の面衝撃強度及びリサイクル性に劣るようになる。
【００３６】
また、（Ａ）ポリアミドの末端カルボキシル基濃度と（Ｂ）ポリフェニレンエーテルの末端ＯＨ基濃度の濃度比には、特に制限はないが下式を満足する事が好ましい。
［ＣＯＯＨ］／［ＯＨ］＝０．２〜１．３
［上式で、［ＯＨ］は（Ｂ）ポリフェニレンエーテルの末端ＯＨ基濃度（単位：ミリ等量／ｋｇ）、［ＣＯＯＨ］は（Ａ）ポリアミドの末端カルボキシル基濃度（単位：ミリ等量／ｋｇ）を表す。］
【００３７】
本発明で使用することのできる（Ｃ）衝撃改良材とは、芳香族化合物−共役ジエンブロック共重合体及び、芳香族化合物−共役ジエンブロック共重合体の水素添加物である。
【００３８】
ここでいう芳香族化合物−共役ジエンブロック共重合体とは、芳香族ビニル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を主体とする重合体ブロック（ｂ）から構成されるブロック共重合体であり、各ブロックの結合形式がａｂ型、ａｂａ型、ａｂａｂ型のいずれかであるブロック共重合体が好ましく、より好ましくは、ａｂａ型、ａｂａｂ型である。更にはａｂａｂ型が最も好ましい。
【００３９】
また、ブロック共重合体中の芳香族ビニル化合物と共役ジエン化合物との重量比は、１０／９０〜７０／３０であることが望ましい。より好ましくは、１５／８５〜５５／４５であり、最も好ましくは２０／８０〜４５／５５である。
更に、これらは芳香族ビニル化合物と共役ジエン化合物との重量比が異なるものを２種以上ブレンドしても構わない。
芳香族ビニル化合物の具体例としてはスチレン、α−メチルスチレン、ビニルトルエン等が挙げられ、これらから選ばれた１種以上の化合物が用いられるが、中でもスチレンが特に好ましい。
【００４０】
共役ジエン化合物の具体例としては、ブタジエン、イソプレン、ピペリレン、１，３−ペンタジエン等が挙げられ、これらから選ばれた１種以上の化合物が用いられるが、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。
ブロック共重合体の共役ジエン化合物としてブタジエンを使用する場合は、ポリブタジエンブロック部分のミクロ構造は１，２−ビニル含量もしくは１，２−ビニル含量と３，４−ビニル含量の合計量が５〜８０％が好ましく、さらには１０〜５０％が好ましく、１５〜４０％が最も好ましい。
【００４１】
また、芳香族ビニル化合物と共役ジエン化合物のブロック共重合体の水素添加物とは、上述の芳香族ビニル化合物と共役ジエン化合物のブロック共重合体を水素添加処理することにより、ジエン化合物を主体とする重合体ブロックの脂肪族二重結合を０を越えて１００％の範囲で制御したものをいう。該ブロック共重合体の水素添加物の好ましい水素添加率は５０％以上であり、より好ましくは８０％以上、最も好ましくは９８％以上である。
【００４２】
また、本発明における芳香族ビニル化合物と共役ジエン化合物のブロック共重合体及びその水素添加物の分子量としては、昭和電工製ＧＰＣ装置［ＳＹＳＴＥＭ２１］で、クロロホルムを溶媒とし、４０℃、ポリスチレンスタンダードで測定した数平均分子量（Ｍｎ）が、１０，０００〜５００，０００のものが好ましく、４０，０００〜２５０，０００のものが最も好ましい。
これら芳香族ビニル化合物−共役ジエン化合物のブロック共重合体は、結合形式の異なるもの、分子量の異なるもの、芳香族ビニル化合物種の異なるもの、共役ジエン化合物種の異なるもの、１，２−ビニル含量もしくは１，２−ビニル含量と３，４−ビニル含量の異なるもの、芳香族ビニル化合物成分含有量の異なるもの、水素添加率の異なるもの等を２種以上を混合して用いても構わない。
【００４３】
また、本発明で使用する（Ｃ）衝撃改良材は、全部又は一部が変性された衝撃改良材であっても構わない。
ここでいう変性された（Ｃ）衝撃改良材とは、分子構造内に少なくとも１個の炭素−炭素二重結合または、三重結合及び少なくとも１個のカルボン酸基、酸無水物基、アミノ基、水酸基、又はグリシジル基を有する、少なくとも１種の変性化合物で変性された衝撃改良材を指す。
【００４４】
該変性された衝撃改良材の製法としては、（１）ラジカル開始剤の存在下、非存在下で衝撃改良材の軟化点温度以上２５０℃以下の範囲の温度で変性化合物と溶融混練し反応させる方法、（２）ラジカル開始剤の存在下、非存在下で衝撃改良材の軟化点以下の温度で、衝撃改良材と変性化合物を溶液中で反応させる方法、（３）ラジカル開始剤の存在下、非存在下で衝撃改良材の軟化点以下の温度で、衝撃改良材と変性化合物を溶融させることなく反応させる方法等が挙げられ、これらいずれの方法でも構わないが、（１）の方法が好ましく、更には（１）の中でもラジカル開始剤存在下で行う方法が最も好ましい。
【００４５】
ここでいう分子構造内に少なくとも１個の炭素−炭素二重結合または、三重結合及び少なくとも１個のカルボン酸基、酸無水物基、アミノ基、水酸基、又はグリシジル基を有する少なくとも１種の変性化合物とは、変性されたポリフェニレンエーテルで述べた変性化合物と同じである。
また、本発明の（Ｃ）衝撃改良材中には、パラフィンを主成分とするオイルをあらかじめ混合したものを用いても構わない。パラフィンを主成分とするオイルをあらかじめ混合する事により、アニール後の面衝撃強度を、さらに向上させることができ、非常に有用である。
【００４６】
この際の好ましいパラフィンを主成分とするオイルの量は衝撃改良材１００重量部に対して、７０重量部以下である。７０重量部以上混合すると取り扱い性に劣る。
ここでいうパラフィンを主成分とするオイルとは、芳香環含有化合物、ナフテン環含有化合物及び、パラフィン系化合物の三者が組み合わさった重量平均分子量５００〜１００００の範囲の炭化水素系化合物の混合物であり、パラフィン系化合物の含有量が５０重量％以上のものである。
【００４７】
より好ましくは、パラフィン系化合物が５０〜９０重量％，ナフテン環含有化合物が１０〜４０重量％、芳香環含有化合物が５重量％以下のものである。
これら、パラフィンを主成分とするオイルは市販されており、例えば出光興産（株）製のＰＷ３８０等が挙げられる。
本発明の（Ｃ）衝撃改良材への上記オイルの混合方法としては、ペレット状またはパウダー状の衝撃改良材に所望量のパラフィン系オイルを均一になるように添加し放置する方法、押出機の途中から所望量のパラフィン系オイルを添加し溶融混練する方法等挙げられるが、これらに限定されるものではない。
また、本発明において式（２）に示したような金属塩を使用しても構わない。
【００４８】
【化２】

【００４９】
式中、Ｍは銅、ニッケル、スズ、セリウム及びアルカリ金属から選ばれる１種以上の金属イオンを表し、ＸはＣｌ，Ｂｒ，Ｆ，Ｉ等のハロゲン化物または例えばステアレート、アセテート等のカルボキシレ−トである負に荷電したイオンを表し、ｎは１〜６の整数、ｙはＭの正イオン電荷を表す整数、ｚはＸの負イオン電荷を表す整数である。
式（２）中の金属イオンＭとして好ましいのは銅及び／またはアルカリ金属であり、アルカリ金属が最も好ましい。また、Ｘとして最も好ましいのは、ハロゲン化イオンであり、その中でも特にヨウ素及び／または臭素が好ましく、ヨウ素が最も好ましい。
【００５０】
本発明で使用することのできる金属塩の具体例としては、ヨウ化銅、塩化銅、酢酸銅、ヨウ化カリウム、ステアリン酸セリウム等が挙げられ、これらの中でもヨウ化銅、ヨウ化カリウム、臭化銅、臭化カリウム及びヨウ化ナトリウムがより好ましく、ヨウ化カリウム、ヨウ化ナトリウムが最も好ましい。これらは併用しても構わない。
該金属塩の好ましい配合量はポリアミド、ポリフェニレンエーテル、衝撃改良材及び、導電用炭素系フィラーの合計量１００重量部に対し、２重量部未満の量である。好ましくは０．００１〜１重量部、より好ましくは０．００１〜０．５重量部である。
【００５１】
この金属塩の添加方法としては、（１）使用するポリアミドの重合時に添加する方法、（２）あらかじめポリアミドに高濃度で配合したマスターバッチの形態で添加する方法、（３）組成物製造時に直接添加する方法等が挙げられ、いずれの方法でも構わないが、（１）または（２）の方法が好ましい。これら手法の併用も、もちろん可能である。
【００５２】
本発明の樹脂組成物は、（Ａ）ポリアミドの連続相中に、（Ｃ）衝撃改良材を内包する（Ｂ）ポリフェニレンエーテル粒子が分散している分散形態を有し、更にその（Ｂ）ポリフェニレンエーテルの全分散粒子の半数以上が１．０μｍ以下の分散径で分散する微細な分散状態を示している必要がある。より好ましい分散形態は、（Ｂ）ポリフェニレンエーテルの全分散粒子の半数以上が０．７μｍ以下の分散径で分散している状態であり、最も好ましくは、（Ｂ）ポリフェニレンエーテルの全分散粒子の半数以上が０．６μｍ以下の分散径で分散している状態である。
（Ｂ）ポリフェニレンエーテルの全分散粒子の半数以上が１．０μｍ以下の分散径で分散する微細な分散状態を示している事の確認は、以下の様な透過型電子顕微鏡観察を行うことにより容易に確認することができる。
【００５３】
（１）ペレット状試料の中央部を、流れ方向が観察できるように切り出した後、８０℃に加熱したりんタングステン酸［１２タングスト（ＶＩ）リン酸ｎ水和物：Ｈ₃（ＰＷ₁₂Ｏ₄₀）・ｎＨ₂Ｏ］１０重量％水溶液に浸漬し、ポリアミド部分を選択的に染色する。（２）染色された成形片ブロックを、ウルトラミクロトームを用いて超薄切片の状態に切削する。（切削条件：切削温度：０℃以下、好ましくは−３０℃以下，切削厚み：６０〜８０ｎｍ）、（３）得られた超薄切片を、透過型電子顕微鏡で撮影する。
【００５４】
得られた電子顕微鏡写真を元に、ポリアミド以外の部分、即ち、ポリフェニレンエーテルの個々の粒子の分散径を、最低２０００個について測定する。この場合、粒子径が球状とみなせない場合には、その短径と長径を測定し、両者の和の１／２を粒子径とする。
本発明においては、測定した全粒子数に対して、分散径１．０μｍ以下の粒子数の割合が、０．５以上である必要がある。より好ましくは、分散径０．７μｍ以下の粒子数の割合が、０．５以上である事であり、更に好ましくは、分散径０．６μｍ以下の粒子数の割合が、０．５以上である事である。
【００５５】
また、本発明において相溶化剤を使用する事は、微細な分散粒子径を示す樹脂組成物を得るために有効である。
本発明で使用する事のできる相溶化剤とは、ポリフェニレンエーテル、ポリアミドまたはこれら両者と相互作用する多官能性の化合物であり、ポリアミドとポリフェニレンエーテルの相溶化に有効とされている公知の相溶化剤は、いずれも問題なく使用することができる。具体的には、特公昭５９−３３６１４号公報、特開平８−４８８６９号公報等に記載されている相溶化剤が上げられる。
【００５６】
これらに記載されている相溶化剤の中で、好ましい相溶化剤として、マレイン酸、無水マレイン酸、クエン酸が挙げられ、最も好ましい相溶化剤は無水マレイン酸である。
これら、相溶化剤の好ましい量は、ポリアミドとポリフェニレンエーテルの混合物１００重量部に対して０．０１〜２０重量部であり、より好ましくは０．１〜１０重量部である。
本発明における各成分の量比は、（Ａ）ポリアミド５０〜９５重量部、（Ｂ）ポリフェニレンエーテル５〜５０重量部の合計１００重量部に対し（Ｃ）衝撃改良材１〜３０重量部の量比である。
【００５７】
本発明では、上記した成分のほかに、本成分の効果を損なわない範囲で必要に応じて付加的成分を添加しても構わない。
本発明中で用いることのできる付加的成分としては、ポリエステル、ポリオレフィン等の他の熱可塑性樹脂、無機充填材（タルク、カオリン、ゾノトライト、ワラストナイト、酸化チタン、チタン酸カリウム、炭素繊維、ガラス繊維、着色用カーボンブラック、導電用カ−ボンブラック、ナノチューブカーボン、炭素繊維、グラファイトなど、）、無機充填材と樹脂との親和性を高める為の公知のシランカップリング剤、難燃剤（ハロゲン化された樹脂、シリコ−ン系難燃剤、水酸化マグネシウム、水酸化アルミニウム、有機燐酸エステル化合物、ポリ燐酸アンモニウム、赤燐など）、滴下防止効果を示すフッ素系ポリマ−、可塑剤（オイル、低分子量ポリオレフィン、ポリエチレングリコ−ル、脂肪酸エステル類等）及び、三酸化アンチモン等の難燃助剤、各種過酸化物、酸化亜鉛、硫化亜鉛、酸化防止剤、紫外線吸収剤、光安定剤等である。
【００５８】
これらの成分は、（Ａ）〜（Ｃ）成分の合計量１００重量部に対して、合計で５０重量部を越えない範囲で添加しても構わない。
また、ポリアミド相に存在させる事が良いとされている成分（例えば、ＰＡ用造核剤等の添加剤、スリップ剤、各種染料、酸化チタン、着色用カーボンブラック等の顔料及び、離型剤等）は（Ａ）〜（Ｃ）成分の合計量１００重量部に対し、それぞれ１０重量部を越えない範囲でポリアミド相に存在させても構わない。もちろんこれら付加的成分を２種以上併用して使用することも可能である。
【００５９】
本発明の組成物を得るための具体的な加工機械としては、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が挙げられるが、中でも二軸押出機が好ましく、特に、上流側供給口と１カ所以上の下流側供給口を備えた二軸押出機が最も好ましい。
この際の溶融混練温度は特に限定されるものではないが、通常２４０〜３６０℃の中から好適な組成物が得られる条件を任意に選ぶことができる。
【００６０】
このようにして得られる本発明の組成物は、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る。本発明の組成物は、例えば、カウル等のオートバイの外装部品用途、自動車の内装部品用途、フェンダー・ドアパネル・フロントパネル・リアーパネル・ロッカーパネル・リアバンパーパネル・バックドアガーニッシュ・エンブレムガーニッシュ・燃料注入口パネル・オーバーフェンダー・アウタードアハンドル・ドアミラーハウジング・ボンネットエアインテ−ク・バンパー・バンパーガード・ルーフレール・ルーフレールレッグ・ピラーカバー・ホイールカバー・各種エアロパーツ等の自動車外板・外装部品用途、電気・電子分野でのＩＣトレー材料用途等に好適に利用することがある。
以下、実施例及び比較例により、本発明を更に詳細に説明する。
【００６１】
【発明の実施の形態】
（ポリフェニレンエーテルの末端ＯＨ基濃度［ＯＨ］の測定）
２５ｍｌメスシリンダーに、ポリフェニレンエーテル１０〜２０ｍｇを精秤し、塩化メチレンで溶解した後、２５ｍｌまでメスアップした。次に、紫外線吸収スペクトル測定装置（セル長１ｃｍ，密栓付きセル使用）を用いて、この溶液の３１８ｎｍの波長における吸光度をゼロとした。
その後、このセル中に、テトラエチルアンモニウムヒドロキシドの１０重量％メタノール溶液を０．２μｌ加え、素早く振り混ぜた後に、再度、紫外線吸収スペクトル測定装置で３１８ｎｍにおける吸光度を測定した。
この時の吸光度を用いて下式（Ｌａｍｂｅｒｔ−Ｂｅｅｒの式に基づく）より、ポリフェニレンエーテルの末端ＯＨ基濃度［ＯＨ］（ミリ当量／ｋｇ）を算出した。
［ＯＨ］＝［（２５×Ａｂｓ）／（４７００×Ｗ）]×１０⁶
（上式中で、Ａｂｓは測定した吸光度、Ｗは秤量したポリフェニレンエーテルの重量、４７００は吸光係数である。）
【００６２】
【製造例１】
ポリフェニレンエーテル−１の製造
底部に酸素吹き込み口を有し、温調用ジャケットのある２５リットルの反応槽に、トルエン８．２２ｋｇと２，６−ジメチルフェノール４４０ｇを入れ、更に酸化銅５．６ｇ、臭化水素４７重量％水溶液２１．６ｇ、ブチルジメチルアミン１４５ｇ、ジブチルアミン４４ｇ及びジ−ｔｅａｔ−ブチルエチレンジアミン１３．５ｇを入れ、４０℃に温調、撹拌しつつ酸素を６ｌ／分の量で吹き込み、重合を開始した。
【００６３】
また、反応槽の気相部分には窒素を８ｌ／分の量で吹き込んだ。酸素吹き込み開始直後より、４０分の間、２，６−ジメチルフェノール３５重量％トルエン溶液を、２８０ｇ／分の添加速度で反応槽に添加し続けた。添加終了後に温調用ジャケット温度を５０℃に上げ、更に重合を続けた。重合開始から２時間後、酸素を閉止し、触媒失活剤であるエチレンジアミン四酢酸・三カリウム塩の１０重量％水溶液を４００ｇ添加することにより重合を停止した。粘調になった重合液を取り出し、メタノール中に滴下し、再沈殿させ濾別した。
その固形物を、さらにメタノールで洗浄した後、濾別し、１４０℃で２時間真空乾燥した後、白色粉体状のＰＰＥを得た。以下これをＰＰＥ−１と称する。この粉体のクロロホルム溶液（０．５ｇ／ｄｌ）の３０℃測定での還元粘度は、０．５３であった。また、末端ＯＨ基濃度を測定したところ、３３ミリ当量／ｋｇであった。
【００６４】
【製造例２】
ポリフェニレンエーテル−２の製造
２，６−ジメチルフェノール３５重量％トルエン溶液添加後の温調用ジャケット温度を６０℃にした以外は、すべて製造例１と同様に実施し、白色粉体状のＰＰＥを得た。以下これをＰＰＥ−２と称する。この粉体のクロロホルム溶液（０．５ｇ／ｄｌ）の３０℃測定での還元粘度は、０．４２であった。また、末端ＯＨ基濃度を測定したところ、４８ミリ当量／ｋｇであった。
【００６５】
【製造例３】
ポリフェニレンエーテル−３の製造
重合時間を２時間３０分にした以外は、重合停止までは、すべて製造例１と同様に実施した。ポリフェニレンエーテルの末端ＯＨ基の調整のため、重合停止後、温調用ジャケットの温度を７０℃に上げ、１時間３０分の間、撹拌を続けた。高温撹拌後の溶液を取り出し、メタノール中に滴下し、再沈殿させ濾別した。
その固形物を、さらにメタノールで洗浄した後、濾別し、１４０℃で２時間真空乾燥した後、白色粉体状のＰＰＥを得た。以下これをＰＰＥ−３と称する。この粉体のクロロホルム溶液（０．５ｇ／ｄｌ）の３０℃測定での還元粘度は、０．４７であった。また、末端ＯＨ基濃度を測定したところ、７５ミリ当量／ｋｇであった。また、重合直後のポリフェニレンエーテルも別途サンプリングし、還元粘度を測定したところ０．６８であった。
【００６６】
【製造例４】
ポリフェニレンエーテル−４の製造
重合停止までは、すべて製造例２と同様に実施した。ポリフェニレンエーテルの末端ＯＨ基の調整のため、重合停止後、温調用ジャケットの温度を６０℃に上げ、２時間撹拌を続けた。高温撹拌後の溶液を取り出し、メタノール中に滴下し、再沈殿させ濾別した。
その固形物を、さらにメタノールで洗浄した後、濾別し、１４０℃で２時間真空乾燥した後、白色粉体状のＰＰＥを得た。以下これをＰＰＥ−４と称する。この粉体のクロロホルム溶液（０．５ｇ／ｄｌ）の３０℃測定での還元粘度は、０．３６であった。また、末端ＯＨ基濃度を測定したところ、１０８ミリ当量／ｋｇであった。また、重合直後のポリフェニレンエーテルも別途サンプリングし、還元粘度を測定したところ０．５８であった。
【００６７】
（使用した原料）
（１）ポリフェニレンエーテル（ＰＰＥ）
ＰＰＥ−１ 還元粘度＝０．５３、［ＯＨ］＝３３ミリ当量／ｋｇ
ＰＰＥ−２ 還元粘度＝０．４２、［ＯＨ］＝４８ミリ当量／ｋｇ
ＰＰＥ−３ 還元粘度＝０．４７、［ＯＨ］＝７５ミリ当量／ｋｇ
ＰＰＥ−４ 還元粘度＝０．３６、［ＯＨ］＝１０８ミリ当量／ｋｇ
【００６８】
（２）ポリアミド（ＰＡ）

【００６９】
（３）衝撃改良材

（４）相溶化剤（ＭＡＨと略記）
ＭＡＨ 無水マレイン酸［日本油脂（株）製］
【００７０】
【実施例１】
上流側に１カ所と、押出機中央部に１カ所の供給口を有する二軸押出機［ＺＳＫ−４０：ウェルナー＆フライデラー社製（ドイツ）］のシリンダー温度を上流側供給口（以下、単にＴｏｐ−Ｆと略す）より下流側供給口（以下、単にＳｉｄｅ−Ｆと略す）までを３２０℃、Ｓｉｄｅ−Ｆよりダイまでを２８０℃に設定し、Ｔｏｐ−Ｆより、ＰＰＥ−１とＳＥＢＳ−１及びＭＡＨを表１記載の割合でドライブレンドし供給し溶融混練し、Ｓｉｄｅ−ＦよりＰＡ−１を表１記載の割合となるよう供給し溶融混練し、ペレット化した。
なお、このときのスクリュー回転数は３００回転／分であり、また、揮発分除去のためＳｉｄｅ−Ｆの直前および、Ｓｉｄｅ−Ｆとダイの間の２カ所に真空ベントを取り付け、真空吸引を行った。
得られたペレットを、以下の項目について測定し、結果を表１に記載した。
【００７１】
（電子顕微鏡観察）
得られたペレットの中央部を、流れ方向に対して垂直の方向に観察できるようにトリミングし、これを、８０℃に加熱したりんタングステン酸［１２タングスト（ＶＩ）リン酸ｎ水和物：Ｈ₃（ＰＷ₁₂Ｏ₄₀）・ｎＨ₂Ｏ］１０重量％水溶液に浸漬し、ポリアミド部分を選択的に染色した。次に染色された成形片ブロックを、ウルトラミクロトームを用いて超薄切片の状態に切削（切削条件：切削温度：−３０℃，切削厚み：７０ｎｍ）し、得られた超薄切片を、透過型電子顕微鏡で撮影した。
得られた電子顕微鏡写真を元に、染色されていない部分、即ち、ポリフェニレンエーテル相の個々の粒子の分散径を、２０１６個について測定した。
測定した全粒子数に対して、分散径１．０μｍ以下の粒子数は１５５３個であり、その割合は０．７７であった。表１には、「分散径１μｍ以下の割合」として記載した。
【００７２】
（リサイクル性試験）
押出で得られたペレットを、シリンダー温度２９０℃、金型温度８０℃に設定した射出成形機［ＩＳ−８０ＥＰＮ：東芝機械（株）社製（日本）］を用いて、１２８ｍｍ、幅１２．８ｍｍ、厚み３．２ｍｍの短冊状成形片を４００本成形し、この内、５本をリワークなしのＩｚｏｄ衝撃強度測定に供した。表１には、単に「Ｉｚｏｄ衝撃強度」として記載した。
また、残りの短冊状成形片すべてを粉砕し粒状にした後、同方向回転二軸押出機［ＰＣＭ−３０：池貝鉄工（株）社製］を用いて、ペレット化した。このペレットで再度、長さ１２８ｍｍ、幅１２．８ｍｍ、厚み３．２ｍｍの短冊状成形片を３００本成形し、うち５本をリワーク１回のＩｚｏｄ衝撃強度測定に供した。表１には、「１回リワーク後 Ｉｚｏｄ」として記載した。
さらに、残りの短冊状成形片すべてを粉砕し、同様にペレット化した。このペレットで、長さ１２８ｍｍ、幅１２．８ｍｍ、厚み３．２ｍｍの短冊状成形片を成形し、この成形片をリワーク２回のＩｚｏｄ衝撃強度測定に供した。なお、Ｉｚｏｄ衝撃試験はＡＳＴＭ Ｄ６４８に準拠して実施した。表１には、「２回リワーク後 Ｉｚｏｄ」として記載した。
【００７３】
（面衝撃試験）
押出で得られたペレットを、シリンダー温度２９０℃、金型温度８０℃に設定した射出成形機［ＩＳ−８０ＥＰＮ：東芝機械（株）社製（日本）］を用いて、、長さ９０ｍｍ、幅５０ｍｍ、厚さ２．５ｍｍの平板状成形片に成形し、グラフィックインパクトテスター［東洋精機製作所（株）製］を用いて面衝撃強度を測定した。
なお、アニール後の面衝撃強度は、面衝撃試験前に平板状成形片を、ギアオーブンに入れ、１９０℃で５時間の空気中で加熱した事だけが異なる。
試験方法は次の通りである。直径が４０ｍｍのサンプルホールダーに試験片をはさみ、先端径が１３ｍｍの球形状のストライカー（重量６．５ｋｇ）を、試験片の上方１００ｃｍの高さより自由落下させ、試験片を破壊させ、その際に、破壊に要した全エネルギーを測定し、全吸収エネルギーとして表示した。
【００７４】
この試験を１０枚のサンプルで実施し、１０回のデータのうち最大値と最小値を除いた８回の測定値の加算平均をもって、そのサンプルの全吸収エネルギー値とした。
また、この測定で破壊された試験片の破壊状況を観察し、延性破壊と脆性破壊に大別し、１０枚の試験片のうち、延性破壊をした試験片の枚数の割合から延性率を計算した。
延性率［％］＝延性破壊をした枚数／１０×１００
表１には、アニール前の結果は、「アニール前 面衝撃強度」及び「延性率」として記載し、アニール後の結果は「アニール後 面衝撃強度」及び「延性率」として記載した。
【００７５】
【実施例２〜５及び比較例１，２】
配合組成を表１に記載した割合に変更した以外はすべて実施例１と同様に実施し、電子顕微鏡にて分散径１．０μｍ以下の粒子割合、リサイクル性、面衝撃強度、アニール後の面衝撃強度を測定した。
測定結果は、表１の各実施例及び比較例の組成の下段に併記した。
【００７６】
【表１】

【００７７】
【発明の効果】
本発明の組成物は、ポリアミドの連続相中にポリフェニレンエーテルを特定の分散状態で分散させ、更にポリフェニレンエーテルとポリアミドのそれぞれの末端基濃度とそれらの末端基濃度比を特定の範囲に限定することにより、アニール後の面衝撃性及びリサイクル性に優れた樹脂組成物が得られることが判る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition excellent in surface impact property and recyclability after annealing.
The composition of the present invention can be suitably used in a wide range of fields such as electric / electronic parts, OA parts, vehicle parts, and machine parts.
[0002]
[Prior art]
Polyphenylene ether resins are used in a wide range because they have excellent mechanical properties, electrical properties, and heat resistance, and also have excellent dimensional stability. In order to improve the technique, a technique for blending polyamide has been proposed in Japanese Patent Publication No. 45-997, and is now a material used for various applications.
[0003]
In recent years, attempts to use polyamide / polyphenylene ether alloys for automobile exterior materials have been extensively studied.
However, since these automobile exterior materials are exposed to an environment close to 200 ° C. in the online painting process, there has been a problem that the surface impact strength of the resin is greatly reduced.
In order to improve impact strength, for example, Japanese Patent Application Laid-Open No. 64-79258 discloses a polyphenylene ether and a vinyl aromatic-olefin block copolymer of a polyphenylene ether, a polyamide, and a vinyl aromatic-olefin block copolymer. A technique for controlling a polymer to a specific dispersion diameter is disclosed.
[0004]
However, although the Izod impact strength is improved by the above technique, the surface impact strength is not sufficiently improved.
In addition, with the recent increase in environmental awareness, recyclability is also required at the same time.
In order to improve recyclability, for example, Japanese Patent Application Laid-Open No. 5-306365 and Japanese Patent Application Laid-Open No. 6-141443 disclose techniques for improving recyclability by adding various additives.
However, the above-described technique has problems such as bleeding out of added components, and the market demanded a material with improved recyclability without relying on additives.
[0005]
[Problems to be solved by the invention]
The present invention is intended to solve the problems that cannot be solved by the conventional technology as described above.
That is, an object of the present invention is to provide a resin composition excellent in surface impact property and recyclability after annealing.
[0006]
  As a result of repeated studies to solve the above-mentioned problems, the present inventors have surprisingly dispersed polyphenylene ether in a specific dispersion state in the continuous phase of polyamide, and furthermore, each of the end group concentrations of polyphenylene ether and polyamide. The inventors have found that a resin composition excellent in surface impact property and recyclability after annealing can be obtained by limiting the concentration ratio of these end groups to a specific range.
  That is, the present invention includes (A) 50 to 95 parts by weight of polyamide and (B) 5 to 50 parts by weight of polyphenylene ether for a total of 100 parts by weight. In the continuous phase, (B) component particles containing component (C) are dispersed, and more than half of the dispersed particles of component (B) are dispersed with a dispersion diameter of 1.0 μm or less. And the concentration of each end group of the component (A) and the component (B) and the concentration ratio of both are in the range satisfying the following formula:Here, the impact improving material of component (C) is a block copolymer composed of a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound, and its One or more resin compositions selected from hydrogenated productsAbout.
[0007]
[NH₂] = 20-80mm equivalent / kg
[OH] = 20-80 milliequivalent / kg
[NH₂] / [OH] = 0.3-2.0
[In the above formula, [OH] is (B) terminal OH group concentration of polyphenylene ether (unit: milliequivalent / kg), [NH₂] Represents the terminal amino group concentration (unit: milliequivalent / kg) of (A) polyamide. ]
The present invention will be described in detail below.
[0008]
As the type of (A) polyamide that can be used in the present invention, any polyamide having an amide bond {—NH—C (═O) —} in the polymer main chain can be used.
In general, polyamides are obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but are not limited thereto.
[0009]
The diamines are roughly classified into aliphatic, alicyclic and aromatic diamines. Specific examples include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 2, 2 , 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnanomethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p -Phenylenediamine, m-xylylenediamine, p-xylylenediamine.
[0010]
Dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecane. Examples include diacid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and dimer acid.
Specific examples of lactams include ε-caprolactam, enantolactam, and ω-laurolactam.
[0011]
Specific examples of aminocarboxylic acids include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotriic acid. Examples include decanoic acid.
In the present invention, any of these lactams, diamines, dicarboxylic acids, and aminocarboxylic acids can be used as a copolymerized polyamide obtained by polycondensation alone or in a mixture of two or more.
[0012]
In addition, those obtained by polymerizing these lactams, diamines, dicarboxylic acids, and aminocarboxylic acids to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight by an extruder or the like can also be suitably used.
In particular, the polyamide (A) that can be usefully used in the present invention includes polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6/6. , 6, polyamide 6 / 6,12, polyamide MXD, 6 (MXD: m-xylylenediamine), polyamide 6 / MXD, 6, polyamide 6,6 / MXD, 6, polyamide 6, T, polyamide 6, I, Polyamide 6/6, T, Polyamide 6/6, I, Polyamide 6, 6/6, T, Polyamide 6, 6/6, I, Polyamide 6/6, T / 6, I, Polyamide 6, 6/6 T / 6, I, polyamide 6/12/6, T, polyamide 6, 6/12/6, T, polyamide 6/12/6, I, polyamide 6, 6/12/6, I, etc. Is, copolymerized polyamides such multiple polyamides with an extruder or the like may be used.
[0013]
Of course, two or more of these may be used in combination.
The number average molecular weight of the polyamide (A) used in the present invention is preferably 5,000 to 100,000, more preferably 7,000 to 30,000, and most preferably 8,000 to 14,000.
The polyamide (A) in the present invention may be a mixture of a plurality of polyamides having different molecular weights. For example, a mixture of a low molecular weight polyamide having a number average molecular weight of 10,000 or less and a high molecular weight polyamide having a molecular weight of 30,000 or more, a low molecular weight polyamide having a number average molecular weight of 10,000 or less, and a general polyamide having about 15,000 Although a mixture etc. are mentioned, it is not limited to these.
Of course, different polyamides having different molecular weights may be mixed.
[0014]
Polyamide generally has amino groups and carboxyl groups as end groups.
The terminal amino group concentration of the polyamide (A) that can be used in the present invention [NH₂] Must be in the range of 20-80 milliequivalents / kg. More preferably, it is in the range of 25-60 milliequivalent / kg. When the terminal amino group concentration is less than 20 meq / kg, there arises a problem that the impact resistance of the resin composition is lowered. Moreover, when it exceeds 80 meq / kg, the problem that the impact resistance after reworking will fall arises.
[0015]
Although there is no restriction | limiting in particular regarding terminal carboxyl group density | concentration [COOH], As a preferable range, it is 50-150 milliequivalent / kg. When the terminal carboxyl group concentration exceeds 150 meq / kg, there arises a problem that the surface impact strength after annealing is lowered. Conversely, if it is less than 50 meq / kg, there arises a problem that the fluidity of the composition is greatly reduced.
Further, the end group concentration when a plurality of polyamides having different end group concentrations are used is represented by the average.
[0016]
Generally, in polyamide / polyphenylene ether alloys, it is known that when the carboxyl group concentration exceeds the amino group concentration, impact resistance is lowered and fluidity is improved. It is known that when the concentration is exceeded, impact resistance is improved and fluidity is lowered.
These terminal amino group concentrations [NH₂] And the preferred ratio of the terminal carboxyl group concentration [COOH] is [NH₂] / [COOH] ratio of 6/4 to 1/9, more preferably 5/5 to 2/8, still more preferably 4/6 to 2/8.
[0017]
The method for adjusting the end groups of these polyamides may be a known method that will be apparent to those skilled in the art. For example, addition of diamines or dicarboxylic acids or addition of monocarboxylic acids may be mentioned during the polymerization of polyamide.
Of course, the polyamide (A) in the present invention may be a mixture of a plurality of polyamides having different terminal group concentrations.
Furthermore, known additives that may be added to the polyamide may be added in an amount of less than 10 parts by weight based on 100 parts by weight of the polyamide.
The (B) polyphenylene ether that can be used in the present invention is a homopolymer and / or copolymer comprising the structural unit of the formula (1).
[0018]
[Chemical 1]

[0019]
[R₁, R_FourAre each independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that at least two carbon atoms are halogen atoms) Represents an oxygen atom) and R₂, R_ThreeAre each independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that at least two carbon atoms are halogen and oxygen atoms) Are separated). ]
[0020]
Specific examples of the (B) polyphenylene ether of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether) ), 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 Polyphenylene ether copolymers such as copolymers with phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol) are also included. 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).
[0021]
The method for producing (B) polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method. For example, as described in US Pat. No. 3,306,874, cuprous chloride is used. Can be easily produced by, for example, oxidative polymerization of 2,6-dimethylphenol, and in addition, US Pat. Nos. 3,306,875, 3,257,357, and 3,257,358. Can be easily produced by the methods described in JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628.
[0022]
The reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of (B) polyphenylene ether that can be used in the present invention is preferably in the range of 0.15 to 0.70 dl / g, Preferably it is the range of 0.20-0.60 dl / g, More preferably, it is the range of 0.40-0.55 dl / g.
These can be used without any problem even if they are blends of two or more polyphenylene ethers having different reduced viscosities. For example, a mixture of a polyphenylene ether having a reduced viscosity of 0.45 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.50 dl / g or more, a low molecular weight polyphenylene ether having a reduced viscosity of 0.40 dl / g or less, and a reduced viscosity of 0.50 dl / g or more. A mixture of polyphenylene ethers, etc., of course, is, of course, not limited to these.
[0023]
Polyphenylene ether has a phenolic OH group as an active end group, but the terminal OH group concentration [OH] of the polyphenylene ether used in the present invention needs to be within a range of 20 to 80 milliequivalent / kg. is there. Moreover, the terminal group density | concentration at the time of using several polyphenylene ether from which terminal group density | concentration differs is represented with the average.
When the terminal OH group concentration is less than 20 meq / kg, there arises a problem that the compatibility with the polyamide is lowered. Moreover, when it exceeds 80 meq / kg, the problem that the impact resistance after reworking will fall arises.
[0024]
These terminal OH group concentrations may be adjusted by a known method that will be apparent to those skilled in the art. Examples thereof include heat treatment in the presence of quinones such as diphenoquinone, which is a by-product during polymerization of polyphenylene ether, and oxidative coupling polymerization in the presence of a bisphenol compound.
In the polyphenylene ether (B) that can be used in the present invention, the organic solvent resulting from the polymerization solvent may remain in an amount of less than 5% by weight based on 100 parts by weight of the polyphenylene ether. These organic solvents resulting from the polymerization solvent are difficult to remove completely in the drying step after polymerization, and usually remain in the range of several hundred ppm to several percent. Examples of the organic solvent resulting from the polymerization solvent include one or more of toluene, xylene isomers, ethylbenzene, C1-5 alcohols, chloroform, dichloromethane, chlorobenzene, dichlorobenzene and the like.
[0025]
In addition, the polyphenylene ether (B) that can be used in the present invention may be a polyphenylene ether modified in whole or in part.
The modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl in the molecular structure. The polyphenylene ether modified with at least one modifying compound having a group.
[0026]
The method for producing the modified polyphenylene ether includes (1) a modified compound without melting the polyphenylene ether at a temperature in the range of 100 ° C. or higher in the presence or absence of a radical initiator and lower than the glass transition temperature of the polyphenylene ether. (2) a method in which a modified compound is melt-kneaded and reacted at a temperature in the range of the glass transition temperature of polyphenylene ether to 360 ° C. in the presence or absence of a radical initiator, and (3) a radical initiator. In the presence or absence, a method of reacting a polyphenylene ether and a modifying compound in a solution at a temperature lower than the glass transition temperature of the polyphenylene ether may be mentioned. Any of these methods may be used, (1) and The method (2) is preferred.
[0027]
Next, at least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure Will be described in detail.
Examples of modified compounds having a carbon-carbon double bond, a carboxylic acid group, and an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and these And acid anhydrides. Fumaric acid, maleic acid, and maleic anhydride are particularly preferable, and fumaric acid and maleic anhydride are particularly preferable.
[0028]
In addition, those in which one or two of the carboxyl groups of the unsaturated dicarboxylic acid are esters can be used.
Examples of the modified compound having a carbon-carbon double bond and a glycidyl group in the molecule include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural fats and oils. Among these, glycidyl acrylate and glycidyl methacrylate are particularly preferable.
[0029]
Examples of the modified compound having both a carbon-carbon double bond and a hydroxyl group in the molecule include general formula C such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadien-3-ol._nH_2n-3OH (n is a positive integer) unsaturated alcohol, general formula C_nH_2n-5OH, C_nH_2n-7Examples thereof include unsaturated alcohols such as OH (n is a positive integer). The above-described modifying compounds may be used alone or in combination of two or more.
[0030]
The amount of the modifying compound added when producing the modified polyphenylene ether is preferably from 0.1 to 10 parts by weight, more preferably from 0.3 to 5 parts by weight, based on 100 parts by weight of the polyphenylene ether.
A preferable amount of the radical initiator in producing the polyphenylene ether modified with the radical initiator is 0.001 to 1 part by weight with respect to 100 parts by weight of the polyphenylene ether.
[0031]
The addition rate of the modifying compound in the modified polyphenylene ether is preferably 0.01 to 5% by weight. More preferably, it is 0.1 to 3% by weight.
In the modified polyphenylene ether, an unreacted modified compound and / or a polymer of the modified compound may remain.
In order to reduce the amount of the modifying compound and / or the polymer of the modifying compound remaining in the modified polyphenylene ether, an amide bond and / or an amino group may be added as necessary when preparing the modified polyphenylene ether. A compound having a group may be added.
[0032]
The compound having an amide bond here is a compound having an amide bond {—NH—C (═O) —} structure in the molecular structure, and the compound having an amino group is terminated with {—NH.₂} A compound having a structure. Specific examples of these compounds include aliphatic amines such as octylamine, nonylamine, tetramethylenediamine, hexamethylenediamine, aniline, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine. Aromatic amines such as the above, reactants of the above amines with carboxylic acid, dicarboxylic acid and the like, lactams such as ε-caprolactam, and polyamide resins, but are not limited thereto.
[0033]
A preferable addition amount when adding the compound having an amide bond or an amino group is 0.001 to 5 parts by weight with respect to 100 parts by weight of the polyphenylene ether. Preferably it is 0.01-1 weight part, More preferably, it is 0.01-0.1 weight part.
In the present invention, the styrenic thermoplastic resin may be blended as long as it is less than 50 parts by weight based on 100 parts by weight of the total of (A) polyamide and (B) polyphenylene ether.
[0034]
The styrenic thermoplastic resin referred to in the present invention is homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubbery polymer-acrylonitrile copolymer (ABS resin), styrene. -Butadiene copolymer, styrene-isoprene copolymer, styrene-ethylenebutylene copolymer, styrene-ethylenepropylene copolymer and the like.
Furthermore, known additives that may be added to polyphenylene ether may be added in an amount of less than 10 parts by weight based on 100 parts by weight of polyphenylene ether.
[0035]
In the present invention, it is important that the concentration ratio of the terminal amino group concentration of (A) polyamide and the terminal OH group concentration of (B) polyphenylene ether satisfies the following formula.
[NH₂] / [OH] = 0.3-2.0
[In the above formula, [OH] is (B) terminal OH group concentration of polyphenylene ether (unit: milliequivalent / kg), [NH₂] Represents the terminal amino group concentration (unit: milliequivalent / kg) of (A) polyamide. ]
This [NH₂] / [OH] concentration ratio is outside the specified range, the surface impact strength after annealing and the recyclability are inferior.
[0036]
Further, the concentration ratio of the terminal carboxyl group concentration of (A) polyamide and the terminal OH group concentration of (B) polyphenylene ether is not particularly limited, but preferably satisfies the following formula.
[COOH] / [OH] = 0.2 to 1.3
[In the above formula, [OH] is the terminal OH group concentration of (B) polyphenylene ether (unit: milliequivalent / kg), and [COOH] is the terminal carboxyl group concentration of (A) polyamide (unit: milliequivalent / kg). ). ]
[0037]
  What is the (C) impact modifier that can be used in the present invention?, YoshiHydrogenated product of aromatic compound-conjugated diene block copolymer and aromatic compound-conjugated diene block copolymerIs.
[0038]
The aromatic compound-conjugated diene block copolymer here is a block copolymer composed of a polymer block (a) mainly composed of an aromatic vinyl compound and a polymer block (b) mainly composed of a conjugated diene compound. It is a polymer, and a block copolymer in which the binding mode of each block is any one of ab type, aba type, and abab type, and more preferably, aba type and abab type. Furthermore, the abab type is most preferable.
[0039]
The weight ratio of the aromatic vinyl compound to the conjugated diene compound in the block copolymer is preferably 10/90 to 70/30. More preferably, it is 15/85 to 55/45, and most preferably 20/80 to 45/55.
Furthermore, these may be blended in two or more types having different weight ratios of the aromatic vinyl compound and the conjugated diene compound.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like, and one or more compounds selected from these are used, and among them, styrene is particularly preferable.
[0040]
Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, and one or more compounds selected from these are used. Of these, butadiene, isoprene and combinations thereof are preferable. .
When butadiene is used as the conjugated diene compound of the block copolymer, the microstructure of the polybutadiene block portion is 1,2-vinyl content or the total amount of 1,2-vinyl content and 3,4-vinyl content is 5-80. %, More preferably 10 to 50%, and most preferably 15 to 40%.
[0041]
In addition, the hydrogenated product of the block copolymer of the aromatic vinyl compound and the conjugated diene compound is mainly composed of the diene compound by subjecting the block copolymer of the aromatic vinyl compound and the conjugated diene compound to a hydrogenation treatment. In the polymer block, the aliphatic double bond of the polymer block is controlled in the range of more than 0 to 100%. A preferable hydrogenation rate of the hydrogenated product of the block copolymer is 50% or more, more preferably 80% or more, and most preferably 98% or more.
[0042]
The molecular weight of the block copolymer of the aromatic vinyl compound and the conjugated diene compound in the present invention and the hydrogenated product thereof was measured by Showa Denko GPC [SYSTEM21] using chloroform as a solvent at 40 ° C. and polystyrene standard. The number average molecular weight (Mn) is preferably 10,000 to 500,000, and most preferably 40,000 to 250,000.
These aromatic vinyl compound-conjugated diene compound block copolymers have different bonding types, different molecular weights, different aromatic vinyl compound types, different conjugated diene compound types, 1,2-vinyl content Alternatively, two or more types having different 1,2-vinyl contents and 3,4-vinyl contents, different aromatic vinyl compound component contents, different hydrogenation rates, and the like may be used.
[0043]
Moreover, the impact improving material (C) used in the present invention may be an impact improving material modified in whole or in part.
The modified (C) impact modifier herein means at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group in the molecular structure, It refers to an impact modifier modified with at least one modifying compound having a hydroxyl group or a glycidyl group.
[0044]
The production method of the modified impact modifier is as follows: (1) In the presence or absence of a radical initiator, the modified compound is melt kneaded and reacted at a temperature in the range of the softening point temperature of the impact modifier to 250 ° C. or less. A method, (2) a method of reacting an impact modifier and a modifying compound in a solution at a temperature below the softening point of the impact modifier in the presence or absence of a radical initiator, and (3) in the presence of a radical initiator. In the absence, a method of reacting the impact modifier and the modifying compound without melting at a temperature below the softening point of the impact modifier may be used, and any of these methods may be used. Further, among (1), the method carried out in the presence of a radical initiator is most preferable.
[0045]
At least one modification having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure referred to herein. The compound is the same as the modified compound described in the modified polyphenylene ether.
Moreover, you may use what mixed beforehand the oil which has a paraffin as a main component in the (C) impact improving material of this invention. By premixing oil mainly composed of paraffin, the surface impact strength after annealing can be further improved, which is very useful.
[0046]
At this time, the preferred amount of oil mainly composed of paraffin is 70 parts by weight or less with respect to 100 parts by weight of the impact modifier. When 70 parts by weight or more is mixed, the handleability is poor.
The oil mainly composed of paraffin here is a mixture of a hydrocarbon compound having a weight average molecular weight of 500 to 10,000, which is a combination of an aromatic ring-containing compound, a naphthene ring-containing compound, and a paraffinic compound. Yes, the paraffinic compound content is 50% by weight or more.
[0047]
More preferably, the paraffinic compound is 50 to 90% by weight, the naphthene ring-containing compound is 10 to 40% by weight, and the aromatic ring-containing compound is 5% by weight or less.
These oils mainly composed of paraffin are commercially available, and examples thereof include PW380 manufactured by Idemitsu Kosan Co., Ltd.
As the method for mixing the oil into the impact modifier (C) of the present invention, a method of adding a desired amount of paraffinic oil uniformly to a pellet or powder impact modifier and leaving it alone, Examples include, but are not limited to, a method of adding a desired amount of paraffinic oil from the middle and melt-kneading.
Moreover, you may use the metal salt as shown to Formula (2) in this invention.
[0048]
[Chemical formula 2]

[0049]
In the formula, M represents one or more metal ions selected from copper, nickel, tin, cerium and alkali metals, and X represents a halide such as Cl, Br, F, I or a carboxylate such as stearate and acetate. -Represents a negatively charged ion, n is an integer from 1 to 6, y is an integer representing the positive ion charge of M, and z is an integer representing the negative ion charge of X.
Copper and / or alkali metal is preferable as the metal ion M in the formula (2), and alkali metal is most preferable. X is most preferably a halide ion, and iodine and / or bromine are particularly preferable, and iodine is most preferable.
[0050]
Specific examples of metal salts that can be used in the present invention include copper iodide, copper chloride, copper acetate, potassium iodide, cerium stearate, and the like. Among these, copper iodide, potassium iodide, odor Copper iodide, potassium bromide and sodium iodide are more preferred, and potassium iodide and sodium iodide are most preferred. These may be used in combination.
A preferable blending amount of the metal salt is less than 2 parts by weight with respect to 100 parts by weight of the total amount of polyamide, polyphenylene ether, impact modifier and conductive carbon filler. Preferably it is 0.001-1 weight part, More preferably, it is 0.001-0.5 weight part.
[0051]
The method for adding this metal salt includes (1) a method of adding at the time of polymerization of the polyamide to be used, (2) a method of adding in the form of a masterbatch previously blended with the polyamide at a high concentration, and (3) directly at the time of producing the composition. Any method may be used, but the method (1) or (2) is preferable. Of course, a combination of these methods is also possible.
[0052]
The resin composition of the present invention has a dispersion form in which (B) polyphenylene ether particles containing (C) an impact modifier are dispersed in a continuous phase of (A) polyamide, and (B) polyphenylene. It is necessary to show a fine dispersion state in which more than half of all the dispersed particles of ether are dispersed with a dispersion diameter of 1.0 μm or less. A more preferable dispersion form is a state in which more than half of all dispersed particles of (B) polyphenylene ether are dispersed with a dispersion diameter of 0.7 μm or less, and most preferably, half of all dispersed particles of (B) polyphenylene ether. The above is the state of dispersion with a dispersion diameter of 0.6 μm or less.
(B) Confirmation of a fine dispersion state in which more than half of all dispersed particles of polyphenylene ether are dispersed with a dispersion diameter of 1.0 μm or less can be easily confirmed by observation with a transmission electron microscope as follows. Can be confirmed.
[0053]
(1) A phosphotungstic acid [12 Tungsto (VI) phosphoric acid n hydrate: H, cut out from the center of the pellet-like sample so that the flow direction can be observed, and then heated to 80 ° C._Three(PW₁₂O₄₀NH₂O] Immerse in a 10 wt% aqueous solution to selectively dye the polyamide part. (2) The dyed molded piece block is cut into an ultrathin section using an ultramicrotome. (Cutting conditions: cutting temperature: 0 ° C. or lower, preferably −30 ° C. or lower, cutting thickness: 60 to 80 nm), (3) The obtained ultrathin slice is photographed with a transmission electron microscope.
[0054]
Based on the obtained electron micrograph, the dispersion diameter of each part other than polyamide, that is, individual particles of polyphenylene ether is measured for at least 2000 particles. In this case, when the particle diameter cannot be regarded as spherical, the short diameter and long diameter are measured, and ½ of the sum of the two is taken as the particle diameter.
In the present invention, the ratio of the number of particles having a dispersion diameter of 1.0 μm or less to the total number of particles measured needs to be 0.5 or more. More preferably, the ratio of the number of particles having a dispersion diameter of 0.7 μm or less is 0.5 or more, and more preferably, the ratio of the number of particles having a dispersion diameter of 0.6 μm or less is 0.5 or more. It is a thing.
[0055]
In addition, the use of a compatibilizing agent in the present invention is effective for obtaining a resin composition exhibiting a fine dispersed particle size.
The compatibilizer that can be used in the present invention is a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both, and is a known compatibilizer that is effective for compatibilization of polyamide and polyphenylene ether. Any agent can be used without any problem. Specifically, the compatibilizers described in JP-B-59-33614, JP-A-8-48869 and the like can be mentioned.
[0056]
Among the compatibilizers described in these, preferred compatibilizers include maleic acid, maleic anhydride, and citric acid, and the most preferred compatibilizer is maleic anhydride.
The preferred amount of these compatibilizers is 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the mixture of polyamide and polyphenylene ether.
The amount ratio of each component in the present invention is as follows: (A) 50 to 95 parts by weight of polyamide, (B) 5 to 50 parts by weight of polyphenylene ether, and 100 parts by weight of (C) impact modifier 1 to 30 parts by weight. Is the ratio.
[0057]
In the present invention, in addition to the above-described components, additional components may be added as necessary within a range that does not impair the effects of this component.
Additional components that can be used in the present invention include other thermoplastic resins such as polyester and polyolefin, inorganic fillers (talc, kaolin, zonotlite, wollastonite, titanium oxide, potassium titanate, carbon fiber, glass Fibers, carbon black for coloring, carbon black for electrical conduction, nanotube carbon, carbon fiber, graphite, etc.), known silane coupling agents and flame retardants (halogenated) to increase the affinity between inorganic fillers and resins Resin, silicone flame retardant, magnesium hydroxide, aluminum hydroxide, organic phosphate ester compound, ammonium polyphosphate, red phosphorus, etc., fluorine polymer showing anti-drip effect, plasticizer (oil, low molecular weight) Polyolefin, polyethylene glycol, fatty acid esters, etc.) and antimony trioxide Flame retardant aid and the like, various peroxides, zinc oxide, zinc sulfide, antioxidants, ultraviolet absorbers and light stabilizers.
[0058]
These components may be added in a range not exceeding 50 parts by weight in total with respect to 100 parts by weight of the total amount of the components (A) to (C).
In addition, components that are preferably present in the polyamide phase (for example, additives such as nucleating agents for PA, slip agents, various dyes, pigments such as titanium oxide, carbon black for coloring, and release agents) ) May be present in the polyamide phase within a range not exceeding 10 parts by weight per 100 parts by weight of the total amount of components (A) to (C). Of course, two or more of these additional components can be used in combination.
[0059]
Specific processing machines for obtaining the composition of the present invention include, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. A twin-screw extruder provided with an upstream supply port and one or more downstream supply ports is most preferable.
The melt kneading temperature at this time is not particularly limited, but the conditions under which a suitable composition can be usually obtained can be arbitrarily selected from 240 to 360 ° C.
[0060]
The composition of the present invention thus obtained can be molded as various parts by various conventionally known methods such as injection molding, extrusion molding and hollow molding. The composition of the present invention is used for, for example, exterior parts of motorcycles such as cowls, interior parts of automobiles, fenders, door panels, front panels, rear panels, rocker panels, rear bumper panels, back door garnishes, emblem garnishes, fuel injections. Inlet panels, over fenders, outer door handles, door mirror housings, bonnet air intakes, bumpers, bumper guards, roof rails, roof rail legs, pillar covers, wheel covers, various aero parts, etc. It may be suitably used for IC tray material applications in the electronic field.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
[0061]
DETAILED DESCRIPTION OF THE INVENTION
(Measurement of terminal OH group concentration [OH] of polyphenylene ether)
In a 25 ml graduated cylinder, 10-20 mg of polyphenylene ether was precisely weighed, dissolved in methylene chloride, and then made up to 25 ml. Next, the absorbance at a wavelength of 318 nm of this solution was set to zero using an ultraviolet absorption spectrum measuring apparatus (cell length: 1 cm, using a cell with a sealed plug).
Thereafter, 0.2 μl of a 10 wt% methanol solution of tetraethylammonium hydroxide was added to the cell, shaken rapidly, and then the absorbance at 318 nm was measured again with an ultraviolet absorption spectrum measuring apparatus.
Using the absorbance at this time, the terminal OH group concentration [OH] (milli equivalent / kg) of polyphenylene ether was calculated from the following formula (based on Lambert-Beer formula).
[OH] = [(25 × Abs) / (4700 × W)] × 10⁶
(In the above formula, Abs is the measured absorbance, W is the weight of the weighed polyphenylene ether, and 4700 is the extinction coefficient.)
[0062]
[Production Example 1]
Production of polyphenylene ether-1
Into a 25-liter reaction tank having an oxygen blowing port at the bottom and a temperature control jacket, 8.22 kg of toluene and 440 g of 2,6-dimethylphenol are added, and further 5.6 g of copper oxide and 47 wt% aqueous solution of hydrogen bromide. 21.6 g, butyldimethylamine 145 g, dibutylamine 44 g and di-teat-butylethylenediamine 13.5 g were added, and the temperature was controlled at 40 ° C. and oxygen was blown in at an amount of 6 l / min while stirring to initiate polymerization.
[0063]
Further, nitrogen was blown into the gas phase portion of the reaction tank at an amount of 8 l / min. Immediately after the start of oxygen blowing, 2,6-dimethylphenol 35 wt% toluene solution was continuously added to the reaction vessel at an addition rate of 280 g / min for 40 minutes. After completion of the addition, the temperature adjustment jacket temperature was raised to 50 ° C., and the polymerization was further continued. Two hours after the start of the polymerization, the oxygen was closed, and the polymerization was terminated by adding 400 g of a 10 wt% aqueous solution of ethylenediaminetetraacetic acid / tripotassium salt as a catalyst deactivator. The viscous polymerization solution was taken out, dropped into methanol, re-precipitated and separated by filtration.
The solid was further washed with methanol, filtered, and vacuum dried at 140 ° C. for 2 hours to obtain white powdery PPE. Hereinafter, this is referred to as PPE-1. The reduced viscosity of this powdery chloroform solution (0.5 g / dl) as measured at 30 ° C. was 0.53. The terminal OH group concentration was measured and found to be 33 meq / kg.
[0064]
[Production Example 2]
Production of polyphenylene ether-2
A white powdery PPE was obtained in the same manner as in Production Example 1 except that the jacket temperature for temperature adjustment after addition of the 35-wt% 2,6-dimethylphenol toluene solution was changed to 60 ° C. Hereinafter, this is referred to as PPE-2. The reduced viscosity of this powdery chloroform solution (0.5 g / dl) as measured at 30 ° C. was 0.42. Further, the terminal OH group concentration was measured and found to be 48 meq / kg.
[0065]
[Production Example 3]
Production of polyphenylene ether-3
Except for setting the polymerization time to 2 hours and 30 minutes, all the same processes as in Production Example 1 were performed until the polymerization was stopped. In order to adjust the terminal OH group of the polyphenylene ether, the temperature of the temperature control jacket was raised to 70 ° C. after the polymerization was stopped, and stirring was continued for 1 hour 30 minutes. The solution after high-temperature stirring was taken out, dropped into methanol, re-precipitated and separated by filtration.
The solid was further washed with methanol, filtered, and vacuum dried at 140 ° C. for 2 hours to obtain white powdery PPE. Hereinafter, this is referred to as PPE-3. The reduced viscosity of this powdery chloroform solution (0.5 g / dl) as measured at 30 ° C. was 0.47. The terminal OH group concentration was measured and found to be 75 meq / kg. Further, the polyphenylene ether immediately after polymerization was also sampled separately and the reduced viscosity was measured and found to be 0.68.
[0066]
[Production Example 4]
Production of polyphenylene ether-4
All processes until the termination of polymerization were carried out in the same manner as in Production Example 2. In order to adjust the terminal OH group of polyphenylene ether, the temperature of the temperature control jacket was raised to 60 ° C. after the polymerization was stopped, and stirring was continued for 2 hours. The solution after high-temperature stirring was taken out, dropped into methanol, re-precipitated and separated by filtration.
The solid was further washed with methanol, filtered, and vacuum dried at 140 ° C. for 2 hours to obtain white powdery PPE. Hereinafter, this is referred to as PPE-4. The reduced viscosity of this powdery chloroform solution (0.5 g / dl) as measured at 30 ° C. was 0.36. Further, the terminal OH group concentration was measured and found to be 108 meq / kg. Further, the polyphenylene ether immediately after polymerization was also sampled separately and the reduced viscosity was measured to be 0.58.
[0067]
(Raw materials used)
(1) Polyphenylene ether (PPE)
PPE-1 Reduced viscosity = 0.53, [OH] = 33 meq / kg
PPE-2 Reduced viscosity = 0.42, [OH] = 48 meq / kg
PPE-3 Reduced viscosity = 0.47, [OH] = 75 meq / kg
PPE-4 Reduced viscosity = 0.36, [OH] = 108 meq / kg
[0068]
(2) Polyamide (PA)

[0069]
(3) Impact modifier

(4) Compatibilizer (abbreviated as MAH)
MAH maleic anhydride [manufactured by NOF Corporation]
[0070]
[Example 1]
The cylinder temperature of a twin screw extruder [ZSK-40: manufactured by Werner & Frederer (Germany)] having one supply port on the upstream side and one supply port in the center of the extruder is set to the upstream supply port (hereinafter simply “Top”). -F) is set to 320 ° C from the downstream supply port (hereinafter simply referred to as Side-F) to 280 ° C from Side-F to die, and from Top-F, PPE-1 and SEBS-1 And MAH were dry blended and supplied at the ratio shown in Table 1 and melt kneaded, and PA-1 was supplied from Side-F so as to have the ratio shown in Table 1, melt kneaded, and pelletized.
The screw speed at this time is 300 rpm, and vacuum suction is performed by attaching vacuum vents immediately before Side-F and between the Side-F and the die for removing volatiles. It was.
The obtained pellets were measured for the following items, and the results are shown in Table 1.
[0071]
(Electron microscope observation)
The center part of the obtained pellet was trimmed so that it could be observed in a direction perpendicular to the flow direction, and this was phosphotungstic acid [12 Tungsto (VI) phosphate n-hydrate: H_Three(PW₁₂O₄₀NH₂O] Dipped in a 10 wt% aqueous solution to selectively dye the polyamide part. Next, the dyed molded block is cut into an ultrathin section using an ultramicrotome (cutting conditions: cutting temperature: −30 ° C., cutting thickness: 70 nm), and the obtained ultrathin section is transmissive. Photographed with an electron microscope.
Based on the obtained electron micrograph, the disperse diameter of the unstained portion, that is, the individual particles of the polyphenylene ether phase was measured for 2016 particles.
The number of particles having a dispersion diameter of 1.0 μm or less was 1553 with respect to the total number of particles measured, and the ratio thereof was 0.77. In Table 1, it is described as “a ratio of a dispersion diameter of 1 μm or less”.
[0072]
(Recyclability test)
The pellets obtained by extrusion were 128 mm in width and 12.8 mm in width using an injection molding machine [IS-80EPN: manufactured by Toshiba Machine Co., Ltd. (Japan)] set at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. 400 strip-shaped molded pieces having a thickness of 3.2 mm were formed, of which 5 pieces were subjected to Izod impact strength measurement without rework. In Table 1, it is simply described as “Izod impact strength”.
Moreover, after grind | pulverizing and granulating all the remaining strip-shaped shaping | molding pieces, it pelletized using the same direction rotation biaxial extruder [PCM-30: Ikegai Iron Works Co., Ltd. product]. 300 pellets having a length of 128 mm, a width of 12.8 mm, and a thickness of 3.2 mm were molded again from this pellet, and five of them were subjected to Izod impact strength measurement for one rework. In Table 1, it is described as “Izod after one rework”.
Furthermore, all the remaining strip-shaped molded pieces were pulverized and similarly pelletized. Using this pellet, a strip-shaped molded piece having a length of 128 mm, a width of 12.8 mm, and a thickness of 3.2 mm was formed, and this molded piece was subjected to Izod impact strength measurement twice for rework. The Izod impact test was performed in accordance with ASTM D648. In Table 1, it is described as “Izod after 2 rework”.
[0073]
(Surface impact test)
Using an injection molding machine [IS-80EPN: manufactured by Toshiba Machine Co., Ltd. (Japan)], the pellets obtained by extrusion were set to a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C., and a width of 90 mm. It was molded into a flat plate-shaped piece having a thickness of 50 mm and a thickness of 2.5 mm, and the surface impact strength was measured using a graphic impact tester [manufactured by Toyo Seiki Seisakusho Co., Ltd.]
The surface impact strength after annealing differs only in that the flat plate-shaped molded piece was placed in a gear oven and heated in air at 190 ° C. for 5 hours before the surface impact test.
The test method is as follows. A test piece is put in a sample holder with a diameter of 40 mm, and a spherical striker (weight 6.5 kg) with a tip diameter of 13 mm is dropped freely from a height of 100 cm above the test piece to break the test piece. The total energy required for destruction was measured and displayed as the total absorbed energy.
[0074]
This test was performed on 10 samples, and the total absorption energy value of the sample was determined by adding the average of 8 measured values excluding the maximum value and the minimum value from the 10 data.
In addition, the fracture condition of the test piece destroyed by this measurement is observed, and it is roughly divided into ductile fracture and brittle fracture, and the ductility ratio is calculated from the ratio of the number of the test pieces that have undergone ductile fracture among the ten test specimens. did.
Ductile ratio [%] = number of ductile fractures / 10 × 100
In Table 1, the results before annealing are described as “surface impact strength before annealing” and “ductility ratio”, and the results after annealing are described as “surface impact strength after annealing” and “ductility ratio”.
[0075]
Examples 2 to 5 and Comparative Examples 1 and 2
Except that the composition was changed to the ratio shown in Table 1, all the same procedures as in Example 1 were performed, and the ratio of particles having a dispersion diameter of 1.0 μm or less, recyclability, surface impact strength, and surface impact after annealing were changed with an electron microscope. The strength was measured.
The measurement results are shown in the lower part of the composition of each Example and Comparative Example in Table 1.
[0076]
[Table 1]

[0077]
【The invention's effect】
In the composition of the present invention, polyphenylene ether is dispersed in a specific dispersion state in a continuous phase of polyamide, and the end group concentrations of polyphenylene ether and polyamide and the ratio of the end group concentrations thereof are limited to a specific range. Thus, it can be seen that a resin composition excellent in surface impact property and recyclability after annealing can be obtained.

Claims (8)

In the continuous phase of component (A), (A) 50 to 95 parts by weight of polyamide and (B) 1 to 30 parts by weight of impact modifier are added to 100 parts by weight of polyphenylene ether in a total of 100 parts by weight. , (B) component particles encapsulating component (B) are dispersed, and more than half of the dispersed particles of component (B) are dispersed with a dispersion diameter of 1.0 μm or less, and (A ) Component and (B) component end group concentration and the concentration ratio of both are in the range satisfying the following formula , wherein (C) component impact modifier Is a block copolymer composed of a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound, and one or more resin compositions selected from hydrogenated products thereof .
_[NH 2] = 20~80 meq / kg
[OH] = 20-80 milliequivalent / kg
_{[NH 2] / [OH]} = 0.3~2.0
[In the above formula, [OH] is the terminal OH group concentration of (B) polyphenylene ether (unit: milliequivalent / kg), and [NH ₂ ] is the terminal amino group concentration of (A) polyamide (unit: milliequivalent / kg). kg). ] 2. The resin composition according to claim 1, wherein the ratio of the terminal OH group concentration [OH] of (B) polyphenylene ether and the terminal carboxyl group concentration [COOH] of (A) polyamide is in the range of 0.2 to 1.3. (A) terminal amino group concentration [NH _2] is the resin composition according to any one of claims 1 or 2 in the range of 25 to 60 milliequivalents / kg of polyamide. The resin composition according to any one of claims 1 to 3, wherein at least half of the dispersed particles of the components (B) and (C) are dispersed with a dispersion diameter of 0.7 µm or less. The impact modifier of component (C) is a block copolymer composed of a polymer block (a) mainly composed of an aromatic vinyl compound and a polymer block (b) mainly composed of a conjugated diene compound, The block copolymer of each block of the block copolymer is one or more selected from a block copolymer selected from aba type and abab type, and a hydrogenated product thereof. 5. The resin composition according to any one of 4 above. The abbab block in which the impact-improving material of the component (C) block copolymer is composed of a polymer block (a) mainly composed of an aromatic vinyl compound and a polymer block (b) mainly composed of a conjugated diene compound. The resin composition according to any one of claims 1 to 5, which is a copolymer and / or a hydrogenated product thereof. The impact modifier of component (C) is an impact modifier that is premixed with oil mainly composed of paraffin, and the amount of oil mainly composed of paraffin is 70 weights with respect to 100 parts by weight of the impact modifier. The resin composition according to any one of claims 1 to 6, which is an amount of at most parts. The resin composition according to any one of claims 1 to 7, wherein the polyamide (A) has a number average molecular weight of 14,000 or less.