JP4069629B2 - Polyphenylene sulfide resin composition and method for producing the same - Google Patents

Description

【００１５】
耐熱性の点から、上記構造式で示される繰返し単位を７０モル％以上、特に９０モル％以上を含む重合体であることが好ましい。またＰＰＳ樹脂はその繰り返し単位の３０モル％以下を、下記の構造式を有する繰り返し単位等で構成することが可能である。
【００１６】
【化２】

【００１７】
本発明で用いられるＰＰＳ樹脂は、通常公知の方法即ち特公昭４５−３３６８号公報に記載される比較的分子量の小さな重合体を得る方法或は特公昭５２−１２２４０号公報や特開昭６１−７３３２号公報に記載される比較的分子量の大きな重合体を得る方法などによって製造できる。本発明において上記の様に得られたＰＰＳ樹脂を空気中加熱による架橋／高分子量化、窒素などの不活性ガス雰囲気下あるいは減圧下での熱処理、有機溶媒、熱水、酸水溶液などによる洗浄、酸無水物、アミン、イソシアネート、官能基含有ジスルフィド化合物などの官能基含有化合物による活性化など種々の処理を施した上で使用することも可能であり、さらに、これらの処理を２種類以上行うことももちろん可能である。また、これらの処理を行ったＰＰＳ樹脂を、２種類以上の混合で使用することももちろん可能であり、２種類以上の混合で使用する場合の具体的方法として、空気中加熱により架橋したＰＰＳ樹脂と熱処理を行っていないＰＰＳ樹脂の混合、酸水溶液による洗浄を行ったＰＰＳ樹脂と有機溶媒による洗浄を行ったＰＰＳ樹脂の混合、有機溶媒で洗浄したＰＰＳ樹脂と有機溶媒で洗浄を行っていないＰＰＳ樹脂の混合などが例示できる。
【００１８】
本発明で用いられるＰＰＳ樹脂の溶融粘度は、溶融混練が可能であれば特に制限はなく、通常５〜１，０００Pa・s（３２０℃、剪断速度１０００ｓｅｃ^-1）のものが使用されるが、中でも１０〜５００Pa・sのものが好ましい。またより優れたバリ低減効果を得るために、異なる溶融粘度のＰＰＳ樹脂を２種類以上併用して用いることは有効であり、例えば、３０Pa・s以上の溶融粘度を有するＰＰＳ樹脂と、３０Pa・s未満の溶融粘度を有するＰＰＳ樹脂を混合して用いる方法が好適な方法として挙げられる。
【００１９】
ＰＰＳ樹脂の加熱による架橋／高分子量化する場合の具体的方法としては、空気、酸素などの酸化性ガス雰囲気下あるいは前記酸化性ガスと窒素、アルゴンなどの不活性ガスとの混合ガス雰囲気下で、所定の温度において希望する溶融粘度が得られるまで加熱を行う方法が例示できる。加熱処理温度は通常、１７０〜２８０℃が選択され、好ましくは２００〜２７０℃であり、時間は通常０．５〜１００時間が選択され、好ましくは２〜５０時間であるが、この加熱処理温度と時間を適宜コントロールすることにより目標とする粘度レベルを得ることができる。加熱処理の装置は減圧仕様、またはシール性の高い仕様の通常の熱風乾燥機でもまた回転式あるいは撹拌翼付の加熱装置であってもよいが、効率よくしかもより均一に処理する場合は回転式あるいは撹拌翼付の加熱装置を用いるのがより好ましい。
【００２０】
ＰＰＳ樹脂を窒素などの不活性ガス雰囲気下あるいは減圧下で熱処理する場合の具体的方法としては、窒素などの不活性ガス雰囲気下あるいは減圧下で、加熱処理温度１５０〜２８０℃、好ましくは２００〜２７０℃、加熱時間は０．５〜１００時間、好ましくは２〜５０時間加熱処理する方法が例示できる。加熱処理の装置は静置型の加熱装置でもまた回転式あるいは撹拌翼付の加熱装置であってもよいが、効率よくしかもより均一に処理する場合は回転式あるいは撹拌翼付の加熱装置を用いるのがより好ましい。
【００２１】
ＰＰＳ樹脂を有機溶媒で洗浄する場合の具体的方法としては以下の方法が例示できる。すなわち、洗浄に用いる有機溶媒としては、ＰＰＳ樹脂を分解する作用などを有しないものであれば特に制限はないが、例えばＮ−メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミドなどの含窒素極性溶媒、ジメチルスルホキシド、ジメチルスルホンなどのスルホキシド・スルホン系溶媒、アセトン、メチルエチルケトン、ジエチルケトン、アセトフェノンなどのケトン系溶媒、ジメチルエーテル、ジプロピルエーテル、テトラヒドロフランなどのエーテル系溶媒、クロロホルム、塩化メチレン、トリクロロエチレン、２塩化エチレン、ジクロルエタン、テトラクロルエタン、クロルベンゼンなどのハロゲン系溶媒、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、エチレングリコール、プロピレングリコール、フェノール、クレゾール、ポリエチレングリコールなどのアルコール・フェノール系溶媒、ベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶媒などがあげられる。これらの有機溶媒のなかでＮ−メチルピロリドン、アセトン、ジメチルホルムアミド、クロロホルムなどの使用が好ましい。また、これらの有機溶媒は、１種類または２種類以上の混合で使用することもできる。有機溶媒による洗浄の方法としては、有機溶媒中にＰＰＳ樹脂を浸漬せしめるなどの方法があり、必要により適宜撹拌または加熱することも可能である。有機溶媒でＰＰＳ樹脂を洗浄する際の洗浄温度については特に制限はなく、常温〜３００℃程度の任意の温度が選択できる。洗浄温度が高くなるほど洗浄効率が高くなる傾向があるが、通常は常温〜１５０℃の洗浄温度で十分効果が得られる。
【００２２】
また有機溶媒洗浄を施されたＰＰＳ樹脂は残留している有機溶媒を除去するため、水または温水で数回洗浄することが好ましい。
【００２３】
ＰＰＳ樹脂を熱水で処理する場合の具体的方法としては以下の方法が例示できる。すなわち熱水洗浄によるＰＰＳ樹脂の好ましい化学的変性の効果を発現するため、使用する水は蒸留水あるいは脱イオン水であることが好ましい。熱水処理の操作は、通常、所定量の水に所定量のＰＰＳ樹脂を投入し、常圧で或いは圧力容器内で加熱、撹拌することにより行われる。ＰＰＳ樹脂と水との割合は、水の多いほうが好ましいが、通常、水１リットルに対し、ＰＰＳ樹脂２００ｇ以下の浴比が選択される。
【００２４】
ＰＰＳ樹脂を酸処理する場合の具体的方法としては以下の方法が例示できる。
【００２５】
すなわち、酸または酸の水溶液にＰＰＳ樹脂を浸漬せしめるなどの方法があり、必要により適宜撹拌または加熱することも可能である。用いられる酸はＰＰＳ樹脂を分解する作用を有しないものであれば特に制限はなく、ギ酸、酢酸、プロピオン酸、酪酸などの脂肪族飽和モノカルボン酸、クロロ酢酸、ジクロロ酢酸などのハロ置換脂肪族飽和カルボン酸、アクリル酸、クロトン酸などの脂肪族不飽和モノカルボン酸、安息香酸、サリチル酸などの芳香族カルボン酸、シュウ酸、マロン酸、コハク酸、フタル酸、フマル酸などのジカルボン酸、硫酸、リン酸、塩酸、炭酸、珪酸などの無機酸性化合物などがあげられる。中でも酢酸、塩酸がより好ましく用いられる。酸処理を施されたＰＰＳ樹脂は残留している酸または塩などを除去するため、水または温水で数回洗浄することが好ましい。また洗浄に用いる水は、酸処理によるＰＰＳ樹脂の好ましい化学的変性の効果を損なわない意味で蒸留水、脱イオン水であることが好ましい。
【００２６】
本発明のＰＰＳ樹脂組成物は、ＰＰＳ樹脂とその他の樹脂とのポリマーアロイであり、ＰＰＳ樹脂以外の樹脂としては、後述のスピノーダル分解可能な樹脂を使用する。具体的には、ポリエステル、ポリアミド、ポリフェニレンオキシド、ポリスルホン、ポリエーテルイミド、ポリアミドイミド、ポリイミド、ポリカーボネート、ポリエーテルスルホン、ポリエーテルケトン、ポリチオエーテルケトン、ポリエーテルエーテルケトンを挙げることができる。
【００２７】
本発明でのＰＰＳ樹脂組成物を構成する樹脂成分の組成については特に制限がないが、ＰＰＳ樹脂組成物を構成する樹脂成分の合計１００重量％に対して、通常ＰＰＳ樹脂が５０〜９７重量％の範囲が好ましく用いられ、さらには５０〜９５重量％の範囲がより好ましく、特に５０〜７５重量％の範囲であれば両相連続構造が比較的得られやすいので好ましく用いられる。
【００２８】
本発明のＰＰＳ樹脂組成物は、構造周期０．０１〜１μｍの両相連続構造、または粒子間距離０．０１〜１μｍの分散構造を有することが必要である。かかる構造物を得るためには、ＰＰＳ樹脂と、ＰＰＳ樹脂以外の樹脂とが、一旦相溶解し、後述のスピノーダル分解によって構造形成せしめることが好ましい。さらにこの構造形成の実現のためには、ＰＰＳ樹脂と、ＰＰＳ樹脂以外の樹脂とが、後述の部分相溶系や、剪断場依存型相溶解・相分解する系や、反応誘発型相分解する系であることが好ましい。
【００２９】
一般に、２成分の樹脂からなるポリマーアロイには、これらの組成に対して、ガラス転移温度以上、熱分解温度以下の実用的な全領域において相溶する相溶系や、逆に全領域で非相溶となる非相溶系や、ある領域で相溶し、別の領域で相分離状態となる、部分相溶系があり、さらにこの部分相溶系では、その相分離状態の条件によってスピノーダル分解によって相分離する場合と、核生成と成長によって相分離する場合がある。
【００３０】
さらに３成分以上からなるポリマーアロイの場合は、３成分以上のいずれもが相溶する系、３成分以上のいずれもが非相溶である系、２成分以上のある相溶した相と、残りの１成分以上の相が非相溶な系、２成分が部分相溶系で、残りの成分がこの２成分からなる部分相溶系に分配される系などがある。本発明で好ましい３成分以上からなるポリマーアロイは、２成分が部分相溶系で、残りの成分がこの２成分からなる部分相溶系に分配される系であり、この場合ポリマーアロイの構造は、２成分からなる部分相溶系の構造で代替できることから、以下２成分の樹脂からなるポリマーアロイで代表して説明する。
【００３１】
スピノーダル分解による相分離とは、異なる２成分の樹脂組成および温度に対する相図においてスピノーダル曲線の内側の不安定状態で生じる相分離のことを指し、また核生成と成長による相分離とは、該相図においてバイノーダル曲線の内側であり、かつスピノーダル曲線の外側の準安定状態で生じる相分離のことを指す。
【００３２】
かかるスピノーダル曲線とは、組成および温度に対して、異なる２成分の樹脂を混合した場合、相溶した場合の自由エネルギーと相溶しない２相における自由エネルギーの合計との差（ΔＧｍｉｘ）を濃度（φ）で二回偏微分したもの（∂²ΔＧmix／∂φ²）が０となる曲線のことであり、またスピノーダル曲線の内側では、∂²ΔＧmix／∂φ²＜０の不安定状態であり、外側では∂²ΔＧmix／∂φ²＞０である。
【００３３】
またかかるバイノーダル曲線とは、組成および温度に対して、系が相溶する領域と相分離する領域の境界の曲線のことである。
【００３４】
ここで本発明における相溶する場合とは、分子レベルで均一に混合している状態のことであり、具体的には異なる２成分の樹脂を主成分とする相がいずれも０．００１μｍ以上の相構造を形成していない場合を指し、また、非相溶の場合とは、相溶状態でない場合のことであり、すなわち異なる２成分の樹脂を主成分とする相が互いに０．００１μｍ以上の相構造を形成している状態のことを指す。相溶するか否かは、例えばPolymer Alloys and Blends, Leszek A Utracki, hanser Publishers,Munich Viema New York,P64,に記載の様に、電子顕微鏡、示差走査熱量計（ＤＳＣ）、その他種々の方法によって判断することができる。
【００３５】
詳細な理論によると、スピノーダル分解では、一旦相溶領域の温度で均一に相溶した混合系の温度を、不安定領域の温度まで急速にした場合、系は共存組成に向けて急速に相分離を開始する。その際濃度は一定の波長に単色化され、構造周期（Λｍ）で両分離相が共に連続して規則正しく絡み合った両相連続構造を形成する。この両相連続構造形成後、その構造周期を一定に保ったまま、両相の濃度差のみが増大する過程をスピノーダル分解の初期過程と呼ぶ。
【００３６】
さらに上述のスピノーダル分解の初期過程における構造周期（Λｍ）は熱力学的に下式のような関係がある。

（ここでＴｓはスピノーダル曲線上の温度）
ここで本発明でいうところの両相連続構造とは、混合する樹脂の両成分がそれぞれ連続相を形成し、互いに三次元的に絡み合った構造を指す。この両相連続構造の模式図は、例えば「ポリマーアロイ 基礎と応用（第２版）（第１０．１章）」（高分子学会編：東京化学同人）に記載されている。
【００３７】
スピノーダル分解では、この様な初期過程を経た後、波長の増大と濃度差の増大が同時に生じる中期過程、濃度差が共存組成に達した後、波長の増大が自己相似的に生じる後期過程を経て、最終的には巨視的な２相に分離するまで進行するが、本発明で規定する構造を得るには、この最終的に巨視的な２相に分離する前の所望の構造周期に到達した段階で構造を固定すればよい。
【００３８】
また中期過程から後期過程にかける波長の増大過程において、組成や界面張力の影響によっては、片方の相の連続性が途切れ、上述の両相連続構造から分散構造に変化する場合もある。この場合には所望の粒子間距離に到達した段階で構造を固定すればよい。
【００３９】
ここで本発明にいうところの分散構造とは、片方の樹脂成分が主成分であるマトリックスの中に、もう片方の樹脂成分が主成分である粒子が点在している、いわゆる海島構造のことをさす。
【００４０】
本発明のＰＰＳ樹脂組成物は、構造周期０．０１〜１μｍの範囲の両相連続構造、または粒子間距離０．０１〜１μｍの範囲の分散構造に構造制御されていることが必要であるが、スピノーダル分解の初期過程の構造周期を０．００１〜０．１μｍの範囲に制御することで、上述の中期過程以降で波長および濃度差が増大しても、構造周期０．０１〜１μｍの範囲の両相連続構造、または粒子間距離０．０１〜１μｍの範囲の分散構造に構造制御することができる。より優れた機械特性を得るためには、構造発展させた後、構造周期０．０１〜０．５μｍの範囲の両相連続構造、または粒子間距離０．０１〜０．５μｍの範囲の分散構造に制御することが好ましく、さらには、構造周期０．０１〜０．３μｍの範囲の両相連続構造、または粒子間距離０．０１〜０．３μｍの範囲の分散構造に制御することがより好ましい。かかる構造周期の範囲、および粒子間距離の範囲に制御することにより本発明効果が得られるが、さらに濃度差を十分発達せしめることで、より優れた機械特性や低バリ性を有する構造物を効果的に得ることができる。
【００４１】
一方、上述の準安定領域での相分離である核生成と成長では、その初期から海島構造である分散構造が形成されてしまい、それが成長するため、本発明の様な規則正しく並んだ構造周期０．０１〜１μｍの範囲の両相連続構造、または粒子間距離０．０１〜１μｍの範囲の分散構造を形成させることは困難である。
【００４２】
またこれらのスピノーダル分解による両相連続構造、もしくは分散構造を確認するためには、規則的な周期構造が確認されることが重要である。これは例えば、光学顕微鏡観察や透過型電子顕微鏡観察により、両相連続構造が形成されることの確認に加えて、光散乱装置や小角Ｘ線散乱装置を用いて行う散乱測定において、散乱極大が現れることの確認が必要である。なお、光散乱装置、小角Ｘ線散乱装置は最適測定領域が異なるため、構造周期の大きさに応じて適宜選択して用いられる。この散乱測定における散乱極大の存在は、ある周期を持った規則正しい相分離構造を持つ証明であり、その周期Λm は、両相連続構造の場合構造周期に対応し、分散構造の場合粒子間距離に対応する。またその値は、散乱光の散乱体内での波長λ、散乱極大を与える散乱角θm を用いて次式により計算することができる。
Λm ＝（λ／２）／ｓｉｎ（θm ／２）
上記スピノーダル分解を実現させるためには、ＰＰＳ樹脂とその他の樹脂を相溶状態とした後、スピノーダル曲線の内側の不安定状態とすることが必要である。
【００４３】
まずこの２成分以上からなる樹脂で相溶状態を実現する方法としては、共通溶媒に溶解後、この溶液から噴霧乾燥、凍結乾燥、非溶媒物質中の凝固、溶媒蒸発によるフィルム生成等の方法により得られる溶媒キャスト法や、部分相溶系を、相溶条件下で溶融混練による溶融混練法が挙げられる。中でも溶媒を用いないドライプロセスである溶融混練による相溶化が、実用上好ましく用いられる。
【００４４】
溶融混練により相溶化させるには、通常の押出機が用いられるが、２軸押出機を用いることが好ましい。また、樹脂の組合わせによっては射出成形機の可塑化工程で相溶化できる場合もある。相溶化のための温度は、部分相溶系の樹脂が相溶する条件である必要がある。
【００４５】
次に上記溶融混練により相溶状態とした樹脂組成物をスピノーダル曲線の内側の不安定状態として、スピノーダル分解せしめるに際し、不安定状態とするための温度、その他の条件は、樹脂の組み合わせによっても異なり一概にはいえないが、相図に基づき、簡単な予備実験をすることにより設定することができる。本発明においては前記の如く、初期過程の構造周期を特定の範囲に制御した後、中期過程以降でさらに構造発展させて本発明で規定する特定の両相連続構造もしくは、分散構造とすることが好ましい。
【００４６】
この初期過程で特定の構造周期に制御する方法に関しては、特に制限はないが、ＰＰＳ樹脂組成物を構成する個々の樹脂成分のガラス転移温度のうち最も低い温度以上で、かつ上述の熱力学的に規定される構造周期を小さくするような温度で熱処理することが好ましく用いられる。ここでガラス転移温度とは、示差走査熱量計（ＤＳＣ）にて、室温から２０℃／分の昇温速度で昇温時に生じる変曲点から求めることができる。
【００４７】
またこの初期過程から構造発展させる方法に関しては、特に制限はないが、ＰＰＳ樹脂組成物を構成する個々の樹脂成分のガラス転移温度のうち最も低い温度以上で熱処理する方法が通常好ましく用いられる。また該熱処理温度を結晶性樹脂の結晶融解温度以上とすることは、熱処理による構造発展を効果的に得られるため好ましく、また該熱処理温度を結晶融解温度±２０℃以内とすることは上記構造発展の制御を容易にするために好ましく、さらには結晶融解温度±１０℃以内とすることがより好ましい。ここで樹脂成分としてＰＰＳ樹脂を含め２種以上の結晶性樹脂を用いる場合、該熱処理温度は、結晶性樹脂の結晶融解温度のうち最も高い温度を基準として、かかる結晶融解温度±２０℃以内とすることが好ましく、さらにはかかる結晶融解温度±１０℃以内とすることが好ましい。ここで結晶性樹脂の結晶融解温度とは、示差走査熱量計（ＤＳＣ）にて、室温から２０℃／分の昇温速度で昇温時に生じる融解曲線のピーク温度から求めることができる。
【００４８】
またスピノーダル分解による構造生成物を固定化する方法としては、急冷等による短時間で相分離相の一方または両方の成分の構造固定や、一方が熱硬化する成分である場合、熱硬化性成分の相が反応によって自由に運動できなくなることを利用した構造固定や、さらに一方が結晶性樹脂である場合、結晶性樹脂相を結晶化によって自由に運動できなくなることを利用した構造固定が挙げられるが、中でもＰＰＳ樹脂組成物の様に少なくとも一方が結晶性樹脂を用いた場合、結晶化による構造固定が好ましく用いられる。
【００４９】
ここで本発明でいう結晶性樹脂とは、示差走査熱量計（ＤＳＣ）にて、結晶融解温度の観測される樹脂であれば特に限定するものではないが、例えば、ナイロン６、ナイロン６６等の脂肪族ポリアミドや、ナイロン６Ｔ、ナイロン６Ｉ等の芳香族ポリアミドや、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレートやそれらの共重合体等の芳香族ポリエステルや、ポリ−ε−カプロラクタム等の脂肪族ポリエステルや、ポリエチレン、ポリプロピレン、ポリビニルアルコール、ポリ塩化ビニル等のポリオレフィン・ビニルや、ポリオキシメチレン等のポリエーテル等を挙げることができる。
【００５０】
本発明においてＰＰＳ樹脂とその他の樹脂とを上記スピノーダル分解により相分離させて本発明のＰＰＳ樹脂組成物とするには、前述したようにＰＰＳ樹脂と部分相溶系や、剪断場依存型相溶解・相分解する系や、反応誘発型相分解する系である樹脂を組み合わせることが好ましい。
【００５１】
一般に部分相溶系には、同一組成において低温側で相溶しやすくなる低温相溶型相図を有するものや、逆に高温側で相溶しやすくなる高温相溶型相図を有するものが知られている。この低温相溶型相図における相溶と非相溶の分岐温度で最も低い温度を、下限臨界共溶温度(lower critical solution temperature略してＬＣＳＴ)と呼び、高温相溶型相図における相溶と非相溶の分岐温度で最も高い温度を、上限臨界共溶温度(upper critical solution temperature略してＵＣＳＴ)と呼ぶ。
【００５２】
部分相溶系を用いて相溶状態となった２成分以上の樹脂は、低温相溶型相図の場合、ＬＣＳＴ以上の温度かつスピノーダル曲線の内側の温度にすることで、また高温相溶型相図の場合、ＵＣＳＴ以下の温度かつスピノーダル曲線の内側の温度にすることでスピノーダル分解を行わせることができる。
【００５３】
またこの部分相溶系によるスピノーダル分解の他に、非相溶系においても溶融混練によってスピノーダル分解を誘発すること、例えば溶融混練時等の剪断下で一旦相溶し、非剪断下で再度不安定状態となり相分解するいわゆる剪断場依存型相溶解・相分解によってもスピノーダル分解による相分離が可能であり、この場合においても、部分相溶系の場合と同じくスピノーダル分解様式で分解が進行し規則的な両相連続構造を有する。さらにこの剪断場依存型相溶解・相分解は、スピノーダル曲線が剪断場により変化し、不安定状態領域が拡大するため、スピノーダル曲線が変化しない部分相溶系の温度変化による方法に比べて、その同じ温度変化幅においても実質的な過冷却度（│Ｔｓ−Ｔ│）が大きくなり、その結果、上述の関係式におけるスピノーダル分解の初期過程における構造周期を小さくすることが容易となるためより好ましく用いられる。かかる溶融混練時の剪断下により相溶化させるには、通常の押出機が用いられるが、２軸押出機を用いることが好ましい。また、樹脂の組合わせによっては射出成形機の可塑化工程で相溶化できる場合もある。この場合における相溶化のための温度、初期過程を形成させるための熱処理温度、および初期過程から構造発展させる熱処理温度や、その他の条件は、樹脂の組み合わせによっても異なり一概にはいえないが、種々の剪断条件下での相図に基づき、簡単な予備実験をすることにより条件を設定することができる。また上記射出成形機の可塑化工程での相溶化を確実に実現させる方法として、予め２軸押出機で溶融混練し相溶化させ、吐出後氷水中などで急冷し相溶化状態で構造を固定させたものを用いて射出成形する方法などが好ましい例として挙げられる。
【００５４】
かかる上記剪断場依存型相溶解・相分解する樹脂の組み合わせとしては、ＰＰＳ樹脂とナイロン４，６混合系などが挙げられる。
【００５５】
さらに相溶系においても化学反応に伴う分子量変化等によって不安定状態となり相分解するいわゆる反応誘発型相分解によってもスピノーダル分解による相分離が可能である。例えばポリマーアロイを構成する樹脂成分の原料、オリゴマー或いは低分子量物など、最終的に含まれる樹脂成分の前駆体が残りの樹脂成分と相溶系であって、上記モノマー、オリゴマー或いは低分子量物を高重合度化し、アロイ化すべき樹脂とした場合に他の樹脂成分と相分離を生じるような場合、ポリマーアロイを構成する樹脂成分のうち少なくとも１成分の前駆体を、残りの樹脂成分の共存下で、化学反応せしめることによりスピノーダル分解を誘発せしめることが可能である。この場合においても、部分相溶系の場合と同じくスピノーダル分解様式で分解が進行し規則的な両相連続構造を有する。さらにこの反応誘発型相分解は、スピノーダル曲線が分子量変化により変化し、不安定状態領域が拡大するため、スピノーダル曲線が変化しない部分相溶系の温度変化による方法に比べて、その同じ温度変化幅においても実質的な過冷却度（│Ｔｓ−Ｔ│）が大きくなり、その結果上述の関係式におけるスピノーダル分解の初期過程における構造周期を小さくすることが容易となるためより好ましく用いられる。またこの場合、重合や架橋による分子量変化に伴い、ガラス転移温度や結晶性樹脂の場合結晶融解温度が変化し、さらには分子量変化による相溶解から相分解への変化は系によって各々異なるため、相溶化のための温度、初期過程を形成させるための熱処理温度、および初期過程から構造発展させる熱処理温度や、その他の条件は、一概にはいえないが、種々の分子量との組み合わせでの相図に基づき、簡単な予備実験をすることにより条件を設定することができる。
【００５６】
また上記反応誘発型相分解する樹脂の組み合わせは、化学反応前には前記前駆体と残りの樹脂成分が一旦相溶状態となり、かかる前駆体を化学反応により樹脂とすることによりスピノーダル分解が誘発されるような樹脂の組み合わせであり、またこの化学反応としては、分子量増加をもたらすものであれば特に限定はなく、重縮合や、ラジカル重合、カチオン重合、アニオン重合、イオン共重合等の付加重合や、重付加、付加縮合、開環重合等の重合反応の他に、架橋反応やカップリング反応が好ましい例として挙げることができる。通常、係る化学反応をアロイ化する残りの樹脂の存在下で行うことにより、反応誘発型相分解が生じる。かかる例としては、ＰＰＳ樹脂とポリフェニレンオキシド樹脂混合系や、ＰＰＳ樹脂と熱硬化性ポリアリルエーテルオリゴマー系などが挙げられる。かかる製造方法としては、例えば、一旦相溶解させたアロイを、再度、単軸または２軸押出機などの押出機中の溶融混練時に重合させる方法や、滞留時間の長い単軸または２軸押出機などの押出機を用いて、一回の押出中で一旦相溶解後、重合し相分解させる方法などが挙げられる。
【００５７】
また、本発明を構成するＰＰＳ樹脂組成物に、さらにポリマーアロイを構成する成分を含むブロックコポリマーやグラフトコポリマーやランダムコポリマーなどのコポリマーである第３成分を添加することは、相分解した相間における界面の自由エネルギーを低下させるため、両相連続構造における構造周期や、分散構造における分散粒子間距離の制御を容易にするため好ましく用いられる。この場合通常、かかるコポリマーなどの第３成分は、それを除く２成分の樹脂からなるポリマーアロイの各相に分配されるため、２成分の樹脂からなるポリマーアロイ同様に取り扱うことができる。
【００５８】
本発明のＰＰＳ樹脂組成物において、アルコキシシラン化合物を併用することは、優れた機械強度を得るために有効である。かかるアルコキシシラン化合物としては、例えばエポキシ基、アミノ基、イソシアネート基、水酸基、メルカプト基、ウレイド基の中から選ばれた少なくとも１種の官能基を有するアルコキシシラン化合物が挙げられる。その具体例としては、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシ基含有アルコキシシラン化合物、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシランなどのメルカプト基含有アルコキシシラン化合物、γ−ウレイドプロピルトリエトキシシラン、γ−ウレイドプロピルトリメトキシシシラン、γ−（２−ウレイドエチル）アミノプロピルトリメトキシシランなどのウレイド基含有アルコキシシラン化合物、γ−イソシアナトプロピルトリエトキシシラン、γ−イソシアナトプロピルトリメトキシシラン、γ−イソシアナトプロピルメチルジメトキシシラン、γ−イソシアナトプロピルメチルジエトキシシラン、γ−イソシアナトプロピルエチルジメトキシシラン、γ−イソシアナトプロピルエチルジエトキシシラン、γ−イソシアナトプロピルトリクロロシランなどのイソシアナト基含有アルコキシシラン化合物、γ−（２−アミノエチル）アミノプロピルメチルジメトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシランなどのアミノ基含有アルコキシシラン化合物、γ−ヒドロキシプロピルトリメトキシシラン、γ−ヒドロキシプロピルトリエトキシシランなどの水酸基含有アルコキシシラン化合物などが挙げられ、中でもγ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシ基含有アルコキシシラン化合物、γ−ウレイドプロピルトリエトキシシラン、γ−ウレイドプロピルトリメトキシシシラン、γ−（２−ウレイドエチル）アミノプロピルトリメトキシシランなどのウレイド基含有アルコキシシラン化合物、γ−イソシアナトプロピルトリエトキシシラン、γ−イソシアナトプロピルトリメトキシシラン、γ−イソシアナトプロピルメチルジメトキシシラン、γ−イソシアナトプロピルメチルジエトキシシラン、γ−イソシアナトプロピルエチルジメトキシシラン、γ−イソシアナトプロピルエチルジエトキシシラン、γ−イソシアナトプロピルトリクロロシランなどのイソシアナト基含有アルコキシシラン化合物等が好ましい。特に好ましくは、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランなどのエポキシ基含有アルコキシシラン化合物が挙げられる。
【００５９】
かかるエポキシ基、アミノ基、イソシアネート基、水酸基、メルカプト基、ウレイド基の中から選ばれた少なくとも１種の官能基を有するアルコキシシラン化合物は、より優れた機械的強度を得るために用いられ、その添加量はＰＰＳ樹脂１００重量部に対して、０．０５〜５重量部の範囲が選択され、０．２〜３重量部の範囲がより好ましく選択される。少なすぎると、アルコキシシラン化合物添加による機械的強度の向上効果が十分発現しなく、また多すぎると、上記改良効果が飽和に達するばかりでなく、組成物のガス発生量を増加させる傾向にある。
【００６０】
本発明においては、強度及び寸法安定性等を向上させるため、必要に応じて充填材を用いてもよい。充填材の形状としては繊維状であっても非繊維状であってもよく、繊維状の充填材と非繊維状充填材を組み合わせて用いてもよい。かかる充填材としては、ガラス繊維、ガラスミルドファイバー、炭素繊維、チタン酸カリウムウィスカ、酸化亜鉛ウィスカ、硼酸アルミニウムウィスカ、アラミド繊維、アルミナ繊維、炭化珪素繊維、セラミック繊維、アスベスト繊維、石コウ繊維、金属繊維などの繊維状充填剤、ワラステナイト、ゼオライト、セリサイト、カオリン、マイカ、クレー、パイロフィライト、ベントナイト、アスベスト、タルク、アルミナシリケートなどの珪酸塩、アルミナ、酸化珪素、酸化マグネシウム、酸化ジルコニウム、酸化チタン、酸化鉄などの金属化合物、炭酸カルシウム、炭酸マグネシウム、ドロマイトなどの炭酸塩、硫酸カルシウム、硫酸バリウムなどの硫酸塩、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウムなどの水酸化物、ガラスビーズ、セラミックビーズ、窒化ホウ素および炭化珪素などの非繊維状充填剤が挙げられ、これらは中空であってもよく、さらにはこれら充填剤を２種類以上併用することも可能である。また、これら繊維状および／または非繊維状充填材をイソシアネート系化合物、有機シラン系化合物、有機チタネート系化合物、有機ボラン系化合物、エポキシ化合物などのカップリング剤で予備処理して使用することは、より優れた機械的強度を得る意味において好ましい。
【００６１】
強度及び寸法安定性等を向上させるため、かかる充填材を用いる場合、その配合量は特に制限はないが、通常ＰＰＳ樹脂１００重量部に対して３０〜４００重量部配合される。
【００６２】
本発明のＰＰＳ樹脂組成物には本発明の効果を損なわない範囲において、ポリアルキレンオキサイドオリゴマ系化合物、チオエーテル系化合物、エステル系化合物、有機リン化合物などの可塑剤、タルク、カオリン、有機リン化合物、ポリエーテルエーテルケトンなどの結晶核剤、ポリオレフィン系化合物、シリコーン系化合物、長鎖脂肪族エステル系化合物、長鎖脂肪族アミド系化合物、などの離型剤、防食剤、着色防止剤、酸化防止剤、熱安定剤、ステアリン酸リチウム、ステアリン酸アルミニウムなどの滑剤、紫外線防止剤、着色剤、難燃剤、発泡剤などの通常の添加剤を添加することができる。
【００６３】
これらの添加剤は、本発明のＰＰＳ樹脂組成物を製造する任意の段階で配合することが可能であり、例えば、少なくとも２成分の樹脂を配合する際に同時に添加する方法や、予め２成分の樹脂を溶融混練した後に添加する方法や、始めに片方の樹脂に添加し溶融混練後、残りの樹脂を配合する方法が挙げられる。
【００６４】
本発明から得られるＰＰＳ樹脂組成物の成形方法は、任意の方法が可能であり、成形形状は、任意の形状が可能である。成形方法としては、例えば、射出成形、押出成形、インフレーション成形、ブロー成形などを挙げることができるが、中でも射出成形は射出後、金型内で熱処理と構造固定化が同時にできることから好ましく、またフィルムおよび／またはシート押出成形であれば、フィルムおよび／またはシート延伸時に熱処理し、その後の巻き取り前の自然冷却時に構造固定ができることから好ましい。もちろん上記成形品を別途熱処理し構造形成させることも可能である。
【００６５】
本発明におけるＰＰＳ樹脂組成物は、中でも片方の樹脂として、耐衝撃性に優れる樹脂を用いた場合は、耐衝撃性を高めた構造材料として有用に用いることができ、例えば自動車部品や電機部品などに好適に使用することができる。
【００６６】
本発明のＰＰＳ樹脂組成物の成形体は、コネクター、コイルをはじめとして、センサー、ＬＥＤランプ、ソケット、抵抗器、リレーケース、小型スイッチ、コイルボビン、コンデンサー、バリコンケース、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント基板、チューナー、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、パワーモジュール、半導体、液晶、ＦＤＤキャリッジ、ＦＤＤシャーシ、モーターブラッシュホルダー、パラボラアンテナ、コンピューター関連部品等に代表される電子部品用途に適している他、発電機、電動機、変圧器、変流器、電圧調整器、整流器、インバーター、継電器、電力用接点、開閉器、遮断機、ナイフスイッチ、他極ロッド、電気部品キャビネットなどの電気機器部品用途、ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザーディスク・コンパクトディスク、ＤＶＤ等の音声・映像機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品、ワードプロセッサー部品等に代表される家庭、事務電気製品部品；オフィスコンピューター関連部品、電話器関連部品、ファクシミリ関連部品、複写機関連部品、洗浄用治具、モーター部品、ライター、タイプライターなどに代表される機械関連部品：顕微鏡、双眼鏡、カメラ、時計等に代表される光学機器、精密機械関連部品；オルタネーターターミナル、オルタネーターコネクター，ＩＣレギュレーター、ライトディヤー用ポテンシオメーターベース、排気ガスバルブ等の各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディー、キャブレタースペーサー、排気ガスセンサー、冷却水センサー、油温センサー、ブレーキパットウェアーセンサー、スロットルポジションセンサー、クランクシャフトポジションセンサー、エアーフローメーター、ブレーキパッド摩耗センサー、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、ウォーターポンプインペラー、タービンベイン、ワイパーモーター関係部品、デュストリビューター、スタータースイッチ、スターターリレー、トランスミッション用ワイヤーハーネス、ウィンドウォッシャーノズル、エアコンパネルスイッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクター、ホーンターミナル、電装部品絶縁板、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルター、点火装置ケース等の自動車・車両関連部品等々、各種用途に適用できる。
【００６７】
また片方の樹脂として、低バリ性に優れる樹脂を用いた場合は、良好なバリ特性をいかして、射出成形に供し、射出成形品とすることが好ましく、中でもコネクター、コイルをはじめとする電子部品とすることが好ましく、さらにコネクターとすることが特に好ましい。
【００６８】
【実施例】
以下、実施例を挙げて本発明の効果をさらに説明する。
【００６９】
参考例（ＰＰＳ樹脂の重合）
（ＰＰＳ−１）
攪拌機付きオートクレーブに硫化ナトリウム９水塩６．００４ｋｇ（２５モル）、およびＮ−メチル−２−ピロリドン（以下ＮＭＰと略す）４．５ｋｇを仕込み、窒素を通じながら徐々に２０５℃まで昇温し、水３．６リットルを留出した。次に反応容器を１８０℃に冷却後、１，４−ジクロロベンゼン３．７１９ｋｇ（２５．３モル）ならびにＮＭＰ３ｋｇを加えて、窒素下に密閉し、２７０℃まで昇温後、２７４℃で１時間反応した。冷却後、反応生成物を温水で２回洗浄し、次にこのスラリーを撹拌基付きオートクレーブにイオン交換水３ｋｇと共に入れ１９０℃まで昇温し、１９０℃到達後、室温まで冷却後濾過し、さらに熱湯で数回洗浄した。これを濾過後、８０℃で２４時間減圧乾燥してＰＰＳ樹脂、２．４８ｋｇを得た。このＰＰＳ樹脂は直鎖状であり、溶融粘度１５Pa・s（３２０℃、剪断速度１０００ｓｅｃ^-1）、ガラス転移温度８９℃、結晶融解温度２８０℃であった。
【００７０】
ガラス転移温度、結晶融解温度はＤＳＣ（ＰＥＲＫＩＮ−ＥＬＭＥＲ社製ＤＳＣ−７）を用いて、昇温速度２０℃／分で測定した。
【００７１】
実施例１〜５
表１記載の組成からなる原料を、押出温度３２０℃に設定した２軸スクリュー押出機（池貝工業社製ＰＣＭ−３０）に供給し、ダイから吐出後のガットをすぐに氷水中に急冷し、構造を固定した。本ガットはいずれも透明であり、また該ガットをリンタングステン酸染色法によりナイロン−４，６を染色後、超薄切片を切り出したサンプルについて、透過型電子顕微鏡にて１０万倍に拡大して観察を行ったが、いずれのサンプルについても０．００１μｍ以上の構造物がみられず相溶化していることを確認した。このことから、本系は、押出温度３２０℃の押出機中の剪断下で相溶化することがわかる。
【００７２】
さらに上記氷水中に急冷し、構造を固定したガットから厚み１００μｍの切片を切り出し、実施例１〜３のサンプルについては２９０℃、実施例４のサンプルについては３１０℃、実施例５のサンプルについては２７０℃でそれぞれ熱処理を行い、この熱処理中の構造形成過程を小角Ｘ線散乱を用いて追跡した。いずれのサンプルも、熱処理開始から１０秒後以降にピークが出現し、またこのピークは、そのピーク位置を変化させずに強度を増加させる様子が観測された。この小角Ｘ線散乱においてピーク位置を変化させずに強度を増加させる過程はスピノーダル分解の初期過程に対応する。表１には該ピーク位置（θm）から下式で計算した、構造周期（Λm）を記した。
Λm ＝（λ／２）／ｓｉｎ（θm ／２）
またこの小角Ｘ線散乱測定中初期過程の切片については、一部をすぐに氷水中に急冷し構造を凍結し、リンタングステン酸染色法によりナイロン４，６を染色後、超薄切片を切り出したサンプルについて透過型電子顕微鏡にて１０万倍に拡大して観察を行ったところ、いずれのサンプルも両相連続構造が観察された。
【００７３】
さらに上記小角Ｘ線散乱を測定した切片は、初期過程において構造を形成させた後、さらにそれぞれ上記記載の各々の温度で計６０秒間熱処理を続け、構造形成を行い、本発明のＰＰＳ樹脂組成物を得た。該サンプルについても、上記初期過程同様に小角Ｘ線散乱から構造周期、及び透過型電子顕微鏡写真から構造の状態を観察した結果を表１に記載した。なお、分散構造を有する場合の粒子間距離も両相連続構造における構造周期と同じ方法で算出される。
【００７４】
また、上記ダイから吐出後、氷水中に急冷し構造を固定したガットを用い、加熱プレスにより上記熱処理と同様の温度、時間で熱処理を行ないシート（厚み０．２ｍｍ）を作製した。さらに該シートから厚み１００μｍの切片を切り出し、上記ガットからの切り出しサンプルと同様に、小角Ｘ線散乱から構造周期または粒子間距離を求めた結果、及び透過型電子顕微鏡写真から構造の状態を観察した結果を表１に記載した。本結果から、加熱プレスでの熱処理によっても、上記ガットからの切り出しサンプルと同様に構造が形成されていることがわかる。次に該シートから、長さ×幅×厚み＝５０ｍｍ×１０ｍｍ×０．２ｍｍのサンプルを切り出し、チャック間距離２０ｍｍ、引張速度１０ｍｍ／分で測定した引張強度、引張伸び、及び、打ち抜きプレスで試験片を取り、ＡＳＴＭ Ｄ１８２２に従って引張衝撃試験を行い、その測定結果を表１に記載した。
【００７５】
また、使用樹脂は、以下に示すものを使用した。
ＰＰＳ−１：ＰＰＳ樹脂（上述の参考例で重合したＰＰＳ樹脂）
ＰＡ−１：ナイロン４，６樹脂（オランダ国ＤＳＭ社製「ＳＴＡＮＹＬ」、９６％硫酸１ｇ／ｄｌでの相対粘度３．０、結晶融解温度２９５℃）。
【００７６】
比較例１
押出温度を３００℃に設定した以外は、実施例１〜５と同様に溶融混練し、ダイから吐出後すぐに氷水中に急冷し、構造を固定したサンプルを得たが、本サンプルは濁っており、また該サンプルをリンタングステン酸染色法によりナイロン−４，６を染色したサンプルについて、透過型電子顕微鏡にて１０００倍に拡大して観察を行うと、１．０μｍ以上の不均一な分散構造物が観測された。このことから、本サンプルは、押出温度３００℃の押出機中の剪断下で相溶化していないことがわかる。これは本系はＬＣＳＴ型相図を有することから、押出温度３００℃で上記押出機内での剪断条件では非相溶であるためと考えられる。本サンプルについても、実施例１〜３と同様に機械特性を測定した結果、および構造の状態を観察した結果を表１に記載した。
【００７７】
比較例２
熱処理温度を２６０℃で６０秒間行ったこと以外は、実施例１〜３と同様であり、該サンプルの機械特性を測定した結果、および構造周期、構造の状態を観察した結果を表１に記載した。但し、本サンプルの構造周期の測定には、小角光散乱装置による測定で求めた。本例の様に、熱処理温度が低く初期過程における構造周期が十分小さくならない場合、両成分の濃度差を十分なものとするために構造発展を施すと、構造周期を本発明範囲内に制御することが困難なものとなる。また本例の様に、かかる構造周期が本発明範囲を外れると、機械特性の劣るものしか得られなかった。
【００７８】
【表１】

【００７９】
これらの結果から、本発明のスピノーダル分解の初期過程で、特定構造周期の両相連続構造物を形成後、構造を発展させたサンプルが、優れた機械特性を有していることがわかる。
【００８０】
実施例６〜８
表２記載の組成からなる原料を、押出温度３２０℃に設定した２軸スクリュー押出機（池貝工業社製ＰＣＭ−３０）に供給し、ダイから吐出後のガットをすぐに氷水中に急冷し、構造を固定した。次に本ガットをストランドカッターを用いてペレット状に切断した押出ペレットを得た。該押出ペレットをリンタングステン酸染色法によりナイロン−４，６を染色後、超薄切片を切り出したサンプルについて、透過型電子顕微鏡にて１０万倍に拡大して観察を行ったが、いずれのサンプルについてもガラス繊維を除いて０．００１μｍ以上の構造物がみられず相溶化していることを確認した。このことから、本系は、押出温度３２０℃の押出機中の剪断下で相溶化することがわかる。
【００８１】
ここで上記押出ペレットの内、一部を樹脂温度３２０℃、金型温度２０℃に設定した射出成形機（日精樹脂工業社製ＰＳ２０Ｅ２ＡＳＥ）に供給し、６０％の射出速度、後述の射出圧力での一速一圧の条件下、射出時間１０秒、保圧時間６０秒のタイムサイクルで射出成形を行い、後述する形状のコネクター成形品を得た（金型温度を２０℃の条件とし、射出成形後の成形品を金型内で急冷することにより、相分解の進行を止め、スピノーダル分解の初期過程で構造を凍結したことを意味する。）。得られた成形品の表層部から切り出し、リンタングステン酸染色法によりナイロン−４，６を染色後、さらに超薄切片を切り出したサンプルについて透過型電子顕微鏡にて１０万倍に拡大して観察を行ったところいずれのサンプルも０．０１μｍの両相連続構造が見られた。
【００８２】
次に上記押出ペレットの内、別途一部を、金型温度１５０℃に設定した以外は上記射出条件と同条件で、上記同様コネクター成形品を射出成形し、得られた成形品の表層部から切り出したサンプルについて同様に小角Ｘ線散乱から構造周期または粒子間距離を求めた結果、及び透過型電子顕微鏡から構造の状態を観察した結果を表２に記載した。本例の金型温度１５０℃では、上記同様にスピノーダル分解の初期過程で構造が形成された後、構造が発展していることがわかる。
【００８３】
バリ長さの測定は、一列に５０個のピン穴（ピン穴間隔１．２７ｍｍ）を２列有し、うちのりが６８ｍｍ×５ｍｍ×高さ７ｍｍ、そとのりが７０ｍｍ×７ｍｍ×高さ９．３ｍｍの箱型形状を有し、長手方向の両端部にリブが設けられた形状を有するコネクター成形品を、先ず樹脂が先端まで充填する最低射出圧力を求め、その圧力＋３ｋｇｆ／ｃｍ²（ゲージ圧）の射出圧力で成形を行い、得られた成形片のピン穴部分に生じたバリ長さを万能投影機を用いて測定し、その平均値から求めた。その結果を表２に記載した。
【００８４】
また、上記押出ペレットの内、さらに別途一部を樹脂温度３２０℃、金型温度１５０℃に設定した射出成形機（日精樹脂工業社製ＰＳ２０Ｅ２ＡＳＥ）に供給し、射出速度６０％、先端まで充填する最低圧力＋３ｋｇｆ／ｃｍ²（ゲージ圧）の射出圧力での一速一圧の条件下、射出時間１０秒、保圧時間６０秒のタイムサイクルで射出成形を行い、ＡＳＴＭ Ｄ２５６準拠のアイゾット衝撃試験片を得た。得られた成形品を、ＡＳＴＭ Ｄ２５６に準拠し、アイゾット衝撃強度を測定した結果を表２に記載した。
【００８５】
また、使用樹脂は、以下に示すものを使用した。
ＰＰＳ−１：ＰＰＳ樹脂（上述の参考例で重合したＰＰＳ樹脂）
ＰＡ−１：ナイロン４，６樹脂（オランダ国ＤＳＭ社製「ＳＴＡＮＹＬ」、９６％硫酸１ｇ／ｄｌでの相対粘度３．０）
ＧＦ−１：平均繊維径１３μｍのＥガラス
Ｒ−１：カルボン酸アマイド系ワックス（ステアリン酸とセバシン酸とエチレンジアミンの反応生成物「ＷＨ２５５」）。
【００８６】
比較例４
押出温度を３００℃に設定した以外は、実施例６〜８と同様に溶融混練し、ダイから吐出後すぐに氷水中に急冷し、構造を固定したサンプルを得た。該サンプルをリンタングステン酸染色法によりナイロン−４，６を染色後、超薄切片を切り出したサンプルについて、透過型電子顕微鏡にて１０００倍に拡大して観察を行うと、ガラス繊維を除いて１．０μｍ以上の不均一な分散構造物が観測された。このことから、本サンプルは、押出温度３００℃の押出機中の剪断下で相溶化していないことがわかる。これは本系はＬＣＳＴ型相図を有することから、押出温度３００℃で上記押出機内での剪断条件では非相溶であるためと考えられる。本サンプルについても、実施例６〜８と同様にアイゾット衝撃強度およびバリ長さを測定した結果、および構造の状態を観察した結果を表２に記載した。
【００８７】
【表２】

【００８８】
これらの結果から、本発明のスピノーダル分解の初期過程で、特定構造周期の両相連続構造物を形成後、構造を発展させたサンプルにおいて、優れたアイゾット衝撃強度であり、またバリ長さが短く優れたバリ特性を有していることがわかる。
【００８９】
実施例９
表３記載の組成からなる原料を、押出温度３２０℃に設定した２軸スクリュー押出機（池貝工業社製ＰＣＭ−３０）に供給し、ダイから吐出後のガットをすぐに氷水中に急冷し、構造を固定した。本ガットはいずれも透明であり、また該ガットをリンタングステン酸染色法によりナイロン６オリゴマーを染色後、超薄切片を切り出したサンプルについて、透過型電子顕微鏡にて１０万倍に拡大して観察を行ったが、いずれのサンプルについても０．００１μｍ以上の構造物がみられず相溶化していることを確認した。このことから、本系は、押出温度３２０℃の押出機中の剪断下で相溶化することがわかる。
【００９０】
さらに上記氷水中に急冷し、構造を固定したガットから厚み１００μｍの切片を切り出し、３２０℃で熱処理を行い、この熱処理中の構造形成過程を小角Ｘ線散乱を用いて追跡した。いずれのサンプルも、熱処理開始から５分後以降にピークが出現し、またこのピークは、そのピーク位置を変化させずに強度を増加させる様子が観測された。この小角Ｘ線散乱においてピーク位置を変化させずに強度を増加させる過程はスピノーダル分解の初期過程に対応する。表３には該ピーク位置（θm）から下式で計算した、構造周期（Λm）を記した。
Λm ＝（λ／２）／ｓｉｎ（θm ／２）
またこの小角Ｘ線散乱測定中初期過程の切片については、一部をすぐに氷水中に急冷し構造を固定し、リンタングステン酸染色法によりナイロン６オリゴマーを染色後、超薄切片を切り出したサンプルについて透過型電子顕微鏡にて１０万倍に拡大して観察を行ったところ、両相連続構造が観察された。
【００９１】
次に、上記ガットをペレタイズし、再度押出温度３２０℃に設定し、滞留時間が５分間となる様スクリュー回転数を調整した２軸スクリュー押出機（日本製鋼所製ＴＥＸ３０α）に供給し、ダイから吐出後のガットをすぐに氷水中に急冷し、構造を固定した。本ガットは若干透明性の低下がみられ、また該ガットをリンタングステン酸染色法でナイロン６オリゴマーを染色後、超薄切片を切り出したサンプルについて、透過型電子顕微鏡にて観察を行ったところ両相連続構造が観察された。これらのことから、本系は再度溶融混練時にナイロン６オリゴマーが重合し、その分子量増加によって相分解が引き起こされたものと考えられる。
【００９２】
上記再度溶融混練したガットは、加熱プレス（３２０℃×３分間）でシート化し、得られたシート（厚み０．２ｍｍ）から、長さ×幅×厚み＝５０ｍｍ×１０ｍｍ×０．２ｍｍのサンプルを切り出し、チャック間距離２０ｍｍ、引張速度１０ｍｍ／分で測定した引張強度、引張伸び、及び、打ち抜きプレスで試験片を取り、ＡＳＴＭ Ｄ１８２２に従って引張衝撃試験を行い、その測定結果、および構造周期、構造の状態を観察した結果を表３に記載した。
【００９３】
また、使用樹脂は、以下に示すものを使用した。
ＰＰＳ−１：ＰＰＳ樹脂（上述の参考例で重合したＰＰＳ樹脂）
ＰＡ−２：ナイロン６オリゴマー（濃硫酸中、濃度１％、２５℃で測定した相対粘度が１．２０、ＤＳＣで測定した結晶融解温度が２２５℃のもの）。
【００９４】
比較例５
ＰＰＳ樹脂に配合する樹脂として分子量の高いナイロン６を用いた以外は、実施例９と同様に溶融混練し、ダイから吐出後すぐに氷水中に急冷し、構造を固定したサンプルを得たが、本サンプルは濁っており、また該サンプルをリンタングステン酸染色法によりナイロン６を染色したサンプルについて、透過型電子顕微鏡にて１０００倍に拡大して観察を行うと、１μｍ以上の不均一な分散構造物が観測された。このことから、本サンプルは、押出温度３２０℃の押出機中の剪断下で相溶化していないことがわかる。本系についても、実施例９と同様に機械特性を測定した結果、および構造周期、構造の状態を観察した結果を表３に記載した。
【００９５】
また、使用樹脂は、以下に示すものを使用した。
ＰＡ−３ ：ナイロン６（濃硫酸中、濃度１％、２５℃で測定した相対粘度が３．２０、ＤＳＣで測定した結晶融解温度が２２５℃のもの）
【００９６】
【表３】

【００９７】
これらの結果から、本発明のスピノーダル分解の初期過程で、特定構造周期の両相連続構造物を形成後、構造を発展させたサンプルが、優れた機械特性を有していることがわかる。
【００９８】
【発明の効果】
本発明により、優れた機械特性を有し、また優れた低バリ性を有し、成形材料として有用なＰＰＳ樹脂組成物が得られるようになった。さらに好ましい態様においては、優れた規則性を有し、かつその構造を微細に制御し、さらにはその構造の２相間の濃度差を十分発達させたＰＰＳ樹脂組成物が得られるようになった。また、本発明により優れた機械特性を活かして構造材料として有用であり、さらには優れた低バリ性をも活かして射出成形材料として有用であるＰＰＳ樹脂組成物が得られるようになった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyphenylene sulfide resin composition that can be usefully used as a structural material making use of excellent mechanical properties and a functional material making use of excellent regularity. The present invention also relates to a method for producing a polyphenylene sulfide resin composition capable of controlling the structure from nanometer order to micron order.
[0002]
[Prior art]
Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has excellent properties as engineering plastics such as excellent heat resistance, flame retardancy, chemical resistance, dimensional stability, rigidity and electrical insulation. It is used for various electrical / electronic parts, machine parts, automobile parts, etc., mainly for molding.
[0003]
However, PPS resins are known to be brittle and inferior in impact resistance and mechanical properties. In most cases, they are used in reinforcing systems to which inorganic reinforcing agents such as glass fibers are added. Therefore, the field of use as a molding material is currently limited. Further, PPS resin generates a relatively large amount of burrs during molding, and its use is limited particularly in applications such as small precision parts that require low burrs.
[0004]
From such a current situation, a method of blending another thermoplastic resin is known as a method for improving the toughness of the PPS resin. JP-A-58-145757 discloses a composition comprising a PPS resin and a glycidyl-modified polyolefin resin, JP-A-60-120653 discloses a composition comprising a PPS resin and a rubbery compound, and JP-A-59-58052. No. 5 discloses a composition comprising a PPS resin and a thermoplastic polyester resin, JP-A-51-59952 discloses a composition comprising a PPS resin and a polycarbonate resin, and JP-A-53-69255 discloses a PPS resin. And a composition comprising a polyamide-based resin. However, even if any resin is used, the compatibility with the PPS resin is poor only by simply blending, and a sufficient effect for improving toughness has not been obtained.
[0005]
JP 2000-248179 discloses a structure in which both phases are continuously connected by kneading a PPS resin and a thermoplastic resin selected from polycarbonate, polysulfone, and polyetherketone under specific melt-kneading conditions. A PPS resin composition is disclosed. However, since the biphasic continuous structure obtained by this method is of the order of several micrometers and the regularity of the structure is low, the present situation is that a sufficient effect for improving toughness has not been obtained.
[0006]
In addition, several studies have been made so far for the purpose of reducing the burr of the PPS resin. JP-A-64-9266 discloses a method of blending a highly crosslinked PPS resin as a property improver, JP-A-63-251430 discloses a method of adding a silane compound to a PPS resin, and JP-A-3-197562. The publication discloses a method of using a specific linear PPS resin and a cross-linked PPS resin in combination with a base polymer, and further using a silane coupling agent.
[0007]
However, the burr can be reduced to some extent by such a conventional technique alone, but there are still more burrs compared to other engineering plastics such as PBT resin and polyamide, and further reduction in burr is desired.
[0008]
On the other hand, as a polymer alloy using spinodal decomposition, JP-A-8-113829 discloses a fiber obtained by melt-spinning a partially compatible polymer blend compatible with each other in a specific temperature range in a compatible state by heat treatment or the like. There is described a polymer blend fiber which is phase-decomposed by spinodal decomposition or nucleation and growth to form a dispersed structure of 0.001 to 0.4 μm in the fiber cross section. However, in the invention described in the publication, polyester resin is mainly used, and use of PPS resin is not described. Further, in the invention described in the publication, a special method of forming the structure through an extensional flow field in melt spinning has been adopted to obtain a finely dispersed structure, which has excellent mechanical properties and low burr properties. The technical idea of obtaining a structural material having the above is not described.
[0009]
[Problems to be solved by the invention]
It is an object of the present invention to provide a PPS resin composition having excellent mechanical properties, excellent low burr properties, and useful as a molding material, and in a more preferred embodiment, excellent regularity. It is an object of the present invention to provide a PPS resin composition that has a finely controlled structure and that has sufficiently developed a concentration difference between two phases of the structure.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in a PPS resin composition containing one or more PPS resins, a two-phase continuous structure having a structural period of 0.01 to 1 μm, or an interparticle distance of 0.01 The inventors have found that a PPS resin composition whose structure is controlled to have a dispersion structure of ˜1 μm has the above-mentioned properties, and has completed the present invention.
[0011]
  That is, the present invention
(1) Polyphenylene sulfide resin comprising at least two components of resinAnd resins other than polyphenylene sulfide resins selected from polyester, polyamide, polyetherimide, polyamideimide, polyimide, polycarbonate, polyetherketone, polythioetherketone, polyetheretherketone, polyphenylene oxide, polysulfone, and polyethersulfoneA polyphenylene sulfide resin composition containing one or more of the above, wherein the polyphenylene sulfide resin composition has a biphasic continuous structure having a structural period of 0.01 to 1 μm or a dispersed structure having a distance between particles of 0.01 to 1 μm. A polyphenylene sulfide resin composition,
(2) Polyphenylene sulfide resin consisting of at least two components, phase-separated by spinodal decompositionAnd resins other than polyphenylene sulfide resin selected from polyester, polyamide, polyetherimide, polyamideimide, polyimide, polycarbonate, polyetherketone, polythioetherketone, polyetheretherketone, polyphenylene oxide, polysulfone, and polyethersulfone.A polyphenylene sulfide resin composition comprising one or more types, and after a biphasic continuous structure having a structural period of 0.001 to 0.1 μm is formed in the initial process of spinodal decomposition, a biphasic continuous structure having a structural period of 0.01 to 1 μm Or a polyphenylene sulfide resin composition characterized by being developed to a dispersed structure having an interparticle distance of 0.01 to 1 μm,
(3)(1) or (1), wherein the polyphenylene sulfide resin composition is in the range of 50 to 97% by weight of polyphenylene sulfide resin with respect to 100% by weight of the total resin components constituting the polyphenylene sulfide resin composition. 2) the polyphenylene sulfide resin composition according to
(4)(3) The polyphenylene sulfide resin composition is in the range of 50 to 75% by weight of polyphenylene sulfide resin with respect to 100% by weight of the total resin components constituting the polyphenylene sulfide resin composition. Polyphenylene sulfide resin composition,
(5)The polyphenylene sulfide resin composition according to any one of (1) to (4), wherein the resin other than the polyphenylene sulfide resin is polyamide.
(6) The polyphenylene sulfide resin composition is produced through melt kneading (1) to (5)The polyphenylene sulfide resin composition according to any one of the above,
(7) The spinodal decomposition is compatible under shear during melt kneading and phase-separated under non-shear after discharge (6)The polyphenylene sulfide resin composition according to the description,
(8) The polyphenylene sulfide resin composition induces spinodal decomposition by chemically reacting at least one precursor of the resin components constituting the polyphenylene sulfide resin composition in the presence of the remaining resin components. The polyphenylene sulfide resin composition according to any one of (1) to (7),
(9) The spinodal decomposition is one which is once dissolved before the chemical reaction and phase-separated after the chemical reaction (8)The polyphenylene sulfide resin composition according to the description,
(10) For injection molding (1) to (9)The polyphenylene sulfide resin composition according to any one of the above,
(11) For film and / or sheet extrusion molding (1) to (9)The polyphenylene sulfide resin composition according to any one of the above,
(12) Polyphenylene sulfide resin comprising at least two components of resinAnd resins other than polyphenylene sulfide resins selected from polyester, polyamide, polyetherimide, polyamideimide, polyimide, polycarbonate, polyetherketone, polythioetherketone, polyetheretherketone, polyphenylene oxide, polysulfone, and polyethersulfoneIs a method for producing a polyphenylene sulfide resin composition in which a polyphenylene sulfide resin composition containing at least one of them is phase-separated by spinodal decomposition, wherein a biphasic continuous structure having a structural period of 0.001 to 0.1 μm is formed in an initial process of spinodal decomposition. A process for producing a polyphenylene sulfide resin composition, which is further developed to a biphasic continuous structure having a structural period of 0.01 to 1 μm or a dispersed structure having a distance between particles of 0.01 to 1 μm after the formation;
(13)(12) In the polyphenylene sulfide resin composition, the polyphenylene sulfide resin is in the range of 50 to 97% by weight with respect to 100% by weight in total of the resin components constituting the polyphenylene sulfide resin composition. A process for producing a polyphenylene sulfide resin composition of
(14)(13) The polyphenylene sulfide resin composition is in the range of 50 to 75% by weight of polyphenylene sulfide resin with respect to 100% by weight of the total resin components constituting the polyphenylene sulfide resin composition. Production method of polyphenylene sulfide resin composition,
(15) A polyphenylene sulfide resin comprising at least two components of resinAnd resins other than polyphenylene sulfide resins selected from polyester, polyamide, polyetherimide, polyamideimide, polyimide, polycarbonate, polyetherketone, polythioetherketone, polyetheretherketone, polyphenylene oxide, polysulfone, and polyethersulfone(12)-(14) The method for producing a polyphenylene sulfide resin composition according to any one of (12) to (14), wherein spinodal decomposition is induced by melt-kneading a polyphenylene sulfide resin composition containing at least one of
(16)The method for producing a polyphenylene sulfide resin composition according to any one of (12) to (15), wherein the resin other than the polyphenylene sulfide resin is polyamide.
(17) It is characterized by compatibilizing at least two components of resin under shear during melt-kneading and phase-separating under non-shear after discharge (15) or (16) descriptionA process for producing a polyphenylene sulfide resin composition of
(18) It is characterized by inducing spinodal decomposition by chemically reacting at least one precursor of the resin components constituting the polyphenylene sulfide resin composition in the presence of the remaining resin components (12) to (14) any one itemA process for producing the polyphenylene sulfide resin composition according to claim 1, and
(19) It is characterized in that it is once dissolved before chemical reaction and phase-separated after chemical reaction (18)It is a manufacturing method of the polyphenylene sulfide resin composition of description.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0013]
The PPS resin used in the present invention is a polymer containing a repeating unit represented by the following structural formula,
[0014]
[Chemical 1]

[0015]
From the viewpoint of heat resistance, a polymer containing 70 mol% or more, particularly 90 mol% or more of the repeating unit represented by the above structural formula is preferable. In addition, the PPS resin can comprise 30 mol% or less of the repeating units with repeating units having the following structural formula.
[0016]
[Chemical formula 2]

[0017]
The PPS resin used in the present invention is a generally known method, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-61. It can be produced by a method described in Japanese Patent No. 7332 for obtaining a polymer having a relatively large molecular weight. In the present invention, the PPS resin obtained as described above is crosslinked / polymerized by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, aqueous acid solution, etc. It can also be used after being subjected to various treatments such as activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, functional group-containing disulfide compounds, and more than two types of these treatments. Of course it is possible. Of course, it is also possible to use two or more types of PPS resins subjected to these treatments. As a specific method for using two or more types of PPS resins, a PPS resin crosslinked by heating in air is used. And PPS resin that has not been heat-treated, PPS resin that has been washed with an aqueous acid solution and PPS resin that has been washed with an organic solvent, PPS resin that has been washed with an organic solvent, and PPS that has not been washed with an organic solvent Examples include mixing of resins.
[0018]
The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible, and is usually 5 to 1,000 Pa · s (320 ° C., shear rate 1000 sec).^-1) Are used, but those having 10 to 500 Pa · s are preferred. In order to obtain a more excellent burr reduction effect, it is effective to use two or more types of PPS resins having different melt viscosities in combination. For example, a PPS resin having a melt viscosity of 30 Pa · s or more and 30 Pa · s A method of mixing and using a PPS resin having a melt viscosity of less than 15 is mentioned as a suitable method.
[0019]
As a specific method for crosslinking / high molecular weight by heating PPS resin, it can be performed in an oxidizing gas atmosphere such as air or oxygen, or in a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Examples of the method include heating until a desired melt viscosity is obtained at a predetermined temperature. The heat treatment temperature is usually selected from 170 to 280 ° C., preferably from 200 to 270 ° C., and the time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. The target viscosity level can be obtained by appropriately controlling the time. The heat treatment apparatus may be a normal hot air dryer with reduced pressure specifications or a high-sealing specification, or a rotary type or a heating apparatus with a stirring blade, but it is a rotary type for efficient and more uniform treatment. Alternatively, it is more preferable to use a heating device with a stirring blade.
[0020]
As a specific method for heat-treating the PPS resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200 to 200 ° C. under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment at 270 ° C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a stationary type heating apparatus, or a rotary type or a heating apparatus with a stirring blade, but a heating apparatus with a rotary type or a stirring blade is used for efficient and more uniform treatment. Is more preferable.
[0021]
The following method can be illustrated as a specific method when the PPS resin is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethyl sulfoxide , Sulfoxide / sulfone solvents such as dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane , Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol Lumpur, phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferable. Moreover, these organic solvents can also be used by 1 type or in mixture of 2 or more types. As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C.
[0022]
The PPS resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.
[0023]
The following method can be illustrated as a specific method when the PPS resin is treated with hot water. That is, in order to express a preferable chemical modification effect of the PPS resin by hot water washing, the water used is preferably distilled water or deionized water. The operation of the hot water treatment is usually performed by putting a predetermined amount of PPS resin into a predetermined amount of water and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably larger, but usually a bath ratio of 200 g or less of PPS resin is selected for 1 liter of water.
[0024]
The following method can be illustrated as a specific method in the case of acid-treating PPS resin.
[0025]
That is, there is a method of immersing a PPS resin in an acid or an aqueous solution of an acid, and stirring or heating can be performed as necessary. The acid used is not particularly limited as long as it does not have an action of decomposing PPS resin, and is saturated with aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acids such as saturated carboxylic acid, acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, sulfuric acid And inorganic acidic compounds such as phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The acid-treated PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by acid treatment is not impaired.
[0026]
  The PPS resin composition of the present invention is a polymer alloy of a PPS resin and another resin, and as a resin other than the PPS resin, a spinodal decomposable resin described later is used.Is used. In particular,Polyester, polyamide, polyphenylene oxide, polysulfoneTheReetherimide, polyamideimide, polyimide, polycarbonate, polyethersulfone, polyetherketone, polythioetherketone, polyetheretherketoTheCan be mentioned.
[0027]
Although there is no restriction | limiting in particular about the composition of the resin component which comprises the PPS resin composition in this invention, Usually PPS resin is 50 to 97 weight% with respect to a total of 100 weight% of the resin component which comprises PPS resin composition. The range of 50 to 95% by weight is more preferred, and the range of 50 to 75% by weight is particularly preferred because it is relatively easy to obtain a biphasic continuous structure.
[0028]
The PPS resin composition of the present invention needs to have a both-phase continuous structure with a structural period of 0.01 to 1 μm or a dispersed structure with a distance between particles of 0.01 to 1 μm. In order to obtain such a structure, it is preferable that the PPS resin and the resin other than the PPS resin are once dissolved in phase and formed into a structure by spinodal decomposition described later. Furthermore, in order to realize this structure formation, a PPS resin and a resin other than the PPS resin, a partial miscibility system described later, a shear field-dependent phase dissolution / phase decomposition system, or a reaction-induced phase decomposition system It is preferable that
[0029]
In general, polymer alloys composed of two-component resins are compatible with these compositions in a practical system where the glass transition temperature is higher than the thermal decomposition temperature or lower, and vice versa. There are incompatible systems that dissolve, and partially compatible systems that are compatible in one region and phase separated in another region. In this partially compatible system, phase separation is performed by spinodal decomposition depending on the conditions of the phase separated state. And phase separation by nucleation and growth.
[0030]
Furthermore, in the case of a polymer alloy composed of three or more components, a system in which all three or more components are compatible, a system in which all three or more components are incompatible, a compatible phase having two or more components, and the rest There is a system in which one or more phases are incompatible, two components are partially compatible, and the remaining components are distributed in a partially compatible system composed of these two components. The polymer alloy composed of 3 or more components preferred in the present invention is a system in which 2 components are partially compatible and the remaining components are distributed to the partially compatible system composed of 2 components. In this case, the structure of the polymer alloy is 2 Since it can be replaced by a partially compatible structure composed of components, the following description will be made on behalf of a polymer alloy composed of a two-component resin.
[0031]
Phase separation by spinodal decomposition refers to phase separation that occurs in an unstable state inside the spinodal curve in phase diagrams for different two-component resin compositions and temperatures, and phase separation by nucleation and growth refers to the phase separation. In the figure, it refers to phase separation that occurs in the metastable state inside the binodal curve and outside the spinodal curve.
[0032]
The spinodal curve refers to the difference (ΔGmix) between the free energy in the case of being compatible and the sum of the free energy in the incompatible phase (ΔGmix) when two different resin components are mixed with respect to the composition and temperature. φ) partial differential twice (∂²ΔGmix / ∂φ²) Is zero, and inside the spinodal curve,²ΔGmix / ∂φ²<Unstable state of 0²ΔGmix / ∂φ²> 0.
[0033]
The binodal curve is a boundary curve between the region where the system is compatible and the region where the system is separated with respect to the composition and temperature.
[0034]
Here, the case of being compatible in the present invention is a state in which they are uniformly mixed at the molecular level. Specifically, both phases having different two-component resins as main components are 0.001 μm or more. The case where the phase structure is not formed is indicated, and the case where the phase is incompatible is the case where the phase is not in a compatible state, that is, the phases mainly composed of two different resin components are 0.001 μm or more. It refers to the state of forming a phase structure. Whether or not they are compatible is determined by, for example, an electron microscope, a differential scanning calorimeter (DSC), or other various methods as described in Polymer Alloys and Blends, Leszek A Utracki, hanser Publishers, Munich Viema New York, P64. Judgment can be made.
[0035]
According to detailed theory, in spinodal decomposition, once the temperature of a mixed system that has been uniformly mixed at the temperature of the compatible region is rapidly increased to the temperature of the unstable region, the system will rapidly phase-separate toward the coexisting composition. To start. At that time, the concentration is monochromatized at a constant wavelength, and a two-phase continuous structure is formed in which both separated phases are continuously intertwined regularly with a structure period (Λm). After the formation of the two-phase continuous structure, the process in which only the concentration difference between the two phases increases while keeping the structure period constant is called the initial process of spinodal decomposition.
[0036]
Further, the structural period (Λm) in the initial process of the above-mentioned spinodal decomposition has a thermodynamic relationship as shown in the following equation.

(Where Ts is the temperature on the spinodal curve)
Here, the two-phase continuous structure referred to in the present invention refers to a structure in which both components of the resin to be mixed each form a continuous phase and are entangled three-dimensionally. A schematic diagram of this two-phase continuous structure is described, for example, in “Polymer Alloy Fundamentals and Applications (Second Edition) (Chapter 10.1)” (edited by the Society of Polymer Science: Tokyo Kagaku Dojin).
[0037]
In spinodal decomposition, after going through such an initial process, it goes through a medium-term process in which an increase in wavelength and an increase in concentration difference occur simultaneously, and a later process in which an increase in wavelength occurs in a self-similar manner after the concentration difference reaches the coexisting composition. In order to obtain the structure defined in the present invention, the desired structural period before the final separation into the macroscopic two phases has been reached. What is necessary is just to fix a structure in a step.
[0038]
In addition, in the process of increasing the wavelength from the mid-stage process to the late-stage process, depending on the influence of the composition and the interfacial tension, the continuity of one phase may be interrupted and the above-described biphasic continuous structure may be changed to a dispersed structure. In this case, the structure may be fixed when the desired interparticle distance is reached.
[0039]
Here, the dispersion structure referred to in the present invention is a so-called sea-island structure in which particles mainly composed of the other resin component are interspersed in a matrix mainly composed of one resin component. Point.
[0040]
The PPS resin composition of the present invention needs to be structurally controlled to have a two-phase continuous structure with a structural period of 0.01 to 1 μm or a dispersed structure with a distance between particles of 0.01 to 1 μm. By controlling the structural period in the initial process of spinodal decomposition in the range of 0.001 to 0.1 μm, the structural period is in the range of 0.01 to 1 μm even if the wavelength and concentration difference increase after the above-mentioned intermediate period. The structure can be controlled to have a continuous structure of both phases, or a dispersed structure having a distance between particles of 0.01 to 1 μm. In order to obtain more excellent mechanical properties, after the structure is developed, a biphasic continuous structure with a structural period in the range of 0.01 to 0.5 μm, or a dispersed structure with a distance between particles of 0.01 to 0.5 μm. It is preferable to control to a two-phase continuous structure with a structural period of 0.01 to 0.3 μm or a dispersed structure with a distance between particles of 0.01 to 0.3 μm. . The effect of the present invention can be obtained by controlling the range of the structural period and the range of the interparticle distance, but by further developing the concentration difference, a structure having more excellent mechanical properties and low burr properties is effective. Can be obtained.
[0041]
On the other hand, in the nucleation and growth, which is the phase separation in the metastable region described above, a dispersed structure that is a sea-island structure is formed from the initial stage, and it grows. It is difficult to form a biphasic continuous structure in the range of 0.01 to 1 μm or a dispersed structure in the range of a distance between particles of 0.01 to 1 μm.
[0042]
Moreover, in order to confirm the biphasic continuous structure by these spinodal decompositions or a disperse structure, it is important to confirm a regular periodic structure. For example, in addition to confirming that a two-phase continuous structure is formed by observation with an optical microscope or a transmission electron microscope, the scattering maximum in a scattering measurement performed using a light scattering device or a small-angle X-ray scattering device Confirmation of appearing is necessary. Note that the light scattering device and the small-angle X-ray scattering device have different optimum measurement regions, so that they are appropriately selected according to the size of the structure period. The existence of the scattering maximum in this scattering measurement is a proof that there is a regular phase separation structure with a certain period, and its period Λm corresponds to the structure period in the case of the biphasic continuous structure, and the interparticle distance in the case of the dispersion structure. Correspond. The value can be calculated by the following equation using the wavelength λ of the scattered light in the scatterer and the scattering angle θm that gives the scattering maximum.
Λm = (λ / 2) / sin (θm / 2)
In order to realize the spinodal decomposition, it is necessary to make the PPS resin and another resin compatible with each other, and then make the unstable state inside the spinodal curve.
[0043]
First, as a method of realizing a compatible state with a resin composed of two or more components, after dissolving in a common solvent, spray drying, freeze drying, coagulation in a non-solvent substance, film formation by solvent evaporation, etc. from this solution is used. Examples thereof include a solvent casting method and a melt-kneading method in which a partially compatible system is melt-kneaded under compatible conditions. Among these, compatibilization by melt kneading, which is a dry process that does not use a solvent, is preferably used in practice.
[0044]
For compatibilization by melt kneading, an ordinary extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing process of the injection molding machine. The temperature for compatibilization needs to be a condition in which the partially compatible resin is compatible.
[0045]
Next, when the resin composition made into a compatible state by the above melt kneading is in an unstable state inside the spinodal curve, the temperature for making the unstable state when the spinodal decomposition is performed, and other conditions vary depending on the combination of the resins. Although it cannot be generally stated, it can be set by performing a simple preliminary experiment based on the phase diagram. In the present invention, as described above, after the structural period of the initial process is controlled to a specific range, the structure is further developed after the intermediate process to obtain a specific biphasic continuous structure or a dispersed structure defined in the present invention. preferable.
[0046]
The method for controlling to a specific structural period in this initial process is not particularly limited, but is not less than the lowest glass transition temperature of the individual resin components constituting the PPS resin composition, and the above-described thermodynamics. It is preferable to perform heat treatment at a temperature that reduces the structural period defined in 1. Here, the glass transition temperature can be obtained from an inflection point generated at the time of temperature increase from room temperature at a temperature increase rate of 20 ° C./min with a differential scanning calorimeter (DSC).
[0047]
The method for developing the structure from the initial process is not particularly limited, but a method of heat treatment at the lowest temperature or higher among the glass transition temperatures of the individual resin components constituting the PPS resin composition is usually preferably used. Further, it is preferable that the heat treatment temperature is equal to or higher than the crystal melting temperature of the crystalline resin because the structural development by the heat treatment can be effectively obtained, and that the heat treatment temperature is within the crystal melting temperature ± 20 ° C. Is preferable in order to facilitate the control of the crystal, and more preferably, the crystal melting temperature is within ± 10 ° C. Here, when two or more kinds of crystalline resins including PPS resin are used as the resin component, the heat treatment temperature is within the crystal melting temperature within ± 20 ° C. based on the highest temperature among the crystal melting temperatures of the crystalline resin. It is preferable that the crystal melting temperature is within ± 10 ° C. Here, the crystal melting temperature of the crystalline resin can be determined from the peak temperature of the melting curve generated at the time of temperature increase from room temperature at a temperature increase rate of 20 ° C./min with a differential scanning calorimeter (DSC).
[0048]
In addition, as a method of immobilizing the structure product by spinodal decomposition, the structure fixing of one or both components of the phase-separated phase in a short time by rapid cooling or the like, and when one is a thermosetting component, Structural fixation utilizing the fact that the phase cannot freely move due to the reaction, and structural fixation utilizing the fact that the crystalline resin phase cannot be freely moved by crystallization when one is a crystalline resin. In particular, when at least one of the PPS resin compositions uses a crystalline resin, structural fixation by crystallization is preferably used.
[0049]
The crystalline resin referred to in the present invention is not particularly limited as long as it is a resin whose crystal melting temperature is observed by a differential scanning calorimeter (DSC). For example, nylon 6, nylon 66, etc. Aliphatic polyamides, aromatic polyamides such as nylon 6T and nylon 6I, aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and copolymers thereof, and poly-ε-caprolactam And aliphatic polyesters such as polyethylene, polypropylene, polyvinyl alcohol, polyvinyl chloride such as polyvinyl chloride, and polyethers such as polyoxymethylene.
[0050]
In the present invention, the PPS resin and other resins are phase-separated by the above spinodal decomposition to obtain the PPS resin composition of the present invention. It is preferable to combine a resin that is a system that undergoes phase decomposition or a reaction-induced phase decomposition.
[0051]
In general, partial compatible systems are known to have a low-temperature compatible phase diagram that is easy to be compatible on the low temperature side in the same composition, and a high temperature compatible phase diagram that is easy to be compatible on the high temperature side. It has been. The lowest temperature between the compatible and incompatible branching temperatures in this low-temperature compatible phase diagram is called the lower critical solution temperature (LCST for short). The highest temperature among the incompatible branching temperatures is called the upper critical solution temperature (UCST).
[0052]
In the case of a low-temperature compatible phase diagram, a resin of two or more components that have become compatible using a partially compatible system can be brought to a temperature higher than the LCST and a temperature inside the spinodal curve. In the case of the figure, spinodal decomposition can be performed by setting the temperature below UCST and the temperature inside the spinodal curve.
[0053]
In addition to spinodal decomposition by this partially compatible system, spinodal decomposition is also induced by melt kneading in non-compatible systems, for example, once compatible under shearing during melt kneading, etc., and then in an unstable state again under non-shearing. Phase separation by spinodal decomposition is also possible by so-called shear field-dependent phase dissolution / phase decomposition in which phase decomposition occurs. Has a continuous structure. Furthermore, this shear field-dependent phase dissolution / phase decomposition is the same as the method based on the temperature change of the partially miscible system in which the spinodal curve does not change because the spinodal curve changes due to the shear field and the unstable region expands. The substantial degree of supercooling (| Ts−T |) also increases in the temperature change range, and as a result, it is easy to reduce the structural period in the initial process of spinodal decomposition in the above relational expression, so that it is preferably used. It is done. In order to achieve compatibilization by shearing during such melt kneading, a normal extruder is used, but a twin screw extruder is preferably used. Further, depending on the combination of resins, there are cases where compatibilization can be achieved in the plasticizing process of the injection molding machine. In this case, the temperature for compatibilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for developing the structure from the initial process, and other conditions differ depending on the combination of the resins, and cannot be generally stated. The conditions can be set by performing a simple preliminary experiment based on the phase diagram under the shear conditions. Also, as a method of reliably realizing the compatibilization in the plasticizing process of the injection molding machine, it is melt-kneaded with a twin-screw extruder in advance and compatibilized, and after discharging, it is rapidly cooled in ice water or the like to fix the structure in the compatibilized state. A preferred example is a method of injection molding using a paste.
[0054]
Examples of the combination of the above-mentioned shear field-dependent phase dissolving / phase-decomposing resin include a PPS resin and nylon 4, 6 mixed system.
[0055]
Furthermore, even in a compatible system, phase separation by spinodal decomposition is possible by so-called reaction-induced phase decomposition in which an unstable state is caused by a change in molecular weight accompanying a chemical reaction and the like and phase decomposition occurs. For example, the precursor of the resin component finally contained, such as the resin component raw material, oligomer, or low molecular weight material constituting the polymer alloy is compatible with the remaining resin component, and the monomer, oligomer, or low molecular weight material is increased. In the case where the degree of polymerization and the resin to be alloyed cause phase separation with other resin components, at least one precursor of the resin components constituting the polymer alloy is added in the presence of the remaining resin components. It is possible to induce spinodal decomposition by causing a chemical reaction. Also in this case, the decomposition proceeds in a spinodal decomposition manner as in the case of the partially compatible system, and a regular biphasic continuous structure is obtained. Furthermore, this reaction-induced phase decomposition has the same temperature change range as compared with the method based on the temperature change of the partially miscible system in which the spinodal curve does not change because the spinodal curve changes due to the molecular weight change and the unstable region expands. Is more preferably used since the substantial degree of supercooling (| Ts−T |) increases, and as a result, it becomes easy to reduce the structural period in the initial stage of the spinodal decomposition in the above relational expression. In this case, the glass transition temperature and the crystalline melting temperature in the case of a crystalline resin change with a change in molecular weight due to polymerization and crosslinking, and further, the change from phase dissolution to phase decomposition due to the change in molecular weight varies depending on the system. The temperature for solubilization, the heat treatment temperature for forming the initial process, the heat treatment temperature for developing the structure from the initial process, and other conditions cannot be generally stated, but they are shown in the phase diagram in combination with various molecular weights. Based on this, conditions can be set by performing a simple preliminary experiment.
[0056]
In addition, the combination of the above resins that undergo reaction-induced phase decomposition is such that the precursor and the remaining resin components are once in a compatible state before the chemical reaction, and spinodal decomposition is induced by using the precursor as a resin through a chemical reaction. This chemical reaction is not particularly limited as long as it causes an increase in molecular weight, and includes polycondensation, addition polymerization such as radical polymerization, cationic polymerization, anionic polymerization, and ionic copolymerization. In addition to polymerization reactions such as polyaddition, addition condensation, and ring-opening polymerization, preferred examples include a crosslinking reaction and a coupling reaction. Usually, such chemical reactions are carried out in the presence of the remaining resin to be alloyed, resulting in reaction-induced phase decomposition. Examples thereof include a PPS resin and polyphenylene oxide resin mixed system, a PPS resin and a thermosetting polyallyl ether oligomer system, and the like. As such a production method, for example, a once melted alloy is polymerized again at the time of melt kneading in an extruder such as a single screw or twin screw extruder, or a single screw or twin screw extruder having a long residence time. The method of superposing | polymerizing and phase-decomposing once after melt | dissolving a phase once in one extrusion using an extruder etc. is mentioned.
[0057]
Further, the addition of a third component which is a copolymer such as a block copolymer, a graft copolymer or a random copolymer containing a component constituting a polymer alloy to the PPS resin composition constituting the present invention is an interface between phase decomposed phases. Is preferably used to facilitate control of the structural period in the biphasic continuous structure and the distance between dispersed particles in the dispersed structure. In this case, the third component such as the copolymer is usually distributed to each phase of the polymer alloy composed of the two-component resin except the copolymer, and thus can be handled in the same manner as the polymer alloy composed of the two-component resin.
[0058]
In the PPS resin composition of the present invention, using an alkoxysilane compound in combination is effective for obtaining excellent mechanical strength. Examples of the alkoxysilane compound include an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. Specific examples thereof include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) amino Ureido group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanate Isocyanato group-containing alkoxysilane compounds such as natopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxy Examples thereof include hydroxyl group-containing alkoxysilane compounds such as silane, among which γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxy Chlohexyl) Epoxy group-containing alkoxysilane compounds such as ethyltrimethoxysilane, ureido groups such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane Alkoxysilane compound, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane are preferred. Particularly preferred are epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. .
[0059]
An alkoxysilane compound having at least one functional group selected from such epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group, and ureido group is used to obtain better mechanical strength. The addition amount is selected in the range of 0.05 to 5 parts by weight and more preferably in the range of 0.2 to 3 parts by weight with respect to 100 parts by weight of the PPS resin. If the amount is too small, the effect of improving the mechanical strength due to the addition of the alkoxysilane compound is not sufficiently exhibited. If the amount is too large, the above-described improvement effect not only reaches saturation but also tends to increase the amount of gas generated in the composition.
[0060]
In the present invention, a filler may be used as necessary in order to improve strength and dimensional stability. The filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used. Examples of the filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal Fibrous fillers such as fibers, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate and other silicates, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, Rasubizu, ceramic beads, non-fibrous fillers such as boron nitride and silicon carbide and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, these fibrous and / or non-fibrous fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, It is preferable in terms of obtaining superior mechanical strength.
[0061]
In order to improve strength, dimensional stability, etc., when such a filler is used, the amount of the filler is not particularly limited, but is usually 30 to 400 parts by weight based on 100 parts by weight of the PPS resin.
[0062]
As long as the effects of the present invention are not impaired in the PPS resin composition of the present invention, a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organic phosphorus compound, talc, kaolin, an organic phosphorus compound, Crystal nucleating agents such as polyether ether ketone, release agents such as polyolefin compounds, silicone compounds, long chain aliphatic ester compounds, long chain aliphatic amide compounds, anticorrosives, coloring inhibitors, antioxidants Conventional additives such as heat stabilizers, lubricants such as lithium stearate and aluminum stearate, UV inhibitors, colorants, flame retardants and foaming agents can be added.
[0063]
These additives can be blended at any stage of producing the PPS resin composition of the present invention. For example, a method of adding at least two components at the same time, Examples thereof include a method of adding the resin after melt-kneading, and a method of adding the resin to one resin first and then melt-kneading and then blending the remaining resin.
[0064]
The molding method of the PPS resin composition obtained from the present invention can be any method, and the molding shape can be any shape. Examples of the molding method include injection molding, extrusion molding, inflation molding, blow molding and the like. Among them, injection molding is preferable because heat treatment and structural fixation can be simultaneously performed in the mold after injection. If it is and / or sheet extrusion molding, heat treatment is preferably performed when the film and / or sheet is stretched, and the structure can be fixed during natural cooling before subsequent winding. Of course, it is possible to heat-treat the molded product separately to form a structure.
[0065]
The PPS resin composition in the present invention can be usefully used as a structural material with improved impact resistance when a resin excellent in impact resistance is used as one of the resins, for example, automotive parts, electrical parts, etc. Can be suitably used.
[0066]
The molded product of the PPS resin composition of the present invention includes connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminals. Board, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts, etc. Suitable for typical electronic component applications, generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, other pole rods , Electrical parts cabinet etc. Electrical equipment parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs / compact discs, audio / video equipment parts such as DVDs, lighting parts, refrigerator parts, Houses represented by air conditioner parts, typewriter parts, word processor parts, office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, Machine-related parts represented by typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, precision machine-related parts; Alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dials, exhaust Gasba Various valves such as fuel, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature Sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, Wiper motor related parts, distributor, starter switch, starter relay, transmission wire , Window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine It can be applied to various applications such as automobile / vehicle-related parts such as oil filters and ignition device cases.
[0067]
In addition, when a resin having excellent low burr properties is used as one of the resins, it is preferable to use injection molding by taking advantage of good burr characteristics, and in particular, electronic parts such as connectors and coils. It is preferable that a connector is used.
[0068]
【Example】
Hereinafter, an example is given and the effect of the present invention is further explained.
[0069]
Reference example (polymerization of PPS resin)
(PPS-1)
A sodium sulfide nonahydrate 6.004 kg (25 mol) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 4.5 kg are charged into an autoclave equipped with a stirrer, and the temperature is gradually raised to 205 ° C. while passing through nitrogen. Distilled 3.6 liters. Next, after cooling the reaction vessel to 180 ° C., 3.719 kg (25.3 mol) of 1,4-dichlorobenzene and 3 kg of NMP were added, sealed under nitrogen, heated to 270 ° C., heated at 274 ° C. for 1 hour. Reacted. After cooling, the reaction product is washed twice with warm water, and then this slurry is placed in an autoclave with a stirring base together with 3 kg of ion-exchanged water, the temperature is raised to 190 ° C., and after reaching 190 ° C., cooled to room temperature and filtered. Washed several times with hot water. This was filtered and then dried under reduced pressure at 80 ° C. for 24 hours to obtain 2.48 kg of PPS resin. This PPS resin is linear and has a melt viscosity of 15 Pa · s (320 ° C., shear rate of 1000 sec.^-1), Glass transition temperature 89 ° C., crystal melting temperature 280 ° C.
[0070]
The glass transition temperature and the crystal melting temperature were measured at a heating rate of 20 ° C./min using DSC (DSC-7 manufactured by PERKIN-ELMER).
[0071]
Examples 1-5
The raw material which consists of a composition of Table 1 is supplied to the twin-screw extruder (Ikegai Kogyo Co., Ltd. PCM-30) set to the extrusion temperature of 320 degreeC, the gut after discharge from a die | dye is rapidly quenched into ice water, Fixed structure. These guts are all transparent, and the gut is stained with nylon-4,6 by the phosphotungstic acid staining method, and then an ultrathin section is cut out to a magnification of 100,000 times with a transmission electron microscope. As a result of the observation, it was confirmed that no structure of 0.001 μm or more was found in any sample and it was incompatible. This shows that this system is compatibilized under shear in an extruder having an extrusion temperature of 320 ° C.
[0072]
Further, a section having a thickness of 100 μm was cut out from the gut that was rapidly cooled in the ice water and the structure was fixed, and the sample of Examples 1 to 3 was 290 ° C., the sample of Example 4 was 310 ° C., and the sample of Example 5 was Heat treatment was performed at 270 ° C., and the structure formation process during the heat treatment was followed using small-angle X-ray scattering. In each sample, a peak appeared after 10 seconds from the start of the heat treatment, and it was observed that this peak increased in intensity without changing its peak position. The process of increasing the intensity without changing the peak position in this small-angle X-ray scattering corresponds to the initial process of spinodal decomposition. Table 1 shows the structural period (Λm) calculated from the peak position (θm) by the following equation.
Λm = (λ / 2) / sin (θm / 2)
In addition, for the section in the initial stage during the small-angle X-ray scattering measurement, a part was immediately cooled in ice water to freeze the structure, and after sung nylon 4 and 6 by phosphotungstic acid staining method, an ultrathin section was cut out. When each sample was observed with a transmission electron microscope at a magnification of 100,000 times, a biphasic continuous structure was observed in each sample.
[0073]
Furthermore, after the section where the small-angle X-ray scattering was measured formed a structure in the initial process, the structure was further formed by continuing heat treatment at each of the temperatures described above for a total of 60 seconds, and the PPS resin composition of the present invention. Got. As for the sample, the results of observation of the structural period from small-angle X-ray scattering and the structure state from transmission electron micrographs are shown in Table 1, as in the initial process. In addition, the interparticle distance in the case of having a dispersed structure is also calculated by the same method as the structural period in the two-phase continuous structure.
[0074]
Further, after discharging from the die, a sheet (thickness 0.2 mm) was prepared by performing heat treatment at the same temperature and time as the heat treatment by a heating press using a gut that was rapidly cooled in ice water and the structure was fixed. Further, a section having a thickness of 100 μm was cut out from the sheet, and the structural period or interparticle distance was obtained from small-angle X-ray scattering and the state of the structure was observed from a transmission electron micrograph as in the cut sample from the gut. The results are shown in Table 1. From this result, it can be seen that the structure is formed in the same manner as the sample cut out from the gut by the heat treatment in the hot press. Next, a sample of length × width × thickness = 50 mm × 10 mm × 0.2 mm was cut out from the sheet and tested with a tensile strength, a tensile elongation, and a punching press measured at a distance between chucks of 20 mm and a tensile speed of 10 mm / min. A piece was taken and a tensile impact test was performed according to ASTM D1822, and the measurement results are shown in Table 1.
[0075]
In addition, the following resins were used.
PPS-1: PPS resin (PPS resin polymerized in the above reference example)
PA-1: Nylon 4,6 resin ("STANYL" manufactured by DSM, The Netherlands, relative viscosity 3.0 with 96% sulfuric acid 1 g / dl, crystal melting temperature 295 ° C).
[0076]
Comparative Example 1
Except that the extrusion temperature was set to 300 ° C., the mixture was melt-kneaded in the same manner as in Examples 1 to 5 and immediately cooled into ice water immediately after discharging from the die to obtain a sample with a fixed structure. In addition, when the sample obtained by dyeing nylon-4,6 by phosphotungstic acid staining method is magnified 1000 times with a transmission electron microscope, a non-uniform dispersion structure of 1.0 μm or more is observed. Things were observed. This shows that this sample is not compatibilized under shear in an extruder having an extrusion temperature of 300 ° C. This is presumably because this system has an LCST type phase diagram and is incompatible with the extrusion temperature of 300 ° C. under shear conditions in the extruder. Also for this sample, the results of measuring the mechanical properties as in Examples 1 to 3 and the results of observing the state of the structure are shown in Table 1.
[0077]
Comparative Example 2
Example 1 is the same as Examples 1 to 3 except that the heat treatment temperature is 260 ° C. for 60 seconds, and the results of measuring the mechanical properties of the sample and the results of observing the structure period and the state of the structure are shown in Table 1. did. However, the structural period of this sample was determined by measurement with a small angle light scattering apparatus. As in this example, when the heat treatment temperature is low and the structure period in the initial process is not sufficiently small, the structure period is controlled within the scope of the present invention when the structure is developed to make the concentration difference between the two components sufficient. It becomes difficult. Further, as in this example, when such a structural period is out of the scope of the present invention, only inferior mechanical properties can be obtained.
[0078]
[Table 1]

[0079]
From these results, it can be seen that the sample in which the structure is developed after the formation of the two-phase continuous structure having a specific structural period in the initial stage of the spinodal decomposition of the present invention has excellent mechanical properties.
[0080]
Examples 6-8
The raw material consisting of the composition shown in Table 2 is supplied to a twin screw extruder (PCM-30 manufactured by Ikegai Kogyo Co., Ltd.) set at an extrusion temperature of 320 ° C., and the gut discharged from the die is immediately quenched into ice water. Fixed structure. Next, an extruded pellet obtained by cutting the gut into pellets using a strand cutter was obtained. The extruded pellet was stained with nylon-4,6 by the phosphotungstic acid staining method, and then the ultrathin section was cut out and observed with a transmission electron microscope at a magnification of 100,000 times. In addition, it was confirmed that a structure of 0.001 μm or more was not seen except for glass fiber and was compatible. This shows that this system is compatibilized under shear in an extruder having an extrusion temperature of 320 ° C.
[0081]
Here, a part of the extruded pellets is supplied to an injection molding machine (PS20E2ASE manufactured by Nissei Plastic Industry Co., Ltd.) set at a resin temperature of 320 ° C. and a mold temperature of 20 ° C., with an injection speed of 60% and an injection pressure described later. Injection molding was performed with a time cycle of 10 seconds for injection time and 60 seconds for holding pressure under the conditions of one speed and one pressure to obtain a connector molded product having a shape described later (the mold temperature was set to 20 ° C. and injection was performed). This means that by rapidly cooling the molded product after molding in the mold, the progress of phase decomposition was stopped, and the structure was frozen in the initial stage of spinodal decomposition.) A sample cut out from the surface layer of the obtained molded product, dyed nylon-4,6 by phosphotungstic acid staining method, and further cut out an ultrathin section, which was magnified 100,000 times with a transmission electron microscope and observed. As a result, a 0.01 μm double-phase continuous structure was observed in all samples.
[0082]
Next, a part of the extruded pellet was separately molded under the same conditions as the above injection conditions except that the mold temperature was set to 150 ° C. As above, a connector molded product was injection molded, and from the surface layer portion of the obtained molded product. The results of obtaining the structural period or interparticle distance from the small-angle X-ray scattering and the results of observing the structural state from the transmission electron microscope are shown in Table 2. At the mold temperature of 150 ° C. in this example, it can be seen that the structure is developed after the structure is formed in the initial process of spinodal decomposition as described above.
[0083]
The burr length is measured by two rows of 50 pin holes (pin hole interval 1.27 mm), the inner glue is 68 mm x 5 mm x height 7 mm, and the glue is 70 mm x 7 mm x height 9 A connector molded product having a box shape of 3 mm and having ribs at both ends in the longitudinal direction, firstly, the minimum injection pressure at which the resin is filled to the tip is obtained, and the pressure +3 kgf / cm²Molding was performed at an injection pressure of (gauge pressure), and the burr length generated in the pin hole portion of the obtained molded piece was measured using a universal projector and obtained from the average value. The results are shown in Table 2.
[0084]
Further, a part of the extruded pellet is supplied to an injection molding machine (PS20E2ASE manufactured by Nissei Plastic Industry Co., Ltd.) set at a resin temperature of 320 ° C. and a mold temperature of 150 ° C., and filled to the tip at an injection speed of 60%. Minimum pressure + 3kgf / cm²Injection molding was performed in a time cycle of an injection time of 10 seconds and a pressure holding time of 60 seconds under the condition of one speed and one pressure at an injection pressure of (gauge pressure) to obtain an Izod impact test piece compliant with ASTM D256. Table 2 shows the results of measuring the Izod impact strength of the obtained molded product in accordance with ASTM D256.
[0085]
In addition, the following resins were used.
PPS-1: PPS resin (PPS resin polymerized in the above reference example)
PA-1: Nylon 4,6 resin ("STANYL" manufactured by DSM, The Netherlands, relative viscosity 3.0 at 96 g sulfuric acid 1 g / dl)
GF-1: E glass having an average fiber diameter of 13 μm
R-1: Carboxylic acid amide wax (reaction product “WH255” of stearic acid, sebacic acid and ethylenediamine).
[0086]
Comparative Example 4
Except that the extrusion temperature was set to 300 ° C., the mixture was melt-kneaded in the same manner as in Examples 6 to 8, and immediately cooled after being discharged from the die into ice water to obtain a sample having a fixed structure. A sample obtained by dyeing nylon-4,6 by phosphotungstic acid staining method and then cutting out an ultrathin section was observed at a magnification of 1000 times with a transmission electron microscope. A non-uniform dispersion structure of 0.0 μm or more was observed. This shows that this sample is not compatibilized under shear in an extruder having an extrusion temperature of 300 ° C. This is presumably because this system has an LCST type phase diagram and is incompatible with the extrusion temperature of 300 ° C. under shear conditions in the extruder. Also for this sample, the results of measuring the Izod impact strength and burr length as in Examples 6 to 8 and the results of observing the state of the structure are shown in Table 2.
[0087]
[Table 2]

[0088]
From these results, in the initial process of spinodal decomposition according to the present invention, a sample in which a structure is developed after forming a biphasic continuous structure having a specific structural period has excellent Izod impact strength and a short burr length. It can be seen that it has excellent burr characteristics.
[0089]
Example 9
The raw material which consists of a composition of Table 3 is supplied to the twin-screw extruder (Ikegai Kogyo Co., Ltd. PCM-30) set to the extrusion temperature of 320 degreeC, and the gut after discharge from die | dye is rapidly cooled to ice water, Fixed structure. All of these guts are transparent, and the gut is stained with nylon 6 oligomer by the phosphotungstic acid staining method, and then the ultrathin section is cut out and observed with a transmission electron microscope at a magnification of 100,000 times. Although it went, about any sample, the structure of 0.001 micrometer or more was not seen but it confirmed that it was compatibilizing. This shows that this system is compatibilized under shear in an extruder having an extrusion temperature of 320 ° C.
[0090]
Further, a section having a thickness of 100 μm was cut out from a gut that had been rapidly cooled in the ice water and the structure was fixed, and heat-treated at 320 ° C., and the structure formation process during the heat treatment was followed using small-angle X-ray scattering. In each sample, a peak appeared after 5 minutes from the start of the heat treatment, and it was observed that this peak increased in intensity without changing its peak position. The process of increasing the intensity without changing the peak position in this small-angle X-ray scattering corresponds to the initial process of spinodal decomposition. Table 3 shows the structural period (Λm) calculated from the peak position (θm) by the following equation.
Λm = (λ / 2) / sin (θm / 2)
In addition, for the section in the initial process during the small-angle X-ray scattering measurement, a part of the specimen was immediately cooled in ice water, the structure was fixed, and after the nylon 6 oligomer was stained by the phosphotungstic acid staining method, a sample was cut out. Was observed with a transmission electron microscope at a magnification of 100,000 times, and a two-phase continuous structure was observed.
[0091]
Next, the above gut is pelletized, supplied again to a twin screw extruder (TEX30α manufactured by Nippon Steel) with an extrusion temperature set at 320 ° C. and adjusted for a residence time of 5 minutes. The gut after discharge was immediately cooled in ice water to fix the structure. The gut showed a slight decrease in transparency, and the gut was stained with nylon 6 oligomer by the phosphotungstic acid staining method, and then a sample obtained by cutting out an ultrathin section was observed with a transmission electron microscope. A phase-continuous structure was observed. From these facts, it is considered that in this system, the nylon 6 oligomer was polymerized again during melt kneading, and the phase decomposition was caused by the increase in the molecular weight.
[0092]
The gut that has been melt-kneaded again is formed into a sheet by a heating press (320 ° C. × 3 minutes), and a sample of length × width × thickness = 50 mm × 10 mm × 0.2 mm is obtained from the obtained sheet (thickness 0.2 mm). Cut out, take test piece with tensile strength, tensile elongation and punching press measured at 20mm distance between chucks, tensile speed 10mm / min, and perform tensile impact test according to ASTM D1822, the measurement results, structure period, structure The results of observation of the state are shown in Table 3.
[0093]
In addition, the following resins were used.
PPS-1: PPS resin (PPS resin polymerized in the above reference example)
PA-2: Nylon 6 oligomer (in a concentrated sulfuric acid, having a concentration of 1%, a relative viscosity measured at 25 ° C. of 1.20, and a crystal melting temperature measured by DSC of 225 ° C.).
[0094]
Comparative Example 5
Except that nylon 6 having a high molecular weight was used as a resin to be blended with the PPS resin, it was melt-kneaded in the same manner as in Example 9 and immediately cooled after being discharged from the die into ice water to obtain a sample having a fixed structure. This sample is cloudy, and when the sample is stained with nylon 6 by the phosphotungstic acid staining method and observed with a transmission electron microscope at 1000 times magnification, a non-uniform dispersion structure of 1 μm or more Things were observed. This shows that this sample is not compatibilized under shear in an extruder having an extrusion temperature of 320 ° C. For this system, the results of measuring the mechanical properties as in Example 9 and the results of observing the structure period and the state of the structure are shown in Table 3.
[0095]
In addition, the following resins were used.
PA-3: Nylon 6 (in concentrated sulfuric acid, concentration 1%, relative viscosity measured at 25 ° C. 3.20, crystal melting temperature measured by DSC 225 ° C.)
[0096]
[Table 3]

[0097]
From these results, it can be seen that the sample in which the structure is developed after the formation of the two-phase continuous structure having a specific structural period in the initial stage of the spinodal decomposition of the present invention has excellent mechanical properties.
[0098]
【The invention's effect】
According to the present invention, a PPS resin composition having excellent mechanical properties and excellent low burr properties and useful as a molding material can be obtained. In a more preferable embodiment, a PPS resin composition having excellent regularity, finely controlling the structure, and further sufficiently developing the concentration difference between the two phases of the structure can be obtained. Moreover, the PPS resin composition which is useful as a structural material by utilizing the excellent mechanical properties according to the present invention, and further useful as an injection molding material by utilizing the excellent low burr property has been obtained.

Claims (19)

Consisting of at least two component resins, polyphenylene sulfide resin , polyester, polyamide, polyetherimide, polyamideimide, polyimide, polycarbonate, polyetherketone, polythioetherketone, polyetheretherketone, polyphenylene oxide, polysulfone, and polyether A polyphenylene sulfide resin composition comprising one or more resins other than polyphenylene sulfide resin selected from sulfones , wherein the polyphenylene sulfide resin composition has a biphasic continuous structure having a structural period of 0.01 to 1 μm, or an interparticle distance of 0.01. A polyphenylene sulfide resin composition having a dispersion structure of ˜1 μm. It consists of at least two components that are phase-separated by spinodal decomposition, and polyphenylene sulfide resin , polyester, polyamide, polyetherimide, polyamideimide, polyimide, polycarbonate, polyetherketone, polythioetherketone, polyetheretherketone, A polyphenylene sulfide resin composition comprising at least one resin other than a polyphenylene sulfide resin selected from polyphenylene oxide, polysulfone, and polyether sulfone, and having a structure period of 0.001 to 0.1 μm in the initial stage of the spinodal decomposition After the formation of the continuous structure, it is further developed into a two-phase continuous structure with a structural period of 0.01 to 1 μm or a dispersed structure with a distance between particles of 0.01 to 1 μm. Phenylene sulfide resin composition. 3. The polyphenylene sulfide resin composition according to claim 1 or 2, wherein the polyphenylene sulfide resin is in the range of 50 to 97% by weight with respect to 100% by weight of the total resin components constituting the polyphenylene sulfide resin composition. The polyphenylene sulfide resin composition described in 1. 4. The polyphenylene sulfide resin composition according to claim 3, wherein the polyphenylene sulfide resin is in the range of 50 to 75% by weight with respect to a total of 100% by weight of the resin components constituting the polyphenylene sulfide resin composition. Polyphenylene sulfide resin composition. The polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein the resin other than the polyphenylene sulfide resin is polyamide. The polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein the polyphenylene sulfide resin composition is produced through melt-kneading. The polyphenylene sulfide resin composition according to claim 6 , wherein the spinodal decomposition is compatible under shearing during melt kneading and phase-separated under non-shearing after discharge. The polyphenylene sulfide resin composition is obtained by inducing spinodal decomposition by chemically reacting at least one precursor of resin components constituting the polyphenylene sulfide resin composition in the presence of the remaining resin components. The polyphenylene sulfide resin composition according to claim 1, wherein The polyphenylene sulfide resin composition according to claim 8 , wherein the spinodal decomposition is one which is once dissolved before a chemical reaction and phase-separated after the chemical reaction. The polyphenylene sulfide resin composition according to any one of claims 1 to 9, which is used for injection molding. The polyphenylene sulfide resin composition according to any one of claims 1 to 9, which is for film and / or sheet extrusion molding. Consisting of at least two component resins, polyphenylene sulfide resin , polyester, polyamide, polyetherimide, polyamideimide, polyimide, polycarbonate, polyetherketone, polythioetherketone, polyetheretherketone, polyphenylene oxide, polysulfone, and polyether A method for producing a polyphenylene sulfide resin composition in which a polyphenylene sulfide resin composition containing at least one resin other than polyphenylene sulfide resin selected from sulfone is phase-separated by spinodal decomposition, wherein the structural period is 0.001 in the initial stage of spinodal decomposition. After forming a continuous structure of both phases of ˜0.1 μm, further to a continuous structure of both phases having a structural period of 0.01 to 1 μm or a dispersed structure having a distance between particles of 0.01 to 1 μm Method for producing a polyphenylene sulfide resin composition characterized in that allowed to exhibition. 13. The polyphenylene sulfide resin composition according to claim 12, wherein the polyphenylene sulfide resin is in the range of 50 to 97% by weight with respect to a total of 100% by weight of the resin components constituting the polyphenylene sulfide resin composition. A method for producing a polyphenylene sulfide resin composition. 14. The polyphenylene sulfide resin composition according to claim 13, wherein the polyphenylene sulfide resin is in the range of 50 to 75% by weight with respect to a total of 100% by weight of the resin components constituting the polyphenylene sulfide resin composition. A method for producing a polyphenylene sulfide resin composition. Consisting of at least two component resins, polyphenylene sulfide resin , polyester, polyamide, polyetherimide, polyamideimide, polyimide, polycarbonate, polyetherketone, polythioetherketone, polyetheretherketone, polyphenylene oxide, polysulfone, and polyether The polyphenylene sulfide resin according to any one of claims 12 to 14, wherein spinodal decomposition is induced by melt-kneading a polyphenylene sulfide resin composition containing one or more resins other than the polyphenylene sulfide resin selected from sulfones. A method for producing the composition. The method for producing a polyphenylene sulfide resin composition according to any one of claims 12 to 15, wherein the resin other than the polyphenylene sulfide resin is polyamide. The method for producing a polyphenylene sulfide resin composition according to claim 15 or 16 , wherein the resin of at least two components is dissolved under shearing during melt kneading and phase separation is performed under non-shearing after discharge. The spinodal decomposition is induced by chemically reacting at least one precursor of the resin components constituting the polyphenylene sulfide resin composition in the presence of the remaining resin components . A method for producing the polyphenylene sulfide resin composition according to claim 1 . 19. The method for producing a polyphenylene sulfide resin composition according to claim 18 , wherein the solution is once dissolved before the chemical reaction and phase-separated after the chemical reaction.