JP3549623B2 - Resin composition - Google Patents

Description

（式中、Ｒは上記のモノカルボン酸からカルボキシル基を除いた残基であり、好ましくはアルキル基、シクロアルキル基、アリール基、アラルキル基である。）
【００２１】
末端封止剤として使用されるモノアミンとしては、カルボキシル基との反応性を有するものであれば特に制限はないが、例えば、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ステアリルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミンなどの脂肪族モノアミン；シクロヘキシルアミン、ジシクロヘキシルアミンなどの脂環式モノアミン；アニリン、トルイジン、ジフェニルアミン、ナフチルアミンなどの芳香族モノアミン、あるいはこれらの任意の混合物を挙げることができる。これらのうち、反応性、沸点、封止末端の安定性および価格などの点から、ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ステアリルアミン、シクロヘキシルアミン、アニリンが特に好ましい。
【００２２】
ポリアミドの末端基をモノアミンで封止する場合は、ポリアミドの製造に際してジカルボン酸成分に対するジアミン成分の使用モル数をわずかに少なくして、ポリアミドの両末端がカルボキシル基になるようにし、モノアミンを末端封止剤として加えるのがよい。
【００２３】
ポリアミドのカルボキシル基末端は、これらのモノアミンで封止されることにより、下記の一般式（ＩＩ）で示される封止末端を形成する。
【００２４】
【化２】

（式中、Ｒ^１は上記のモノアミンからアミノ基を除いた残基であり、好ましくはアルキル基、シクロアルキル基、アリール基、アラルキル基である。Ｒ^２は水素原子または上記のモノアミンからアミノ基を除いた残基であり、好ましくは水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基である。）
【００２５】
ポリアミドを製造する際に用いられる末端封止剤の使用量は、用いる末端封止剤の反応性、沸点、反応装置、反応条件などによって変化するが、通常、ジカルボン酸とジアミンの総モル数に対して０．１〜１５モル％の範囲内で使用されるのが好ましい。
【００２６】
本発明に用いられるポリアミドは、従来よりポリアミドを製造する方法として知られている、溶融重合法、溶液重合法、反応型押出機を使用する重合法などの方法を用いて製造することができる。本発明者らの研究によれば、触媒および必要に応じて末端封止剤を、最初にジアミンおよびジカルボン酸に一括して添加し、ナイロン塩を製造した後、いったん２８０℃以下の温度において濃硫酸中３０℃における極限粘度［η］が０．１０〜０．６０ｄｌ／ｇのプレポリマーとし、さらに固相重合するか、あるいは溶融押出機を用いて重合を行うことにより、容易にポリアミドを得ることができる。プレポリマーの極限粘度［η］が０．１０〜０．６０ｄｌ／ｇの範囲内であると、後重合の段階においてカルボキシル基とアミノ基のモルバランスのずれや重合速度の低下が少なく、さらに分子量分布の小さな、各種性能や成形性に優れたポリアミドが得られる。重合の最終段階を固相重合により行う場合、減圧下または不活性ガス流通下に行うのが好ましく、重合温度が１８０〜２８０℃の範囲内であれば、重合速度が大きく、生産性に優れ、着色やゲル化を有効に押さえることができるので好ましい。重合の最終段階を溶融押出機により行う場合、重合温度が３７０℃以下であるとポリアミドの分解がほとんどなく、劣化の無いポリアミドが得られるので好ましい。
【００２７】
ポリアミドの製造の際に用いることができる触媒としては、リン酸、亜リン酸、次亜リン酸、またはそれらのアンモニウム塩、それらの金属塩（カリウム、ナトリウム、マグネシウム、バナジウム、カルシウム、亜鉛、コバルト、マンガン、錫、タングステン、ゲルマニウム、チタン、アンチモンなどの金属塩）、それらのエステル類（エチルエステル、イソプロピルエステル、ブチルエステル、ヘキシルエステル、イソデシルエステル、オクタデシルエステル、デシルエステル、ステアリルエステル、フェニルエステル）などを挙げることができる。
【００２８】
本発明に用いられるポリアミドは、濃硫酸中３０℃で測定した極限粘度［η］が０．４〜３．０ｄｌ／ｇの範囲内であり、０．６〜２．０ｄｌ／ｇの範囲内のものが好ましく、０．８〜１．８ｄｌ／ｇの範囲内のものがより好ましい。ポリアミドの極限粘度［η］が上記の範囲内であれば、成形性に優れるだけでなく、力学特性、耐熱特性などの諸物性に優れた樹脂組成物が得られる。
【００２９】
本発明に用いられるポリフェニレンスルフィドは、下記の一般式（ＩＩＩ）で示される構造単位を全構造単位の７０モル％以上、好ましくは９０モル％以上含有する重合体である。
【００３０】
【化３】

【００３１】
上記の一般式（ＩＩＩ）で示される構造単位以外の構造単位としては、以下に示す一般式（ＩＶ）〜（ＶＩＩＩ）で示される構造単位を挙げることができ、これらのうち１種または２種以上を含んでいてもよい。
【００３２】
【化４】

【００３３】
【化５】

【００３４】
【化６】

【００３５】
【化７】

【００３６】
【化８】

【００３７】
なお、一般式（ＩＶ）〜（ＶＩＩＩ）で示される構造単位は、芳香族環にアルキル基、ニトロ基、フェニル基、アルコキシ基などの置換基を有していてもよい。
【００３８】
さらに、全構造単位の１０モル％以下であれば、下記の一般式（ＩＸ）で示されるような３官能の構造単位を含んでいてもよい。
【００３９】
【化９】

【００４０】
本発明に用いられるポリフェニレンスルフィドは、フローテスターを使用して、荷重２０Ｋｇ、温度３００℃で測定した溶融粘度が、１００〜１００００ｐｏｉｓｅであるものが好ましく、２００〜５０００ｐｏｉｓｅであるものがより好ましく 、３００〜３０００ｐｏｉｓｅであるものがさらに好ましい。溶融粘度がこの範囲内のポリフェニレンスルフィドを使用すれば、得られる樹脂組成物の成形性が良く、力学強度にも優れる。
【００４１】
このようなポリフェニレンスルフィドは、公知の方法を利用して製造することができる。例えば、ｐ−ジクロルベンゼンをイオウと炭酸ナトリウムとの存在下に重合させる方法、ｐ−ジクロルベンゼンを極性溶媒中で硫化ナトリウムと水酸化ナトリウムの存在下に重合させる方法、ｐ−ジクロルベンゼンを硫化水素と水酸化ナトリウムの存在下に重合させる方法、ｐ−クロルチオフェノールの自己重合法などを挙げることができる。このような重合法のうちでも、Ｎ−メチルピロリドンあるいはジメチルアセトアミドなどのアミド系溶媒、またはスルホラン等のスルホン系溶媒中で、硫化ナトリウムとｐ−ジクロルベンゼンとを反応させる方法が好ましい。なお、このような重合反応に際して、得られるポリフェニレンスルフィドの重合度を制御するために、カルボン酸あるいはスルホン酸の金属塩を添加することもできる。
【００４２】
本発明の樹脂組成物は、上記のポリアミドおよびポリフェニレンスルフィドからなり、ポリアミドとポリフェニレンスルフィドの重量比は、５：９５〜９９．９：０．１であり、５：９５〜９５：５であるのが好ましく、２０：８０〜８０：２０であるのがより好ましい。ポリアミドとポリフェニレンスルフィドの重量比が上記の割合である樹脂組成物は、力学強度、低吸水性、耐薬品性などに優れている。
【００４３】
上記の樹脂組成物１００重量部に対して、さらに充填剤を１〜２００重量部配合することができる。このような割合で充填剤を配合することにより、力学特性、熱変形温度などの特性がより向上した樹脂組成物が得られるので好ましい。充填剤の配合割合は、ポリアミド１００重量部に対して、１〜１５０重量部であるのがより好ましく、２〜１００重量部であるのがさらに好ましい。
【００４４】
充填剤としては、従来より知られている粉末状、繊維状、クロス状などの各種形態を有する充填剤を用いることができる。
【００４５】
粉末状充填剤としては、シリカ、シリカアルミナ、アルミナ、酸化チタン、酸化亜鉛、窒化ホウ素、タルク、マイカ、チタン酸カリウム、ケイ酸カルシウム、硫酸マグネシウム、ホウ酸アルミニウム、アスベスト、ガラスビーズ、カーボンブラック、グラファイト、二硫化モリブデン、ポリテトラフルオロエチレンなどを挙げることができる。このような粉末状充填剤としては、通常、平均粒径が０．１μｍ〜２００μｍの範囲ものを用いるのが好ましく、１μｍ〜１００μｍの範囲のものを用いるのがより好ましい。これらの粉末状充填剤を用いると、樹脂組成物から得られる成形品の力学強度、低吸水性、耐熱性などが向上する。
【００４６】
繊維状充填剤としては、ポリパラフェニレンテレフタルアミド繊維、ポリメタフェニレンテレフタルアミド繊維、ポリパラフェニレンイソフタルアミド繊維、ポリメタフェニレンイソフタルアミド繊維、ジアミノジフェニルエーテルとテレフタル酸またはイソフタル酸との縮合物から得られる繊維などの全芳香族ポリアミド繊維、全芳香族液晶ポリエステル繊維などの有機系の繊維状充填剤；あるいはガラス繊維、炭素繊維またはホウ素繊維などの無機系の繊維状充填剤が挙げられる。このような繊維状充填剤を使用すると、樹脂組成物から得られる成形品の摺動特性が向上するだけでなく、機械特性、耐熱特性、物理化学的特性などが向上するので好ましい。このような繊維状充填剤としては、通常、平均長が０．０５〜５０ｍｍの範囲のものを用いるのが好ましい。さらに、成形性が良好であり、得られる成形品の摺動特性、耐熱性、機械的特性がより向上する点で、平均長が１〜１０ｍｍの範囲のものを用いるのがより好ましい。これらの繊維状充填剤は、クロス状などに二次加工されていてもよい。
【００４７】
これらの充填剤は、１種または２種以上混合して使用することができる。特に、上記の繊維状充填剤と、粉末状充填剤とを組合わせて使用することにより、成形性、表面美麗性、力学特性、および耐熱性がより優れた樹脂組成物を得ることができるので好ましい。また、これらの充填剤として、シランカップリング剤あるいはチタンカップリング剤などで表面処理した物を使用することもできる。充填剤の表面をこれらのカップリング剤で処理したものを使用すると、得られる成形品の力学特性が優れる点で好ましい。シランカップリング剤のなかでも、得られる成形品の力学特性が特に優れることから、アミノシラン系のカップリング剤を使用することがより好ましい。
【００４８】
その他必要に応じて、銅化合物などの安定剤；着色剤；紫外線吸収剤；光安定化剤；ヒンダードフェノール系、ヒンダードアミン系、リン系、チオ系などの酸化防止剤；帯電防止剤；臭素化ポリマー、酸化アンチモン、金属水酸化物などの難燃剤；結晶核剤；可塑剤；潤滑剤、スリップ防止剤、アンチブロッキング剤、防曇剤、顔料、染料、天然油、合成油およびワックスなどをポリアミドの重縮合反応時、またはその後に添加することもできる。
【００４９】
また、本発明の樹脂組成物には、本発明の効果を損なわない範囲内で、耐熱性の熱可塑性樹脂を配合することもできる。このような耐熱性の熱可塑性樹脂としては、例えば、ＰＰＥ（ポリフェニルエーテル）、ＰＥＳ（ポリエーテルスルフォン）、ＰＥＩ（ポリエーテルイミド）、ＬＣＰ（液晶ポリマー）およびこれらの樹脂の変性物などを挙げることができる。
【００５０】
本発明の樹脂組成物は、上記のポリアミドとポリフェニレンスルフィドとを、さらに、必要に応じて上記の充填剤や耐熱性の熱可塑性樹脂を、所望の方法で混合することにより製造することができる。例えば、樹脂材料の混合に通常用いられるような縦型または水平型の混合機を用いて予備混合した後、一軸または二軸の押出機、ニーダー、ミキシングロール、バンバリーミキサーなどの混練装置を用いて、加熱下に溶融混練することにより、本発明の樹脂組成物が製造される。
【００５１】
上記のようにして製造した樹脂組成物を用いて、通常の溶融成形法、例えば、圧縮成形法、射出成形法、押出成形法などにより所望の形状の成形品を製造することができる。
【００５２】
例えば、本発明の樹脂組成物を、シリンダ温度がポリアミドおよびポリフェニレンスルフィドの融点以上の温度に調節された射出成形機のシリンダ内で樹脂を溶融させ、所定の形状の金型内に導入（射出）することにより成形品を製造することができる。また、上記のシリンダ温度に調節された押出機内で樹脂を溶融させ、口金ノズルより紡出することにより、繊維を製造することができる。さらに、上記のシリンダ温度に調節された押出機内で樹脂を溶融させ、Ｔダイから樹脂を押出すことにより、フィルムを製造することができる。さらに、インフレーション成形、吹き込み成形などによってもフィルムやボトルなどの成形品を得ることができる。
【００５３】
本発明の樹脂組成物からなる成形品としては、例えば、電動工具、一般工業用部品、ギヤ、カムなどの機械部品、コネクタ、スイッチ、リレー、ＭＩＤ、プリント配線板、電子部品のハウジングなどのような電子部品、フィルム、シート、繊維など種々の形態の成形品を挙げることができる。特に、自動車用途の成形品、例えば、自動車の内外装部品、自動車のエンジンルーム内の部品、自動車の電装部品などに好適に使用することができる。
【００５４】
【実施例】
以下、実施例を挙げて本発明を具体的に説明するが、本発明はこれらにより何ら制限されるものではない。なお、以下の例において、ポリアミドの末端封止率、極限粘度、融点；成形品の引張強度、熱水処理後の引張強度保持率、アルコール処理後の引張強度保持率、耐ハンダ性、耐熱老化性は、下記の方法により測定または評価した。
【００５５】
末端封止率：
^１Ｈ−ＮＭＲ（５００ＭＨｚ，重水素化トリフルオロ酢酸中、５０℃で測定）を用い、各末端基ごとの特性シグナルの積分値よりカルボキシル基末端、アミノ基末端および封止末端の数をそれぞれ測定し、前記の式（１）から末端封止率を求めた。測定に用いた代表的なシグナルの化学シフト値を以下に示す。
【００５６】
【表１】

【００５７】
極限粘度［η］：
濃硫酸中、３０℃にて、０．０５，０．１，０．２，０．４ｇ／ｄｌの濃度の試料の固有粘度（ηｉｎｈ ）を測定し、これを濃度０に外挿した値を極限粘度［η］とした。
ηｉｎｈ ＝［ｌｎ（ｔ_１／ｔ_０）］／ｃ
〔式中、ηｉｎｈ は固有粘度（ｄｌ／ｇ）、ｔ_０は溶媒の流下時間（秒）、ｔ_１は試料溶液の流下時間（秒）、ｃは溶液中の試料の濃度（ｇ／ｄｌ）を表す。〕
【００５８】
融点：
示差走査熱量計（メトラー社製「ＤＳＣ３０」）を用いて、試料を１００℃／分の速度で昇温して完全に融解させた後、１０℃／分の降温速度で５０℃まで冷却し、再び１０℃／分の速度で昇温した時に現れる吸熱ピークの位置の温度を測定し、これを融点とした。
【００５９】
引張強度：
絶乾状態のＪＩＳ１号ダンベル型射出成形片を用い、ＪＩＳ Ｋ ７１１３に準拠して測定した。
【００６０】
熱水処理後の引張強度保持率：
ＪＩＳ１号ダンベル型射出成形片を、８０℃の熱水中に１週間浸漬した。浸漬前後の成形品の引張強度を測定し、引張強度の保持率（％）を求めた。
【００６１】
アルコール処理後の引張強度保持率：
ＪＩＳ１号ダンベル型射出成形片を、２３℃のメタノール中に１週間浸漬した。浸漬前後の成形品の引張強度を測定し、引張強度の保持率（％）を求めた。
【００６２】
耐ハンダ性：
４０×１００×１ｍｍの射出成形品を、ハンダ浴に３０秒間浸漬し、成形品の変形が生じた時のハンダ浴の温度を測定した。
【００６３】
耐熱老化性：
ＪＩＳ１号ダンベル型射出成形片を、１５０℃のギヤオーブン中で１００時間（充填剤を含まない系）、または１９０℃のギヤオーブン中で９００時間（充填剤を含む系）処理した。処理前後の成形品の引張強度を測定し、引張強度の保持率（％）を求めた。
【００６４】
参考例１
テレフタル酸３２５６．２ｇ（１９．６０モル）、１，９−ノナンジアミン３１６５．８ｇ（２０．０モル）、安息香酸９７．７ｇ（０．８０モル）、次亜リン酸ナトリウム一水和物６．５ｇ（原料に対して０．１重量％）および蒸留水２．２リットルを内容積２０リットルのオートクレーブに入れ、窒素置換した。１００℃で３０分間撹拌し、２時間かけて内部温度を２１０℃に昇温した。この時、オートクレーブは２２ｋｇ／ｃｍ^２まで昇圧した。そのまま１時間反応を続けた後２３０℃に昇温し、その後２時間、２３０℃に温度を保ち、水蒸気を徐々に抜いて圧力を２２ｋｇ／ｃｍ^２に保ちながら反応させた。次に、３０分かけて圧力を１０ｋｇ／ｃｍ^２まで下げ、更に１時間反応させて、極限粘度［η］が０．２５ｄｌ／ｇのプレポリマーを得た。これを、１００℃、減圧下で１２時間乾燥し、２ｍｍ以下の大きさまで粉砕した。これを２３０℃、０．１ｍｍＨｇ下にて、１０時間固相重合し、融点が３１７℃、極限粘度［η］が１．１０ｄｌ／ｇ、末端の封止率が９０％である白色のポリアミドを得た。
【００６５】
参考例２〜８
ジカルボン酸成分、ジアミン成分および末端封止剤（安息香酸）を、下記の表２に示した割合で用いる以外は、参考例１と同様に製造することによりポリアミドを得た。得られたポリアミドの極限粘度［η］、末端封止率および融点を併せて下記の表２に示す。
【００６６】
【表２】

【００６７】
実施例１〜３、比較例１〜３および参考例９〜１０
参考例１〜８で得られたポリアミドと、ポリフェニレンスルフィド（東レ製「Ｍ２５８８」）とを、下記の表３に示した割合で混合し、東洋精機製作所製の二軸押出機「ラボプラストミル２Ｄ２５Ｗ」を使用して、シリンダー温度をポリアミドの融点よりも２０〜４０℃高い温度に設定し、４０ｒｐｍの回転速度で溶融状態で押出すことにより樹脂組成物を得た。この樹脂組成物を、日精樹脂工業製の射出成形機「ＦＳ８０Ｓ１２ＡＳＥ」を用いて、シリンダー温度を樹脂の融点よりも２０〜４０℃高い温度に、金型温度を１５０℃に設定して射出成形した。得られた成形品について評価した結果を下記の表３に示す。
【００６８】
【表３】

【００６９】
実施例４〜８
参考例２で得られたポリアミドおよびポリフェニレンスルフィド（東レ製「Ｍ２５８８」）を、下記の表４に示した割合で混合し、東洋精機製作所製の二軸押出機「ラボプラストミル２Ｄ２５Ｗ」を使用して、シリンダー温度をポリアミドの融点よりも２０〜４０℃高い温度に設定し、４０ｒｐｍの回転速度で溶融状態で押出すことにより樹脂組成物を得た。この樹脂組成物を、日精樹脂工業製の射出成形機「ＦＳ８０Ｓ１２ＡＳＥ」を用いて、シリンダー温度を樹脂の融点よりも２０〜４０℃高い温度に、金型温度を１５０℃に設定して射出成形した。得られた成形品について評価した結果を下記の表４に示す。
【００７０】
【表４】

【００７１】
実施例９〜１１、比較例４および参考例１１
下記の表５に示したポリアミドおよびポリフェニレンスルフィド（東レ製「Ｍ２５８８」）を、下記の表５に示した割合で混合し、東洋精機製作所製の二軸押出機「ラボプラストミル２Ｄ２５Ｗ」を使用して、シリンダー温度をポリアミドの融点よりも２０〜４０℃高い温度に設定し、４０ｒｐｍの回転速度で溶融状態で押出してペレット化した。こうして得られたペレットと下記の表５に記載した充填剤を、表５に示した割合で混合し、プラスチック工学研究所製の一軸押出機「ＵＴ−４０Ｈ」を用いて、シリンダー温度をポリアミドの融点よりも２０〜４０℃高い温度に設定し、溶融状態で押出すことにより充填剤が配合された樹脂組成物を得た。この樹脂組成物を、日精樹脂工業製の射出成形機「ＦＳ８０Ｓ１２ＡＳＥ」を用いて、シリンダー温度を樹脂の融点よりも２０〜４０℃高い温度に、金型温度を１５０℃に設定して射出成形した。得られた成形品について評価した結果を下記の表５に示す。
【００７２】
【表５】

【００７３】
【発明の効果】
本発明の樹脂組成物は、優れた耐熱老化性を示すと共に、靱性、耐ハンダ性、耐熱水性、耐薬品性、低吸水性、成形性のいずれにも優れており、これらの樹脂組成物から得られる成形品は、産業資材、工業材料、家庭用品などの用途に好適に使用することができる。[0001]
[Industrial applications]
The present invention relates to a resin composition comprising a specific semi-aromatic polyamide and polyphenylene sulfide, a resin composition obtained by blending a filler with the resin composition, and a molded article comprising these resin compositions. The resin composition of the present invention exhibits excellent heat aging resistance, and is excellent in toughness, solder resistance, hot water resistance, chemical resistance, low water absorption, and moldability. The obtained molded article can be suitably used for applications such as industrial materials, industrial materials, and household goods.
[0002]
[Prior art]
Conventionally, aliphatic polyamides such as nylon 6, nylon 66, and nylon 610 have been used as engineering plastics. Although such an aliphatic polyamide has good moldability, it has a low glass transition temperature (for example, the glass transition temperature of nylon 66 is about 60 ° C.), and is not suitable as an engineering plastic used at a high temperature. .
[0003]
For the purpose of improving the heat resistance of the aliphatic polyamide, there has been proposed a method of blending polyphenylene sulfide with the aliphatic polyamide. For example, JP-A-61-126172 describes a resin composition comprising nylon 66, polyphenylene sulfide and reinforcing fibers. However, when a molded article obtained from the resin composition using such an aliphatic polyamide is left under a condition of about 180 ° C. or higher, the tensile strength is significantly reduced. Therefore, as long as the aliphatic polyamide is used, the working temperature at which the excellent mechanical strength can be sufficiently exerted is about 60 to 80 ° C., and the temperature is higher than this (for example, 100 ° C. or more). It is not suitable for various uses.
[0004]
Further, in order to obtain a polyamide having excellent heat resistance, a method using an aromatic polyamide instead of an aliphatic polyamide has been proposed. For example, JP-A-5-5060 and JP-A-7-126525 describe a resin composition comprising an aromatic polyamide and polyphenylene sulfide.
[0005]
[Problems to be solved by the invention]
According to the study of the present inventors, the resin composition obtained by additionally testing the methods described in JP-A-5-5060 and JP-A-7-126525 has improved heat resistance to some extent. However, in addition to the increasing demands for heat resistance in recent years, it has not been possible to sufficiently respond to requirements for solder resistance, hot water resistance, chemical resistance, and the like. Further, in the above publication, although it is mentioned that a longer-chain aliphatic diamine can be used as the diamine component of the aromatic polyamide in addition to 1,6-hexanediamine, the number of carbon atoms is 7 or more. There is no specific disclosure that the use of a diamine of the formula (1) exhibits higher performance than the case of using 1,6-hexamethylenediamine.
[0006]
An object of the present invention is to provide a resin composition exhibiting excellent heat aging resistance, and having excellent toughness, solder resistance, hot water resistance, chemical resistance, low water absorption, and moldability. is there. Still another object of the present invention is to provide a molded article comprising the resin composition having the above excellent properties.
[Means for Solving the Problems]
[0007]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a semi-aromatic polyamide containing terephthalic acid units and 1,9-nonanediamine units as main components.ToOnly when a specific amount of polyphenylene sulfide is added to a semi-aromatic polyamide obtained by copolymerizing a specific amount of 2-methyl-1,8-octanediamine unit, very excellent heat aging resistance, toughness, and solder resistance are exhibited. The present inventors have found that a resin composition excellent in all of the properties, hot water resistance, chemical resistance, low water absorption, and moldability can be obtained, and completed the present invention.
[0008]
That is, the present inventionIs60-100 mol% of the carboxylic acid units consist of terephthalic acid units, 60-100 mol% of the diamine units consist of 1,9-nonanediamine units and 2-methyl-1,8-octanediamine units, and A polyamide having a molar ratio of 9-nonanediamine unit to 2-methyl-1,8-octanediamine unit of 60:40 to 99: 1, and an intrinsic viscosity [η] of 0.3 measured in concentrated sulfuric acid at 30 ° C. Polyamide having 4-3.0 dl / g (A) And polyphenylene sulfide (B),AAnd (B) the resin composition has a weight ratio of 5:95 to 99.9: 0.1. Further, the present invention is a resin composition obtained by mixing 1 to 200 parts by weight of a filler with 100 parts by weight of the above resin composition. Further, the present invention is a molded article comprising the above resin composition.
[0009]
Hereinafter, the present invention will be described specifically.
The polyamide used in the present invention substantially consists of dicarboxylic acid units and diamine units. The dicarboxylic acid unit needs to contain a terephthalic acid unit in an amount of at least 60 mol%, preferably at least 75 mol%, more preferably at least 90 mol%. When the content of the terephthalic acid unit is less than 60 mol%, various properties such as heat resistance and low water absorption of the obtained resin composition are undesirably reduced.
[0010]
Other dicarboxylic acid units other than the terephthalic acid unit include malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, and 2-methyladipic acid Aliphatic dicarboxylic acids such as trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid and suberic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid; 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4 '-Oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4, '- dicarboxylic acid, there may be mentioned units derived from aromatic dicarboxylic acids such as 4,4'-biphenyl dicarboxylic acid, it is possible to include one or more of these. From the viewpoint of heat resistance and the like, it is preferable to include an aromatic dicarboxylic acid unit among the above dicarboxylic acid units. Further, a unit derived from a polycarboxylic acid having three or more functional groups such as trimellitic acid, trimesic acid, and pyromellitic acid can be included in a range where melt molding is possible.
[0011]
Also,As diamine unitIs1,9-nonanediamine unitAnd 2-methyl-1,8-octanediamine unitTo 60~ 100Mole% IncludedNeed to haveYou.
And, the molar ratio of 1,9-nonanediamine unit to 2-methyl-1,8-octanediamine unit is 60:40 to 99: 1, preferably 70:30 to 99: 1, and 80:20. ９８98: 2 is more preferable. By containing 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit as the diamine unit in the above ratio, the moldability, low water absorption, heat resistance, chemical resistance, and mechanical properties are all reduced. An excellent resin composition can be obtained.
[0012]
1,9-nonanediamine unit, 2-Methyl-1,8-octanediamine unitOther diamine units other than the above include, for example, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine , 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6- Hexanediamine, 5Aliphatic diamines such as -methyl-1,9-nonanediamine; alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine; p-phenylenediamine, m-phenylenediamine, xylylenediamine, 4,4'-diamino Examples include units derived from aromatic diamines such as diphenylmethane, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenylether, and one or more of these units may be included.You.
[0013]
Polyamide used in the present invention (A) Is, That10% or more of the terminal groups of the molecular chain are blocked by a terminal blocking agentthingIs preferred, and 40% or more of the terminal groups are sealed.thingIs more preferable, and 60% or more of the terminal groups are sealed.thingIs more preferred. By sealing the terminal group of the polyamide, a resin composition having more excellent hot water resistance and a small change in viscosity during melt molding can be obtained.
[0014]
In determining the terminal capping ratio, the number of carboxyl group terminals, amino group terminals, and the number of terminals capped by the terminal capping agent present in the polyamide are measured, and the terminal capping is performed by the following formula (1). Rate can be determined. The number of each terminal group is¹It is preferable from the viewpoints of accuracy and simplicity that it be determined from the integrated value of the characteristic signal corresponding to each terminal group by H-NMR. When the characteristic signal of the terminal capped by the terminal blocking agent cannot be identified, the intrinsic viscosity [η] of the polyamide is measured,
Mn = 21900 [η] -7900 (Mn represents a number average molecular weight)
Total number of molecular chain terminal groups (eq / g) = 2 / Mn
Is used to calculate the total number of molecular chain terminal groups. Further, the number of carboxyl group terminals of the polyamide (eq / g) [titrate the benzyl alcohol solution of polyamide with 0.1 N sodium hydroxide] and the number of amino group terminals (eq / g) of the polyamide [ Titration with 0.1N hydrochloric acid], and the end capping ratio can be determined by the following equation (1).
[0015]
Terminal blocking rate (%) = [(AB) −A] × 100 (1)
[Wherein A represents the total number of molecular chain terminal groups (this is usually equal to twice the number of polyamide molecules), and B represents the total number of carboxyl group terminals and amino group terminals]
[0016]
The terminal capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the polyamide terminus. Acids or monoamines are preferred, and monocarboxylic acids are more preferred from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols can also be used.
[0017]
The monocarboxylic acid used as the terminal capping agent is not particularly limited as long as it has reactivity with an amino group.For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Aliphatic monocarboxylic acids such as lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutylic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid Examples thereof include acids, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, aromatic monocarboxylic acids such as phenylacetic acid, and arbitrary mixtures thereof. Among them, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, from the viewpoints of reactivity, sealed terminal stability, and price. And benzoic acid are particularly preferred.
[0018]
When the terminal group of the polyamide is sealed with a monocarboxylic acid, the number of moles of the diamine component to the dicarboxylic acid component is slightly increased in the production of the polyamide so that both ends of the polyamide are amino groups, An acid may be added as a terminal blocking agent.
[0019]
The amino terminal of the polyamide is blocked with these monocarboxylic acids to form a blocked terminal represented by the following general formula (I).
[0020]
Embedded image

(In the formula, R is a residue obtained by removing the carboxyl group from the above monocarboxylic acid, and is preferably an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.)
[0021]
The monoamine used as an end capping agent is not particularly limited as long as it has reactivity with a carboxyl group.For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, Aliphatic monoamines such as stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, or any of these Mixtures can be mentioned. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferred from the viewpoints of reactivity, boiling point, stability of the sealed terminal, and price.
[0022]
When the end groups of the polyamide are sealed with a monoamine, the number of moles of the diamine component with respect to the dicarboxylic acid component is slightly reduced in the production of the polyamide so that both ends of the polyamide are carboxyl groups, and the monoamine is end-sealed. It is good to add it as a blocking agent.
[0023]
The carboxyl group terminal of the polyamide is blocked with these monoamines to form a blocked terminal represented by the following general formula (II).
[0024]
Embedded image

(Where R¹Is a residue obtained by removing an amino group from the above monoamine, and is preferably an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. R²Is a hydrogen atom or a residue obtained by removing the amino group from the above monoamine, and is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. )
[0025]
The amount of the end-capping agent used when producing the polyamide varies depending on the reactivity of the end-capping agent used, the boiling point, the reaction apparatus, the reaction conditions, and the like. It is preferably used in the range of 0.1 to 15 mol%.
[0026]
The polyamide used in the present invention can be produced by a method conventionally known as a method for producing a polyamide, such as a melt polymerization method, a solution polymerization method, or a polymerization method using a reactive extruder. According to the study of the present inventors, a catalyst and, if necessary, an end capping agent are first added to a diamine and a dicarboxylic acid at a time, and a nylon salt is produced. A polyamide can be easily obtained by forming a prepolymer having an intrinsic viscosity [η] of 0.10 to 0.60 dl / g in sulfuric acid at 30 ° C. and further performing solid phase polymerization or performing polymerization using a melt extruder. be able to. When the intrinsic viscosity [η] of the prepolymer is in the range of 0.10 to 0.60 dl / g, the deviation of the molar balance between the carboxyl group and the amino group and the decrease in the polymerization rate in the post-polymerization stage are small, and the molecular weight is further reduced. A polyamide having a small distribution and excellent in various properties and moldability can be obtained. When the final stage of the polymerization is carried out by solid-phase polymerization, it is preferable to carry out under reduced pressure or under an inert gas flow.If the polymerization temperature is in the range of 180 to 280 ° C., the polymerization rate is large and the productivity is excellent. It is preferable because coloring and gelation can be effectively suppressed. When the final stage of the polymerization is carried out by a melt extruder, it is preferable that the polymerization temperature is 370 ° C. or lower, since the polyamide is hardly decomposed and a polyamide without deterioration is obtained.
[0027]
Catalysts that can be used in the production of polyamide include phosphoric acid, phosphorous acid, hypophosphorous acid, or ammonium salts thereof, and metal salts thereof (potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, etc.). , Manganese, tin, tungsten, germanium, titanium, antimony, etc.) and their esters (ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester ).
[0028]
The polyamide used in the present invention has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. in the range of 0.4 to 3.0 dl / g, and in the range of 0.6 to 2.0 dl / g. Are preferable, and those in the range of 0.8 to 1.8 dl / g are more preferable. When the intrinsic viscosity [η] of the polyamide is within the above range, a resin composition having not only excellent moldability but also excellent physical properties such as mechanical properties and heat resistance can be obtained.
[0029]
The polyphenylene sulfide used in the present invention is a polymer containing a structural unit represented by the following general formula (III) in an amount of 70 mol% or more, preferably 90 mol% or more of all the structural units.
[0030]
Embedded image

[0031]
Examples of the structural unit other than the structural unit represented by the general formula (III) include structural units represented by the following general formulas (IV) to (VIII). The above may be included.
[0032]
Embedded image

[0033]
Embedded image

[0034]
Embedded image

[0035]
Embedded image

[0036]
Embedded image

[0037]
The structural units represented by the general formulas (IV) to (VIII) may have a substituent such as an alkyl group, a nitro group, a phenyl group, or an alkoxy group on the aromatic ring.
[0038]
Furthermore, if it is 10 mol% or less of all the structural units, it may contain a trifunctional structural unit represented by the following general formula (IX).
[0039]
Embedded image

[0040]
The polyphenylene sulfide used in the present invention has a melt viscosity measured at a load of 20 kg and a temperature of 300 ° C. using a flow tester, preferably 100 to 10,000 poise, more preferably 200 to 5000 poise, and 300 to 500 poise. Those having 3000 poise are more preferred. When polyphenylene sulfide having a melt viscosity within this range is used, the resulting resin composition has good moldability and excellent mechanical strength.
[0041]
Such a polyphenylene sulfide can be produced using a known method. For example, a method of polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, a method of polymerizing p-dichlorobenzene in a polar solvent in the presence of sodium sulfide and sodium hydroxide, a method of p-dichlorobenzene In the presence of hydrogen sulfide and sodium hydroxide, and a self-polymerization method of p-chlorothiophenol. Among such polymerization methods, a method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is preferable. In such a polymerization reaction, a metal salt of a carboxylic acid or a sulfonic acid may be added in order to control the degree of polymerization of the obtained polyphenylene sulfide.
[0042]
The resin composition of the present invention comprises the above polyamide and polyphenylene sulfide, and the weight ratio of the polyamide to the polyphenylene sulfide is 5:95 to 99.9: 0.1 and 5:95 to 95: 5. Is preferred, and the ratio is more preferably 20:80 to 80:20. The resin composition in which the weight ratio between the polyamide and the polyphenylene sulfide is the above ratio is excellent in mechanical strength, low water absorption, chemical resistance, and the like.
[0043]
A filler can be further blended in an amount of 1 to 200 parts by weight based on 100 parts by weight of the resin composition. Mixing the filler in such a ratio is preferable because a resin composition having more improved properties such as mechanical properties and heat distortion temperature can be obtained. The compounding ratio of the filler is more preferably from 1 to 150 parts by weight, and even more preferably from 2 to 100 parts by weight, based on 100 parts by weight of the polyamide.
[0044]
As the filler, conventionally known fillers having various forms such as powder, fiber, cloth and the like can be used.
[0045]
Powdered fillers include silica, silica alumina, alumina, titanium oxide, zinc oxide, boron nitride, talc, mica, potassium titanate, calcium silicate, magnesium sulfate, aluminum borate, asbestos, glass beads, carbon black, Examples include graphite, molybdenum disulfide, and polytetrafluoroethylene. Usually, as such a powdery filler, one having an average particle size in the range of 0.1 μm to 200 μm is preferably used, and one having an average particle size in the range of 1 μm to 100 μm is more preferably used. Use of these powdery fillers improves the mechanical strength, low water absorption, heat resistance, and the like of a molded product obtained from the resin composition.
[0046]
As the fibrous filler, polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, obtained from a condensate of diaminodiphenyl ether and terephthalic acid or isophthalic acid Organic fibrous fillers such as wholly aromatic polyamide fibers such as fibers and wholly aromatic liquid crystal polyester fibers; and inorganic fibrous fillers such as glass fibers, carbon fibers or boron fibers. The use of such a fibrous filler is preferable because not only the sliding properties of the molded article obtained from the resin composition are improved, but also the mechanical properties, heat resistance properties, physicochemical properties and the like are improved. Usually, as such a fibrous filler, one having an average length in the range of 0.05 to 50 mm is preferably used. Furthermore, it is more preferable to use those having an average length in the range of 1 to 10 mm from the viewpoint that the moldability is good and the sliding properties, heat resistance, and mechanical properties of the obtained molded article are further improved. These fibrous fillers may be subjected to secondary processing such as cloth.
[0047]
These fillers can be used alone or in combination of two or more. In particular, by using the fibrous filler and the powdery filler in combination, it is possible to obtain a resin composition having more excellent moldability, surface beauty, mechanical properties, and heat resistance. preferable. Further, as these fillers, those subjected to a surface treatment with a silane coupling agent, a titanium coupling agent or the like can also be used. It is preferable to use a filler whose surface is treated with these coupling agents, since the resulting molded article has excellent mechanical properties. Among the silane coupling agents, it is more preferable to use an aminosilane-based coupling agent because the obtained molded article has particularly excellent mechanical properties.
[0048]
In addition, if necessary, a stabilizer such as a copper compound; a coloring agent; an ultraviolet absorber; a light stabilizer; an antioxidant such as a hindered phenol-based, hindered amine-based, phosphorus-based, or thio-based; an antistatic agent; Flame retardants such as polymers, antimony oxide, metal hydroxides; crystal nucleating agents; plasticizers; lubricants, anti-slip agents, anti-blocking agents, anti-fogging agents, pigments, dyes, polyamides such as natural oils, synthetic oils and waxes Can be added during or after the polycondensation reaction.
[0049]
In addition, a heat-resistant thermoplastic resin may be added to the resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of such a heat-resistant thermoplastic resin include PPE (polyphenyl ether), PES (polyether sulfone), PEI (polyetherimide), LCP (liquid crystal polymer), and modified products of these resins. be able to.
[0050]
The resin composition of the present invention can be produced by mixing the above-mentioned polyamide and polyphenylene sulfide, and if necessary, the above-mentioned filler and heat-resistant thermoplastic resin by a desired method. For example, after pre-mixing using a vertical or horizontal mixer as commonly used for mixing resin materials, using a kneading device such as a single-screw or twin-screw extruder, kneader, mixing roll, Banbury mixer, etc. By melt-kneading under heating, the resin composition of the present invention is produced.
[0051]
Using the resin composition produced as described above, a molded article having a desired shape can be produced by a usual melt molding method, for example, a compression molding method, an injection molding method, an extrusion molding method, or the like.
[0052]
For example, the resin composition of the present invention is melted in a cylinder of an injection molding machine whose cylinder temperature is adjusted to a temperature equal to or higher than the melting points of polyamide and polyphenylene sulfide, and is introduced into a mold having a predetermined shape (injection). By doing so, a molded article can be manufactured. Further, fibers can be produced by melting the resin in an extruder adjusted to the above-mentioned cylinder temperature and spinning the resin through a die nozzle. Further, a film can be produced by melting the resin in an extruder adjusted to the above-mentioned cylinder temperature and extruding the resin from a T-die. Further, molded articles such as films and bottles can be obtained by inflation molding, blow molding and the like.
[0053]
Examples of the molded article made of the resin composition of the present invention include electric tools, general industrial parts, gears, mechanical parts such as cams, connectors, switches, relays, MIDs, printed wiring boards, housings for electronic parts, and the like. Various forms of molded articles such as electronic parts, films, sheets, and fibers can be given. In particular, it can be suitably used for molded articles for automobiles, for example, interior and exterior parts of automobiles, parts in an engine room of automobiles, and electrical parts of automobiles.
[0054]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the following examples, the terminal sealing rate, intrinsic viscosity, and melting point of polyamide; tensile strength of molded product, tensile strength retention rate after hot water treatment, tensile strength retention rate after alcohol treatment, solder resistance, heat aging The property was measured or evaluated by the following method.
[0055]
Terminal sealing rate:
¹Using H-NMR (500 MHz, measured in deuterated trifluoroacetic acid at 50 ° C.), the number of carboxyl group ends, amino group ends, and sealed ends was measured from the integrated value of the characteristic signal for each terminal group. The terminal blocking ratio was determined from the above formula (1). The chemical shift values of typical signals used for the measurement are shown below.
[0056]
[Table 1]

[0057]
Intrinsic viscosity [η]:
The intrinsic viscosity (ηinh) of a sample having a concentration of 0.05, 0.1, 0.2, 0.4 g / dl was measured in concentrated sulfuric acid at 30 ° C. The intrinsic viscosity [η] was used.
ηinh = [ln (t₁/ T₀)] / C
[Wherein, ηinh is the intrinsic viscosity (dl / g), t₀Is the flow time (second) of the solvent, t₁Represents the flow time (second) of the sample solution, and c represents the concentration of the sample in the solution (g / dl). ]
[0058]
Melting point:
Using a differential scanning calorimeter (“DSC30” manufactured by Mettler), the sample was heated at a rate of 100 ° C./min to completely melt, and then cooled to 50 ° C. at a rate of 10 ° C./min. The temperature at the position of the endothermic peak appearing when the temperature was raised again at a rate of 10 ° C./min was measured and defined as the melting point.
[0059]
Tensile strength:
It was measured according to JIS K 7113 using a JIS No. 1 dumbbell type injection molded piece in a completely dry state.
[0060]
Tensile strength retention after hot water treatment:
The JIS No. 1 dumbbell-shaped injection molded piece was immersed in hot water at 80 ° C. for one week. The tensile strength of the molded article before and after immersion was measured, and the retention rate (%) of the tensile strength was determined.
[0061]
Tensile strength retention after alcohol treatment:
The JIS No. 1 dumbbell-shaped injection molded piece was immersed in methanol at 23 ° C. for one week. The tensile strength of the molded article before and after immersion was measured, and the retention rate (%) of the tensile strength was determined.
[0062]
Solder resistance:
An injection molded product of 40 × 100 × 1 mm was immersed in a solder bath for 30 seconds, and the temperature of the solder bath when the molded product was deformed was measured.
[0063]
Heat aging resistance:
The JIS No. 1 dumbbell-shaped injection molded piece was treated in a gear oven at 150 ° C. for 100 hours (system without filler) or in a gear oven at 190 ° C. for 900 hours (system with filler). The tensile strength of the molded article before and after the treatment was measured, and the retention rate (%) of the tensile strength was determined.
[0064]
Reference Example 1
3256.2 g (19.60 mol) of terephthalic acid, 3165.8 g (20.0 mol) of 1,9-nonanediamine, 97.7 g (0.80 mol) of benzoic acid, sodium hypophosphite monohydrate 5 g (0.1% by weight based on the raw material) and 2.2 liters of distilled water were put into an autoclave having an internal volume of 20 liters, and the atmosphere was replaced with nitrogen. The mixture was stirred at 100 ° C for 30 minutes, and the internal temperature was raised to 210 ° C over 2 hours. At this time, the autoclave is 22 kg / cm²Pressurized to After continuing the reaction for 1 hour, the temperature was raised to 230 ° C., and then maintained at 230 ° C. for 2 hours.²The reaction was carried out while keeping Next, the pressure is increased to 10 kg / cm over 30 minutes.²Then, the mixture was further reacted for 1 hour to obtain a prepolymer having an intrinsic viscosity [η] of 0.25 dl / g. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid-state polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain a white polyamide having a melting point of 317 ° C., an intrinsic viscosity [η] of 1.10 dl / g, and a terminal sealing rate of 90%. Obtained.
[0065]
Reference Examples 2 to 8
A polyamide was obtained in the same manner as in Reference Example 1, except that the dicarboxylic acid component, the diamine component, and the terminal blocking agent (benzoic acid) were used in the proportions shown in Table 2 below. The intrinsic viscosity [η], terminal capping rate and melting point of the obtained polyamide are shown in Table 2 below.
[0066]
[Table 2]

[0067]
Example 13, Comparative Examples 1 to 3And Reference Examples 9 to 10
The polyamides obtained in Reference Examples 1 to 8 and polyphenylene sulfide (“M2588” manufactured by Toray) were mixed at a ratio shown in Table 3 below, and a twin-screw extruder “Laboplast Mill 2D25W” manufactured by Toyo Seiki Seisaku-Sho, Ltd. was used. And a resin composition was obtained by extruding in a molten state at a rotation speed of 40 rpm by setting the cylinder temperature to a temperature 20 to 40 ° C. higher than the melting point of the polyamide. This resin composition was injection-molded using an injection molding machine “FS80S12ASE” manufactured by Nissei Plastic Industry Co., Ltd. with the cylinder temperature set to 20 to 40 ° C. higher than the melting point of the resin and the mold temperature set to 150 ° C. . Table 3 below shows the results of the evaluation of the obtained molded product.
[0068]
[Table 3]

[0069]
Example4~8
The polyamide and polyphenylene sulfide (“M2588” manufactured by Toray) obtained in Reference Example 2 were mixed at a ratio shown in Table 4 below, and a twin-screw extruder “Laboplast Mill 2D25W” manufactured by Toyo Seiki Seisaku-Sho, Ltd. was used. Then, a resin composition was obtained by setting the cylinder temperature to a temperature 20 to 40 ° C. higher than the melting point of the polyamide and extruding in a molten state at a rotation speed of 40 rpm. This resin composition was injection-molded using an injection molding machine “FS80S12ASE” manufactured by Nissei Plastic Industry Co., Ltd. with the cylinder temperature set to 20 to 40 ° C. higher than the melting point of the resin and the mold temperature set to 150 ° C. . Table 4 below shows the results of the evaluation of the obtained molded products.
[0070]
[Table 4]

[0071]
Example9~11, Comparative Example 4And Reference Example 11
The polyamide and polyphenylene sulfide ("M2588" manufactured by Toray) shown in Table 5 below were mixed at the ratio shown in Table 5 below, and a twin screw extruder "Laboplast Mill 2D25W" manufactured by Toyo Seiki Seisaku-Sho, Ltd. was used. Then, the cylinder temperature was set to a temperature 20 to 40 ° C. higher than the melting point of the polyamide, and the mixture was extruded in a molten state at a rotation speed of 40 rpm to be pelletized. The pellets thus obtained and the fillers described in Table 5 below were mixed in the proportions shown in Table 5, and the cylinder temperature of the polyamide was adjusted using a single screw extruder “UT-40H” manufactured by Plastics Engineering Laboratory. The temperature was set to 20 to 40 ° C. higher than the melting point, and the mixture was extruded in a molten state to obtain a resin composition containing a filler. This resin composition was injection-molded using an injection molding machine “FS80S12ASE” manufactured by Nissei Plastic Industry Co., Ltd. with the cylinder temperature set to 20 to 40 ° C. higher than the melting point of the resin and the mold temperature set to 150 ° C. . Table 5 below shows the results of the evaluation of the obtained molded product.
[0072]
[Table 5]

[0073]
【The invention's effect】
The resin composition of the present invention exhibits excellent heat aging resistance, and is excellent in toughness, solder resistance, hot water resistance, chemical resistance, low water absorption, and moldability. The obtained molded article can be suitably used for applications such as industrial materials, industrial materials, and household goods.

Claims (3)

60-100 mol% of dicarboxylic acid units consist of terephthalic acid units, 60-100 mol% of diamine units consist of 1,9-nonanediamine units and 2-methyl-1,8-octanediamine units, and A polyamide having a molar ratio of 9-nonanediamine unit to 2-methyl-1,8-octanediamine unit of 60:40 to 99: 1, and an intrinsic viscosity [η] of 0.3 measured in concentrated sulfuric acid at 30 ° C. It consists of polyamide ( A ) of 4-3.0 dl / g and polyphenylene sulfide (B), and the weight ratio of component ( A ) to component (B) is from 5:95 to 99.9: 0.1. Resin composition. A resin composition comprising 100 parts by weight of the resin composition of claim 1 and 1 to 200 parts by weight of a filler. A molded article comprising the resin composition according to claim 1.