JP3624410B2 - Polyarylene sulfide resin composition - Google Patents

Description

酸素含有雰囲気下でＰＡＳを熱酸化処理して得られる酸化架橋ＰＡＳは、ＥＳＲにより測定したラジカル発生量が本発明の範囲を超えるものであり、本発明のＰＡＳとは異なる。
【００１６】
本発明においては、成分（Ａ）ＰＡＳの溶融粘度Ｖ_６ は、その上限が好ましくは４８００ポイズ、特に好ましくは４０００ポイズであり、下限が好ましくは５００ポイズ、特に好ましくは８００ポイズである。溶融粘度Ｖ_６ が上記下限未満では樹脂組成物の引張強度等の機械的強度が低下する。上記上限を超えては流動性が低下し成形加工性が悪化するため好ましくない。ここで、溶融粘度Ｖ_６ は、フローテスターを用いて３００℃、荷重２０ｋｇｆ／ｃｍ^２ 、Ｌ／Ｄ＝１０で６分間保持した後に測定した粘度（ポイズ）である。
【００１７】
上記の（Ａ）ＰＡＳは、好ましくは下記の方法により製造することができる。即ち、有機アミド系溶媒中でアルカリ金属硫化物とジハロ芳香族化合物とを反応させてＰＡＳを製造する方法において、アルカリ金属硫化物とジハロ芳香族化合物とのモル比を０．９４０〜１．０００とし、更に仕込アルカリ金属硫化物に対して０．３５〜１．０モル％のポリハロ芳香族化合物を重合反応系内に添加し、かつ反応中に反応缶の気相部分を冷却することにより反応缶内の気相の一部を凝縮させ、これを液相に還流せしめる方法である。
【００１８】
上記製造方法において、アルカリ金属硫化物とジハロ芳香族化合物とのモル比は、上限が１．０００、好ましくは０．９８０であり、下限が０．９４０、好ましくは０．９５０である。上記下限未満では、ＰＡＳの溶融粘度Ｖ_６ が低くなり成形性が悪化する。上記上限を超えては、成形時の加工性が劣るため好ましくない。
【００１９】
また、上記製造方法において、重合反応系内に添加するポリハロ芳香族化合物は、仕込アルカリ金属硫化物に対して、上限が１．００モル％、好ましくは０．８０モル％であり、下限が０．３５モル％、好ましくは０．４０モル％である。上記下限未満では、生成したＰＡＳにおいて、上記非ニュートン指数Ｎが小さく、上記上限を超えては、成形時の加工性が劣るため好ましくない。
【００２０】
ポリハロ芳香族化合物の重合反応系内への添加方法は、特に限定されるものではない。例えばアルカリ金属硫化物及びジハロ芳香族化合物と同時に添加してもよいし、あるいは反応途中の任意の時点で、ポリハロ芳香族化合物を有機溶媒例えばＮ‐メチルピロリドンに溶解させて、高圧ポンプで反応缶内に圧入してもよい。
【００２１】
上記の反応缶の気相部分を冷却することにより反応缶内の気相の一部を凝縮させ、これを液相に還流せしめてＰＡＳを製造する方法としては、特開平５‐２２２１９６号公報に記載の方法を使用することができる。
【００２２】
還流される液体は、水とアミド系溶媒の蒸気圧差の故に、液相バルクに比較して水含有率が高い。この水含有率の高い還流液は、反応溶液上部に水含有率の高い層を形成する。その結果、残存のアルカリ金属硫化物（例えばＮａ_２ Ｓ）、ハロゲン化アルカリ金属（例えばＮａＣｌ）、オリゴマー等が、その層に多く含有されるようになる。従来法においては２３０℃以上の高温下で、生成したＰＡＳとＮａ_２ Ｓ等の原料及び副生成物とが均一に混じりあった状態では、高分子量のＰＡＳが得られないばかりでなく、せっかく生成したＰＡＳの解重合も生じ、チオフェノールの副生成が認められる。しかし、本発明では、反応缶の気相部分を積極的に冷却して、水分に富む還流液を多量に液相上部に戻してやることによって上記の不都合な現象が回避でき、反応を阻害するような因子を真に効率良く除外でき、高分子量ＰＡＳを得ることができるものと思われる。但し、本発明は上記現象による効果のみにより限定されるものではなく、気相部分を冷却することによって生じる種々の影響によって、高分子量のＰＡＳが得られるのである。
【００２３】
この方法においては、反応の途中で水を添加することを要しない。しかし、水を添加することを全く排除するものではない。但し、水を添加する操作を行えば、この方法の利点のいくつかは失われる。従って、好ましくは、重合反応系内の全水分量は反応の間中一定である。
【００２４】
反応缶の気相部分の冷却は、外部冷却でも内部冷却でも可能であり、自体公知の冷却手段により行える。たとえば、反応缶内の上部に設置した内部コイルに冷媒体を流す方法、反応缶外部の上部に巻きつけた外部コイルまたはジャケットに冷媒体を流す方法、反応缶上部に設置したリフラックスコンデンサーを用いる方法、反応缶外部の上部に水をかける又は気体（空気、窒素等）を吹き付ける等の方法が考えられるが、結果的に缶内の還流量を増大させる効果があるものならば、いずれの方法を用いても良い。外気温度が比較的低いなら（たとえば常温）、反応缶上部に従来備えられている保温材を取外すことによって、適切な冷却を行うことも可能である。外部冷却の場合、反応缶壁面で凝縮した水／アミド系溶媒混合物は反応缶壁を伝わって液相中に入る。従って、該水分に富む混合物は、液相上部に溜り、そこの水分量を比較的高く保つ。内部冷却の場合には、冷却面で凝縮した混合物が同様に冷却装置表面又は反応缶壁を伝わって液相中に入る。
【００２５】
一方、液相バルクの温度は、所定の一定温度に保たれ、あるいは所定の温度プロフィールに従ってコントロールされる。一定温度とする場合、 ２３０〜２７５ ℃の温度で ０．１〜２０時間反応を行うことが好ましい。より好ましくは、 ２４０〜２６５ ℃の温度で１〜６時間である。より高い分子量のＰＡＳを得るには、２段階以上の反応温度プロフィールを用いることが好ましい。この２段階操作を行う場合、第１段階は １９５〜２４０ ℃の温度で行うことが好ましい。温度が低いと反応速度が小さすぎ、実用的ではない。 ２４０℃より高いと反応速度が速すぎて、十分に高分子量なＰＡＳが得られないのみならず、副反応速度が著しく増大する。第１段階の終了は、重合反応系内ジハロ芳香族化合物残存率が１モル％〜４０モル％、且つ分子量が ３，０００〜２０，０００の範囲内の時点で行うことが好ましい。より好ましくは、重合反応系内ジハロ芳香族化合物残存率が２モル％〜１５モル％、且つ分子量が ５，０００〜１５，０００の範囲である。残存率が４０モル％を越えると、第２段階の反応で解重合など副反応が生じやすく、一方、１モル％未満では、最終的に高分子量ＰＡＳを得難い。その後昇温して、最終段階の反応は、反応温度 ２４０〜２７０ ℃の範囲で、１時間〜１０時間行うことが好ましい。温度が低いと十分に高分子量化したＰＡＳを得ることができず、また ２７０℃より高い温度では解重合等の副反応が生じやすくなり、安定的に高分子量物を得難くなる。
【００２６】
実際の操作としては、先ず不活性ガス雰囲気下で、アミド系溶媒中のアルカリ金属硫化物中の水分量が所定の量となるよう、必要に応じて脱水または水添加する。水分量は、好ましくは、アルカリ金属硫化物１モル当り０．５ 〜２．５ モル、特に０．８ 〜１．２ モルとする。２．５ モルを超えては、反応速度が小さくなり、しかも反応終了後の濾液中にフェノール等の副生成物量が増大し、重合度も上がらない。０．５ モル未満では、反応速度が速すぎ、十分な高分子量の物を得ることができない。
【００２７】
反応時の気相部分の冷却は、一定温度での１段反応の場合では、反応開始時から行うことが望ましいが、少なくとも ２５０℃以下の昇温途中から行わなければならない。多段階反応では、第１段階の反応から冷却を行うことが望ましいが、遅くとも第１段階反応の終了後の昇温途中から行うことが好ましい。冷却効果の度合いは、通常反応缶内圧力が最も適した指標である。圧力の絶対値については、反応缶の特性、攪拌状態、系内水分量、ジハロ芳香族化合物とアルカリ金属硫化物とのモル比等によって異なる。しかし、同一反応条件下で冷却しない場合に比べて、反応缶圧力が低下すれば、還流液量が増加して、反応溶液気液界面における温度が低下していることを意味しており、その相対的な低下の度合いが水分含有量の多い層と、そうでない層との分離の度合いを示していると考えられる。そこで、冷却は反応缶内圧が、冷却をしない場合と比較して低くなる程度に行うのが好ましい。冷却の程度は、都度の使用する装置、運転条件などに応じて、当業者が適宜設定できる。
【００２８】
ここで使用する有機アミド系溶媒は、ＰＡＳ重合のために知られており、たとえばＮ‐メチルピロリドン、Ｎ，Ｎ‐ジメチルホルムアミド、Ｎ，Ｎ‐ジメチルアセトアミド、Ｎ‐メチルカプロラクタム等、及びこれらの混合物を使用でき、Ｎ‐メチルピロリドンが好ましい。これらは全て、水よりも低い蒸気圧を持つ。アルカリ金属硫化物も公知であり、たとえば、硫化リチウム、硫化ナトリウム、硫化カリウム、硫化ルビジウム、硫化セシウム及びこれらの混合物である。これらの水和物及び水溶液であっても良い。又、これらにそれぞれ対応する水硫化物及び水和物を、それぞれに対応する水酸化物で中和して用いることができる。安価な硫化ナトリウムが好ましい。
【００２９】
ジハロ芳香族化合物は、たとえば特公昭４５‐３３６８号公報記載のものから選ぶことができるが、好ましくはｐ‐ジクロロベンゼンである。又、少量（２０モル％以下）のジフェニルエーテル、ジフェニルスルホン又はビフェニルのパラ、メタ又はオルトジハロ物を１種類以上用いて共重合体を得ることができる。例えば、ｍ‐ジクロロベンゼン、ｏ‐ジクロロベンゼン、ｐ，ｐ´‐ジクロロジフェニルエーテル、ｍ，ｐ´‐ジクロロジフェニルエーテル、ｍ，ｍ´‐ジクロロジフェニルエーテル、ｐ，ｐ´‐ジクロロジフェニルスルホン、ｍ，ｐ´‐ジクロロジフェニルスルホン、ｍ，ｍ´‐ジクロロジフェニルスルホン、ｐ，ｐ´‐ジクロロビフェニル、ｍ，ｐ´‐ジクロロビフェニル、ｍ，ｍ´‐ジクロロビフェニルである。
【００３０】
ポリハロ芳香族化合物は、１分子に３個以上のハロゲン置換基を有する化合物であり、例えば１，２，３‐トリクロロベンゼン、１，２，４‐トリクロロベンゼン、１，３，５‐トリクロロベンゼン、１，３‐ジクロロ‐５‐ブロモベンゼン、２，４，６‐トリクロロトルエン、１，２，３，５‐テトラブロモベンゼン、ヘキサクロロベンゼン、１，３，５‐トリクロロ‐２，４，６‐トリメチルベンゼン、２，２´，４，４´‐テトラクロロビフェニル、２，２´，６，６´‐テトラブロモ‐３，３´，５，５´‐テトラメチルビフェニル、１，４，６‐トリクロロナフタレン、１，２，３，４‐テトラクロロナフタレン、１，２，４‐トリブロモ‐６‐メチルナフタレン等及びそれらの混合物が挙げられ、１，２，４‐トリクロロベンゼン、１，３，５‐トリクロロベンゼンが好ましい。
【００３１】
また、他の少量添加物として、末端停止剤、修飾剤としてのモノハロ化物を併用することもできる。
【００３２】
また、本発明の（Ａ）ＰＡＳは、好ましくは下記の方法によっても製造することができる。
【００３３】
即ち、極性溶媒中で（ａ）アルカリ金属硫化物と（ｂ）ジハロ芳香族化合物と（ｃ）官能基を３個以上有する芳香族化合物を反応させてポリアリーレンスルフィドを製造する方法において、（ａ）／（ｂ）のモル比が０．９７０〜１．０２０であり、（ｃ）／（ａ）のモル比が０．００２〜０．０１５であるように上記（ａ）、（ｂ）及び（ｃ）を反応系に仕込み、かつ反応系内の（ｂ）の反応率が５０〜９５％の時点で、仕込み（ａ）アルカリ金属硫化物に対してモル比で０．００１〜０．０２の（ｄ）分子量調節剤を反応系に添加することを特徴とする方法である。
【００３４】
上記のＰＡＳ製造法において、（ａ）アルカリ金属硫化物／（ｂ）ジハロ芳香族化合物のモル比は、下限が０．９７０、好ましくは０．９８０であり、上限が１．０２０、好ましくは１．０００である。上記下限未満では、ＰＡＳの非ニュートン指数Ｎが低く、また、ＰＡＳの溶融粘度Ｖ_６ が著しく低くなり成形性が悪化する。上記上限を超えては、ＰＡＳが解重合を起こすので好ましくない。（ｃ）官能基を３個以上有する芳香族化合物／（ａ）アルカリ金属硫化物のモル比は、下限が０．００２、好ましくは０．００３であり、上限が０．０１５、好ましくは０．０１である。上記下限未満では、ＰＡＳの非ニュートン指数Ｎが低く、また、ＰＡＳの溶融粘度Ｖ_６ が著しく低くなり成形性が悪化する。上記上限を超えては、ＰＡＳの分岐、架橋が進行し過ぎて成形時においてＰＡＳのゲル化が生じ成形性が悪化するため好ましくない。
【００３５】
該方法において、（ｄ）分子量調節剤は、反応系内の（ｂ）ジハロ芳香族化合物の反応率の上限が９５％、好ましくは９０％、下限が５０％、好ましくは７０％、特に好ましくは８０％の時点で添加される。添加時の（ｂ）ジハロ芳香族化合物の反応率が上記下限未満では、分岐構造の導入が不十分であり、非ニュートン指数Ｎが低くなる。上記上限を超えると、極度に溶融粘度Ｖ_６ が高くなりゲル化して成形不能となる。重合反応系に添加する（ｄ）分子量調節剤は、（ａ）アルカリ金属硫化物に対してモル比で、下限が０．００１、好ましくは０．００２、特に好ましくは０．００４であり、上限が０．０２、好ましくは０．０１、特に好ましくは０．００８である。上記範囲外では、非ニュートン指数Ｎが低くなると共に、成形性も悪化する。（ｄ）の添加は、上記の反応率の範囲内であれば、１回で全量をまとめて添加してもよいし、あるいは数回に分けて添加してもよい。該添加は、（ｄ）をそのまま、あるいは使用する極性溶媒（例えば、Ｎ‐メチル‐２‐ピロリドン）に溶解して、加圧注入機を用いて反応缶内に圧入することにより行うことができる。
【００３６】
本発明の（ｄ）分子量調節剤としては、以下に掲げるものを使用することができる。例えば、モノ又はジハロ芳香族化合物例えばモノクロロベンゼン、モノブロモベンゼン、ｍ‐ジクロロベンゼン等；メルカプト基を１又は２個有する芳香族化合物例えばチオフェノール、１，４‐ジチオフェノール、モノクロロチオフェノール等；ジスルフィド化合物例えばジフェニルジスルフィド、ｐ，ｐ´‐ジトリルジスルフィド、ジベンジルジスルフィド、ジベンゾイルジスルフィド、ジチオベンゾイルジスルフィド等；電子吸引基（例えばカルボキシル基、ニトロ基、スルホニル基、カルボニル基等）を有するハロ置換芳香族化合物例えばニトロクロロベンゼン、ジクロロジフェニルスルホン、４，４´‐ジクロロベンゾフェノン等が挙げられる。好ましくは、（ｄ）分子量調節剤として、チオフェノール、ジフェニルジスルフィド又はｍ‐ジクロロベンゼンから成る群から選ばれた少なくとも一つのものを使用し得る。
【００３７】
（ａ）アルカリ金属硫化物及び（ｂ）ジハロ芳香族化合物はいずれも上記記載のものを使用することができる。
【００３８】
（ｃ）官能基を３個以上有する芳香族化合物は、例えば特公平６‐４５６９３号公報に記載されているものを使用することができる。（ｃ）官能基を３個以上有する芳香族化合物とは、芳香族環に結合した反応性官能基を３個以上、好ましくは３〜４個、特に好ましくは３個有する芳香族化合物である。該反応性官能基としては、例えばアミノ基、ヒドロキシル基、メルカプト基、カルボキシル基、スルホニル基、スルフィノ基、スルファモイル基、ヒドラジノ基及びカルバモイル基等の活性水素含有基、ハロゲン原子、並びにニトロ基等を挙げることができる。上記反応性官能基中、アミノ基、ハロゲン原子、ニトロ基が好ましい。ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素等の各原子が挙げられ、塩素原子が好ましい。芳香族環に結合する上記反応性官能基は夫々同一であっても異なっていてもよい。また、上記（ｃ）の芳香族化合物としては、ベンゼン類、ビフェニル類、ジフェニルエーテル類、ジフェニルスルフィド類、ナフタレン類等を挙げることができ、ベンゼン類が好ましい。
【００３９】
（ｃ）官能基を３個以上有する芳香族化合物としては、好ましくは活性水素含有ハロゲン芳香族化合物、ポリハロ芳香族化合物及びハロゲン芳香族ニトロ化合物等を使用することができる。
【００４０】
活性水素含有ハロゲン芳香族化合物としては、例えば、２，６‐ジクロロアニリン、２，５‐ジクロロアニリン、２，４‐ジクロロアニリン、２，３‐ジクロロアニリン等のジハロアニリン類；２，３，４‐トリクロロアニリン、２，４，６‐トリクロロアニリン、３，４，５‐トリクロロアニリン等のトリハロアニリン類；２，２´‐ジアミノ‐４，４´‐ジクロロジフェニルエーテル、２，４´‐ジアミノ‐２´，４‐ジクロロジフェニルエーテル等のジハロアミノジフェニルエーテル類等のアミノ基含有ハロゲン芳香族化合物、及びこれら化合物中のアミノ基がメルカプト基やヒドロキシル基に置き換えられた化合物等が挙げられる。また、これらの活性水素含有ハロゲン芳香族化合物中の芳香族環を形成する炭素原子に結合した水素原子が、他の不活性基例えばアルキル基等の炭化水素基に置換しているアミノ基含有ハロゲン芳香族化合物も使用することができる。上記の活性水素含有ハロゲン芳香族化合物中、活性水素含有ジハロ芳香族化合物を好適に使用することができ、なかでもアミノ基含有ジハロ芳香族化合物が好ましく、特に好ましいのはジクロロアニリンである。
【００４１】
ポリハロ芳香族化合物としては、上記に記載したと同じものを使用し得る。
【００４２】
ハロゲン芳香族ニトロ化合物としては、例えば２，４‐ジニトロクロロベンゼン、２，５‐ジクロロニトロベンゼン等のモノ又はジハロニトロベンゼン類；２‐ニトロ‐４，４´‐ジクロロジフェニルエーテル等のジハロニトロジフェニルエーテル類；３，３´‐ジニトロ‐４，４´‐ジクロロジフェニルスルホン等のジハロニトロジフェニルスルホン類；２，５‐ジクロロ‐３‐ニトロピリジン、２‐クロロ‐３，５‐ジニトロピリジン等のモノ又はジハロニトロピリジン類、あるいは各種ジハロニトロナフタレン類等が挙げられる。
【００４３】
本発明の方法において、上記（ｃ）官能基を３個以上有する芳香族化合物は、一種単独で使用してもよく、また二種以上を併用してもよい。
【００４４】
本発明の方法で使用する極性溶媒は、ＰＡＳ重合のために知られており、例えば特公平６‐４５６９３号公報に記載されているもの、例えば有機アミド化合物、ラクタム化合物、尿素化合物、環式有機リン化合物等を使用することができる。該極性溶媒としては、例えば、上記に掲げた有機アミド系溶媒、Ｎ，Ｎ‐ジエチルアセトアミド、Ｎ，Ｎ‐ジプロピルアセトアミド、Ｎ，Ｎ‐ジメチル安息香酸アミド、カプロラクタム、Ｎ‐エチルカプロラクタム、Ｎ‐イソプロピルカプロラクタム、Ｎ‐イソブチルカプロラクタム、Ｎ‐ノルマルプロピルカプロラクタム、Ｎ‐ノルマルブチルカプロラクタム、Ｎ‐シクロヘキシルカプロラクタム、Ｎ‐エチル‐２‐ピロリドン、Ｎ‐イソプロピル‐２‐ピロリドン、Ｎ‐イソブチル‐２‐ピロリドン、Ｎ‐ノルマルプロピル‐２‐ピロリドン、Ｎ‐ノルマルブチル‐２‐ピロリドン、Ｎ‐シクロヘキシル‐２‐ピロリドン、Ｎ‐メチル‐３‐メチル‐２‐ピロリドン、Ｎ‐エチル‐３‐メチル‐２‐ピロリドン、Ｎ‐メチル‐３，４，５‐トリメチル‐２‐ピロリドン、Ｎ‐メチル‐２‐ピペリドン、Ｎ‐イソプロピル‐２‐ピペリドン、Ｎ‐エチル‐２‐ピペリドン、Ｎ‐メチル‐６‐メチル‐２‐ピペリドン、Ｎ‐メチル‐３‐エチル‐２‐ピペリドン、テトラメチル尿素、Ｎ，Ｎ´‐ジメチルエチレン尿素、Ｎ，Ｎ´‐ジメチルプロピレン尿素、１‐メチル‐１‐オキソスルホラン、１‐エチル‐１‐オキソスルホラン、１‐フェニル‐１‐オキソスルホラン、１‐メチル‐１‐オキソホスホラン、１‐ノルマルプロピル‐１‐オキソホスホラン及び１‐フェニル‐１‐オキソホスホラン等が挙げられる。これらの溶媒は、夫々単独でもよいし、２種以上を混合して用いてもよい。上記極性溶媒中、非プロトン性の有機アミド若しくはラクタム類が好ましく、そのなかでもＮ‐アルキルラクタム及びＮ‐アルキルピロリドンが好ましく、Ｎ‐メチルピロリドンが特に好ましい。
【００４５】
極性溶媒中で（ａ）アルカリ金属硫化物と（ｂ）ジハロ芳香族化合物と（ｃ）官能基を３個以上有する芳香族化合物を反応させてＰＡＳを製造する方法において、好ましくは上記と同じく、反応中、反応缶の気相部分を冷却することにより反応缶内の気相の一部を凝縮させ、これを液相に還流せしめる方法（特開平５‐２２２１９６号公報）を用いることができる。
【００４６】
いずれの方法においても得られたＰＡＳは、当業者にとって公知の後処理法によって副生物から分離することができる。
【００４７】
（Ｂ）ゼオライトは、結晶性のアルミノケイ酸塩であり、下記の一般式で示される公知の物質である。
（Ｍ^Ｉ _２ ，Ｍ^ＩＩ）Ｏ・Ａｌ_２ Ｏ_３ ・ ｎＳｉＯ_２ ・ ｍＨ_２ Ｏ
ここで、Ｍ^Ｉ は１価の金属、例えばＬｉ、Ｎａ、Ｋ等のアルカリ金属、あるいはアンモニウム、アルキルアンモニウム、ピリジニウム、アニリニウム、水素イオン等を示し、Ｍ^ＩＩは２価の金属、例えばＣａ、Ｍｇ、Ｂａ、Ｓｒ等のアルカリ土類金属を示す。Ｍ^Ｉ とＭ^ＩＩは、一方若しくは両方存在してよい。好ましくはＭ^ＩＩがＣａであり、Ｍ^Ｉ が実質上存在しない。
【００４８】
本発明で使用する（Ｂ）ゼオライトとしては天然または合成品の何れのゼオライトも使用可能である。天然ゼオライトとしては、例えば、ホウふっ石、ワイラカイト、ソーダふっ石、メソふっ石、トムソンふっ石、ゴナルドふっ石、スコレふっ石、エジングトふっ石、ギスモンふっ石、ダクふっ石、モルデンふっ石、ニガワラふっ石、エリオナイト、アシュクロフティン、キふっ石、クリノプチロライト、タバふっ石、ハクふっ石、ダキアルドふっ石、カイジュウジふっ石、ジュウジふっ石、グメリンふっ石、リョウふっ石、フォージャサイト等を挙げることができる。合成ゼオライトとしては、例えば、Ａ型、Ｘ型、Ｙ型、Ｌ型、モルデナイト、チャバサイト等を挙げることができる。上記ゼオライト中、好ましくは合成ゼオライトが用いられる。合成ゼオライトとしては、市販のものを使用することができ、例えば、ＣＳ‐１００、ＣＳ‐１００Ｓ（いずれも商標、株式会社耕正製）、ＡＭＴ‐２５（商標、水澤化学工業株式会社製）、ミズカライザーＥＳ（商標、水澤化学工業株式会社製）等が挙げられる。
【００４９】
（Ｂ）ゼオライトの形状は粉末粒子状が好ましく、平均粒径の上限が好ましくは３μｍ、特に好ましくは２μｍである。上記上限を超えると樹脂組成物の流動性の低下や成形品の引張強度の低下等をもたらすため好ましくない。ここで、平均粒径はコールターカウンター法により求めた値である（Ｄ_５０）。
【００５０】
本発明において成分（Ａ）ＰＡＳと成分（Ｂ）ゼオライトの配合比は、（Ａ）１００重量部に対して、（Ｂ）の上限が１５重量部、好ましくは１０重量部、特に好ましくは５重量部であり、下限が０．１重量部、好ましくは０．５重量部、特に好ましくは１重量部である。上記上限を超えると、加工性の低下及び引張強度等の機械的強度の低下が生じ、また結晶化温度及び成形品の白色度の更なる顕著な向上は認められない。上記下限未満では、結晶化温度及び成形品の白色度を高めることができない。
【００５１】
本発明の樹脂組成物には更に、任意成分として無機充填剤を配合することができる。無機充填剤としては特に限定されないが、例えば粉末状／リン片状の充填剤、繊維状充填剤などが使用できる。粉末状／リン片状の充填剤としては、例えばシリカ、アルミナ、タルク、マイカ、カオリン、クレー、シリカアルミナ、酸化チタン、炭酸カルシウム、ケイ酸カルシウム、リン酸カルシウム、硫酸カルシウム、酸化マグネシウム、リン酸マグネシウム、窒化ケイ素、ガラス、ハイドロタルサイト、酸化ジルコニウム、ガラスビーズ、カーボンブラック等が挙げられる。また、繊維状充填剤としては、例えばガラス繊維、アスベスト繊維、炭素繊維、シリカ繊維、シリカ／アルミナ繊維、チタン酸カリ繊維、ポリアラミド繊維等が挙げられる。また、この他にＺｎＯテトラポット、金属塩（例えば塩化亜鉛、硫酸鉛など）、酸化物（例えば酸化鉄、二酸化モリブデンなど）、金属（例えばアルミニウム、ステンレスなど）等の充填剤を使用することもできる。これらを１種単独でまたは２種以上組合せて使用できる。また、無機充填剤は、その表面が、シランカップリング剤やチタネートカップリング剤で処理してあってもよい。無機充填剤は、（Ａ）１００重量部に対して４００重量部以下の量で、好ましくは３００重量部以下の量で使用される。無機充填剤の量が上記値を超えると粘度変化が大きくなって成形不能となることがある。また機械的強度を高めるためには、０．０１重量部以上配合するのが好ましい。
【００５２】
本発明の樹脂組成物には、上記の成分の他に、必要に応じて公知の添加剤及び充填剤、例えば酸化防止剤、紫外線吸収剤、離型剤、熱安定剤、滑剤、着色剤等を配合することができる。
【００５３】
本発明の樹脂組成物の製造方法は特に限定されない。例えば、上記の各成分を予めヘンシェルミキサー等の混合機で混合後、押出機等の慣用の装置にて溶融混練し、押出し、ペレット化することができる。
【００５４】
本発明の樹脂組成物は、例えば射出成形して所望の形状に成形され、特に外観の美しさが要求される成形品、例えば電子部品、家電部品、あるいはカメラ、時計等の精密機器部品等に使用され得る。
【００５５】
以下、本発明を実施例により更に詳細に説明するが、本発明はこれら実施例により限定されるものではない。
【００５６】
【実施例】
実施例において、ＰＰＳの溶融粘度Ｖ_６ 測定の際に用いたフローテスターは、島津製作所製フローテスターＣＦＴ‐５００Ｃである。
【００５７】
非ニュートン指数Ｎの測定に用いたキャピログラフは、東洋精機製作所製キャピログラフ１Ｂ Ｐ‐Ｃである。
【００５８】
ラジカル発生量の測定に用いたＥＳＲは、日本電子製ＪＥＳ‐ＦＥ２ＸＧである。
【００５９】
合成例１
１５０リットルオートクレーブに、フレーク状硫化ソーダ（６０．３重量％Ｎａ_２ Ｓ）１９．４１３ｋｇとＮ‐メチル‐２‐ピロリドン（以下ではＮＭＰと略すことがある）４５．０ｋｇを仕込んだ。窒素気流下攪拌しながら液温２０４℃まで昇温して、水４．８７２ｋｇを留出させた。その後、オートクレーブを密閉して１８０℃まで冷却し、ｐ‐ジクロロベンゼン（以下ではｐ‐ＤＣＢと略すことがある）２２．８５０ｋｇ、１，２，４‐トリクロロベンゼン（以下では１，２，４‐ＴＣＢと略すことがある）１２２．４８ｇ（仕込硫化ソーダに対して、約０．５５モル％）及びＮＭＰ１８．０ｋｇを仕込んだ。液温１５０℃で窒素ガスを用いて１ｋｇ／ｃｍ^２ Ｇまで加圧して昇温を開始した。液温２２０℃で３時間攪拌しつつ、オートクレーブ上部の外側に取り付けた散水装置により散水し、オートクレーブ上部を冷却した。その後、昇温して液温を２５５℃とし、次いで該温度で３時間攪拌し反応を進めた。次に、降温させると共にオートクレーブ上部の冷却を止めた。オートクレーブ上部を冷却中、液温が下がらないように一定に保持した。
【００６０】
得られたスラリーに対し常法により濾過、温水洗を繰り返し、１２０℃で５時間熱風循環乾燥機中で乾燥し、白色粉末状のＰＰＳを得た。得られたＰＰＳ（Ｐ‐０１）の溶融粘度Ｖ_６ は１８５０ポイズであり、非ニュートン指数Ｎは１．４９であり、ラジカル発生量は１．７×１０^１６ｓｐｉｎ／ｇであった。
【００６１】
合成例２（比較成分）
１５０リットルオートクレーブに、フレーク状硫化ソーダ（６０．３重量％Ｎａ_２ Ｓ）１９．４１３ｋｇとＮＭＰ４５．０ｋｇを仕込んだ。窒素気流下攪拌しながら液温２０４℃まで昇温して、水５．０７２ｋｇを留出させた。その後、オートクレーブを密閉して１８０℃まで冷却し、ｐ‐ＤＣＢ２２．２７３ｋｇ、１，２，４‐ＴＣＢ５４．４４ｇ（仕込硫化ソーダに対して、約０．２０モル％）及びＮＭＰ１８．０ｋｇを仕込んだ。液温１５０℃で窒素ガスを用いて１ｋｇ／ｃｍ^２ Ｇまで加圧して昇温を開始した。液温２１５℃で５時間攪拌しつつ、オートクレーブ上部の外側に取り付けた散水装置により散水し、オートクレーブ上部を冷却した。その後、昇温して液温を２６０℃とし、次いで該温度で２時間攪拌し反応を進めた。次に、降温させると共にオートクレーブ上部の冷却を止めた。オートクレーブ上部を冷却中、液温が下がらないように一定に保持した。
【００６２】
得られたスラリーに対し常法により濾過、温水洗を繰り返し、１２０℃で５時間熱風循環乾燥機中で乾燥し、白色粉末状のＰＰＳを得た。得られたＰＰＳ（Ｐ‐Ｃ１）の溶融粘度Ｖ_６ は２０３０ポイズであり、非ニュートン指数Ｎは１．２５であり、ラジカル発生量は１．４×１０^１６ｓｐｉｎ／ｇであった。
【００６３】
合成例３（比較成分）
１５０リットルオートクレーブに、フレーク状硫化ソーダ（６０．７重量％Ｎａ_２ Ｓ）１９．２２２ｋｇとＮＭＰ４５．０ｋｇを仕込んだ。窒素気流下攪拌しながら液温２０４℃まで昇温して、水４．６００ｋｇを留出させた。その後、オートクレーブを密閉して１８０℃まで冷却し、ｐ‐ＤＣＢ２２．８９４ｋｇ及びＮＭＰ１８．０ｋｇを仕込んだ。液温１５０℃で窒素ガスを用いて１ｋｇ／ｃｍ^２ Ｇまで加圧して昇温を開始した。液温２５０℃になったところで昇温をやめ、そのまま３時間攪拌し反応を進めた。
【００６４】
得られたスラリーに対し常法により濾過、温水洗を繰り返し、１２０℃で約５時間熱風循環乾燥機中で乾燥し、白色粉末状のＰＰＳを得た。得られたＰＰＳの溶融粘度Ｖ_６ は１３０ポイズであった。
【００６５】
該ＰＰＳを２３０℃で４７時間、熱酸化処理した。得られたＰＰＳ（Ｐ‐Ｃ２）の溶融粘度Ｖ_６ は１３２０ポイズであり、非ニュートン指数Ｎは１．４３であり、ラジカル発生量は４．２×１０^１６ｓｐｉｎ／ｇであった。
【００６６】
【実施例１〜７及び比較例１〜１１】
実施例及び比較例で使用したゼオライト及び他の添加物は下記の通りである。＜ゼオライト＞
・ＣＳ‐１００、商標、株式会社耕正製（Ａ型ゼオライトのＮａをＣａで置換したもの）
・ＣＳ‐１００Ｓ、商標、株式会社耕正製（ＣＳ‐１００の細粒品である）
・ＡＭＴ‐２５、商標、水澤化学工業株式会社製（Ａ型ゼオライト）
・ミズカライザーＥＳ、商標、水澤化学工業株式会社製（Ａ型ゼオライトのＮａをＣａで置換したもの）
＜他の添加物（比較成分）＞
・リン化合物：ＰＥＰ３６、商標、旭電化株式会社製（下記の化学式（ＩＩＩ） で示される物質）
【００６７】
【化２】

・白色顔料：ドライカラー ＨＳ‐Ｄ ９２１２８５、商標、大日精化株式会社製
・タルク
・カオリン
各実施例及び比較例とも、各成分を表１に示す量（重量部）でヘンシェルミキサーを使用して５分間予備混合した後、更に溶融混練して、白色度（ホットプレスＬ値）及び結晶化温度（Ｔｃ）の測定に供した。
【００６８】
白色度（ホットプレスＬ値）は下記の如く測定した。
＜白色度（ホットプレスＬ値）＞
試料を３２０℃で１．５分間、３０ｋｇ／ｃｍ^２ の圧力でホットプレスにより加圧成形して円盤状プレートを作り、これについて、色彩色差計（東京電色株式会社製、Ｃｏｌｏｒ Ａｃｅ）を用いて測定した。
【００６９】
結晶化温度（Ｔｃ）は下記の如く測定した。
＜結晶化温度（Ｔｃ）＞
ＤＳＣにより測定した。装置としては、セイコー電子製示差走査熱量計ＳＳＣ／５２００を用い、以下のようにして測定した。試料１０ｍｇを窒素気流中、昇温速度２０℃／分で室温から３２０℃まで昇温した後、３２０℃で５分間保持して溶融した。次いで、１０℃／分の速度で冷却した。この時の発熱ピーク温度を結晶化温度Ｔｃとした。
【００７０】
引張強度は、下記の如く測定した。
＜引張強度＞
各実施例及び比較例とも、表１に示す量（重量部）の各成分及びガラス繊維 （３Ｊ９６１Ｓ、商標、日東紡績株式会社製）６７重量部を加えて、ヘンシェルミキサーを使用して、５分間予備混合し均一化した。次いで、２０ｍｍφ二軸異方向回転押出機を用いてバレル設定温度３００℃、回転数４００ｒｐｍで溶融混練して押出し、ペレットを作成した。得られたペレットから、シリンダー温度３２０℃、金型温度１３０℃に設定した射出成形機により、ＡＳＴＭ Ｄ６３８に従うダンベル片を作成した。該ダンベル片を用い、ＡＳＴＭ Ｄ６３８に準拠して引張強度を測定した。
【００７１】
以上の結果を表１及び２に示す。表中の「ΔＴｃ」は、ゼオライト又は比較成分を用いた実施例又は比較例のＴｃと、これらを含まない比較例（ブランク）のＴｃとの差を意味す。
【００７２】
【表１】

【００７３】
【表２】

実施例１〜４は、本発明の（Ａ）ＰＰＳに（Ｂ）ゼオライトを種々の量で配合したものである。ゼオライトを配合していない比較例１と比べて、いずれも結晶化温度Ｔｃ 及び白色度Ｌ値は非常に高く、著しく良好な改善効果を示した。また、引張強度も増加する傾向にあった。（Ｂ）ゼオライトの配合量を増加すると、Ｔｃ 、Ｌ値及び引張強度は、いずれも増加した。実施例５〜７は、いずれも実施例３と同一配合比の下、（Ｂ）ゼオライトの種類を代えたものである。Ｔｃ 、Ｌ値及び引張強度は、いずれも実施例３とほぼ同等であり、良好な改善効果を示した。
【００７４】
一方、比較例２は、（Ｂ）ゼオライトの配合量が本発明の範囲を超えたものである。引張強度が著しく低下した。また、成形性が悪化し実用性に乏しいものであった。比較例３〜６は、いずれも実施例３と同一配合比の下、（Ｂ）ゼオライトに代えて、夫々リン化合物、白色顔料、タルク、カオリンを配合したものである。リン化合物を配合した比較例３では、Ｔｃ が比較例１より低く、逆効果であり、また成形時にガスの発生が認められた。白色顔料を配合した比較例４においても、Ｔｃ が低下し、また、引張強度が大幅に低下した。比較例５はタルクを配合したものであり、また比較例６はカオリンを配合したものであるが、Ｔｃ 及びＬ値のいずれにも殆ど改善効果が認められなかった。比較例７は、非ニュートン指数が本発明の範囲未満のＰＰＳ（Ｐ‐Ｃ１）、つまり比較的線状のＰＰＳのブランクテストであり、比較例８は、このＰ‐Ｃ１に（Ｂ）ゼオライトを配合したものである。比較例８においてはＴｃ は僅かしか増加しない。比較例９は、比較例５と同一配合比の下、Ｐ‐０１（分岐状）をＰ‐Ｃ１（比較的線状）に代えたものであり、ΔＴｃ は２０である。一方、比較例５ではΔＴｃ は１である。つまり、従来技術に従い、タルクを線状ＰＰＳに用いると結晶化温度が著しく増大する（但し、白色度は向上しない）が、分岐状ＰＰＳに用いたのでは効果がない。一方、本発明に従いゼオライトを分岐状ＰＰＳに用いると結晶化温度及び白色度ともに著しく改善され（実施例３）、しかし、線状ＰＰＳに用いたのでは結晶化温度は僅かしか改善されない（比較例８）。比較例１０は、ラジカル発生量が本発明の範囲を超えるＰＰＳ（Ｐ‐Ｃ２）、つまり熱酸化処理して得られた架橋ＰＰＳのブランクテストであり、比較例１１は、このＰ‐Ｃ２に（Ｂ）ゼオライトを配合したものである。比較例１１においてはＴｃ は殆ど増加せず、ゼオライトの添加効果が殆どない。即ち、実施例３、比較例５、８、９、１０及び１１から、本発明に従うＰＰＳとゼオライトの組合せの特異な挙動が判る。
【００７５】
【発明の効果】
本発明は、いわゆる分岐型ＰＡＳにおいて、引張強度等の機械的強度を低下させることなく、結晶化温度及び白色度を高めたＰＡＳ樹脂組成物を提供する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyarylene sulfide resin composition.
[0002]
[Prior art]
In recent years, thermoplastic resins having high heat resistance and chemical resistance have been required as materials for electrical / electronic equipment parts, automobile equipment parts, chemical equipment parts, and the like. In recent years, polyarylene sulfide (hereinafter sometimes abbreviated as PAS) typified by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) has attracted attention as one of the resins that meet this requirement.
[0003]
However, PAS has a slower crystallization rate than other engineering plastics. Therefore, at the time of injection molding, it has been necessary to perform molding with a relatively long molding cycle at a high mold temperature of 120 ° C or higher.
[0004]
Various attempts have been made to solve such problems. For example, Japanese Patent Laid-Open No. 61-204267 discloses a method for producing a resin composition in which an organic acid or organic acid anhydride having a high boiling point or a high melting point is added to PAS and heated to a temperature higher than the melting point of PAS. Japanese Laid-Open Patent Publication No. 63-245463 discloses a composition in which kaolin having an average particle size of 0.05-2 μm is blended with PAS to reduce the half-crystallization time, and Japanese Patent Laid-Open No. 64-54066 discloses a PAS. Discloses a resin composition containing an organometallic alkali metal salt compound. However, these are less effective in improving the molding cycle than so-called branched PAS. In the above Japanese Patent Application Laid-Open No. 64-54066, zeolite is exemplified in a long list of optional fillers, but there is no description of the combination of zeolite and branched PAS (this is Naturally, the organophosphate is less effective for branched PAS).
[0005]
Japanese Patent Application Laid-Open No. 3-146556 discloses a molding material containing a predetermined amount of PAS, glass fiber, crystalline zeolite and organosiloxane each obtained by curing PAS which is substantially linear before curing. However, the molding material is for shortening the molding cycle time of the crosslinked PAS cured by thermal oxidation treatment, and is suitable for the so-called branched PAS (not subjected to thermal oxidation treatment) used in the present invention. It is not something that can be done. Such a cross-linked PAS has a drawback that the viscosity is remarkably increased at the time of molding, and the flowability is difficult to control and the moldability is poor. Further, the effect of improving the crystallization temperature was low, and the shortening of the molding cycle time was insufficient. Japanese Patent Publication No. 6-57137 discloses a resin composition comprising PAS and zeolite. The invention is characterized by the composition of the zeolite. In this specification, a monomer having a special branched structure is described as one of optional monomers, but there is no specific disclosure and description of effects using such a PAS.
[0006]
Japanese Patent Publication No. 6-11864 discloses a resin composition comprising PPS as a main component and zeolite added thereto. The resin composition is intended to reduce corrosion of metal parts. Although there is a sentence that a branched structure may be used as an optional copolymerization component, there is no description about a specific example using branched PAS and its effect.
[0007]
In addition, PAS is usually light yellow in many cases, and even when PAS having high whiteness is obtained, coloring is likely to occur during melt molding. Therefore, a special means is required to obtain a PAS molded product having a high whiteness. For example, Japanese Patent Application Laid-Open No. 62-97821 discloses a method of stabilizing a polymer chain end by adding a halo-substituted organic compound such as a polyhaloaromatic compound to a polymerization system at a later stage of polymerization. However, it has been found that the melt viscosity tends to be small. Japanese Patent Application Laid-Open No. 60-8359 proposes mixing a white pigment into a PPS resin to make it white, and compensating for a decrease in mechanical strength caused by the addition of the white pigment by adding an epoxy resin. However, this leads to high costs. Titanium oxide and zinc sulfide are described as white pigments. JP-A-3-229760 discloses a composition comprising PAS and an inorganic filler, in order to prevent discoloration caused by the inorganic filler, a method of previously attaching an organic stabilizer to the surface of the composition, In addition, JP-A-3-28267 and JP-A-3-28268 disclose compositions obtained by adding an organophosphorus compound to PAS. However, the melt viscosity is reduced during melt molding, and the decomposition gas is generated.
[0008]
[Problems to be solved by the invention]
The present invention provides a PAS resin composition having an increased crystallization temperature and whiteness without decreasing mechanical strength such as tensile strength in so-called branched PAS.
[0009]
[Means for Solving the Problems]
The present inventors have made various studies in order to improve the crystallization speed of so-called branched PAS, which has poor crystallinity as compared with linear PAS and has conventionally been difficult to improve the crystallization speed. As a result, although zeolite is less effective in improving the crystallization rate of linear PAS, it is unexpectedly expected that for branched PAS having a predetermined radical generation amount and a non-Newtonian index N, It has been found that the crystallization temperature can be significantly increased by increasing the crystallization temperature. At the same time, it has been found that the whiteness of a molded product produced from the resin composition can be increased, and that the mechanical strength such as the tensile strength is hardly reduced, and the present invention has been completed.
[0010]
That is, the present invention
(1) (A) Radical generation amount measured by ESR is 2.5 × 10¹⁶100 parts by weight of polyarylene sulfide having a spin / g or less and a non-Newtonian index N of 1.35 or more, and
(B) 0.1-15 parts by weight of zeolite
Is a resin composition.
[0011]
As a preferred embodiment,
(2) (A) In the polyarylene sulfide, the non-Newtonian index N is 1.45 to 2.00, the resin composition according to the above (1),
(3) (A) In polyarylene sulfide, melt viscosity V₆The resin composition according to the above (1) or (2), wherein is 500 to 4800 poise,
(4) (A) A polyarylene sulfide reacts an alkali metal sulfide, a dihaloaromatic compound and a polyhaloaromatic compound in an organic amide solvent, wherein the molar ratio between the alkali metal sulfide and the dihaloaromatic compound Is set to 0.940 to 1.000, the molar ratio of the polyhaloaromatic compound to the alkali metal sulfide is set to 0.0035 to 0.010, and the gas phase portion of the reaction vessel is cooled during the reaction. The resin composition according to any one of the above (1) to (3), which is produced by condensing a part of the gas phase in the reaction can and refluxing it to a liquid phase,
(5) (A) polyarylene sulfide reacts (a) an alkali metal sulfide, (b) a dihaloaromatic compound, and (c) an aromatic compound having three or more functional groups in a polar solvent, The above (a), (b) so that the molar ratio of (a) / (b) is 0.970 to 1.020 and the molar ratio of (c) / (a) is 0.002 to 0.015. ) And (c) are charged into the reaction system, and when the reaction rate of (b) in the reaction system is 50 to 95%, the charge is 0.001 to 0 in molar ratio to the alkali metal sulfide. The resin composition according to any one of the above (1) to (3), which is produced by adding 0.02 (d) a molecular weight regulator to the reaction system.
Can be mentioned.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The component (A) PAS used in the resin composition of the present invention is a known polymer having an arylene sulfide repeating unit, and particularly preferably PPS. In the present invention, the component (A) PAS must have a non-Newtonian index N of 1.35 or more, preferably 1.45 or more, particularly preferably 1.50 or more. If it is less than the above value, the effect of improving the crystallization temperature due to the addition of zeolite is small, and the molding cycle cannot be shortened. The upper limit is not particularly limited, but is preferably 2.00 or less. Here, the non-Newtonian index N is a value calculated by measuring the shear rate and the shear stress under the conditions of 300 ° C. and L / D = 40 using a capillograph and using the following formula (I). The closer the N value is to 1, the closer the PAS is to a linear structure, and the higher the N value is, the more branched the structure is.
[0013]
[Expression 1]
SR = K · SS^N  (I)
[Where SR is the shear rate (seconds^-1), SS is the shear stress (Dyne / cm²), And K represents a constant. ]
Component (A) PAS has an upper limit of the amount of radicals measured by ESR of 2.5 × 10¹⁶spin / g, preferably 2.0 × 10¹⁶spin / g, particularly preferably 1.5 × 10¹⁶spin / g. When the above upper limit is exceeded, the viscosity is remarkably increased at the time of molding, and it becomes difficult to control the fluidity and the moldability is deteriorated. The lower limit is not particularly limited, but preferably 0.1 × 10¹⁶spin / g. Here, the radical generation amount is M_n ²⁺Is a value (spin / g) obtained from an ESR spectrum obtained after heating at 30 ° C. to 300 ° C. at a rate of 5 ° C./min and then holding at 300 ° C. for 30 minutes.
[0014]
The PAS of the present invention having the above radical generation amount is a so-called branched PAS. PAS produced by the method as shown below is preferable. For example, the arylene sulfide repeating unit preferably contains 0.2 mol% or more of a branched structure represented by the following formula (II).
[0015]
[Chemical 1]

Oxidized crosslinked PAS obtained by thermally oxidizing PAS in an oxygen-containing atmosphere has a radical generation amount measured by ESR exceeding the range of the present invention, and is different from PAS of the present invention.
[0016]
In the present invention, the melt viscosity V of component (A) PAS₆The upper limit is preferably 4800 poise, particularly preferably 4000 poise, and the lower limit is preferably 500 poise, particularly preferably 800 poise. Melt viscosity V₆However, if it is less than the above lower limit, the mechanical strength such as tensile strength of the resin composition is lowered. Exceeding the upper limit is not preferable because the fluidity is lowered and the molding processability is deteriorated. Where melt viscosity V₆Using a flow tester at 300 ° C. and a load of 20 kgf / cm², Viscosity (poise) measured after holding for 6 minutes at L / D = 10.
[0017]
Said (A) PAS can be preferably manufactured by the following method. That is, in the method for producing PAS by reacting an alkali metal sulfide and a dihaloaromatic compound in an organic amide solvent, the molar ratio of the alkali metal sulfide and the dihaloaromatic compound is 0.940 to 1.000. Further, 0.35 to 1.0 mol% of a polyhaloaromatic compound based on the charged alkali metal sulfide is added to the polymerization reaction system, and the reaction is carried out by cooling the gas phase portion of the reaction vessel during the reaction. In this method, a part of the gas phase in the can is condensed and refluxed to the liquid phase.
[0018]
In the above production method, the molar ratio of the alkali metal sulfide and the dihaloaromatic compound has an upper limit of 1.000, preferably 0.980, and a lower limit of 0.940, preferably 0.950. Below the above lower limit, the melt viscosity V of PAS₆Decreases and the moldability deteriorates. Exceeding the upper limit is not preferable because the workability during molding is poor.
[0019]
In the above production method, the polyhaloaromatic compound added to the polymerization reaction system has an upper limit of 1.00 mol%, preferably 0.80 mol%, and a lower limit of 0 with respect to the charged alkali metal sulfide. .35 mol%, preferably 0.40 mol%. If it is less than the lower limit, in the produced PAS, the non-Newtonian index N is small, and if it exceeds the upper limit, the processability at the time of molding is inferior.
[0020]
The method for adding the polyhaloaromatic compound into the polymerization reaction system is not particularly limited. For example, the alkali metal sulfide and the dihaloaromatic compound may be added at the same time, or at any point during the reaction, the polyhaloaromatic compound is dissolved in an organic solvent such as N-methylpyrrolidone, and the reaction vessel is heated with a high-pressure pump. You may press-fit inside.
[0021]
Japanese Patent Laid-Open No. 5-222196 discloses a method for producing PAS by condensing a part of the gas phase in the reaction vessel by cooling the gas phase portion of the reaction vessel and refluxing it to the liquid phase. The described method can be used.
[0022]
The liquid to be refluxed has a higher water content than the liquid phase bulk due to the difference in vapor pressure between water and the amide solvent. This reflux solution with a high water content forms a layer with a high water content at the top of the reaction solution. As a result, residual alkali metal sulfide (eg, Na₂S), alkali metal halides (for example, NaCl), oligomers and the like are contained in a large amount in the layer. In the conventional method, the produced PAS and Na at a high temperature of 230 ° C. or higher.₂In a state where raw materials such as S and by-products are uniformly mixed, not only high molecular weight PAS can be obtained, but also depolymerization of the generated PAS occurs, and thiophenol by-product is recognized. However, in the present invention, the above-mentioned disadvantageous phenomenon can be avoided by actively cooling the gas phase portion of the reaction vessel and returning a large amount of moisture-rich reflux liquid to the upper part of the liquid phase, thereby inhibiting the reaction. It is considered that such a factor can be removed truly efficiently and a high molecular weight PAS can be obtained. However, the present invention is not limited only by the effect of the above phenomenon, and a high molecular weight PAS can be obtained by various influences caused by cooling the gas phase portion.
[0023]
In this method, it is not necessary to add water during the reaction. However, adding water is not completely excluded. However, if the operation of adding water is performed, some of the advantages of this method are lost. Therefore, preferably the total water content in the polymerization reaction system is constant throughout the reaction.
[0024]
Cooling of the gas phase portion of the reactor can be performed by external cooling or internal cooling, and can be performed by a cooling means known per se. For example, a method of flowing a refrigerant through an internal coil installed at the top of a reaction can, a method of flowing a coolant through an external coil or jacket wound around the top of the reaction can, and a reflux condenser installed at the top of the reaction can A method such as spraying water on the upper part outside the reaction can or blowing a gas (air, nitrogen, etc.) is conceivable. Any method can be used as long as it has an effect of increasing the reflux amount in the can as a result. May be used. If the outside air temperature is relatively low (for example, normal temperature), it is possible to perform appropriate cooling by removing the heat insulating material conventionally provided at the top of the reaction can. In the case of external cooling, the water / amide solvent mixture condensed on the wall surface of the reaction vessel passes through the wall of the reaction vessel and enters the liquid phase. Accordingly, the water-rich mixture accumulates at the top of the liquid phase and keeps the water content relatively high. In the case of internal cooling, the mixture condensed on the cooling surface likewise travels through the cooling device surface or the reaction vessel wall and enters the liquid phase.
[0025]
On the other hand, the temperature of the liquid phase bulk is kept at a predetermined constant temperature or controlled according to a predetermined temperature profile. When making it constant temperature, it is preferable to react for 0.1 to 20 hours at the temperature of 230-275 degreeC. More preferably, it is 1 to 6 hours at a temperature of 240 to 265 ° C. In order to obtain higher molecular weight PAS, it is preferred to use a reaction temperature profile of two or more stages. When performing this two-stage operation, the first stage is preferably performed at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too low to be practical. If it is higher than 240 ° C., the reaction rate is too high, and not only a sufficiently high molecular weight PAS cannot be obtained, but also the side reaction rate is remarkably increased. The completion of the first stage is preferably performed when the residual ratio of the dihaloaromatic compound in the polymerization reaction system is in the range of 1 mol% to 40 mol% and the molecular weight is in the range of 3,000 to 20,000. More preferably, the residual ratio of the dihaloaromatic compound in the polymerization reaction system is in the range of 2 to 15 mol% and the molecular weight is in the range of 5,000 to 15,000. If the residual ratio exceeds 40 mol%, side reactions such as depolymerization are likely to occur in the second stage reaction, whereas if it is less than 1 mol%, it is difficult to finally obtain a high molecular weight PAS. Thereafter, the temperature is raised, and the final reaction is preferably carried out at a reaction temperature of 240 to 270 ° C. for 1 to 10 hours. If the temperature is low, a sufficiently high molecular weight PAS cannot be obtained, and if the temperature is higher than 270 ° C., side reactions such as depolymerization tend to occur, making it difficult to stably obtain a high molecular weight product.
[0026]
As an actual operation, first, under an inert gas atmosphere, dehydration or water addition is performed as necessary so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount. The water content is preferably 0.5 to 2.5 mol, in particular 0.8 to 1.2 mol, per mol of alkali metal sulfide. If it exceeds 2.5 moles, the reaction rate decreases, and the amount of by-products such as phenol increases in the filtrate after completion of the reaction, and the degree of polymerization does not increase. If the amount is less than 0.5 mol, the reaction rate is too high and a sufficiently high molecular weight product cannot be obtained.
[0027]
In the case of a one-stage reaction at a constant temperature, it is desirable to cool the gas phase portion during the reaction from the beginning of the reaction, but it must be performed at least during the temperature rise of 250 ° C. or less. In the multistage reaction, it is desirable to cool from the first stage reaction, but it is preferable to carry out from the middle of the temperature increase after the completion of the first stage reaction at the latest. The degree of cooling effect is usually the most suitable index for the pressure in the reaction vessel. The absolute value of the pressure varies depending on the characteristics of the reactor, the stirring state, the moisture content in the system, the molar ratio of the dihaloaromatic compound and the alkali metal sulfide, and the like. However, compared with the case where the reactor is not cooled under the same reaction conditions, if the reaction vessel pressure decreases, the amount of the reflux liquid increases, which means that the temperature at the reaction solution gas-liquid interface decreases. It is considered that the degree of relative decrease indicates the degree of separation between the layer having a high water content and the layer not having the moisture content. Therefore, the cooling is preferably performed to such an extent that the internal pressure of the reaction can becomes lower than that in the case where cooling is not performed. The degree of cooling can be appropriately set by those skilled in the art according to the equipment to be used and the operating conditions.
[0028]
The organic amide solvents used here are known for PAS polymerization, such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, and mixtures thereof. N-methylpyrrolidone is preferred. These all have a lower vapor pressure than water. Alkali metal sulfides are also known, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof. These hydrates and aqueous solutions may also be used. In addition, hydrosulfides and hydrates corresponding to these can be used after neutralizing with the corresponding hydroxides. Inexpensive sodium sulfide is preferred.
[0029]
The dihaloaromatic compound can be selected from those described in, for example, Japanese Patent Publication No. 45-3368, and is preferably p-dichlorobenzene. Further, a copolymer can be obtained by using one or more kinds of a small amount (20 mol% or less) of diphenyl ether, diphenyl sulfone or biphenyl para, meta or ortho dihalo compounds. For example, m-dichlorobenzene, o-dichlorobenzene, p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenyl sulfone, m, p'- Dichlorodiphenyl sulfone, m, m′-dichlorodiphenyl sulfone, p, p′-dichlorobiphenyl, m, p′-dichlorobiphenyl, m, m′-dichlorobiphenyl.
[0030]
A polyhaloaromatic compound is a compound having three or more halogen substituents per molecule, such as 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,3-dichloro-5-bromobenzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene, 1,3,5-trichloro-2,4,6-trimethyl Benzene, 2,2 ', 4,4'-tetrachlorobiphenyl, 2,2', 6,6'-tetrabromo-3,3 ', 5,5'-tetramethylbiphenyl, 1,4,6-trichloronaphthalene 1,2,3,4-tetrachloronaphthalene, 1,2,4-tribromo-6-methylnaphthalene and the like, and mixtures thereof, 1,2,4-trichlorobenzene, , 3,5-trichlorobenzene is preferable.
[0031]
In addition, as other small amount additives, a terminal terminator and a monohalide as a modifier can be used in combination.
[0032]
The (A) PAS of the present invention can also be preferably produced by the following method.
[0033]
That is, in a method of producing polyarylene sulfide by reacting (a) an alkali metal sulfide, (b) a dihaloaromatic compound, and (c) an aromatic compound having three or more functional groups in a polar solvent, ) / (B) is from 0.970 to 1.020 and (c) / (a) is from 0.002 to 0.015 above (a), (b) and When (c) is charged into the reaction system and the reaction rate of (b) in the reaction system is 50 to 95%, (a) 0.001 to 0.02 in molar ratio to the alkali metal sulfide. (D) adding a molecular weight regulator to the reaction system.
[0034]
In the above PAS production method, the molar ratio of (a) alkali metal sulfide / (b) dihaloaromatic compound has a lower limit of 0.970, preferably 0.980, and an upper limit of 1.020, preferably 1. .000. Below the lower limit, the non-Newtonian index N of PAS is low, and the melt viscosity V₆Becomes remarkably low and formability deteriorates. Exceeding the upper limit is not preferable because PAS causes depolymerization. The molar ratio of (c) aromatic compound having 3 or more functional groups / (a) alkali metal sulfide has a lower limit of 0.002, preferably 0.003, and an upper limit of 0.015, preferably 0.8. 01. Below the lower limit, the non-Newtonian index N of PAS is low, and the melt viscosity V₆Becomes remarkably low and formability deteriorates. Exceeding the above upper limit is not preferred because PAS branching and cross-linking proceed excessively, and gelation of PAS occurs at the time of molding, resulting in deterioration of moldability.
[0035]
In this method, the (d) molecular weight regulator is such that the upper limit of the reaction rate of the (b) dihaloaromatic compound in the reaction system is 95%, preferably 90%, the lower limit is 50%, preferably 70%, particularly preferably. It is added at 80%. When the reaction rate of the (b) dihaloaromatic compound at the time of addition is less than the above lower limit, the introduction of the branched structure is insufficient and the non-Newtonian index N becomes low. Exceeding the above upper limit will cause an extremely high melt viscosity V₆Becomes high and becomes gelled and cannot be molded. The molecular weight regulator (d) added to the polymerization reaction system is (a) a molar ratio to the alkali metal sulfide, and the lower limit is 0.001, preferably 0.002, particularly preferably 0.004, and the upper limit. Is 0.02, preferably 0.01, particularly preferably 0.008. Outside the above range, the non-Newtonian index N decreases and the moldability also deteriorates. Addition of (d) may be added all at once in a range of the above reaction rate, or may be added in several times. The addition can be performed by injecting (d) as it is or in a polar solvent to be used (for example, N-methyl-2-pyrrolidone) and press-fitting it into a reaction vessel using a pressure injector. .
[0036]
As the (d) molecular weight regulator of the present invention, those listed below can be used. For example, mono or dihalo aromatic compounds such as monochlorobenzene, monobromobenzene, m-dichlorobenzene, etc .; aromatic compounds having one or two mercapto groups such as thiophenol, 1,4-dithiophenol, monochlorothiophenol, etc .; disulfide Compounds such as diphenyl disulfide, p, p'-ditolyl disulfide, dibenzyl disulfide, dibenzoyl disulfide, dithiobenzoyl disulfide, etc .; halo-substituted fragrances having electron withdrawing groups (eg carboxyl groups, nitro groups, sulfonyl groups, carbonyl groups, etc.) Group compounds such as nitrochlorobenzene, dichlorodiphenylsulfone, 4,4'-dichlorobenzophenone and the like. Preferably, (d) at least one selected from the group consisting of thiophenol, diphenyl disulfide or m-dichlorobenzene can be used as the molecular weight regulator.
[0037]
Any of (a) alkali metal sulfide and (b) dihaloaromatic compound described above can be used.
[0038]
(C) As the aromatic compound having three or more functional groups, for example, those described in JP-B-6-45693 can be used. (C) The aromatic compound having 3 or more functional groups is an aromatic compound having 3 or more, preferably 3 to 4 and particularly preferably 3 reactive functional groups bonded to an aromatic ring. Examples of the reactive functional group include an amino group, a hydroxyl group, a mercapto group, a carboxyl group, a sulfonyl group, a sulfino group, a sulfamoyl group, a hydrazino group, a carbamoyl group and other active hydrogen-containing groups, a halogen atom, and a nitro group. Can be mentioned. Of the reactive functional groups, amino groups, halogen atoms, and nitro groups are preferred. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like, and a chlorine atom is preferable. The reactive functional groups bonded to the aromatic ring may be the same or different. In addition, examples of the aromatic compound (c) include benzenes, biphenyls, diphenyl ethers, diphenyl sulfides, naphthalenes, and the like, and benzenes are preferable.
[0039]
(C) As the aromatic compound having 3 or more functional groups, preferably active hydrogen-containing halogen aromatic compounds, polyhaloaromatic compounds, halogen aromatic nitro compounds and the like can be used.
[0040]
Examples of the active hydrogen-containing halogen aromatic compound include dihaloanilines such as 2,6-dichloroaniline, 2,5-dichloroaniline, 2,4-dichloroaniline, and 2,3-dichloroaniline; Trihaloanilines such as trichloroaniline, 2,4,6-trichloroaniline, 3,4,5-trichloroaniline; 2,2′-diamino-4,4′-dichlorodiphenyl ether, 2,4′-diamino-2 ′ Amino group-containing halogen aromatic compounds such as dihaloaminodiphenyl ethers such as 1,4-dichlorodiphenyl ether, and compounds in which the amino group in these compounds is replaced with a mercapto group or a hydroxyl group. In addition, an amino group-containing halogen in which a hydrogen atom bonded to a carbon atom forming an aromatic ring in these active hydrogen-containing halogen aromatic compounds is substituted with another inert group, for example, a hydrocarbon group such as an alkyl group. Aromatic compounds can also be used. Among the above active hydrogen-containing halogen aromatic compounds, active hydrogen-containing dihaloaromatic compounds can be suitably used. Among them, amino group-containing dihaloaromatic compounds are preferable, and dichloroaniline is particularly preferable.
[0041]
As the polyhaloaromatic compound, the same compounds as described above can be used.
[0042]
Examples of the halogen aromatic nitro compound include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; dihalonitrodiphenyl ethers such as 2-nitro-4,4'-dichlorodiphenyl ether; Dihalonitrodiphenyl sulfones such as 3,3'-dinitro-4,4'-dichlorodiphenyl sulfone; mono- or di- such as 2,5-dichloro-3-nitropyridine, 2-chloro-3,5-dinitropyridine Examples thereof include halonitropyridines and various dihalonitronaphthalenes.
[0043]
In the method of the present invention, the aromatic compound (c) having three or more functional groups may be used alone or in combination of two or more.
[0044]
The polar solvent used in the method of the present invention is known for PAS polymerization, for example, those described in JP-B-6-45693, such as organic amide compounds, lactam compounds, urea compounds, cyclic organics. Phosphorus compounds and the like can be used. Examples of the polar solvent include the organic amide solvents listed above, N, N-diethylacetamide, N, N-dipropylacetamide, N, N-dimethylbenzoic acid amide, caprolactam, N-ethylcaprolactam, N- Isopropyl caprolactam, N-isobutyl caprolactam, N-normal propyl caprolactam, N-normal butyl caprolactam, N-cyclohexyl caprolactam, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N -N-propyl-2-pyrrolidone, N-normalbutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N -Methyl-3,4,5 Trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-isopropyl-2-piperidone, N-ethyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethyl- 2-piperidone, tetramethylurea, N, N'-dimethylethyleneurea, N, N'-dimethylpropyleneurea, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1- Examples include oxosulfolane, 1-methyl-1-oxophosphorane, 1-normalpropyl-1-oxophosphorane, and 1-phenyl-1-oxophosphorane. These solvents may be used alone or in combination of two or more. Among the polar solvents, aprotic organic amides or lactams are preferable, and among them, N-alkyl lactams and N-alkylpyrrolidones are preferable, and N-methylpyrrolidone is particularly preferable.
[0045]
In a method for producing PAS by reacting (a) an alkali metal sulfide, (b) a dihaloaromatic compound, and (c) an aromatic compound having three or more functional groups in a polar solvent, preferably as described above, During the reaction, a method of condensing a part of the gas phase in the reaction vessel by cooling the gas phase portion of the reaction vessel and refluxing it to the liquid phase (JP-A-5-222196) can be used.
[0046]
The PAS obtained by either method can be separated from by-products by post-treatment methods known to those skilled in the art.
[0047]
(B) Zeolite is a crystalline aluminosilicate and is a known substance represented by the following general formula.
(M^I ₂, M^II) O ・ Al₂O₃・ NSiO₂・ MH₂O
Where M^IRepresents a monovalent metal, for example, an alkali metal such as Li, Na, or K, or ammonium, alkylammonium, pyridinium, anilinium, hydrogen ion, etc.^IIRepresents a divalent metal, for example, an alkaline earth metal such as Ca, Mg, Ba, or Sr. M^IAnd M^IIMay be present in one or both. Preferably M^IIIs Ca and M^IIs virtually absent.
[0048]
As the zeolite (B) used in the present invention, any natural or synthetic zeolite can be used. Natural zeolites include, for example, borofluorite, wilakite, soda fluorite, mesofluorite, Thomson fluorite, gonardo fluorite, scole fluorite, egingt fluorite, gizmon fluorite, mordenite, mordenite, nigawara. Fluorite, erionite, ashcroftin, kifluorite, clinoptilolite, taba fluorite, haku fluorite, daciardo fluorite, kaijuji fluorite, juzi fluorite, gmelin fluorite, rhyolite, faujasite Etc. can be mentioned. Examples of the synthetic zeolite include A type, X type, Y type, L type, mordenite, chabazite and the like. Among the above zeolites, synthetic zeolite is preferably used. As the synthetic zeolite, commercially available ones can be used. For example, CS-100, CS-100S (both are trademarks, manufactured by Kosho Co., Ltd.), AMT-25 (trademark, manufactured by Mizusawa Chemical Industry Co., Ltd.), Mizcalizer ES (trademark, manufactured by Mizusawa Chemical Co., Ltd.) and the like.
[0049]
The shape of the (B) zeolite is preferably powder particles, and the upper limit of the average particle diameter is preferably 3 μm, particularly preferably 2 μm. Exceeding the upper limit is not preferable because it causes a decrease in fluidity of the resin composition, a decrease in tensile strength of the molded product, and the like. Here, the average particle diameter is a value obtained by the Coulter counter method (D₅₀).
[0050]
In the present invention, the mixing ratio of the component (A) PAS and the component (B) zeolite is 15 parts by weight, preferably 10 parts by weight, particularly preferably 5 parts by weight with respect to 100 parts by weight of (A). The lower limit is 0.1 parts by weight, preferably 0.5 parts by weight, particularly preferably 1 part by weight. When the upper limit is exceeded, workability and mechanical strength such as tensile strength are lowered, and further remarkable improvement in crystallization temperature and whiteness of the molded product is not recognized. If it is less than the said minimum, the crystallization temperature and the whiteness of a molded article cannot be raised.
[0051]
The resin composition of the present invention can further contain an inorganic filler as an optional component. Although it does not specifically limit as an inorganic filler, For example, a powdery / flaky filler, a fibrous filler, etc. can be used. Examples of the powder / flaky filler include silica, alumina, talc, mica, kaolin, clay, silica alumina, titanium oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, Examples thereof include silicon nitride, glass, hydrotalcite, zirconium oxide, glass beads, and carbon black. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. In addition, fillers such as ZnO tetrapots, metal salts (such as zinc chloride and lead sulfate), oxides (such as iron oxide and molybdenum dioxide), metals (such as aluminum and stainless steel) may be used. it can. These can be used alone or in combination of two or more. The surface of the inorganic filler may be treated with a silane coupling agent or a titanate coupling agent. The inorganic filler is used in an amount of 400 parts by weight or less, preferably 300 parts by weight or less based on 100 parts by weight of (A). If the amount of the inorganic filler exceeds the above value, the change in viscosity becomes large and molding may be impossible. In order to increase the mechanical strength, it is preferable to blend 0.01 parts by weight or more.
[0052]
In the resin composition of the present invention, in addition to the above-mentioned components, known additives and fillers, for example, antioxidants, ultraviolet absorbers, mold release agents, heat stabilizers, lubricants, colorants, etc., if necessary Can be blended.
[0053]
The method for producing the resin composition of the present invention is not particularly limited. For example, each of the above components can be mixed in advance with a mixer such as a Henschel mixer, then melt kneaded with a conventional apparatus such as an extruder, extruded, and pelletized.
[0054]
The resin composition of the present invention is molded into a desired shape by, for example, injection molding, and particularly molded products that require a beautiful appearance, such as electronic parts, home appliance parts, or precision equipment parts such as cameras and watches. Can be used.
[0055]
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples.
[0056]
【Example】
In the examples, the melt viscosity of PPS V₆The flow tester used for the measurement is a flow tester CFT-500C manufactured by Shimadzu Corporation.
[0057]
The capillograph used for the measurement of the non-Newton index N is Capillograph 1B PC manufactured by Toyo Seiki Seisakusho.
[0058]
The ESR used for measuring the amount of radical generation is JES-FE2XG manufactured by JEOL.
[0059]
Synthesis example 1
In a 150 liter autoclave, flaky sodium sulfide (60.3% by weight Na₂S) 19.413 kg and 45.0 kg of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) were charged. While stirring under a nitrogen stream, the liquid temperature was raised to 204 ° C. to distill 4.872 kg of water. Thereafter, the autoclave was sealed and cooled to 180 ° C., and p-dichlorobenzene (hereinafter sometimes abbreviated as p-DCB) 22.850 kg, 1,2,4-trichlorobenzene (hereinafter, 1,2,4- 122.48 g (may be abbreviated as TCB) (about 0.55 mol% with respect to the charged sodium sulfide) and 18.0 kg of NMP were charged. 1kg / cm using nitrogen gas at a liquid temperature of 150 ° C²The pressure was increased to G and the temperature increase was started. While stirring at a liquid temperature of 220 ° C. for 3 hours, water was sprinkled by a watering device attached to the outside of the upper part of the autoclave to cool the upper part of the autoclave. Thereafter, the temperature was raised to a liquid temperature of 255 ° C., and the mixture was stirred at that temperature for 3 hours to proceed the reaction. Next, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping.
[0060]
The obtained slurry was repeatedly filtered and washed with warm water by a conventional method, and dried in a hot air circulating dryer at 120 ° C. for 5 hours to obtain white powdery PPS. The melt viscosity V of the obtained PPS (P-01)₆Is 1850 poise, the non-Newtonian index N is 1.49, and the radical generation amount is 1.7 × 10¹⁶spin / g.
[0061]
Synthesis example 2(Comparative ingredients)
In a 150 liter autoclave, flaky sodium sulfide (60.3% by weight Na₂S) Charged 19.413 kg and NMP 45.0 kg. While stirring under a nitrogen stream, the temperature was raised to 204 ° C. to distill 5.072 kg of water. Thereafter, the autoclave was sealed and cooled to 180 ° C., and charged with 22.273 kg of p-DCB, 54.44 g of 1,2,4-TCB (about 0.20 mol% with respect to the sodium sulfide charged) and 18.0 kg of NMP. . 1kg / cm using nitrogen gas at a liquid temperature of 150 ° C²The pressure was increased to G and the temperature increase was started. While stirring at a liquid temperature of 215 ° C. for 5 hours, water was sprinkled by a watering device attached to the outside of the upper part of the autoclave to cool the upper part of the autoclave. Thereafter, the temperature was raised to 260 ° C., and the reaction was continued by stirring for 2 hours at this temperature. Next, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping.
[0062]
The obtained slurry was repeatedly filtered and washed with warm water by a conventional method, and dried in a hot air circulating dryer at 120 ° C. for 5 hours to obtain white powdery PPS. The melt viscosity V of the obtained PPS (P-C1)₆Is 2030 poise, non-Newtonian index N is 1.25, and radical generation amount is 1.4 × 10¹⁶spin / g.
[0063]
Synthesis example 3(Comparative ingredients)
In a 150 liter autoclave, flaky sodium sulfide (60.7 wt% Na₂S) 19.222 kg and 45.0 kg of NMP were charged. While stirring under a nitrogen stream, the liquid temperature was raised to 204 ° C. to distill 4.600 kg of water. Then, the autoclave was sealed and cooled to 180 ° C., and p-DCB 22.894 kg and NMP 18.0 kg were charged. 1kg / cm using nitrogen gas at a liquid temperature of 150 ° C²The pressure was increased to G and the temperature increase was started. When the liquid temperature reached 250 ° C., the temperature was raised and the reaction was allowed to proceed with stirring for 3 hours.
[0064]
The obtained slurry was repeatedly filtered and washed with warm water by a conventional method, and dried in a hot air circulating drier at 120 ° C. for about 5 hours to obtain white powdery PPS. The melt viscosity V of the obtained PPS₆Was 130 poise.
[0065]
The PPS was thermally oxidized at 230 ° C. for 47 hours. The melt viscosity V of the obtained PPS (P-C2)₆Is 1320 poise, the non-Newtonian index N is 1.43, and the amount of radicals generated is 4.2 × 10¹⁶spin / g.
[0066]
Examples 1-7 and Comparative Examples 1-11
Zeolite and other additives used in Examples and Comparative Examples are as follows. <Zeolite>
CS-100, trademark, manufactured by Kosho Co., Ltd. (Na of A type zeolite replaced with Ca)
CS-100S, trademark, manufactured by Kosho Co., Ltd. (CS-100 fine-grained product)
・ AMT-25, trademark, made by Mizusawa Chemical Co., Ltd. (Type A zeolite)
・ Mizcalizer ES, trademark, made by Mizusawa Chemical Co., Ltd. (Na of A-type zeolite replaced with Ca)
<Other additives (comparative ingredients)>
Phosphorus compound: PEP36, trademark, manufactured by Asahi Denka Co., Ltd. (substance represented by the following chemical formula (III))
[0067]
[Chemical 2]

-White pigment: Dry color HS-D 921285, trademark, manufactured by Dainichi Seika Co., Ltd.
·talc
・ Kaolin
In each example and comparative example, each component was premixed for 5 minutes in the amount (parts by weight) shown in Table 1 using a Henschel mixer, and then melt-kneaded to obtain whiteness (hot press L value) and crystals. It used for the measurement of crystallization temperature (Tc).
[0068]
The whiteness (hot press L value) was measured as follows.
<Whiteness (hot press L value)>
Sample was 30 kg / cm at 320 ° C. for 1.5 minutes²A disk-shaped plate was formed by pressure molding with a hot press at a pressure of 5 mm, and this was measured using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd., Color Ace).
[0069]
The crystallization temperature (Tc) was measured as follows.
<Crystallization temperature (Tc)>
Measured by DSC. As a device, a differential scanning calorimeter SSC / 5200 manufactured by Seiko Electronics was used, and measurement was performed as follows. 10 mg of a sample was heated from room temperature to 320 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen stream, and then held at 320 ° C. for 5 minutes to melt. Then it was cooled at a rate of 10 ° C./min. The exothermic peak temperature at this time was defined as the crystallization temperature Tc.
[0070]
The tensile strength was measured as follows.
<Tensile strength>
In each example and comparative example, the components (parts by weight) shown in Table 1 and 67 parts by weight of glass fiber (3J961S, trademark, manufactured by Nitto Boseki Co., Ltd.) are added, and a Henschel mixer is used for 5 minutes. Premixed and homogenized. Subsequently, it was melt-kneaded and extruded at a barrel set temperature of 300 ° C. and a rotational speed of 400 rpm using a 20 mmφ biaxial different-direction rotary extruder to produce pellets. From the obtained pellets, dumbbell pieces according to ASTM D638 were prepared by an injection molding machine set at a cylinder temperature of 320 ° C and a mold temperature of 130 ° C. Using the dumbbell piece, the tensile strength was measured according to ASTM D638.
[0071]
The above results are shown in Tables 1 and 2. “ΔTc” in the table means the difference between Tc of an example or comparative example using zeolite or a comparative component and Tc of a comparative example (blank) not containing these.
[0072]
[Table 1]

[0073]
[Table 2]

Examples 1-4 mix | blend (B) zeolite with various quantity to (A) PPS of this invention. Compared with Comparative Example 1 in which no zeolite was blended, the crystallization temperature Tc and the whiteness L value were both very high, and a remarkably good improvement effect was exhibited. Also, the tensile strength tended to increase. (B) When the blending amount of zeolite was increased, Tc, L value and tensile strength were all increased. In Examples 5 to 7, all of the types of (B) zeolite were changed under the same blending ratio as in Example 3. Tc, L value, and tensile strength were all almost the same as in Example 3 and showed a good improvement effect.
[0074]
On the other hand, in Comparative Example 2, the blending amount of (B) zeolite exceeds the range of the present invention. The tensile strength was significantly reduced. Moreover, the moldability deteriorated and the practicality was poor. In Comparative Examples 3 to 6, the same compounding ratio as in Example 3 was used, and instead of (B) zeolite, a phosphorus compound, a white pigment, talc, and kaolin were blended, respectively. In Comparative Example 3 in which a phosphorus compound was blended, Tc was lower than that in Comparative Example 1, which had an adverse effect, and generation of gas was observed during molding. Also in the comparative example 4 which mix | blended the white pigment, Tc fell and the tensile strength fell significantly. Comparative Example 5 was formulated with talc, and Comparative Example 6 was formulated with kaolin, but almost no improvement effect was observed in both Tc and L values. Comparative Example 7 is a blank test of PPS (P-C1) having a non-Newtonian index less than the range of the present invention, that is, a relatively linear PPS, and Comparative Example 8 includes (B) zeolite in P-C1. It is a blend. In Comparative Example 8, Tc increases only slightly. In Comparative Example 9, P-01 (branched) was replaced with P-C1 (relatively linear) under the same blending ratio as Comparative Example 5, and ΔTc was 20. On the other hand, in Comparative Example 5, ΔTc is 1. That is, according to the prior art, when talc is used for linear PPS, the crystallization temperature is remarkably increased (however, the whiteness is not improved), but it is not effective when used for branched PPS. On the other hand, when the zeolite is used for the branched PPS according to the present invention, both the crystallization temperature and the whiteness are remarkably improved (Example 3). However, when the zeolite is used for the linear PPS, the crystallization temperature is only slightly improved (Comparative Example). 8). Comparative Example 10 is a blank test of PPS (P-C2) having a radical generation amount exceeding the range of the present invention, that is, a crosslinked PPS obtained by thermal oxidation treatment. B) It contains zeolite. In Comparative Example 11, Tc hardly increases and there is almost no effect of adding zeolite. That is, the specific behavior of the combination of PPS and zeolite according to the present invention can be seen from Example 3 and Comparative Examples 5, 8, 9, 10, and 11.
[0075]
【The invention's effect】
The present invention provides a PAS resin composition having an increased crystallization temperature and whiteness without decreasing mechanical strength such as tensile strength in so-called branched PAS.

Claims (5)

(A) 100 parts by weight of a polyarylene sulfide having a radical generation amount measured by ESR of 2.5 × 10 ¹⁶ spin / g or less and a non-Newtonian index N of 1.35 or more, and (B) zeolite 0. A resin composition containing 1 to 15 parts by weight. (A) In the polyarylene sulfide, the non-Newton index N is 1.45 to 2.00. (A) In the polyarylene sulfide according to claim 1 or 2 resin composition according melt viscosity _{V 6} is 500-4800 poise. (A) The polyarylene sulfide reacts the alkali metal sulfide, the dihaloaromatic compound, and the polyhaloaromatic compound in an organic amide solvent, and the molar ratio of the alkali metal sulfide to the dihaloaromatic compound is set to 0. 940 to 1.000, the molar ratio of the polyhaloaromatic compound and the alkali metal sulfide is set to 0.0035 to 0.010, and the reaction is carried out by cooling the gas phase portion of the reaction vessel during the reaction. The resin composition according to any one of claims 1 to 3, wherein the resin composition is produced by condensing a part of a gas phase in a can and refluxing it to a liquid phase. (A) polyarylene sulfide reacts in a polar solvent with (a) an alkali metal sulfide, (b) a dihaloaromatic compound, and (c) an aromatic compound having three or more functional groups, wherein (a) (A), (b) and (b) such that the molar ratio of / (b) is 0.970 to 1.020 and the molar ratio of (c) / (a) is 0.002 to 0.015. c) is charged into the reaction system, and when the reaction rate of (b) in the reaction system is 50 to 95%, (a) the molar ratio with respect to the alkali metal sulfide is 0.001 to 0.02. (D) The resin composition according to any one of claims 1 to 3, which is produced by adding a molecular weight regulator to the reaction system.