JP3641906B2 - Process for producing polyphenylene sulfide resin composition - Google Patents

Description

含む重合体であり、上記単位を７０モル％以上、特に９０モル％以上を含む重合体が耐熱性の点から好ましい。またＰＰＳ樹脂はその繰り返し単位の３０モル％未満を、下記の構造を有する繰り返し単位等で構成することが可能である。
【００１０】
【化２】

【００１１】
本発明のＰＰＳ樹脂の製造方法については上記の必要条件を満たす限り特に限定されず、通常公知の方法すなわち特公昭４５−３３６８号公報に記載される方法あるいは特公昭５２−１２２４０号公報に記載される方法などによって製造できる。本発明において上記のように得られたＰＰＳ樹脂を有機溶媒、熱水、酸水溶液などによる洗浄、酸無水物基、エポキシ基、イソシアネート基などの官能基含有化合物による活性化など種々の処理を施した上で使用することも可能である。
【００１２】
次に、本発明において（Ｂ）成分として用いられるアルコキシシラン化合物としては、分子中に一個以上のエポキシ基、アミノ基、イソシアネート基、水酸基、メルカプト基あるいはウレイド基を有するアルコキシシラン化合物であることが好ましく、具体的には３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジエトキシシラン、Ｎ−フェニルアミノメチルトリメトキシシラン、Ｎ−フェニルアミノプロピルトリメトキシシラン、ジメトキシメチル−３−ピペラジノプロピルシラン、３−ピペラジノプロピルトリメトキシシラン、３−イソシアナトプロピルトリメトキシシラン、３−イソシアナトプロピルトリエトキシシラン、３−イソシアナトプロピルメチルジメトキシシラン、３−イソシアナトプロピルメチルジエトキシシラン、３−イソシアナトプロピルエチルジメトキシシラン、３−ヒドロキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルトリエトキシシラン、３−メルカプトメチルジメトキシシラン、γ−ウレイドプロピルトリメトキシシランなどを好ましく挙げることができる。
【００１３】
これらアルコキシシラン化合物は各々単独または２種以上の混合物の形で用いることができ、また上記アルコキシシラン化合物の内で特に好適なアルコキシシラン化合物としては、３−グリシドキシプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−イソシアナトプロピルトリメトキシシラン、３−ヒドロキシプロピルトリメトキシシランならびに３−メルカプトプロピルトリメトキシシランなどを挙げることができる。
【００１４】
本発明に用いられるこれらアルコキシシラン化合物（Ｂ）の配合量は、ＰＰＳ樹脂１００重量部に対して得られる組成物の流動性および成形品の機械的強度およびウェルド強度の点から通常、０．１〜５重量部であり、好ましくは０．３〜３重量部である。
【００１５】
ポリフェニレンスルフィド樹脂には、一般的に添加剤（例えば繊維状および／または非繊維状の補強材、それ以外のその他無機添加剤および／または有機添加剤など）が配合される場合があるが、本発明においては、ポリフェニレンスルフィド樹脂、上記（Ｂ）成分および添加剤を配合して組成物を製造する際、用いる添加剤がアマニ油吸油量が２０ｍｌ／１００ｇを越えるものである場合、特定の方法で各成分を配合することが重要である。
【００１６】
上記繊維状および／または非繊維状の補強材における繊維状補強材としては、一般にガラス繊維、アルミナ繊維、炭化珪素繊維、セラミック繊維、アスベスト繊維、石コウ繊維、金属繊維、チタン酸カリウィスカなどの無機繊維および炭素繊維などが挙げられる。なかでもガラス繊維、炭素繊維、チタン酸カリウムウィスカーなどが好ましい。
【００１７】
また非繊維状の補強材としては、一般にワラステナイト、セリサイト、カオリン、マイカ、クレー、ベントナイト、アスベスト、タルク、アルミナシリケートなどの珪酸塩、アルミナ、塩化珪素、酸化マグネシウム、酸化ジルコニウム、酸化チタンなどの金属化合物、炭酸カルシウム、炭酸マグネシウム、ドロマイトなどの炭酸塩、硫酸カルシウム、硫酸バリウムなどの硫酸塩、ガラスビーズ、窒化ホウ素、炭化珪素およびシリカなどが挙げられ、これらは中空であっても良い。なかでも炭酸カルシウム、タルク、ワラステナイト、マイカ、硫酸カルシウム、酸化マグネシウム、または次亜リン酸カルシウムが好ましい。
【００１８】
これらの補強材は２種以上併用することが可能であり、必要によりシラン系ならびにチタン系カップリング剤で予備処理して使用することが出来る。特に好ましい補強材は、繊維状補強材ではガラス繊維ならびに炭素繊維であり、非繊維状補強材ではワラステナイト、タルクならびに炭酸カルシウムである。
【００１９】
本発明における上記以外のその他有機および／または無機添加剤としては、一般に離型剤、例えばヒンダードフェノール、ヒドロキノン、チオエーテル、ホスファイト類およびこれらの置換体およびその組合せなどの酸化防止剤および／または熱安定剤、滑剤、結晶核剤、紫外線防止剤（例えば種々のレゾルシノール、サリシレート、ベンゾトリアゾール、ベンゾフェノンなど）、着色剤（例えばニトロシンなどの染料および例えば硫化カドミウム、フタロシアニン、カーボンブラックなどの顔料など）、難燃剤（例えばデカブロモジフェニルエーテル、臭素化ポリカーボネートのようなハロゲン系、メラミンあるいはシアヌル酸系、リン系など）、難燃助剤（例えば酸化アンチモンなど）、帯電防止剤（例えばドデシルベンゼンスルホン酸ナトリウム、ポリアルキレングリコールなど）などの通常の添加剤および少量の他種ポリマを意味する。例えば離型剤としては、ポリエチレン、ポリプロピレン等のポリオレフィン、またはモンタン酸ワックス類、またはステアリン酸リチウム、ステアリン酸アルミニウム等の金属石鹸などをあげることができる。また、結晶核剤としてはポリエ−テルエ−テルケトン樹脂、ナイロン樹脂等をあげることができる。これらの添加剤は１種または２種以上で用いることができる。
【００２０】
本発明においては、上記（Ａ）成分、（Ｂ）成分およびアマニ油吸油量が２０（ｍｌ／１００ｇ）を超える添加剤（Ｃ）を配合する際に、（Ａ）成分および（Ｂ）成分を溶融混練した後、アマニ油吸油量が２０（ｍｌ／１００ｇ）を超える添加剤（Ｃ）を配合することにより、安定した高ウエルド強度と低バリ性能を出現するＰＰＳ樹脂組成物が得られるものである。
【００２１】
（Ａ）成分および（Ｂ）成分を溶融混練した後に添加する方法が有効な添加剤はアマニ油吸油量が２０（ｍｌ／１００ｇ）を超えるものである。例えば平均粒径１ミクロン前後の汎用的な炭酸カルシウムは通常３０（ｍｌ／１００ｇ）程度のアマニ油吸油量を示すが、この種の炭酸カルシウムはＰＰＳ樹脂の補強材としてよく使用する。同様に例えば平均粒径５ミクロン前後の汎用的なタルクは通常５０（ｍｌ／１００ｇ）程度のアマニ油吸油量を示すが、この種のタルクはＰＰＳ樹脂の結晶核剤としてよく使用する。アマニ油吸油量はＪＩＳ Ｋ５１０１に定める方法で測定することができる。
【００２２】
アマニ油吸油量が２０（ｍｌ／１００ｇ）を超える添加剤としては下記（Ｃ−１）および（Ｃ−２）から選ばれた１種以上であって、かつアマニ油吸油量が２０ｍｌ／１００ｇを越える添加剤などが挙げられる。
【００２３】
（Ｃ−１）繊維状および／または非繊維状の補強材
（Ｃ−２）上記以外のその他無機添加剤および／または有機添加剤
具体的には前述の繊維状および／または非繊維状の補強材、それ以外のその他無機添加剤および／または有機添加剤のうち、アマニ油吸油量が２０ｍｌ／１００ｇを越えるものなどが挙げられる。
【００２４】
上記添加剤（Ｃ）の配合量はポリフェニレンスルフィド樹脂１００重量部に対して０．１〜１６０重量部であることが好ましい。
【００２５】
また、アマニ油吸油量が２０ｍｌ／１００ｇを越える繊維状および／または非繊維状の補強材の配合量は、組成物の流動性の点から成分（Ａ）からなるＰＰＳ樹脂１００重量部に対して０〜１５０重量部の範囲であることが好ましいが、配合効果を発揮せしめるには下限が０．１重量部であることが好ましく、生成する組成物の耐熱性と機械的強度とのバランスの上からは、４０〜１００重量部の補強材の配合量が好ましい。
【００２６】
また、（Ｃ−２）から選ばれた１種以上であって、かつアマニ油吸油量が２０ｍｌ／１００ｇを越える添加剤の添加量はポリフェニレンスルフィド樹脂１００重量部に対して０〜１０重量部であることが好ましく、特に好ましくは０〜５重量部の範囲である。
【００２７】
本発明においてはアマニ油吸油量が２０（ｍｌ／１００ｇ）を越える添加剤（Ｃ）を（Ａ）成分および（Ｂ）成分の溶融混練後に配合するものである。アマニ油吸油量が２０（ｍｌ／１００ｇ）を越える添加剤として、２種以上の添加剤を用いる場合、少なくとも１種を（Ａ）成分および（Ｂ）成分の溶融混練後に配合すればよく、少なくとも、添加剤としてアマニ油吸油量が２０（ｍｌ／１００ｇ）を越える繊維状および／または非繊維状の補強材が含まれる場合には（Ａ）成分および（Ｂ）成分の溶融混練後に配合することが好ましい。いうまでもなくアマニ油吸油量が２０（ｍｌ／１００ｇ）を越える添加剤に相当する添加剤の全てを（Ａ）成分および（Ｂ）成分の溶融混練後に配合することが最も好ましい。
【００２８】
本発明においては必要に応じて、アマニ油吸油量が２０（ｍｌ／１００ｇ）以下の添加剤、例えば各種充填材、補強材、離型剤、酸化防止剤、熱安定剤、滑剤、結晶核剤、紫外線防止剤、着色剤、難燃剤、難燃助剤、帯電防止剤などの添加剤をさらに配合することも可能である。具体的には前述の繊維状および／または非繊維状の補強材、それ以外のその他無機添加剤および／または有機添加剤のうち、アマニ油吸油量が２０（ｍｌ／１００ｇ）以下のものが挙げられる。
【００２９】
本発明においてはポリフェニレンスルフィド樹脂（Ａ）およびアルコキシシラン化合物（Ｂ）を溶融混練した後にアマニ油吸油量２０ｍｌ／１００ｇを越える添加剤（Ｃ）を配合するものである。
【００３０】
本発明のＰＰＳ樹脂組成物の製造に用いることができる装置としてはとくに制限はないが、押出機が好ましく、かかる押出機としては、通常の単軸あるいは２軸の押出機で、溶融混練する原料の供給口が少なくとも２箇所以上あるものが望ましい。仮に供給口が１つしかない押出機であっても、ベント孔等の穴を原料の供給孔に流用することは可能である。また、ＰＰＳ樹脂（Ａ）とアルコキシシラン化合物（Ｂ）をあらかじめ溶融混練ペレタイズしたあと、そのペレットをアマニ油吸油量２０ｍｌ／１００ｇを越える添加剤（Ｃ）を溶融混練することも可能である。
【００３１】
なかでも、２以上の原料供給口を備えた押出機を用い、ポリフェニレンスルフィド樹脂（Ａ）およびアルコキシシラン化合物（Ｂ）の供給口よりも下手の供給口からアマニ油吸油量２０ｍｌ／１００ｇを越える添加剤（Ｃ）を供給する方法などが、効率、効果の点で好ましい。
【００３２】
さらに具体的にはアルコキシシラン化合物（Ｂ）をポリフェニレンスルフィド樹脂（Ａ）に添加して予めヘンシェルミキサー等で予備ブレンドした後、押出機に供給して予備ブレンド物の供給口より下手の供給口からアマニ油吸油量２０ｍｌ／１００ｇを越える添加剤（Ｃ）を供給する方法、ポリフェニレンスルフィド樹脂（Ａ）とアルコキシシラン化合物（Ｂ）を各々単独に供給し、それらの供給口より下手の供給口からアマニ油吸油量２０ｍｌ／１００ｇを越える添加剤（Ｃ）を供給する方法等が挙げられる。
【００３３】
ポリフェニレンスルフィド樹脂（Ａ）とアルコキシシラン化合物（Ｂ）を十分反応させるための溶融混練条件としては特に制限はない。しかし、アルコキシシラン化合物の添加効果を最大限に発揮させる意味から、次のような条件で行なうことが好ましい。すなわちポリフェニレンスルフィド樹脂（Ａ）とアルコキシシラン化合物（Ｂ）の溶融混練温度は、２８０〜３８０℃の範囲で行なうことが（Ａ）および（Ｂ）成分を十分に反応させる点で好ましい。また、溶融混練時間も（Ａ）および（Ｂ）成分を十分に反応させる時間であればよく、例えば５秒以上の時間が挙げられる。１台の押出機で（Ａ）〜（Ｃ）を配合する場合、（Ａ）および（Ｂ）成分が押出機内で遭遇してから（Ｃ）成分と遭遇するまでの時間を溶融混練時間とするが、このような溶融混練時間を得るための方法は種々あるが、例えばＰＰＳ樹脂（Ａ）およびアルコキシシラン化合物（Ｂ）が遭遇する位置から下手であって、かつ、ある程度離れた位置にアマニ油吸油量が２０（ｍｌ／１００ｇ）を超える成分（Ｃ）の供給口を設けることが好ましい。
【００３４】
アマニ油吸油量が２０（ｍｌ／１００ｇ）を超える成分（Ｃ）、ポリフェニレンスルフィド樹脂（Ａ）およびアルコキシシラン化合物（Ｂ）以外の材料、例えばアマニ油吸油量が２０（ｍｌ／１００ｇ）以下の添加剤については、供給の方法に制限はなく、各供給口分ごとにヘンシェルミキサー等で予備ブレンドしてもよいし、各原料ごとにフィーダーを用意して供給しても良く、原料の混合順序にも特に制限はない。
【００３５】
溶融混練条件も特に制限はないが２８０〜３８０℃の温度で混練する条件を代表例として挙げることができる。また、少量添加剤成分については、他の成分を上記の方法などで混練しペレット化した後、成形前に添加することもできる。
【００３６】
本発明に規定する製造法により得られたＰＰＳ樹脂組成物は、ウエルド強度が高く且つ低バリ性に優れており、例えばコネクタ、電子封止部品、コイル封止部品等の用途に有用である。
【００３７】
【実施例】
以下に実施例を挙げて本発明を更に詳細に説明する。
【００３８】
実施例および比較例の中で述べられるウェルド強度、バリ長さは各々次の方法に従って測定した。
【００３９】
ウェルド強度の測定：両端にゲートを有し、試験片中央部付近にウェルドラインを有するＡＳＴＭ４号ダンベル片を、型締力２０トンの射出成形機を用いてシリンダー温度３２０℃、金型温度１３５℃の条件で成形し、歪速度５mm/min、支点間距離６４mmの条件で引張強度測定を行なった。
【００４０】
成形下限圧の測定：上記のダンベル片を射出成形する際、充填不良を起こさないために必要な最低射出圧力を成形下限圧とした。成形下限圧が低いほど流動性が優れていることになる。
【００４１】
バリ長さの測定：一方の端にゲートを有し、他方の端にガス抜き用の間隙を有するＡＳＴＭ ４号ダンベル片を、シリンダー温度３２０℃、金型温度１３５℃の条件で射出成形し、得られたダンベル片のガス抜き用の間隙部分に発生したバリの長さを測定した。バリ長さが短いほどバリ特性は優れていることになる。
【００４２】
参考例１（ＰＰＳの重合）
オートクレーブに３０％水硫化ナトリウム水溶液４．６７ｋｇ（水硫化ナトリウム２５モル）、５０％水酸化ナトリウム２．００ｋｇ（水酸化ナトリウム２５モル）ならびにＮ−メチル−２−ピロリドン（以下ＮＭＰと略す）８ｋｇを仕込み、撹拌しながら徐々に２０５℃まで昇温し、水３．８ｋｇを含む留出水４．１ｌを除去した。残留混合物に１，４−ジクロロベンゼン３．７５ｋｇ（２５．５モル）ならびにＮＭＰ２ｋｇを加えて２３０℃で１時間、更に２６０℃で３０分加熱した。反応生成物を温水で５回洗浄し、８０℃で２４時間減圧乾燥して、数平均分子量３７００の粉末のＰＰＳ樹脂（ＰＰＳ−１）を得た。該ＰＰＳ樹脂を実施例ならびに比較例で使用した。
【００４３】
参考例２（ＰＰＳの重合）
オートクレーブに３０％水硫化ナトリウム水溶液４．６７ｋｇ、５０％水酸化ナトリウム２．００ｋｇならびにＮＭＰ８ｋｇを仕込み、撹拌しながら徐々に２０５℃まで昇温し、水３．８ｋｇを含む留出水４．１ｌを除去した。残留混合物に１，４−ジクロロベンゼン３．７５ｋｇならびにＮＭＰ２ｋｇを加えて２３０℃で１時間、更に２６０℃で２時間加熱した。反応生成物を温水で５回洗浄し、８０℃で２４時間減圧乾燥して、数平均分子量５４００の粉末のＰＰＳ樹脂（ＰＰＳ−２）を得た。該ＰＰＳ樹脂を実施例ならびに比較例で使用した。
【００４４】
実施例１
ＰＰＳ−１と３−グリシドキシプロピルトリメトキシシランを表１に示す割合でヘンシェルミキサでドライブレンド後、押出機の上手の供給口（第１の供給口）より供給し、一方、ＪＩＳ Ｋ５１０１に定めるアマニ油吸油量が４０ｍｌ／１００ｇの炭酸カルシウムとアマニ油吸油量２０ｍｌ／１００ｇ以下のガラス繊維を表１に示す割合で各々計量フィーダーで押出機の下手の供給口（第２の供給口）から供給し、３２０℃の温度条件に設定したスクリュ−式押出機により溶融混練後ペレタイズした。なお押出機はφ５０ｍｍの二軸押出機で、第１の供給口から先端までの長さが２００ｃｍ、第１の供給口から第２の供給口までの距離が９０ｃｍのものを用いた。なお、ポリフェニレンスルフィド樹脂とアルコキシシラン化合物の溶融混練時間は約２０秒であった。
【００４５】
得られたペレットを用い、型締力２０トンの射出成形機を用いてシリンダー温度３２０℃、金型温度１３５℃の条件で前述のＡＳＴＭ４号ダンベル片の成形を行なった。
【００４６】
得られた試験片について測定したウェルド強度およびバリ長さを表２に示す。ここで得られた樹脂組成物はウエルド強度、低バリに優れた実用価値の高いものであった。
【００４７】
比較例１
ＪＩＳ Ｋ５１０１に定めるアマニ油吸油量が４０ｍｌ／１００ｇの炭酸カルシウムをＰＰＳ−１と３−グリシドキシプロピルトリメトキシシランとともに押出機の上手の供給口より供給すること以外は、実施例１と同様にして、表１に示す割合でドライブレンド、溶融混練、ペレタイズ、成形、物性評価を行なった。その結果を表２に併せて示す。実施例１と同一原料組成にかかわらず実施例１に比べてウエルド強度が低く、また十分なバリ低減効果が得られなかった。
【００４８】
比較例２
ＪＩＳ Ｋ５１０１に定めるアマニ油吸油量が４５ｍｌ／１００ｇのタルクをＰＰＳ−１と３−グリシドキシプロピルトリメトキシシランとともに押出機の上手の供給口より供給すること以外は、実施例１と同様にして、表１に示す割合でドライブレンド、溶融混練、ペレタイズ、成形、物性評価を行なった。その結果を表２に併せて示す。ウエルド強度が低く、また十分なバリ低減効果が得られなかった。
【００４９】
実施例２〜８
使用するＰＰＳ樹脂、補強材、アルコキシシラン化合物の種類、その他添加剤の種類、配合比を種々変え、実施例１と同様にして、表１に示す割合でドライブレンド、溶融混練、ペレタイズ、成形、物性評価を行なった。その結果を表２に示す。
【００５０】
ここで得られた樹脂組成物はいずれもウエルド強度、低バリに優れた実用価値の高いものであった。
【００５１】
【表１】

【００５２】
【表２】

【００５３】
【発明の効果】
本発明の製造法によるポリフェニレンスルフィド樹脂組成物はウエルド強度が強く且つ成形時に発生するバリが少ないので、特に射出成形によるコネクタ、電子封止部品、コイル封止部品等の用途に有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polyphenylene sulfide resin composition useful for applications requiring low burr properties and high weld strength, such as sealing parts such as connectors, electronic sealing parts, and coil sealing parts. It is.
[0002]
[Prior art]
Since polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has suitable properties as engineering plastics such as excellent heat resistance, flame retardancy, rigidity and electrical insulation, various types of electric power are mainly used for injection molding. It is used for applications such as parts, machine parts and automobile parts.
[0003]
However, the use of PPS resin is restricted due to the significant occurrence of burrs, for example, in sealing applications such as connector or electronic component sealing and coil sealing.
[0004]
Under such circumstances, some studies have been made so far for the purpose of reducing burrs and high weld strength of PPS resin. For example, a method of blending a highly crosslinked PPS resin as a property improver (Japanese Patent Laid-Open No. 64-92266), a method of adding a silane compound to a PPS resin (Japanese Patent Laid-Open No. 63-251430), and a base polymer There is a method of using a specific linear PPS resin and a cross-linked PPS resin in combination, and further using a silane coupling agent (Japanese Patent Laid-Open No. 3-197562).
[0005]
[Problems to be solved by the invention]
However, there is a problem that the weld strength or low burr performance of a resin composition obtained by melt-kneading a PPS resin, a silane compound and other additives greatly varies depending on the selection of the extruder and the extrusion conditions during melt-kneading even with the same raw material composition. It was.
[0006]
Thus, as a result of searching for the main factors of the above-mentioned variation, the present inventors have found that the raw material supply method to the extruder has a great influence on the weld strength and the low burr performance. When melt-kneading the PPS resin, silane compound and other additives with an extruder, if the PPS resin, the silane compound and a specific additive are supplied from the same supply port of the extruder, the additive absorbs the silane compound. As a result, it was found that the reaction between the PPS resin and the silane compound is inhibited, and the weld characteristics and the low burr performance are adversely affected. In particular, it was found that an additive having a linseed oil absorption exceeding 20 ml / 100 g as defined in JIS K5101 is particularly easy to absorb silane compounds regardless of organic or inorganic. Therefore, when the PPS resin, the silane compound and other additives are melt-kneaded with an extruder, an additive such that the linseed oil absorption exceeds 20 ml / 100 g is blended after the PPS resin and the silane compound are melt-kneaded. As a result, it was found that the PPS resin and the coupling agent reacted effectively, and a PPS resin composition exhibiting stable high weld strength and low burr performance was obtained, and the present invention was achieved.
[0007]
[Means for Solving the Problems]
That is, the present invention
(1) When producing a polyphenylene sulfide resin composition comprising (A) a polyphenylene sulfide resin and (B) an alkoxysilane compound and (C) an additive in which linseed oil absorption exceeds 20 ml / 100 g. A process for producing a polyphenylene sulfide resin composition comprising blending an additive (C) exceeding 20 ml / 100 g of linseed oil after melt-kneading the polyphenylene sulfide resin (A) and the alkoxysilane compound (B).
[0008]
(2) (B) an alkoxysilane compound, (C-1) a fibrous and / or non-fibrous reinforcing material with a linseed oil absorption exceeding 20 ml / 100 g is blended with (A) polyphenylene sulfide resin. A fibrous and / or non-fibrous reinforcing material having a linseed oil absorption exceeding 20 ml / 100 g after melt-kneading the polyphenylene sulfide resin (A) and the alkoxysilane compound (B) in producing the polyphenylene sulfide resin composition (C-1) is blended, a method for producing a polyphenylene sulfide resin composition,
(3) (A) Polyphenylene sulfide resin, (B) alkoxysilane compound, (C) one or more selected from the following (C-1) and (C-2), and linseed oil absorption In the production of a polyphenylene sulfide resin composition comprising an additive exceeding 20 ml / 100 g, after the polyphenylene sulfide resin (A) and the alkoxysilane compound (B) are melt-kneaded, the linseed oil absorption amount is 20 ml / 100 g. A method for producing a polyphenylene sulfide resin composition, comprising adding an additive (C) exceeding
(C-1) Fibrous and / or non-fibrous reinforcing material
(C-2) Other inorganic additives and / or organic additives other than the above
(4) Using an extruder equipped with two or more raw material supply ports, addition of polyphenylene sulfide resin (A) and alkoxysilane compound (B) exceeding the linseed oil absorption amount of 20 ml / 100 g from the lower supply port than the supply port The method for producing a polyphenylene sulfide resin composition according to any one of the above (1) to (3), wherein an agent (C) is supplied,
(5) The method for producing a polyphenylene sulfide resin composition according to any one of the above (1) to (4), wherein the compounding amount of the alkoxysilane compound is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin.
(6) The above (1) to (1), wherein the alkoxysilane compound (B) is an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. (5) The method for producing a polyphenylene sulfide resin composition according to any one of
(7) The polyphenylene sulfide resin according to any one of (1) and (3) to (6), wherein the additive (C) is added in an amount of 0.1 to 160 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin. Production method of the composition,
(8) Any one of the above (2) to (6), wherein the amount of the fibrous and / or non-fibrous reinforcing material (C-1) is 150 parts by weight or less with respect to 100 parts by weight of the polyphenylene sulfide resin. A process for producing a polyphenylene sulfide resin composition of
(9) Fibrous and / or non-fibrous reinforcing material is glass fiber, carbon fiber, potassium titanate whisker, calcium carbonate, talc, wollastonite, mica, calcium sulfate, magnesium oxide, lithium stearate or calcium hypophosphite Above ( 2 ) To (8), a method for producing a polyphenylene sulfide resin composition,
(10) The polyphenylene sulfide resin composition according to any one of the above (1) to (9), wherein an additive having a linseed oil absorption of 20 ml / 100 g or less is further added to 200 parts by weight or less with respect to 100 parts by weight of the polyphenylene sulfide resin. It is a manufacturing method of a thing.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The PPS resin used in the present invention is a repeating unit represented by the following structural formula.
[Chemical 1]

A polymer containing 70 mol% or more, particularly 90 mol% or more of the above unit is preferable from the viewpoint of heat resistance. Further, the PPS resin can constitute less than 30 mol% of the repeating units with repeating units having the following structure.
[0010]
[Chemical formula 2]

[0011]
The method for producing the PPS resin of the present invention is not particularly limited as long as the above-mentioned requirements are satisfied, and is generally known, that is, the method described in Japanese Patent Publication No. 45-3368 or Japanese Patent Publication No. 52-12240. Can be manufactured by a method such as In the present invention, the PPS resin obtained as described above is subjected to various treatments such as washing with an organic solvent, hot water, an aqueous acid solution, etc., and activation with a functional group-containing compound such as an acid anhydride group, an epoxy group, or an isocyanate group. In addition, it can be used.
[0012]
Next, the alkoxysilane compound used as the component (B) in the present invention is an alkoxysilane compound having at least one epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group or ureido group in the molecule. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-amino Propyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, dimethoxymethyl-3-piperazinopropylsilane, 3-piperazinopropyl Trimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylethyldimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptomethyldimethoxysilane, γ-ureidopropylate Preferred examples include limethoxysilane.
[0013]
These alkoxysilane compounds can be used alone or in the form of a mixture of two or more. Among the alkoxysilane compounds, particularly preferred alkoxysilane compounds include 3-glycidoxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.
[0014]
The compounding amount of these alkoxysilane compounds (B) used in the present invention is usually 0.1 from the viewpoint of the fluidity of the composition obtained with respect to 100 parts by weight of the PPS resin and the mechanical strength and weld strength of the molded product. -5 parts by weight, preferably 0.3-3 parts by weight.
[0015]
In general, additives (for example, fibrous and / or non-fibrous reinforcing materials, other inorganic additives and / or organic additives, etc.) may be blended in the polyphenylene sulfide resin. In the invention, when a composition is prepared by blending the polyphenylene sulfide resin, the component (B) and the additive, and the additive used is a linseed oil absorption amount exceeding 20 ml / 100 g, a specific method is used. It is important to blend each component.
[0016]
In general, the fibrous reinforcing material in the fibrous and / or non-fibrous reinforcing material is an inorganic material such as glass fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal fiber, or california titanate. Examples thereof include fibers and carbon fibers. Of these, glass fiber, carbon fiber, potassium titanate whisker and the like are preferable.
[0017]
Non-fibrous reinforcing materials generally include silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, alumina, silicon chloride, magnesium oxide, zirconium oxide, titanium oxide, etc. Metal carbonates, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, boron nitride, silicon carbide and silica. These may be hollow. Of these, calcium carbonate, talc, wollastonite, mica, calcium sulfate, magnesium oxide, or calcium hypophosphite is preferable.
[0018]
These reinforcing materials can be used in combination of two or more, and can be used after pretreatment with a silane-based or titanium-based coupling agent if necessary. Particularly preferred reinforcing materials are glass fibers and carbon fibers for fibrous reinforcing materials, and wollastonite, talc and calcium carbonate for non-fibrous reinforcing materials.
[0019]
Other organic and / or inorganic additives other than those described above in the present invention generally include mold release agents, for example, antioxidants such as hindered phenols, hydroquinones, thioethers, phosphites, and their substitution products and combinations thereof, and / or Heat stabilizers, lubricants, crystal nucleating agents, UV protection agents (for example, various resorcinols, salicylates, benzotriazoles, benzophenones, etc.), colorants (for example, dyes such as nitrocin and pigments such as cadmium sulfide, phthalocyanine, carbon black) Flame retardants (eg decabromodiphenyl ether, halogenated like brominated polycarbonate, melamine or cyanuric acid, phosphorous), flame retardant aid (eg antimony oxide), antistatic agent (eg dodecylbenzenesulfonic acid) Thorium, polyalkylene glycol, etc.) refers to the conventional additives and a small amount of other types polymers such as. For example, examples of the release agent include polyolefins such as polyethylene and polypropylene, montanic acid waxes, and metal soaps such as lithium stearate and aluminum stearate. Examples of the crystal nucleating agent include polyether ether ketone resin and nylon resin. These additives can be used alone or in combination of two or more.
[0020]
In the present invention, when blending the above component (A), component (B) and linseed oil additive (C) exceeding 20 (ml / 100 g), component (A) and component (B) are combined. After melt-kneading, a PPS resin composition that exhibits stable high weld strength and low burr performance can be obtained by blending the additive (C) with a linseed oil absorption exceeding 20 (ml / 100 g). is there.
[0021]
Additives for which the method of adding the components (A) and (B) after melting and kneading are effective are those in which the linseed oil absorption exceeds 20 (ml / 100 g). For example, general-purpose calcium carbonate having an average particle size of about 1 micron usually shows a linseed oil absorption of about 30 (ml / 100 g). This type of calcium carbonate is often used as a reinforcing material for PPS resin. Similarly, for example, general-purpose talc having an average particle size of about 5 microns usually shows a linseed oil absorption of about 50 (ml / 100 g), but this type of talc is often used as a crystal nucleating agent for PPS resin. The linseed oil absorption can be measured by the method defined in JIS K5101.
[0022]
The additive of linseed oil absorption exceeding 20 (ml / 100g) is at least one selected from the following (C-1) and (C-2), and the linseed oil absorption is 20 ml / 100g. Additives that exceed it.
[0023]
(C-1) Fibrous and / or non-fibrous reinforcing material
(C-2) Other inorganic additives and / or organic additives other than the above
Specifically, among the above-mentioned fibrous and / or non-fibrous reinforcing materials, other inorganic additives and / or organic additives, linseed oil absorption amount exceeding 20 ml / 100 g may be mentioned.
[0024]
The amount of the additive (C) is preferably 0.1 to 160 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin.
[0025]
Further, the amount of the linseed oil absorption amount exceeding 20 ml / 100 g of the fibrous and / or non-fibrous reinforcing material is 100 parts by weight of the PPS resin composed of the component (A) from the viewpoint of the fluidity of the composition. The range is preferably from 0 to 150 parts by weight, but the lower limit is preferably 0.1 parts by weight for exhibiting the blending effect, and the balance between the heat resistance and mechanical strength of the resulting composition is preferred. Is preferably 40 to 100 parts by weight of the reinforcing material.
[0026]
Further, the additive amount of one or more selected from (C-2) and the linseed oil absorption amount exceeding 20 ml / 100 g is 0 to 10 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin. It is preferable that it is in the range of 0 to 5 parts by weight.
[0027]
In the present invention, the additive (C) having an oil absorption amount of linseed oil exceeding 20 (ml / 100 g) is blended after the components (A) and (B) are melt-kneaded. In the case where two or more additives are used as the linseed oil absorption amount exceeding 20 (ml / 100 g), at least one kind may be blended after the melt kneading of the component (A) and the component (B), In the case where fibrous and / or non-fibrous reinforcing material with linseed oil absorption exceeding 20 (ml / 100 g) is included as an additive, it should be blended after melt kneading of component (A) and component (B) Is preferred. Needless to say, it is most preferable to add all of the additives corresponding to the additive in which the linseed oil absorption exceeds 20 (ml / 100 g) after the melt kneading of the component (A) and the component (B).
[0028]
In the present invention, if necessary, additives having a linseed oil absorption of 20 (ml / 100 g) or less, such as various fillers, reinforcing materials, mold release agents, antioxidants, thermal stabilizers, lubricants, crystal nucleating agents. In addition, additives such as an ultraviolet ray inhibitor, a colorant, a flame retardant, a flame retardant aid, and an antistatic agent can be further blended. Specifically, among the above-mentioned fibrous and / or non-fibrous reinforcing materials, other inorganic additives and / or organic additives, those having a linseed oil absorption of 20 (ml / 100 g) or less are listed. It is done.
[0029]
In the present invention, the polyphenylene sulfide resin (A) and the alkoxysilane compound (B) are melt-kneaded, and then the additive (C) exceeding the linseed oil absorption of 20 ml / 100 g is blended.
[0030]
The apparatus that can be used for the production of the PPS resin composition of the present invention is not particularly limited, but an extruder is preferable, and such an extruder is a raw material that is melt-kneaded with a normal single-screw or twin-screw extruder. It is desirable that there are at least two supply ports. Even if the extruder has only one supply port, it is possible to use a hole such as a vent hole as a raw material supply hole. It is also possible to melt-knead and pelletize the PPS resin (A) and the alkoxysilane compound (B) in advance, and then melt-knead the pellets with an additive (C) exceeding the linseed oil absorption amount of 20 ml / 100 g.
[0031]
In particular, using an extruder equipped with two or more raw material supply ports, addition of linseed oil exceeding 20 ml / 100 g from the lower supply port than the supply port of polyphenylene sulfide resin (A) and alkoxysilane compound (B) A method of supplying the agent (C) is preferable in terms of efficiency and effect.
[0032]
More specifically, the alkoxysilane compound (B) is added to the polyphenylene sulfide resin (A), preliminarily blended in advance with a Henschel mixer, etc., and then supplied to the extruder from a lower supply port than the preblend supply port. A method for supplying an additive (C) exceeding the amount of linseed oil absorption of 20 ml / 100 g, supplying a polyphenylene sulfide resin (A) and an alkoxysilane compound (B) individually, and supplying linseed from a supply port lower than those supply ports Examples thereof include a method of supplying an additive (C) having an oil absorption of 20 ml / 100 g.
[0033]
There is no particular limitation on the melt-kneading conditions for sufficiently reacting the polyphenylene sulfide resin (A) and the alkoxysilane compound (B). However, in order to maximize the effect of adding the alkoxysilane compound, the following conditions are preferable. That is, the melt kneading temperature of the polyphenylene sulfide resin (A) and the alkoxysilane compound (B) is preferably in the range of 280 to 380 ° C. from the viewpoint of sufficiently reacting the components (A) and (B). Further, the melt kneading time may be a time for sufficiently reacting the components (A) and (B), for example, a time of 5 seconds or more. When blending (A) to (C) with one extruder, the time from when the components (A) and (B) are encountered in the extruder to when they are encountered with the component (C) is the melt kneading time. However, there are various methods for obtaining such a melt-kneading time. For example, linseed oil is poor at a position where the PPS resin (A) and the alkoxysilane compound (B) are encountered, and at a certain distance. It is preferable to provide a supply port for the component (C) whose oil absorption exceeds 20 (ml / 100 g).
[0034]
Addition of ingredients other than component (C), polyphenylene sulfide resin (A), and alkoxysilane compound (B), such as linseed oil absorption amount of 20 (ml / 100 g) or less, For the agent, there is no restriction on the supply method, and it may be pre-blended with a Henschel mixer etc. for each supply port, or a feeder may be prepared and supplied for each raw material. There is no particular restriction.
[0035]
The melt-kneading conditions are not particularly limited, but typical conditions include kneading at a temperature of 280 to 380 ° C. Moreover, about a small amount additive component, after kneading | mixing and pelletizing another component by said method etc., it can also add before shaping | molding.
[0036]
The PPS resin composition obtained by the production method defined in the present invention has high weld strength and excellent low burr properties, and is useful for applications such as connectors, electronic sealing parts, and coil sealing parts.
[0037]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0038]
The weld strength and burr length described in the examples and comparative examples were measured according to the following methods.
[0039]
Measurement of weld strength: ASTM No. 4 dumbbell piece having gates at both ends and a weld line in the vicinity of the center of the test piece, cylinder temperature 320 ° C., mold temperature 135 ° C. using an injection molding machine with a clamping force of 20 tons. The tensile strength was measured under the conditions of a strain rate of 5 mm / min and a fulcrum distance of 64 mm.
[0040]
Measurement of molding lower limit pressure: When the above dumbbell pieces were injection molded, the minimum injection pressure required to prevent filling failure was taken as the molding lower limit pressure. The lower the molding lower limit pressure, the better the fluidity.
[0041]
Measurement of burr length: ASTM No. 4 dumbbell piece having a gate at one end and a degassing gap at the other end was injection molded under conditions of a cylinder temperature of 320 ° C and a mold temperature of 135 ° C. The length of burrs generated in the gap portion for degassing the obtained dumbbell pieces was measured. The shorter the burr length, the better the burr characteristics.
[0042]
Reference example 1 (polymerization of PPS)
In an autoclave, 4.67 kg of 30% aqueous sodium hydrosulfide solution (25 mol of sodium hydrosulfide), 2.00 kg of 50% sodium hydroxide (25 mol of sodium hydroxide) and 8 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) While charging and gradually stirring, the temperature was raised to 205 ° C. to remove 4.1 l of distilled water containing 3.8 kg of water. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added and heated at 230 ° C. for 1 hour and further at 260 ° C. for 30 minutes. The reaction product was washed 5 times with warm water and dried under reduced pressure at 80 ° C. for 24 hours to obtain a powdery PPS resin (PPS-1) having a number average molecular weight of 3700. The PPS resin was used in the examples and comparative examples.
[0043]
Reference example 2 (polymerization of PPS)
An autoclave was charged with 4.67 kg of 30% aqueous sodium hydrosulfide solution, 2.00 kg of 50% sodium hydroxide and 8 kg of NMP. The temperature was gradually raised to 205 ° C. with stirring, and 4.1 l of distilled water containing 3.8 kg of water was added. Removed. To the residual mixture, 3.75 kg of 1,4-dichlorobenzene and 2 kg of NMP were added and heated at 230 ° C. for 1 hour and further at 260 ° C. for 2 hours. The reaction product was washed 5 times with warm water and dried under reduced pressure at 80 ° C. for 24 hours to obtain a powdery PPS resin (PPS-2) having a number average molecular weight of 5400. The PPS resin was used in the examples and comparative examples.
[0044]
Example 1
PPS-1 and 3-glycidoxypropyltrimethoxysilane are dry-blended with a Henschel mixer at the ratio shown in Table 1, and then supplied from the upper supply port (first supply port) of the extruder, while being supplied to JIS K5101. Calcium carbonate with a linseed oil absorption amount of 40 ml / 100 g and glass fiber with a linseed oil absorption amount of 20 ml / 100 g or less are each fed at a ratio shown in Table 1 from the lower supply port (second supply port) of the extruder. The mixture was fed, melt-kneaded and pelletized by a screw type extruder set at a temperature of 320 ° C. The extruder was a twin screw extruder with a diameter of 50 mm, and the length from the first supply port to the tip was 200 cm, and the distance from the first supply port to the second supply port was 90 cm. The melt kneading time of the polyphenylene sulfide resin and the alkoxysilane compound was about 20 seconds.
[0045]
Using the obtained pellets, the above-mentioned ASTM No. 4 dumbbell pieces were molded using an injection molding machine with a clamping force of 20 tons under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 135 ° C.
[0046]
Table 2 shows the weld strength and burr length measured for the obtained test pieces. The resin composition obtained here had high practical value with excellent weld strength and low burr.
[0047]
Comparative Example 1
Except for supplying calcium carbonate having a linseed oil absorption of 40 ml / 100 g as defined in JIS K5101 from the upper supply port of the extruder together with PPS-1 and 3-glycidoxypropyltrimethoxysilane, the same as in Example 1. Then, dry blending, melt kneading, pelletizing, molding, and physical property evaluation were performed at the ratios shown in Table 1. The results are also shown in Table 2. Regardless of the same raw material composition as in Example 1, the weld strength was lower than that in Example 1, and a sufficient burr reduction effect was not obtained.
[0048]
Comparative Example 2
Example 1 except that talc having a linseed oil absorption of 45 ml / 100 g as defined in JIS K5101 is supplied from the upper supply port of the extruder together with PPS-1 and 3-glycidoxypropyltrimethoxysilane. The dry blending, melt-kneading, pelletizing, molding, and physical property evaluation were performed at the ratios shown in Table 1. The results are also shown in Table 2. The weld strength was low, and a sufficient burr reduction effect was not obtained.
[0049]
Examples 2-8
The PPS resin used, the reinforcing material, the type of alkoxysilane compound, the type of other additives, and the blending ratio were variously changed in the same manner as in Example 1, and in the proportions shown in Table 1, dry blending, melt-kneading, pelletizing, molding, The physical properties were evaluated. The results are shown in Table 2.
[0050]
All of the resin compositions obtained here had high practical value with excellent weld strength and low burr.
[0051]
[Table 1]

[0052]
[Table 2]

[0053]
【The invention's effect】
Since the polyphenylene sulfide resin composition according to the production method of the present invention has high weld strength and few burrs generated during molding, it is particularly useful for applications such as injection molding connectors, electronic sealing parts, and coil sealing parts.

Claims (10)

When producing a polyphenylene sulfide resin composition comprising (B) an alkoxysilane compound and (C) an additive in which linseed oil absorption exceeds 20 ml / 100 g to (A) polyphenylene sulfide resin. A method for producing a polyphenylene sulfide resin composition, comprising melting and kneading a resin (A) and an alkoxysilane compound (B) and then blending an additive (C) exceeding 20 ml / 100 g of linseed oil absorption. (A) Polyphenylene sulfide resin comprising (B) alkoxysilane compound, (C-1) fibrous and / or non-fibrous reinforcing material with linseed oil absorption exceeding 20 ml / 100 g. When the resin composition is produced, a fibrous and / or non-fibrous reinforcing material (C-) exceeding 20 ml / 100 g of linseed oil absorption after melt-kneading the polyphenylene sulfide resin (A) and the alkoxysilane compound (B). 1) is blended, and a method for producing a polyphenylene sulfide resin composition. (A) With respect to polyphenylene sulfide resin, (B) alkoxysilane compound, (C) one or more selected from the following (C-1) and (C-2), and linseed oil absorption is 20 ml / Addition of linseed oil absorption exceeding 20 ml / 100 g after melt-kneading polyphenylene sulfide resin (A) and alkoxysilane compound (B) when producing a polyphenylene sulfide resin composition comprising an additive exceeding 100 g The manufacturing method of the polyphenylene sulfide resin composition characterized by mix | blending an agent (C).
(C-1) Fibrous and / or non-fibrous reinforcing material (C-2) Other inorganic additives and / or organic additives other than those described above Additives exceeding the amount of linseed oil absorption of 20 ml / 100 g from the lower supply port of the polyphenylene sulfide resin (A) and alkoxysilane compound (B) using an extruder equipped with two or more raw material supply ports (C ) Is supplied, The method for producing a polyphenylene sulfide resin composition according to claim 1. The method for producing a polyphenylene sulfide resin composition according to any one of claims 1 to 4, wherein the compounding amount of the alkoxysilane compound is 0.1 to 5 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin. The alkoxysilane compound (B) is an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. The manufacturing method of the polyphenylene sulfide resin composition of description. The method for producing a polyphenylene sulfide resin composition according to any one of claims 1 and 3 to 6, wherein the compounding amount of the additive (C) is 0.1 to 160 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to any one of claims 2 to 6, wherein the blending amount of the fibrous and / or non-fibrous reinforcing material (C-1) is 150 parts by weight or less with respect to 100 parts by weight of the polyphenylene sulfide resin. Manufacturing method. The fibrous and / or non-fibrous reinforcing material is glass fiber, carbon fiber, potassium titanate whisker, calcium carbonate, talc, wollastonite, mica, calcium sulfate, magnesium oxide, lithium stearate or calcium hypophosphite Item 9. A method for producing a polyphenylene sulfide resin composition according to any one of Items 2 to 8. The method for producing a polyphenylene sulfide resin composition according to any one of claims 1 to 9, wherein an additive having a linseed oil absorption of 20 ml / 100 g or less is further added to 200 parts by weight or less with respect to 100 parts by weight of the polyphenylene sulfide resin.