JP3560048B2 - Polyarylene sulfide resin composition - Google Patents

Description

【０００９】
（式中、Ｒ^１は炭素数６以下のアルキル基、アルコキシ基、フェニル基、カルボキシル基、シアノ基、アミノ基、ハロゲン原子から選ばれる置換基であり、ｍは０〜４の整数である。また、ｎは平均重合度を示し１．３〜３０の範囲である）で示される繰り返し単位を７０モル％以上有するポリフェニレンスルフィドである。中でもα−クロロナフタレン溶液（濃度０．４ｇ／ｄｌ）、２０６℃における対数粘度が０．１〜０．５（ｄｌ／ｇ）、好ましくは０．１３〜０．４（ｄｌ／ｇ）、さらに好ましくは０．１５〜０．３５（ｄｌ／ｇ）の範囲にあるものが適当である。ＰＡＳは一般にその製造法により実質上線状で分岐、架橋構造を有しない分子構造のものと、分岐や架橋構造を有する構造のものが知られているが本発明においてはその何れのタイプのものについても有効である。本発明に用いるのに好ましいＰＡＳは繰り返し単位としてパラフェニレンスルフィド単位を７０モル％以上、さらに好ましくは８０モル％以上含有するホモポリマーまたはコポリマーである（以下ＰＰＳと略称）。この繰り返し単位が７０モル％未満だと結晶性ポリマーとしての特徴である本来の結晶性が低くなり充分な機械的物性が得られなくなる傾向があり好ましくない。共重合構成単位としては、例えばメタフェニレンスルフィド単位、オルソフェニレンスルフィド単位、ｐ，ｐ’−ジフェニレンケトンスルフィド単位、ｐ，ｐ’−ジフェニレンスルホンスルフィド単位、ｐ，ｐ’−ビフェニレンスルフィド単位、ｐ，ｐ’−ジフェニレンエーテルスルフィド単位、２，６−ナフタレンスルフィド単位などが挙げられる。また、本発明のポリアリーレンスルフィドとしては、前記の実質上線状ポリマーの他に、モノマーの一部分として３個以上の官能基を有するモノマーを少量混合使用して重合した分岐または架橋ポリアリーレンスルフィドも用いることができ、また、これを前記の線状ポリマーにブレンドした配合ポリマーも用いることがで好適である。さらにまた、本発明に使用する（Ａ）成分としてのＰＡＳは、比較的低分子量の線状ポリマーを酸化架橋または熱架橋により溶融粘度を上昇させ、成形加工性を改良したポリマーも使用できる。
【００１０】
（２）無水マレイン酸含有オレフィン系エラストマー共重合体（Ｂ）
本発明に用いられる無水マレイン酸含有オレフィン系エラストマー共重合体（Ｂ）としては、特に制限はないが、例えば、その単量体成分が、エチレン、α、β−不飽和カルボン酸アルキルエステル、および無水マレイン酸からなり、各々の割合が、５０〜９０重量％、５〜４９重量％、０．５〜１０重量％、好ましくは６０〜８５重量％、７〜４５重量％、１〜８重量％のエチレン系共重合体を挙げることができる。
また、この他に、無水マレイン酸変性ＳＥＢＳ、無水マレイン酸変性ＥＰＲ等の無水マレイン酸を含んでなるオレフィン系エラストマーを用いることもできる。
【００１１】
（３）エポキシ変性したビニル系またはオレフィン系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体（Ｃ）
本発明に用いられるエポキシ変性したビニル系またはオレフィン系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体（Ｃ）には、たとえばマクロモノマー法によって製造されるものであり、マクロモノマーに由来するポリマーセグメントを枝成分に、エポキシ基を含むポリマーセグメントを幹成分に有するものを挙げることができる。
本発明に用いられる上記マクロモノマーは、ビニル重合体連鎖の片末端にラジカル重合性基を有する高分子量単量体であり、このマクロモノマーを単一または複数の他のビニル単量体と共重合させることによって、グラフトポリマーを製造することができ、この方法によって得られるグラフトポリマーは、マクロモノマーに由来するポリマーセグメントを枝成分とし、ビニル単量体の単独または共重合体セグメントを幹成分とする構造を有し、一般的にマクロモノマー法グラフトポリマーと称されている。
【００１２】
このグラフトポリマーの幹成分は、エポキシ基を含むポリマーセグメントであり、エポキシ基含有ビニル単量体またはそれと他のビニル単量体との単量体混合物などから形成される。
エポキシ基含有ビニル単量体としては、メタクリル酸グリシジル、アクリル酸グリシジル、エタクリル酸グリシジル、イタコン酸グリシジル等のグリシジルエステル類や、アリルグリシジルエーテル、２−メチルアリルグリシジルエーテル等のグリシジルエーテル類が使用され、好適にはメタクリル酸グリシジル、アクリル酸グリシジル、アリルグリシジルエーテルが使用され、さらに好適にはメタクリル酸グリシジルが使用される。
幹成分の分子量は、数平均分子量で１，０００〜２００，０００が好ましく、２，０００〜１００，０００がさらに好ましい。数平均分子量が２００，０００を超えるとポリアリーレンスルフィドへの分散性が低下し相溶化効果が小さく、一方１，０００未満ではポリアリーレンスルフィドの増粘によって成形性が低下する。
【００１３】
上記枝成分および幹成分を構成単位とするグラフトポリマーにおける、エポキシ基含有ビニル単量体単位の含有量は、グラフトポリマーを構成する単量体単位の合計量を基準にして１〜３０重量％が好ましく、３〜２０重量％がさらに好ましい。
また、枝成分と幹成分の重量割合は、枝成分５〜８０重量％で幹成分２０〜９５重量％の割合が好ましく、枝成分１０〜５０重量％で幹成分５０〜９０重量％の割合がさらに好ましい。
一方、幹成分が２０重量％未満であると、ポリアリーレンスルフィドへの反応の程度が低くポリアリーレンスルフィドに対する相溶性が劣る。
グラフトポリマーの分子量は、数平均分子量で２，０００〜３００，０００が好ましい。
【００１４】
（４）充填材（Ｄ）
本発明においては、必要に応じて充填材（Ｄ）を用いることができる。
この充填材（Ｄ）は、必ずしも必須とされる成分ではないが、機械的物性、耐熱性、寸法安定性（耐変形、そり）、電気的性質等の性能に優れた成形品を得るためには配合することが好ましく、これには目的に応じて繊維状、粉粒状、板状の充填材が用いられる。繊維状充填材としては、ガラス繊維，アスベスト繊維，カーボン繊維，シリカ繊維，シリカ・アルミナ繊維，ジルコニア繊維，窒化硼素繊維，窒化珪素繊維，硼素繊維，チタン酸カリ繊維，さらにステンレス，アルミニウム，チタン，銅，真鍮等の金属の繊維状物などの無機質繊維状物質を挙げることができる。特に代表的な繊維状充填材はガラス繊維，またはカーボン繊維である。なお、芳香族ポリアミド，フッ素樹脂，アクリル樹脂などの高融点有機質繊維状物質も使用することができる。一方、粉粒状充填物としてはカーボンブラック，溶融または結晶シリカ，石英粉末，カラスビーズ，ガラス粉，硅酸カルシウム，硅酸アルミニウム，カオリン，タルク，クレー，硅藻土，ウォラストナイトのような硅酸塩、酸化鉄，酸化チタン，酸化亜鉛，アルミナのような金属の酸化物、炭酸カルシウム，炭酸マグネシウムのような金属の炭酸塩、硫酸カルシウム，硫酸バリウムのような金属の硫酸塩、その他炭化珪素，窒化硼素，各種金属粉末を挙げることができる。また、板状充填材としてはマイカ，ガラスフレーク，各種の金属箔等を挙げることができる。これらの無機充填材は一種または二種以上併用することができる。繊維状充填材、特にガラス繊維または炭素繊維と粒状および／または板状充填材の併用は特に機械的強度と寸法精度、電気的性質等を兼備する上で好ましい組み合わせである。これらの充填材の使用にあたっては必要ならば収束剤または表面処理剤を使用することが望ましい。この例を示せば、エポキシ系化合物，イソシアネート系化合物，シラン系化合物，チタネート系化合物等の官能性化合物である。これらの化合物はあらかじめ充填材に表面処理または収束処理を施して用いるか、または材料調製の際同時に添加してもよい。
【００１５】
２．組成割合
本発明における各成分の組成割合は、（Ａ）成分と（Ｂ）成分との割合（（Ａ）：（Ｂ））が、６０：４０〜９９：１（重量比）、好ましくは、８０：２０〜９５：５（重量比）であり、（Ｃ）成分の割合が、（Ａ）成分と（Ｂ）成分との合計（（Ａ）＋（Ｂ））１００重量部に対して、０．１〜３０重量部、好ましくは、０．５〜２０重量部、さらに好ましくは、１〜１０重量部である。
【００１６】
（Ａ）成分と（Ｂ）成分との割合に関し、（Ｂ）成分が、６０：４０を超えると、耐熱性，弾性率，難燃性のようなＰＡＳを特徴づける性質が著しく低下し、９９：１未満であると、耐衝撃，靱性の改良効果が不十分である。
また、（Ｃ）成分の割合が、（Ａ）成分と（Ｂ）成分との合計量１００重量部に対して、０．１重量部未満であると、相溶化剤としての働きが不十分であり、３０重量部を超えると粘度上昇，耐熱性や耐衝撃性の低下につながる場合がある。
【００１７】
また、必要に応じて配合する充填材の配合割合は、（Ａ），（Ｂ），および（Ｃ）の合計量（（Ａ）＋（Ｂ）＋（Ｃ））１００重量部に対して３〜３５０重量部とすることが好ましい。
３重量部未満であると、機械的強度，弾性率等の改良効果が乏しく、３５０重量部を超えると流動性や成形性の低下を引き起こす場合がある。
【００１８】
３．樹脂組成物の調製
本発明のポリアリーレンスルフィド樹脂組成物を調製する方法としては、特に制限はなく、たとえば、（Ａ）、（Ｂ）、および（Ｃ）の三成分、さらに必要に応じ充填材（Ｄ）をヘンシェルミキサーのような混合機で均一に混合したのち、一軸または二軸混練押出機に供給し、２８０〜３４０℃の温度範囲下で溶融混練し、ペレットとして樹脂組成物を得ることができる。
【００１９】
【実施例】
以下、本発明を実施例によってさらに具体的に説明する。
［実施例１］
ポリアリーレンスルフィド（出光石油化学社製 リニア型ＰＰＳ）８５０ｇ、無水マレイン酸含有オレフィン系エラストマー共重合体（住友化学社製 ボンダイン）１５０ｇ、およびエポキシ変性したビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体（東亜合成化学工業社製 レゼダＧＰ−５００）１０ｇをヘンシエルミキサーで２分間混合した。
次に、二軸混練押出機に供給し、３００℃の温度範囲下で溶融混練しペレットを得た。
【００２０】
［実施例２］
実施例１において、エポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体の配合量を１０ｇから２０ｇに変えたこと以外は実施例１と同様にした。
【００２１】
［実施例３］
実施例１において、エポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体の配合量を１０ｇから５０ｇに変えたこと以外は実施例１と同様にした。
【００２２】
［実施例４］
実施例１において、ポリアリーレンスルフィドを８５０ｇから５６７ｇに、無水マレイン酸含有オレフィン系エラストマー共重合体を１５０ｇから１００ｇに、また、エポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体の配合量を５０ｇから３３ｇに変えるとともに、グラスファイバー（ＧＦ）（旭ファイバーガラス社製 ＪＡＦＴ５９１）を３００ｇ用いたこと以外は、実施例１と同様にした。
【００２３】
［比較例１］
実施例１において、ポリアリーレンスルフィドを８５０ｇから１，０００ｇに変えるとともに、無水マレイン酸含有オレフィン系エラストマー共重合体およびエポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体を加えなかったこと以外は実施例１と同様にした。
【００２４】
［比較例２］
実施例１において、エポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体を加えなかったこと以外は実施例１と同様にした。
【００２５】
［比較例３］
実施例１において、エポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体を加えず、その代わりにエポキシカップリング剤（東レシリコーン社製 エポキシシランＳＨ６０４０）１０ｇ加えたこと以外は実施例１と同様にした。
【００２６】
［比較例４］
実施例１において、ポリアリーレンスルフィドを８５０ｇから７００ｇに変え、無水マレイン酸含有オレフィン系エラストマー共重合体およびエポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体を加えず、その代わりに前記ＧＦを３００ｇ加えたこと以外は実施例１と同様にした。
【００２７】
［比較例５］
実施例４において、エポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体を加えなかったこと以外は実施例４と同様にした。
【００２８】
［比較例６］
実施例４において、エポキシ変性ビニル系の幹ポリマーにビニル系グラフト鎖が共重合したビニル系共重合体を加えず、その代わりに前記エポキシカップリング剤を６．９ｇ加えたこと以外は実施例４と同様にした。
【００２９】
以上の実施例および比較例のそれぞれの配合（組成）割合および得られた樹脂組成物のペレットの物性評価を表１に示す。
なお、評価は、以下の方法に基づいて行なった。
・引張強度（ＭＰａ）：ＡＳＴＭ Ｄ６３８に準拠した。
・引張弾性率（ＭＰａ）：ＡＳＴＭ Ｄ６３８に準拠した。
・引張伸び（％）：ＡＳＴＭ Ｄ６３８に準拠した。
・ＩＺＯＤ衝撃強度（ＫＪ／ｍ^２）：ＡＳＴＭ Ｄ２５６に準拠した。
・ＨＤＴ（℃）：ＡＳＴＭ Ｄ６４８に準拠した。
・溶融粘度（ＰａＳ）：測定温度３００℃、剪断速度２００／ｓｅｃにおける溶融粘度を、キャピラリーレオメーターで測定した。
・スパイラルフローレート（ＳＦＬ）（ｍｍ）：クリアランス１ｍｍのスパイラルフローレート測定用金型を用い、シリンダー温度３２０℃、金型温度１３５℃での流動長を測定した。
【００３０】
【表１】

【００３１】
【発明の効果】
以上、説明したように本発明によって、きわめて高い靱性、耐衝撃性を有し、高い機械的性質をばらつきなく再現性良く保持し、成形性、流動性外観にも優れたポリアリーレンスルフィド樹脂組成物を提供することができる。[0001]
[Industrial applications]
The present invention relates to a polyarylene sulfide resin composition. More specifically, the present invention relates to a polyarylene sulfide resin composition that is suitably used as a component material for various precision equipment, electric / electronic equipment, and transportation equipment such as automobiles that require toughness and impact resistance.
[0002]
[Prior art]
Polyarylene sulfide resin (PAS) is an engineering plastic having extremely high heat resistance and chemical resistance, but has a problem that it is brittle.
To solve this problem, attempts have been made to mix various elastomers with the PAS resin. In order to compensate for the brittleness of the PAS resin, a modified olefin copolymer has been frequently used as an elastomer component.
However, such an olefin-based copolymer has extremely low compatibility with the PAS resin, and thus is not sufficient in terms of improvement in toughness, impact resistance, and appearance.
Further, since the dispersion state of the elastomer component is not uniform, there is a problem that mechanical properties (strength and elongation) vary greatly and reproducibility is extremely low.
From such a viewpoint, attempts have been made mainly to add a reactive compatibilizer (coupling agent), especially an epoxy resin or a silane coupling agent from the viewpoint of improving the physical properties.
[0003]
[Problems to be solved by the invention]
However, when such a coupling agent is used, the viscosity at the time of melting of the obtained resin composition is remarkably increased, so that it has been difficult to improve the physical properties while maintaining the viscosity. Further, the epoxy resin and the silane coupling agent are liquids, and there is a problem that uniform mixing is difficult by kneading with a usual kneading machine.
[0004]
The present invention has been made in view of the above problems, and has greatly improved the fragility, which is one of the greatest drawbacks of PAS resin, and has excellent toughness and impact resistance, and has excellent appearance and mechanical properties. It is an object of the present invention to provide a polyarylene sulfide resin composition which is not reproducibly retained, and has good fluidity and moldability.
[0005]
[Means for Solving the Problems]
According to the present invention, there is provided a polyarylene sulfide resin composition comprising the following composition components in the following composition ratio.
Composition component (A): polyarylene sulfide (B): an elastomer copolymer composed of ethylene, an α, β-unsaturated carboxylic acid alkyl ester, and maleic anhydride (provided that the α, β-unsaturated glycidyl carboxylate is Not included)
(C): Composition ratio of a vinyl copolymer obtained by copolymerizing a vinyl-based graft chain with an epoxy-modified vinyl-based or olefin-based trunk polymer (A) and (B) ((A): (B )) Is 60:40 to 99: 1 (weight ratio), and the ratio of the component (C) is 0.1 to 30 parts by weight (the total amount of the component (A) and the component (B) ( (A) + (B)) 100 parts by weight).
[0006]
In a preferred embodiment, there is provided a polyarylene sulfide resin composition further comprising (D) a filler in addition to the components (A), (B) and (C). You.
[0007]
Hereinafter, the polyarylene sulfide resin composition of the present invention will be specifically described.
1. Component (1) Polyarylene sulfide (A)
The polyarylene sulfide (PAS) (A) used in the present invention is a polymer containing a repeating unit represented by the structural formula -Ar-S- (where Ar is an arylene group) in an amount of 70 mol% or more, and a representative substance thereof. Is represented by the following structural formula (I)
[0008]
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[0009]
(Wherein, R ¹ is a substituent selected from an alkyl group having 6 or less carbon atoms, an alkoxy group, a phenyl group, a carboxyl group, a cyano group, an amino group, and a halogen atom, and m is an integer of 0 to 4. N is an average degree of polymerization and is in the range of 1.3 to 30), and is a polyphenylene sulfide having a repeating unit of 70 mol% or more. Among them, α-chloronaphthalene solution (concentration 0.4 g / dl), logarithmic viscosity at 206 ° C. is 0.1 to 0.5 (dl / g), preferably 0.13 to 0.4 (dl / g), Preferably, those in the range of 0.15 to 0.35 (dl / g) are suitable. In general, PAS is known to have a substantially linear, molecular structure having no branched or cross-linked structure, and a structure having a branched or cross-linked structure. Is also effective. Preferred PASs for use in the present invention are homopolymers or copolymers containing at least 70 mol%, more preferably at least 80 mol%, of paraphenylene sulfide units as repeating units (hereinafter abbreviated as PPS). If this repeating unit is less than 70 mol%, the original crystallinity, which is a characteristic of a crystalline polymer, tends to be low, and sufficient mechanical properties tend not to be obtained. Examples of the copolymerizable structural unit include a metaphenylene sulfide unit, an orthophenylene sulfide unit, a p, p′-diphenylene ketone sulfide unit, a p, p′-diphenylene sulfone sulfide unit, a p, p′-biphenylene sulfide unit, and p , P'-diphenylene ether sulfide unit and 2,6-naphthalene sulfide unit. In addition, as the polyarylene sulfide of the present invention, in addition to the above-mentioned substantially linear polymer, a branched or cross-linked polyarylene sulfide polymerized using a small amount of a monomer having three or more functional groups as a part of the monomer is also used. It is also preferable to use a blended polymer obtained by blending this with the linear polymer. Furthermore, as the PAS used as the component (A) in the present invention, a polymer having a relatively low molecular weight linear polymer whose viscosities are increased by oxidative crosslinking or thermal crosslinking to improve the moldability can be used.
[0010]
(2) Maleic anhydride-containing olefin elastomer copolymer (B)
The maleic anhydride-containing olefin-based elastomer copolymer (B) used in the present invention is not particularly limited. For example, the monomer components are ethylene, α, β-unsaturated carboxylic acid alkyl ester, and Consisting of maleic anhydride in proportions of 50 to 90% by weight, 5 to 49% by weight, 0.5 to 10% by weight, preferably 60 to 85% by weight, 7 to 45% by weight, 1 to 8% by weight Ethylene copolymer.
In addition, olefin elastomers containing maleic anhydride such as maleic anhydride-modified SEBS and maleic anhydride-modified EPR can also be used.
[0011]
(3) Vinyl copolymer (C) in which a vinyl-based graft chain is copolymerized with an epoxy-modified vinyl- or olefin-based trunk polymer
The vinyl copolymer (C) which is obtained by copolymerizing a vinyl-based graft chain with an epoxy-modified vinyl- or olefin-based trunk polymer used in the present invention is produced by, for example, a macromonomer method. And a polymer component having an epoxy group-containing polymer segment as a trunk component.
The macromonomer used in the present invention is a high molecular weight monomer having a radical polymerizable group at one end of a vinyl polymer chain, and this macromonomer is copolymerized with one or more other vinyl monomers. By doing so, a graft polymer can be produced, and the graft polymer obtained by this method has a polymer segment derived from a macromonomer as a branch component and a homo- or copolymer segment of a vinyl monomer as a trunk component. It has a structure and is generally called a macromonomer method graft polymer.
[0012]
The trunk component of the graft polymer is a polymer segment containing an epoxy group, and is formed from an epoxy group-containing vinyl monomer or a monomer mixture of the vinyl monomer and another vinyl monomer.
As the epoxy group-containing vinyl monomer, glycidyl esters such as glycidyl methacrylate, glycidyl acrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl ethers such as allyl glycidyl ether and 2-methylallyl glycidyl ether are used. Glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether are preferably used, and glycidyl methacrylate is more preferably used.
The molecular weight of the stem component is preferably from 1,000 to 200,000, more preferably from 2,000 to 100,000 in number average molecular weight. When the number average molecular weight exceeds 200,000, the dispersibility in polyarylene sulfide is reduced and the compatibilizing effect is small. On the other hand, when the number average molecular weight is less than 1,000, the moldability is reduced due to thickening of the polyarylene sulfide.
[0013]
In the graft polymer having the branch component and the trunk component as constituent units, the content of the epoxy group-containing vinyl monomer unit is 1 to 30% by weight based on the total amount of the monomer units constituting the graft polymer. Preferably, it is more preferably 3 to 20% by weight.
The weight ratio between the branch component and the stem component is preferably from 5 to 80% by weight of the branch component and from 20 to 95% by weight of the stem component, and from 10 to 50% by weight of the branch component and from 50 to 90% by weight of the stem component. More preferred.
On the other hand, when the content of the trunk component is less than 20% by weight, the degree of reaction with polyarylene sulfide is low, and the compatibility with polyarylene sulfide is poor.
The molecular weight of the graft polymer is preferably from 2,000 to 300,000 in number average molecular weight.
[0014]
(4) Filler (D)
In the present invention, a filler (D) can be used as necessary.
The filler (D) is not an essential component, but is used to obtain a molded article having excellent performance such as mechanical properties, heat resistance, dimensional stability (deformation resistance, warpage), and electrical properties. Is preferably blended, and for this purpose, a fibrous, powdery, granular or plate-like filler is used depending on the purpose. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium, Inorganic fibrous materials such as fibrous materials of metals such as copper and brass can be mentioned. Particularly typical fibrous fillers are glass fibers or carbon fibers. In addition, a high melting point organic fibrous substance such as an aromatic polyamide, a fluorine resin, or an acrylic resin can also be used. On the other hand, powdered granular fillers include carbon black, fused or crystalline silica, quartz powder, crow beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, and wollastonite. Metal oxides such as acid salts, iron oxides, titanium oxides, zinc oxides, and aluminas; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; and other silicon carbide , Boron nitride, and various metal powders. Examples of the plate-like filler include mica, glass flake, various metal foils, and the like. These inorganic fillers can be used alone or in combination of two or more. The combined use of a fibrous filler, especially a glass fiber or a carbon fiber, and a granular and / or plate-like filler is a preferable combination, particularly in terms of having both mechanical strength, dimensional accuracy, electrical properties and the like. When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. This example is a functional compound such as an epoxy compound, an isocyanate compound, a silane compound and a titanate compound. These compounds may be used after being subjected to a surface treatment or a convergence treatment on the filler in advance, or may be added simultaneously with the preparation of the material.
[0015]
2. Composition ratio The composition ratio of each component in the present invention is such that the ratio of the component (A) to the component (B) ((A) :( B)) is 60:40 to 99: 1 (weight ratio), preferably 80:20 to 95: 5 (weight ratio), and the ratio of the component (C) is 100 parts by weight based on 100 parts by weight of the total of the components (A) and (B) ((A) + (B)). 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight.
[0016]
Regarding the ratio of the component (A) to the component (B), when the component (B) exceeds 60:40, properties that characterize the PAS such as heat resistance, elastic modulus, and flame retardancy are remarkably reduced. If the ratio is less than 1: 1, the effect of improving impact resistance and toughness is insufficient.
When the proportion of the component (C) is less than 0.1 part by weight based on 100 parts by weight of the total of the components (A) and (B), the function as a compatibilizer is insufficient. Yes, if it exceeds 30 parts by weight, it may lead to an increase in viscosity and a decrease in heat resistance and impact resistance.
[0017]
The mixing ratio of the filler to be added as required is 3 parts per 100 parts by weight of the total amount of (A), (B) and (C) ((A) + (B) + (C)). It is preferable to set it to 350 parts by weight.
If the amount is less than 3 parts by weight, the effect of improving mechanical strength, elastic modulus and the like is poor, and if it exceeds 350 parts by weight, fluidity and moldability may be reduced.
[0018]
3. Preparation of Resin Composition The method for preparing the polyarylene sulfide resin composition of the present invention is not particularly limited. For example, the three components (A), (B), and (C) and, if necessary, a filler After uniformly mixing (D) with a mixer such as a Henschel mixer, the mixture is supplied to a single-screw or twin-screw kneading extruder, and melt-kneaded in a temperature range of 280 to 340 ° C. to obtain a resin composition as pellets. Can be.
[0019]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[Example 1]
850 g of polyarylene sulfide (linear PPS manufactured by Idemitsu Petrochemical), 150 g of maleic anhydride-containing olefin elastomer copolymer (Bondyne manufactured by Sumitomo Chemical Co., Ltd.), and a vinyl-based graft polymer co-polymerized with an epoxy-modified vinyl base polymer. 10 g of the polymerized vinyl copolymer (Reseda GP-500 manufactured by Toa Gosei Chemical Industry Co., Ltd.) was mixed with a Hensiel mixer for 2 minutes.
Next, the mixture was supplied to a twin-screw kneading extruder and melt-kneaded at a temperature of 300 ° C. to obtain pellets.
[0020]
[Example 2]
Example 1 was the same as Example 1 except that the blending amount of the vinyl-based copolymer in which the vinyl-based graft chain was copolymerized with the epoxy-modified vinyl-based trunk polymer was changed from 10 g to 20 g.
[0021]
[Example 3]
Example 1 was the same as Example 1 except that the blending amount of the vinyl copolymer in which the vinyl-based graft chain was copolymerized with the epoxy-modified vinyl-based trunk polymer was changed from 10 g to 50 g.
[0022]
[Example 4]
In Example 1, a polyarylene sulfide was changed from 850 g to 567 g, a maleic anhydride-containing olefin elastomer copolymer was changed from 150 g to 100 g, and a vinyl-based graft copolymer was copolymerized with an epoxy-modified vinyl-based backbone polymer. Example 1 was repeated except that the amount of the copolymer was changed from 50 g to 33 g, and 300 g of glass fiber (GF) (JAFT591 manufactured by Asahi Fiber Glass Co., Ltd.) was used.
[0023]
[Comparative Example 1]
In Example 1, the polyarylene sulfide was changed from 850 g to 1,000 g, and a vinyl copolymer in which a vinyl graft chain was copolymerized with a maleic anhydride-containing olefin elastomer copolymer and an epoxy-modified vinyl base polymer. The procedure was the same as in Example 1 except that was not added.
[0024]
[Comparative Example 2]
Example 1 was the same as Example 1 except that the vinyl copolymer copolymerized with the vinyl graft chain was not added to the epoxy-modified vinyl base polymer.
[0025]
[Comparative Example 3]
In Example 1, 10 g of an epoxy coupling agent (Epoxysilane SH6040 manufactured by Toray Silicone Co., Ltd.) was added without adding a vinyl-based copolymer in which a vinyl-based graft chain was copolymerized to the epoxy-modified vinyl-based trunk polymer. Other than that, it carried out similarly to Example 1.
[0026]
[Comparative Example 4]
In Example 1, the amount of polyarylene sulfide was changed from 850 g to 700 g, and a vinyl copolymer having a vinyl graft chain copolymerized with a maleic anhydride-containing olefin elastomer copolymer and an epoxy-modified vinyl base polymer was not added. In the same manner as in Example 1 except that 300 g of the GF was added instead.
[0027]
[Comparative Example 5]
In Example 4, it carried out similarly to Example 4 except not having added the vinyl copolymer which the vinyl graft graft copolymerized to the epoxy modified vinyl base polymer.
[0028]
[Comparative Example 6]
Example 4 Example 4 was repeated except that a vinyl-based copolymer in which a vinyl-based graft chain was copolymerized was not added to the epoxy-modified vinyl-based trunk polymer, and 6.9 g of the epoxy coupling agent was added instead. Same as.
[0029]
Table 1 shows the respective compounding (composition) ratios of the above Examples and Comparative Examples and evaluation of physical properties of pellets of the obtained resin composition.
In addition, evaluation was performed based on the following method.
-Tensile strength (MPa): Based on ASTM D638.
-Tensile modulus (MPa): Based on ASTM D638.
-Tensile elongation (%): Based on ASTM D638.
· IZOD impact strength ^(KJ / m 2): conforming to ASTM D256.
-HDT (° C): based on ASTM D648.
Melt viscosity (PaS): The melt viscosity at a measurement temperature of 300 ° C. and a shear rate of 200 / sec was measured with a capillary rheometer.
Spiral flow rate (SFL) (mm): The flow length at a cylinder temperature of 320 ° C. and a mold temperature of 135 ° C. was measured using a spiral flow rate measuring mold having a clearance of 1 mm.
[0030]
[Table 1]

[0031]
【The invention's effect】
As described above, according to the present invention, a polyarylene sulfide resin composition having extremely high toughness and impact resistance, maintaining high mechanical properties without variation and good reproducibility, and excellent in moldability and fluid appearance. Can be provided.

Claims (2)

A polyarylene sulfide resin composition comprising the following composition components in the following composition ratio.
Composition component (A): polyarylene sulfide (B): an elastomer copolymer composed of ethylene, an α, β-unsaturated carboxylic acid alkyl ester, and maleic anhydride (provided that the α, β-unsaturated glycidyl carboxylate is Not included)
(C): Composition ratio of a vinyl copolymer obtained by copolymerizing a vinyl-based graft chain with an epoxy-modified vinyl-based or olefin-based trunk polymer (A) and (B) ((A): (B )) Is 60:40 to 99: 1 (weight ratio), and the ratio of the component (C) is 0.1 to 30 parts by weight (the total amount of the component (A) and the component (B) ( (A) + (B)) 100 parts by weight). The polyarylene sulfide resin composition according to claim 1, further comprising a filler (D) in addition to the components (A), (B) and (C).