JP4371440B2 - Polyphenylene ether resin thin film sheet - Google Patents

Description

【０００９】
【化２】

【００１０】
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６は独立に炭素１〜４のアルキル基、アリール基、ハロゲン、水素を表す。但し、Ｒ５、Ｒ６は同時に水素ではない）を繰り返し単位とする単独重合体、あるいは共重合体が使用できる。
ポリフェニレンエーテルの単独重合体の代表例としては、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル１，４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル等のホモポリマーが挙げられる。
【００１１】
ポリフェニレンエーテル共重合体は、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体あるいはｏ−クレゾールとの共重合体あるいは２，３，６−トリメチルフェノール及びｏ−クレゾールとの共重合体等、ポリフェニレンエーテル構造を主体としてなるポリフェニレンエーテル共重合体を包含する。
【００１２】
また、本発明のポリフェニレンエーテルには、本発明の主旨に反しない限り、従来ポリフェニレンエーテル中に存在させてもよいことが提案されている他の種々のフェニレンエーテルユニットを部分構造として含んでいても構わない。少量共存させることが提案されているものの例としては、特願昭６３−１２６９８号公報及び特開昭６３−３０１２２２号公報に記載されている、２−（ジアルキルアミノメチル）−６−メチルフェニレンエーテルユニットや、２−（Ｎ−アルキル−Ｎ−フェニルアミノメチル）−６−メチルフェニレンエーテルユニット等が挙げられる。また、ポリフェニレンエーテルの主鎖中にジフェノキノン等が少量結合したものも含まれる。さらに、例えば特開平２−２７６８２３号公報、特開昭６３−１０８０５９号公報、特開昭５９−５９７２４号公報等に記載されている、炭素−炭素二重結合を持つ化合物により変性されたポリフェニレンエーテルも含む。
【００１３】
本発明に用いるポリフェニレンエーテルは、３０℃下のクロロホルム溶液で測定された固有粘度が０．３５〜０．６０のものが好ましく、０．４５〜０．５５のものがより好ましい。
本発明においては、耐熱性および他の特性を損なわない範囲で、ポリフェニレンエーテルの一部をスチレン系樹脂で置き換えることができる。
【００１４】
本発明で（ａ）を構成する他の成分としてポリフェニレンエーテルと混合して用いられるスチレン系樹脂とは、スチレン系化合物、スチレン系化合物と共重合可能な化合物をゴム質重合体存在または非存在下に重合して得られる重合体である。
スチレン系化合物の具体例としては、スチレン、α−メチルスチレン、２，４−ジメチルスチレン、モノクロロスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレン、エチルスチレン等が挙げられる。また、スチレン系化合物と共重合可能な化合物としては、メチルメタクリレート、エチルメタクリレート等のメタクリル酸エステル類；アクリロニトリル、メタクリロニトリル等の不飽和ニトリル化合物類；無水マレイン酸等の酸無水物等が挙げられ、スチレン系化合物とともに使用される。共重合可能な化合物の使用量は、スチレン系化合物との合計量に対して２０重量％以下が好ましく、さらに好ましくは１５重量％以下である。
【００１５】
また、ゴム質重合体としては共役ジエン系ゴムあるいは共役ジエンと芳香族ビニル化合物との共重合体あるいはエチレン−プロピレン共重合体系ゴム等が挙げられる。具体的には特に、ポリブタジエンおよびスチレン−ブタジエン共重合体が好ましい。また、不飽和ゴム質重合体を用いる場合に、部分的に水素添加した部分水添ゴム状重合体を用いることが好ましい。
【００１６】
該スチレン系樹脂として特に好ましいのは、ポリスチレンおよびゴム変性ポリスチレンである。本発明のスチレン系樹脂の製造方法は限定されるものではなく、当業者に良く知られている塊状重合、溶液重合、乳化重合、懸濁重合のいずれを用いても良い。
本発明で用いる（ｂ）ポリオレフィンは、通常の成形材料として用いられる数平均分子量が３０，０００以上のポリオレフィンであり、例えば、高密度ポリエチレン、低密度ポリエチレン、超高分子量高密度ポリエチレン、低密度ポリエチレン、線状低密度ポリエチレン、密度０．９０未満の超低密度ポリエチレン、アイソタクチックポリプロピレンや、エチレン、プロピレン、他のα−オレフィン、不飽和カルボン酸またはその誘導体の中から選ばれる２種以上の化合物の共重合体、例えばエチレン／ブテン−１共重合体、エチレン−（メタ）アクリル酸共重合体、エチレン−（メタ）アクリル酸エステル共重合体、プロピレン／エチレン（ランダム、ブロック）共重合体、プロピレン／１−ヘキセン共重合体、プロピレン／４−メチル−１−ペンテン共重合体、およびポリ（４−メチル−１−ペンテン）、ポリブテン−１等を挙げることができ、これらは１種のみならず２種以上を併用することができる。これらのポリオレフィンのうち、ポリエチレンが好ましく、低密度ポリエチレン、線状低密度ポリエチレン、高密度ポリエチレンが好ましい。
【００１７】
本発明で用いる（ｃ）および（ｄ）の水添ブロック共重合体は、ビニル芳香族化合物と共役ジエン化合物から成るブロック共重合体に水素添加したものであり、共重合した共役ジエン化合物に基づくオレフィン性二重結合の少なくとも８０％以上、好ましくは９５％以上が水素添加されたものである。そしてこの水素添加率は通常、赤外分光光度計やＮＭＲ等で知ることができる。ビニル芳香族化合物の重合体ブロック（Ａ）と共役ジエン化合物の重合体ブロック（Ｂ）の結合の具体例としては、Ａ−Ｂ、Ａ−Ｂ−Ａ、Ａ−Ｂ−Ａ−Ｂ、（Ａ−Ｂ）₄ ・Ｓｉなどが挙げられる。
【００１８】
ビニル芳香族化合物−共役ジエン化合物のブロック共重合体を構成するビニル芳香族化合物としては、例えば、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−第３ブチルスチレン、ジフェニルエチレン等のうちから１種または２種以上が選択でき、中でもスチレンが好ましい。また、共役ジエン化合物としては、例えばブタジエン、イソプレン、１，３−ペンタジエン、２，３−ジメチル−１，３−ブタジエン等のうちから１種または２種以上が選ばれ、中でもブタジエン、イソプレンおよびこれらの組み合わせが好ましい。
【００１９】
また、本発明で用いる（ｃ）ビニル芳香族化合物と共役ジエン化合物との水添ブロック共重合体（ＨＡ）は、結合スチレン量が２０〜４０重量％、好ましくは３０〜４０重量％、かつ重量平均分子量が１５万以上、好ましくは２０万以上である。
さらに、本発明で用いる（ｄ）ビニル芳香族化合物と共役ジエン化合物との水添ブロック共重合体（ＨＢ）は、ビニル芳香族化合物の結合量が４０重量％以上、好ましくは５０〜９０重量％であり、重量平均分子量が５万以上のものである。
【００２０】
これらの上記した水添ブロック共重合体は、上記した構造を有するものであればどのような製造方法で得られるものであってもかまわない。公知の製造方法の例としては、例えば、特開昭４７−１１４８６号公報、特開昭４９−６６７４３号公報、特開昭５０−７５６５１号公報、特開昭５４−１２６２５５号公報、特開昭５６−１０５４２号公報、特開昭５６−６２８４７号公報、特開昭５６−１００８４０号公報、英国特許第１１３０７７０号および米国特許第３２８１３８３号および同第３６３９５１７号に記載された方法や英国特許第１０２０７２０号および米国特許第３３３３０２４号および同第４５０１８５７号に記載された方法がある。
【００２１】
水添ブロック共重合体は、例えば、商品名「タフテック」、「クレイトンＧ」、「セプトン」などが市販されている。
本発明の薄肉シートおよびそのシートを加工して得られる物品を基本的に構成する樹脂組成物の各成分の配合割合は、（ａ）ポリフェニレンエーテル、またはポリフェニレンエーテルとスチレン系樹脂からなる混合物が５０〜８５重量％、好ましくは６０〜８０重量％、（ｂ）ポリオレフィンが３〜２０重量％、好ましくは５〜１５重量％、（ｃ）水添ブロック共重合体（ＨＡ）が５〜３０重量％、好ましくは１０〜２５重量％であり、かつ（ｄ）水添ブロック共重合体（ＨＢ）を使用する場合は３〜２０重量％である。
【００２２】
押出成形法については、前記の原材料を用いたものであれば、通常熱可塑性樹脂のフィルム、シート成形において用いられるＴダイを用いた押出成形が可能である。押出成形条件は、構成する樹脂組成物の耐熱性や溶融粘度により適宜選択するが、通常の押出温度およびダイ温度としては２５０〜３５０℃の範囲である。Ｔダイの構造については、フィルムあるいはシートの厚薄精度の向上のため、ストレートマニホールドあるいはコートハンガー型マニホールドが用いられ、コートハンガー型が好ましく用いられる。また、キャスティングロールは、一般的なロールでも構わないが、複数のロールがベルトでつながれたベルト式のものが好ましく、その後の熱成形品の賦形性や偏肉性などの品質の上で優れている。
【００２３】
押出成形により得られた薄肉シートは所望の大きさに裁断し、そのまま使用することもできるが、さらに、そのシートを圧空成形や真空成形等の熱成形により所望の形状に成形でき、高耐熱・高耐久性が要求される各種シートおよびフィルム、各種耐熱トレイ用途に使用できる。
本発明においては、シートおよび成形品の性質（耐熱性、剛性、優れた耐衝撃性、摺動性のバランス、フィルム・シート上のブツの発生）を損なわない範囲で、可塑剤、安定剤、紫外線吸収剤、難燃剤、着色剤、離型剤及びガラス繊維、炭素繊維等の繊維状補強剤、更にはガラスビーズ、炭酸カルシュウム、タルク等の充填剤を添加することができる。安定剤としては、亜リン酸エステル類、ヒンダードフェノール類、アルカノールアミン類、酸アミド類、ジチオカルバミン酸金属塩類、無機硫化物、金属酸化物類の中から単独でまたは組み合わせて配合することができる。また、従来より樹脂の加工助剤として用いられるワックス等の滑剤や超高分子量ポリマーなどの金属剥離剤はシート押出性の向上やシートの外観不良を抑制するために有効である。その他の配合剤として、特に導電性カーボンブラックの配合はＩＣ部材用途に有用である。
【００２４】
本発明の薄肉シートを構成する樹脂組成物を得る方法としては、例えば、単軸押出機、二軸押出機、ロール、ニーダー、バンバリーミキサー等による加熱溶融混練方法が挙げられるが、中でも二軸押出機を用いた溶融混練方法が最も好ましい。この際の溶融混練温度は、特に限定されるものではないが、通常２５０〜３５０℃の範囲で任意に選択する。
【００２５】
【発明の実施の態様】
以下、実施例によって本発明を具体的に説明するが、本発明は以下の例に限定されるものではない。
実施例における材料の特性は、下記の方法で評価した。ここで、熱変形温度とアイゾット衝撃強度については薄肉シートでは測定できないため、射出成形品を用いて測定した。
１）加熱変形温度
ＡＳＴＭ Ｄ−６４８に準拠し、荷重１８．６ｋｇ／ｃｍ² で測定した。
２）アイゾット衝撃強度
ＡＳＴＭ Ｄ−２５６に準拠して測定した。
３）シート押出性・シート外観
スクリュー径４０ｍｍφの単軸シート押出機、リップすき間を１．２ｍｍに調節した巾５００ｍｍのＴダイを用いて、押出機のシリンダー温度３００℃、ダイ温度３００℃にて、厚さ０．１５ｍｍのシートを押出成形した。その際に、シートの厚み調節のし易さや引き取りのし易さなどのシート押出性および引き取られたシートの表面外観（フィッシュアイやブツの発生量）を目視判定した。その結果、良好なものは○、劣るものは×、その中間レベルと判断されたものは△、で表示した。
４）摺動性試験
直径５ｍｍ、長さ１５ｍｍの円柱形状の先端に、半径が１．２５ｍｍで水平長さ４．５ｍｍの半円柱の平面部がついた形をしたポリエチレンテレフタレート樹脂製ピン（射出成形品）を半円柱が押出シートと接するように取付け、可動プレート上に貼付された、厚み０．１５ｍｍの押出シートに押し付け、ピンの上部に５００ｇの荷重をかける。その後、可動プレートを速度３０ｍｍ／秒で、２０ｍｍを往復運動させるピン／プレート法の摩擦・磨耗促進試験を行い、往復回数１００００回の時の摩擦係数を測定した。摩擦係数が小さいほど摺動性に優れる。その結果、良好なものは○、劣るものは×、その中間レベルと判断されたものは△、で表示した。
５）層状剥離試験
型締圧８０トンの射出成形機を用い、シリンダー温度３１０℃、金型温度１２０℃にて、ＡＳＴＭ Ｄ−６３８に準じた引っ張り試験片を成形し、繰り返し折り曲げたときの層状剥離の有無を目視判定した。
【００２６】
実施例で用いた各成分は、以下のものである。
ＰＰＥ−１：３０℃下のクロロホルム溶液で測定した固有粘度が０．４６（ｄｌ／ｇ）のポリ（２，６−ジメチル−１，４−フェニレン）エーテル
ＰＰＥ−２：３０℃下のクロロホルム溶液で測定した固有粘度が０．３８（ｄｌ／ｇ）のポリ（２，６−ジメチル−１，４−フェニレン）エーテル
ＰＳ−１ ：旭化成工業（株）製、ホモポリスチレン６８５
ＰＳ−２ ：ゴム含量１２重量％のハイインパクトポリスチレン
ＰＥ−１ ：旭化成工業（株）製、低密度ポリエチレン サンテックＬＤ−Ｍ１８０４
ＥＰ−１ ：三井石油化学（株）製、エチレン−プロピレン共重合体、タフマーＰ−０６８０
ＳＥＢ−１：Ａ−Ｂ−Ａ型のスチレン−ブタジエンブロック共重合体の水素添加物。（重量平均分子量２４０，０００、スチレンブロック含有量３０重量％、ポリブタジエン部の水素添加率９９．９％）
ＳＥＢ−２：Ａ−Ｂ−Ａ−Ｂ型のスチレン−ブタジエンブロック共重合体の水素添加物。（重量平均分子量９０，０００、スチレンブロック含有量６０重量％、ポリブタジエン部の水素添加率９９．９％）
ＳＥＢ−３：Ａ−Ｂ−Ａ−Ｂ型のスチレン−ブタジエンブロック共重合体の水素添加物。（重量平均分子量８０，０００、スチレンブロック含有量３０重量％、ポリブタジエン部の水素添加率９９．９％）
ＳＢ−１ ：水素添加していない（Ａ−Ｂ）₄ −Ｓｉ型のスチレン−ブタジエンブロック共重合体。（重量平均分子量１４０，０００、スチレンブロック含有量３０重量％）
【００２７】
【実施例１〜６、比較例１〜３】
表１に示す各組成物を、シリンダー温度３２０℃に設定したスクリュー径２５ｍｍの二軸押出機により２５０ｒｐｍで溶融混練し、組成物ペレットを得た。
次に、その組成物ペレットを、型締圧８０トンの射出成形機を用い、シリンダー温度３１０℃、金型温度１２０℃にて試験片を成形し、加熱変形温度およびアイゾット衝撃強度を測定した。
【００２８】
さらに、その組成物ペレットを、スクリュー径４０ｍｍφの単軸シート押出機、リップすき間を１．２ｍｍに調節した巾５００ｍｍのＴダイを用いて、押出機のシリンダー温度３００℃、ダイ温度３００℃、ロール温度約１００℃にて、厚さ０．１５ｍｍのシートを押出成形した。評価結果を表１に示す。
【００２９】
【表１】

【００３０】
【発明の効果】
本発明の特定のポリフェニレンエーテル系樹脂組成物から成る、薄肉シートおよびそれを加工して得られる摺動性物品は、優れた摺動特性と耐熱性および耐衝撃性を有し、表面外観にも優れており、繰り返し動的接触がある各種摺動部材として有用である。[0001]
[Industrial application fields]
The present invention is excellent in heat resistance, slidability and impact resistance, generally referred to as fisheye and butt, has a thin gel sheet with little gel-like foreign matter and excellent in slidability, and a slide obtained by processing the sheet. It relates to a mobile article.
[0002]
[Prior art]
Polyphenylene ether has excellent mechanical properties, electrical properties, heat resistance, low water absorption and excellent dimensional stability. For example, industrial parts, electrical / electronic parts, office equipment, housings, automotive parts, precision parts, etc. It has been put into practical use for various purposes.
However, these polyphenylene ether resin plastics that have been put to practical use have poor self-lubrication, which can be said to be a disadvantage of amorphous resins, and have a high coefficient of dynamic friction, so they melt due to frictional heat and contact / rotation of bearings, gears, etc. It has a drawback that it cannot be used as a sliding member having the above part. For this reason, for example, in Japanese Patent Laid-Open No. 50-22040, although proposals have been made to improve slidability by adding mineral oil or the like to polyphenylene ether, silver-like marks are generated on the surface of the molded product, and practical use is made. I can't stand it. JP-A-61-185560 discloses that a composition comprising potassium polytitanate whisker and powdered high-density polyethylene in a polyphenylene ether resin provides a resin composition for a sliding member having excellent wear resistance. Although there is a proposal, the molded body of the composition obtained here causes an extreme delamination phenomenon, and also deforms (dents) on the friction surface after the continuous friction running test.
[0003]
Further, JP-A-62-141062 proposes a resin composition comprising a polyphenylene ether resin and an alkyldiphenyl ether, which has a reduced dynamic friction coefficient and an improved limit PV value. The melting phenomenon occurs during the continuous wear running test, and the frictional wear amount increases, making it unusable for practical use. Further, JP-A-4-7357 and JP-A-4-2799797 disclose polyphenylene ether, a polyolefin having a low dynamic friction coefficient, a vinyl aromatic compound having a Young's modulus of 1500 kg / cm ² or more and a conjugated diene as a compatibilizer. A resin sliding member excellent in delamination, weld strength, friction resistance and wear characteristics by controlling a block copolymer with a compound or a hydrogenated product thereof to a specific dispersion form is disclosed. However, in these inventions, although an excellent sliding effect is exhibited, it is not sufficient for the demand for high durability having higher impact strength. In particular, the extrudability of a thin sheet having a thickness of 1 mm or less was not satisfactory, and a thin sheet excellent in heat resistance and durability could not be obtained. Furthermore, there was no knowledge for obtaining a highly durable thin sheet excellent in heat resistance, impact resistance and sliding characteristics.
[0004]
[Problems to be solved by the invention]
An object of the present invention is composed of a polyphenylene ether-based resin composition, which is excellent in heat resistance, sliding resistance and impact resistance, and is generally called fish eye or butt, and has high durability sliding with little gel-like foreign matter It is to provide a thin sheet having excellent properties and a slidable article obtained by processing the sheet.
[0005]
[Means for Solving the Problems]
As a result of diligent studies to achieve the above-mentioned object, the present inventors have, as a basic component, a polyphenylene ether, a polyolefin, and a hydrogenated block copolymer of a specific vinyl aromatic compound and a conjugated diene compound, and each component has a specific ratio. It was found that the resulting resin composition was excellent in extrudability of the thin sheet, and that the obtained thin sheet and a molded article obtained by processing the sheet achieved the above-mentioned problems, and reached the present invention.
[0006]
That is, the present invention
[1] (a) 50 to 85% by weight of polyphenylene ether or polyphenylene ether resin comprising a mixture of polyphenylene ether and styrene resin, (b) 3 to 20% by weight of polyolefin, (c) vinyl aromatic compound A resin composition having a hydrogenated block copolymer (HA) of a vinyl aromatic compound and a conjugated diene compound having a bond amount of 20 to 40% by weight and a weight average molecular weight of 150,000 or more, and 5 to 30% by weight 1 A slidable part obtained by processing a thin sheet having a thickness of 1 mm or less, characterized by being obtained by extrusion molding,
[2] Further, (d) a resin containing 3 to 20% by weight of a hydrogenated block copolymer (HB) of a vinyl aromatic compound and a conjugated diene compound in which the binding amount of the vinyl aromatic compound is 50 to 90% by weight. It is obtained by processing a thin sheet according to the above [1], comprising a composition
Sliding parts ,
[3] (c) The sliding block obtained by processing the thin sheet according to the above [1] or [2], wherein the hydrogenated block copolymer (HA) has a weight average molecular weight of 200,000 or more Sex parts,
It is.
[0007]
The present invention will be described in detail below.
The (a) polyphenylene ether used in the present invention is the following general formula (1) and / or general formula (2),
[0008]
[Chemical 1]

[0009]
[Chemical formula 2]

[0010]
Wherein R 1, R 2, R 3, R 4, R 5 and R 6 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, and hydrogen, provided that R 5 and R 6 are not hydrogen at the same time. Homopolymers or copolymers can be used.
Representative examples of polyphenylene ether homopolymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl 1,4-phenylene) ether, poly (2,6 -Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether Poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1) , 4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) Homopolymers such as ether can be mentioned.
[0011]
The polyphenylene ether copolymer is a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of o-cresol, or 2,3,6-trimethylphenol and o-cresol. And a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure.
[0012]
In addition, the polyphenylene ether of the present invention may include various other phenylene ether units that have been proposed to exist in the polyphenylene ether as a partial structure, unless they are contrary to the gist of the present invention. I do not care. Examples of those proposed to coexist in a small amount include 2- (dialkylaminomethyl) -6-methylphenylene ether described in Japanese Patent Application Nos. 63-12698 and 63-301222. Unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like. Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of polyphenylene ether. Furthermore, polyphenylene ether modified with a compound having a carbon-carbon double bond described in, for example, JP-A-2-276823, JP-A-63-108059, JP-A-59-59724, etc. Including.
[0013]
The polyphenylene ether used in the present invention preferably has an intrinsic viscosity measured with a chloroform solution at 30 ° C. of 0.35 to 0.60, more preferably 0.45 to 0.55.
In the present invention, a part of polyphenylene ether can be replaced with a styrenic resin as long as heat resistance and other characteristics are not impaired.
[0014]
In the present invention, the styrenic resin used by mixing with polyphenylene ether as another component constituting (a) is a styrenic compound or a compound copolymerizable with the styrenic compound in the presence or absence of a rubbery polymer. It is a polymer obtained by polymerization.
Specific examples of the styrene compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds. The amount of the copolymerizable compound used is preferably 20% by weight or less, more preferably 15% by weight or less, based on the total amount with the styrene compound.
[0015]
Examples of rubbery polymers include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Specifically, polybutadiene and styrene-butadiene copolymer are particularly preferable. Moreover, when using an unsaturated rubbery polymer, it is preferable to use a partially hydrogenated rubber-like polymer partially hydrogenated.
[0016]
Particularly preferred as the styrenic resin are polystyrene and rubber-modified polystyrene. The method for producing the styrenic resin of the present invention is not limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization well known to those skilled in the art may be used.
The (b) polyolefin used in the present invention is a polyolefin having a number average molecular weight of 30,000 or more, which is used as a normal molding material. For example, high density polyethylene, low density polyethylene, ultrahigh molecular weight high density polyethylene, low density polyethylene. , Linear low density polyethylene, ultra-low density polyethylene having a density of less than 0.90, isotactic polypropylene, ethylene, propylene, other α-olefins, unsaturated carboxylic acids or derivatives thereof. Copolymers of compounds, such as ethylene / butene-1 copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, propylene / ethylene (random, block) copolymers , Propylene / 1-hexene copolymer, propylene / 4-methyl- - pentene copolymer, and poly (4-methyl-1-pentene), can be mentioned polybutene, etc., it can be used in combination of two or more not only one kind. Among these polyolefins, polyethylene is preferable, and low density polyethylene, linear low density polyethylene, and high density polyethylene are preferable.
[0017]
The hydrogenated block copolymers (c) and (d) used in the present invention are obtained by hydrogenating a block copolymer comprising a vinyl aromatic compound and a conjugated diene compound, and are based on the copolymerized conjugated diene compound. At least 80% or more, preferably 95% or more of the olefinic double bonds are hydrogenated. This hydrogenation rate can usually be known with an infrared spectrophotometer, NMR, or the like. Specific examples of the bond between the polymer block (A) of the vinyl aromatic compound and the polymer block (B) of the conjugated diene compound include A-B, A-B-A, A-B-A-B, (A -B) ₄ · Si and the like.
[0018]
The vinyl aromatic compound constituting the vinyl aromatic compound-conjugated diene compound block copolymer is, for example, one of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. Alternatively, two or more types can be selected, and among them, styrene is preferable. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and these The combination of is preferable.
[0019]
Further, the hydrogenated block copolymer (HA) of (c) vinyl aromatic compound and conjugated diene compound used in the present invention has a bound styrene content of 20 to 40% by weight, preferably 30 to 40% by weight, and weight. The average molecular weight is 150,000 or more, preferably 200,000 or more.
Further, in the hydrogenated block copolymer (HB) of (d) vinyl aromatic compound and conjugated diene compound used in the present invention, the amount of vinyl aromatic compound bonded is 40% by weight or more, preferably 50 to 90% by weight. And the weight average molecular weight is 50,000 or more.
[0020]
These hydrogenated block copolymers may be obtained by any production method as long as they have the structure described above. Examples of known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-54-126255. No. 56-10542, JP-A 56-62847, JP-A 56-100900, British Patent No. 1130770 and US Pat. Nos. 3,281,383 and 3639517, and British Patent No. 1020720. And U.S. Pat. Nos. 3,333,024 and 4,501,857.
[0021]
As the hydrogenated block copolymer, for example, trade names “Tuftec”, “Clayton G”, “Septon” and the like are commercially available.
The blending ratio of each component of the resin composition that basically constitutes the thin sheet of the present invention and the article obtained by processing the sheet is 50 (a) polyphenylene ether or a mixture of polyphenylene ether and styrene resin. -85 wt%, preferably 60-80 wt%, (b) polyolefin 3-20 wt%, preferably 5-15 wt%, (c) hydrogenated block copolymer (HA) 5-30 wt% , Preferably 10 to 25% by weight, and (d) 3 to 20% by weight when the hydrogenated block copolymer (HB) is used.
[0022]
As for the extrusion molding method, as long as the above-mentioned raw materials are used, extrusion molding using a T-die which is usually used in thermoplastic resin film and sheet molding is possible. Extrusion molding conditions are appropriately selected depending on the heat resistance and melt viscosity of the resin composition to be constituted, and the normal extrusion temperature and die temperature are in the range of 250 to 350 ° C. As for the structure of the T die, a straight manifold or a coat hanger type manifold is used for improving the thickness or thinness accuracy of the film or sheet, and a coat hanger type is preferably used. The casting roll may be a general roll, but is preferably a belt type in which a plurality of rolls are connected by a belt, and is excellent in terms of quality such as shaping and uneven thickness of a subsequent thermoformed product. ing.
[0023]
The thin sheet obtained by extrusion molding can be cut into a desired size and used as it is, but the sheet can be formed into a desired shape by thermoforming such as pressure forming or vacuum forming, It can be used for various sheets and films that require high durability and various heat-resistant tray applications.
In the present invention, as long as the properties of the sheet and the molded product (heat resistance, rigidity, excellent impact resistance, balance of slidability, occurrence of irregularities on the film and sheet) are not impaired, a plasticizer, a stabilizer, Ultraviolet absorbers, flame retardants, colorants, mold release agents and fibrous reinforcing agents such as glass fibers and carbon fibers, and fillers such as glass beads, calcium carbonate and talc can be added. As a stabilizer, phosphites, hindered phenols, alkanolamines, acid amides, dithiocarbamic acid metal salts, inorganic sulfides, metal oxides can be used alone or in combination. . Conventionally, lubricants such as waxes and metal release agents such as ultra-high molecular weight polymers, which are conventionally used as processing aids for resins, are effective for improving sheet extrudability and suppressing sheet appearance defects. As other compounding agents, especially compounding of conductive carbon black is useful for IC member applications.
[0024]
Examples of the method for obtaining the resin composition constituting the thin sheet of the present invention include a heat melt kneading method using a single screw extruder, a twin screw extruder, a roll, a kneader, a Banbury mixer, etc. A melt kneading method using a machine is most preferred. The melt kneading temperature at this time is not particularly limited, but is usually arbitrarily selected within the range of 250 to 350 ° C.
[0025]
BEST MODE FOR CARRYING OUT THE INVENTION
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following examples.
The characteristics of the materials in the examples were evaluated by the following methods. Here, since the heat distortion temperature and the Izod impact strength cannot be measured with a thin sheet, they were measured using an injection molded product.
1) Heat deformation temperature It measured by load 18.6kg / cm < ² > based on ASTMD-648.
2) Izod impact strength Measured according to ASTM D-256.
3) Sheet extrudability / sheet appearance A single-screw sheet extruder with a screw diameter of 40 mmφ, a T-die with a width of 500 mm with a lip clearance adjusted to 1.2 mm, an extruder cylinder temperature of 300 ° C. and a die temperature of 300 ° C. A sheet having a thickness of 0.15 mm was extruded. At that time, the sheet extrudability such as the ease of adjusting the thickness of the sheet and the ease of taking it out, and the surface appearance of the taken sheet (the amount of fish eyes and bumps) were visually determined. As a result, a good one was indicated by ◯, an inferior one was indicated by ×, and an intermediate one was indicated by △.
4) Slidability test Pin made of polyethylene terephthalate resin (injection) with a cylindrical tip with a diameter of 5 mm and a length of 15 mm and a semi-cylindrical flat part with a radius of 1.25 mm and a horizontal length of 4.5 mm The molded product is attached so that the semi-cylinder is in contact with the extruded sheet, pressed against the extruded sheet having a thickness of 0.15 mm, which is stuck on the movable plate, and a load of 500 g is applied to the top of the pin. Thereafter, a friction / wear acceleration test of the pin / plate method in which the movable plate was reciprocated by 20 mm at a speed of 30 mm / sec was performed, and the friction coefficient at the time of 10,000 reciprocations was measured. The smaller the friction coefficient, the better the slidability. As a result, a good one was indicated by ◯, an inferior one by ×, and an intermediate one judged by △.
5) Laminar peel test mold The layer shape when a tensile test piece according to ASTM D-638 is molded and repeatedly bent at an injection temperature of 80 tons and a cylinder temperature of 310 ° C and a mold temperature of 120 ° C. The presence or absence of peeling was visually determined.
[0026]
Each component used in the examples is as follows.
PPE-1: poly (2,6-dimethyl-1,4-phenylene) ether PPE-2 having an intrinsic viscosity of 0.46 (dl / g) measured with a chloroform solution at 30 ° C .: chloroform solution at 30 ° C. Poly (2,6-dimethyl-1,4-phenylene) ether PS-1 having an intrinsic viscosity of 0.38 (dl / g) measured by Asahi Kasei Kogyo Co., Ltd., Homopolystyrene 685
PS-2: High impact polystyrene PE-1 having a rubber content of 12% by weight: Asahi Kasei Kogyo Co., Ltd., low density polyethylene Suntech LD-M1804
EP-1: manufactured by Mitsui Petrochemical Co., Ltd., ethylene-propylene copolymer, TAFMER P-0680
SEB-1: A hydrogenated product of ABA type styrene-butadiene block copolymer. (Weight average molecular weight 240,000, styrene block content 30% by weight, hydrogenation rate of polybutadiene part 99.9%)
SEB-2: A hydrogenated product of ABAB type styrene-butadiene block copolymer. (Weight average molecular weight 90,000, styrene block content 60% by weight, hydrogenation rate of polybutadiene part 99.9%)
SEB-3: Hydrogenated product of ABABA type styrene-butadiene block copolymer. (Weight-average molecular weight 80,000, styrene block content 30% by weight, polybutadiene part hydrogenation rate 99.9%)
SB-1: not hydrogenated (AB) ₄ -Si type styrene-butadiene block copolymer. (Weight average molecular weight 140,000, styrene block content 30% by weight)
[0027]
Examples 1-6, Comparative Examples 1-3
Each composition shown in Table 1 was melt-kneaded at 250 rpm by a twin screw extruder with a screw diameter of 25 mm set at a cylinder temperature of 320 ° C. to obtain composition pellets.
Next, a test piece of the composition pellet was molded at a cylinder temperature of 310 ° C. and a mold temperature of 120 ° C. using an injection molding machine with a clamping pressure of 80 tons, and the heat deformation temperature and Izod impact strength were measured.
[0028]
Furthermore, the composition pellets were used in a single-screw sheet extruder having a screw diameter of 40 mmφ, a T-die having a width of 500 mm with a lip gap adjusted to 1.2 mm, an extruder cylinder temperature of 300 ° C., a die temperature of 300 ° C., a roll A sheet having a thickness of 0.15 mm was extruded at a temperature of about 100 ° C. The evaluation results are shown in Table 1.
[0029]
[Table 1]

[0030]
【The invention's effect】
The thin sheet comprising the specific polyphenylene ether resin composition of the present invention and the slidable article obtained by processing the sheet have excellent sliding characteristics, heat resistance and impact resistance, and also have a surface appearance. It is excellent and useful as various sliding members with repeated dynamic contact.

Claims (3)

(A) polyphenylene ether, or polyphenylene ether resin 50 to 85% by weight comprising a mixture of polyphenylene ether and styrene resin, (b) 3 to 20% by weight of polyolefin, and (c) the amount of vinyl aromatic compound bound. A hydrogenated block copolymer (HA) of a vinyl aromatic compound having a weight average molecular weight of 150,000 or more and a conjugated diene compound (HA) comprising 5 to 30% by weight of a resin composition, A slidable part obtained by processing a thin sheet having a thickness of 1 mm or less, which is obtained by molding. Further, (d) from a resin composition containing 3 to 20% by weight of a hydrogenated block copolymer (HB) of a vinyl aromatic compound and a conjugated diene compound in which the binding amount of the vinyl aromatic compound is 50 to 90% by weight. A slidable part obtained by processing the thin sheet according to claim 1. (C) The slidable part obtained by processing a thin sheet according to claim 1 or 2, wherein the hydrogenated block copolymer (HA) has a weight average molecular weight of 200,000 or more.