JP4128801B2 - Resin composition for sliding member and sliding member - Google Patents
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Description
【０００１】
【発明が属する技術分野】
本発明は、摺動部材用樹脂組成物に関し、詳しくは、アルミニウム合金などの軟質金属を摺動相手材として使用した場合において、とくに優れた摩擦摩耗特性を発揮する摺動部材用樹脂組成物および摺動部材に関する。
【０００２】
【従来の技術】
従来より、ポリアミド樹脂、ポリアセタール樹脂などの熱可塑性合成樹脂は、機械的強度、耐摩耗性に優れるため、軸受、歯車などの機械要素として広く使用されている。しかしながら、これらの合成樹脂は樹脂単独では充分な摩擦摩耗特性が得られないため、これらの樹脂に黒鉛、二硫化モリブデン、四ふっ化エチレン樹脂などの固体潤滑剤、鉱油やロウなどの潤滑油剤を含有したり、ポリエチレン樹脂などの低摩擦性を有する他の合成樹脂を配合したりして摩擦摩耗特性の向上を図っている。
【０００３】
例えば、ポリエチレン樹脂を配合した樹脂組成物として、ポリアミド樹脂、ポリアセタール樹脂、ポリエステル樹脂およびポリカーボネート樹脂から選ばれる熱可塑性樹脂７０〜９８重量％と、超高分子量ポリエチレン樹脂粉末２〜３０重量％とを溶融混練してなる熱可塑性樹脂組成物が知られている（特公昭６３−６５２３２号公報）。
【０００４】
一方、合成樹脂製の摺動部材に限らず、軸受などの摺動部材においては、相手材、例えば軸の材質、表面性状なども優れた摩擦摩耗特性を得るためには重要な要素となる。近年の複写機などＯＡ機器の発達にともない、軽量化が要求される機械装置、機器類においては、摺動相手材としてアルミニウム合金の使用が不可欠とされており、アルミニウム合金を相手材とした場合においても、良好な摩擦摩耗特性が要求される。
【０００５】
上述した特公昭６３−６５２３２号公報に開示された熱可塑性樹脂組成物からなる摺動部材は、アルミニウム合金を相手材とする摺動においては、摩擦係数が高く、摩耗量も大きいという問題があり、上記の要求を満たしているとは言い難いものである。
【０００６】
【発明が解決しようとする課題】
本発明は上記の実情に鑑みなされたもので、その目的は、アルミニウム合金などの軟質金属を相手材とする場合において、優れた摩擦摩耗特性を発揮する摺動部材用樹脂組成物および摺動部材を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者は、上記目的を達成するべく鋭意研究を重ねた結果、ポリアミド樹脂を主成分とし、これに一定割合のポリエチレン樹脂、炭化水素系ワックスおよび硫酸バリウムを配合した樹脂組成物、あるいはこの樹脂組成物にさらにフェノキシ樹脂を配合した樹脂組成物からなる摺動部材が、上記目的を達成し得るとの知見を得た。
【０００８】
本発明は上記知見に基づき完成されたものであり、本発明によれば、上記目的は、ポリエチレン樹脂０．５〜３０重量％と、炭化水素系ワックス１〜１５重量％と、硫酸バリウム０．１〜５重量％と、残部ポリアミド樹脂とからなる摺動部材用樹脂組成物によって達成される。
【０００９】
また、本発明によれば、上記目的は、上記成分組成からなる樹脂組成物に、さらにフェノキシ樹脂３〜２５重量％を配合した摺動部材用樹脂組成物によっても達成される。
【００１０】
さらに、本発明によれば、上記目的は、これら摺動部材用樹脂組成物を成形してなる摺動部材によっても達成される。
【００１１】
【発明の実施の形態】
以下、本発明を説明する。先ず、摺動部材用樹脂組成物について説明する。本発明の摺動部材用樹脂組成物においては、主成分としてポリアミド樹脂を使用し、配合成分としてポリエチレン樹脂、炭化水素系ワックスおよび硫酸バリウムを使用する。
【００１２】
主成分をなすポリアミド樹脂は、脂肪族ポリアミド樹脂であり、具体的には、ナイロン６、ナイロン６６、ナイロン６１０、ナイロン１１、ナイロン１２等が挙げられ、これらの一種もしくは二種が選択されて使用される。
【００１３】
本発明で使用するポリエチレン樹脂としては、低密度ポリエチレン樹脂、直鎖状低密度ポリエチレン樹脂、中密度ポリエチレン樹脂、高密度ポリエチレン樹脂が挙げられる。また、超高分子量ポリエチレン樹脂、超高分子量ポリエチレン成分と低分子量ポリエチレン成分とからなる高分子量ポリエチレン樹脂も使用できる。
【００１４】
また、エチレンと少量の他のα−オレフィン、例えばプロピレン、１−ブテン、１−ヘキセン、１−オクテン、４−メチル−１−ペンテン等との共重合体も使用できる。さらに、前記エチレン単独重合体または共重合体が、不飽和カルボン酸、その誘導体またはビニル系重合体などにより変性されたポリエチレン樹脂も使用できる。この変性ポリエチレン樹脂は、ポリアミド樹脂との親和性を向上させる。
【００１５】
上記の不飽和カルボン酸としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、エンドシス−ビシクロ［２，２，１］ヘプト−５−エン−２，３−ジカルボン酸（ナジック酸）等が挙げられる。また、不飽和カルボン酸の誘導体としては、塩化マレニル、マレイミド、アクリル酸アミド、メタクリル酸アミド、グリシジルメタクリレート、無水マレイン酸、無水シトラコン酸、マレイン酸モノメチル、マレイン酸ジメチル、グリシジルマレエート等が挙げられる。これらの不飽和カルボン酸またはその誘導体は、単独でまたは組合わせて使用される。とくに、不飽和ジカルボン酸またはその酸無水物が好ましく、マレイン酸、ナジック酸またはこれらの酸無水物がより好ましい。
【００１６】
ポリエチレン樹脂をカルボン酸またはその誘導体で変性する方法としては、不飽和カルボン酸またはその誘導体から選ばれるグラフトモノマーをポリエチレン樹脂にグラフト重合する方法が挙げられる。グラフト重合する方法としては、従来公知の方法が採用できる。例えば、ポリエチレン樹脂を溶融し、グラフトモノマーを添加してグラフト重合する方法あるいはポリエチレン樹脂を溶媒に溶解し、グラフトモノマーを添加してグラフト重合する方法である。このとき、ラジカル開始剤を併用するのが好ましい。グラフトモノマーの添加割合としては、ポリエチレン樹脂１００重量部に対して０．０１〜１０重量部が好ましい。
【００１７】
ビニル系重合体としては、ポリスチレン、ポリメチルメタクリレート、アクリロニトリル−スチレン共重合体などが挙げられる。
【００１８】
ポリエチレン樹脂をビニル系重合体で変性する方法としては、ポリエチレン樹脂の懸濁水溶液に、スチレン等のビニル単量体、ベンゾイルペルオキシド等のラジカル重合開始剤およびｔ−ブチルペルオキシメタクリロイロキシエチルカーボネート等の有機過酸化物含有ビニルモノマーからなる溶液を添加して、ラジカル重合開始剤、有機過酸化物含有ビニルモノマーおよびビニル単量体をポリエチレン樹脂に含浸させた後、ポリエチレン樹脂中でビニル単量体と有機過酸化物含有ビニルモノマーとを重合して有機ペルオキシド基含有ビニル系重合体を生成し、得られた樹脂組成物を、または、この樹脂組成物にポリエチレン樹脂を加えたものを溶融混練することによって、ビニル系重合体がグラフトしたポリエチレン樹脂を得る方法が挙げられる。ビニル系重合体で変性されたポリエチレン樹脂中のビニル系重合体の含有割合は、１０〜６０重量％が好ましい。
【００１９】
上記のようなビニル系共重合体がグラフトしたポリエチレン樹脂の市販品としては、日本油脂製の「モディパー（商品名）」が挙げられる。
【００２０】
上述したポリエチレン樹脂は、ポリアミド樹脂とのポリマーアロイの形態で配合されるのが好ましい。このポリマーアロイとしては、ポリエチレン樹脂２０〜５０重量％とポリアミド樹脂８０〜５０重量％からなる。
【００２１】
主成分をなすポリアミド樹脂に、上記ポリエチレン樹脂を配合することにより成形性を向上させる。また、摺動部材の摩擦係数を低下させ、相手材に対するアタック性を緩和し、かつなじみ性を向上させる。ポリエチレン樹脂の配合量は通常０．５〜３０重量％、好ましくは５〜２５重量％、さらに好ましくは１０〜２０重量％である。ポリエチレン樹脂の配合量が０．５重量％未満の場合は、上記した効果が発揮されず、また配合量が３０重量％を超える場合は、耐摩耗性を低下させるとともに摺動部材としての強度を低下させる。
【００２２】
本発明で使用する炭化水素系ワックスとしては、パラフィンワックス、ポリエチレンワックス、マイクロクリスタリンワックスが挙げられる。
【００２３】
これらの炭化水素系ワックスは、摺動部材の低摩擦性に寄与するとともに相手材の損傷を著しく低減させるものである。炭化水素系ワックスの配合量は通常１〜１５重量％、好ましくは３〜１０重量％、さらに好ましくは５〜７重量％である。炭化水素系ワックスの配合量が１重量％未満の場合は、低摩擦性に充分寄与せず、また配合量が１５重量％を超えると成形性を著しく低下させるとともに摺動部材としての強度を低下させる。
【００２４】
本発明で使用する硫酸バリウム（ＢａＳＯ４）は、それ自体何ら潤滑性を示すものではないが、前記ポリアミド樹脂、ポリエチレン樹脂および炭化水素系ワックスからなる成分組成に配合されることにより、ポリアミド樹脂、ポリエチレン樹脂および炭化水素系ワックスの混合被膜の相手材表面への造膜性を助長し、かつ該被膜の相手材表面への保持性を高め、被膜の耐久性を高めるという効果を発揮する。
【００２５】
そして、この硫酸バリウムは、均一な樹脂組成物を得るためには平均粒径が２０μｍ以下のものが好ましい。硫酸バリウムの配合量は、０．１〜５重量％、好ましくは１〜３重量％である。配合量が０．１重量％より少ないと前記したポリアミド樹脂、ポリエチレン樹脂および炭化水素系ワックスの混合被膜の相手材表面への造膜性、該被膜の相手材表面での保持性、該被膜の耐久性に効果が発揮されず、また５重量％を超えて配合すると、前記混合被膜の相手材表面への造膜性に問題を生じ、相手材表面に良好な混合被膜の形成が行われ難くなり、結果として摩擦摩耗特性を悪化させるという欠点が現れる。
【００２６】
本発明においては、上述した成分組成からなる摺動部材用樹脂組成物に、さらに一定割合のフェノキシ樹脂を配合することができる。本発明で使用するフェノキシ樹脂は、ビスフェノールＡとエピクロルヒドリンの縮合によって得られる線状ポリマーで、次の構造式を有している。
【００２７】
【化１】
このフェノキシ樹脂は、上記ポリアミド樹脂、ポリエチレン樹脂、炭化水素系ワックスおよび硫酸バリウムに所定の割合で配合されることにより、摺動部材の耐摩耗性を向上させる。そして、その配合量は３〜２５重量％、好ましくは５〜２０重量％が適当である。このフェノキシ樹脂の配合量が３重量％未満では、摺動部材の耐摩耗性の向上に充分な効果が得られず、また２５重量％を超えて配合すると、相手材との摺動において相手材表面を損傷させる虞があるのと、摺動部材としての機械的強度を低下させる。
【００２９】
本発明の摺動部材用樹脂組成物は、定法に従い、上述の各成分の所定量をヘンシェルミキサー、スーパーミキサー、ボールミル、タンブラーミキサー等の混合機によって混合することによって得られる。また、上記のポリマーアロイは各成分を所定の割合で溶融混練して得ることができる。
【００３０】
つぎに、本発明の摺動部材について説明する。本発明の摺動部材は、前述の摺動部材用樹脂組成物を成形して得られる。摺動部材用樹脂組成物の成形は、直接に射出成形機または押出成形機により成形する方法、摺動部材用樹脂組成物から得られたペレットを射出成形機または押出成形機により成形する方法のいずれであってもよい。
【００３１】
本発明の摺動部材は、アルミニウム合金などの軟質金属を摺動相手材とした場合において、とくに摩擦摩耗特性に優れ、事務・情報機器、電装機器、家電機器などのすべり軸受、すべり軸受装置、シール材などの摺動接触する摺動部材として使用される。
【００３２】
以下、実施例により本発明を詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。実施例および比較例で使用したポリアミド樹脂およびポリエチレン樹脂を下記表１に示す。
【００３３】
【表１】
＜ポリアミド樹脂＞
Ａ−１：ナイロン６〔宇部興産社製「宇部ナイロンＰ１０１１Ｆ（商品名）」〕
Ａ−２：ナイロン６６〔東レ社製「アミランＣＭ３００１Ｎ（商品名）」〕
＜ポリエチレン樹脂＞
Ｂ−１：無水マレイン酸をグラフトさせた変性ポリエチレン樹脂〔三井化学社製高分子量ポリエチレン樹脂「リュブマーＬ５０００（商品名）」１００重量部、無水マレイン酸１重量部、ベンゾイルペルオキシド０．１重量部を混合し、押出機で溶融混練して得た。〕
Ｂ−２：高密度ポリエチレン樹脂〔三井化学社製「ハイゼックス２１００ＪＰ（商品名）」〕
Ｂ−３：低密度ポリエチレン樹脂にポリスチレンをグラフトさせた変性ポリエチレン樹脂（低密度ポリエチレン７０重量％／ポリスチレン３０重量％）
〔日本油脂社製「モディパーＡ１１００（商品名）」〕
＜フェノキシ樹脂＞
東都化成社製「フェノトートＹＰ−５０Ｐ（商品名）」
【００３４】
実施例１〜５
ポリアミド樹脂（Ａ−１）８０〜９７．５重量％、ポリエチレン樹脂（Ｂ−１）０．５〜１０重量％、炭化水素系ワックスとしてパラフィンワックス１〜７重量％、硫酸バリウム０．５〜３重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、（１）ポリアミド樹脂９７．５重量％、ポリエチレン樹脂０．５重量％、パラフィンワックス１重量％および硫酸バリウム１重量％からなるペレットを、（２）ポリアミド樹脂８９．５重量％、ポリエチレン樹脂５重量％、パラフィンワックス５重量％および硫酸バリウム０．５重量％からなるペレットを、（３）ポリアミド樹脂８９重量％、ポリエチレン樹脂５重量％、パラフィンワックス５重量％および硫酸バリウム１重量％からなるペレットを、（４）ポリアミド樹脂８１重量％、ポリエチレン樹脂１０重量％、パラフィンワックス７重量％および硫酸バリウム２重量％からなるペレットを、（５）ポリアミド樹脂８０重量％、ポリエチレン樹脂１０重量％、パラフィンワックス７重量％および硫酸バリウム３重量％からなるペレットを、それぞれ作製した。ついで、これらのペレットを射出成形機のホッパーに投入し、成形して各成分組成からなる内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００３５】
実施例６〜８
ポリアミド樹脂（Ａ−１）８０重量部およびポリエチレン樹脂（Ｂ−１）２０重量部の混合物を押出機で溶融混練し、ポリアミド樹脂８０重量％およびポリエチレン樹脂２０重量％からなるペレットを作製した（以下「ポリマーアロイＡ」という）。ついで、ポリアミド樹脂（Ａ−１）６３〜６８重量％、得られたポリマーアロイＡ２５重量％、炭化水素系ワックスとしてポリエチレンワックス５〜１０重量％、硫酸バリウム２重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、（１）ポリアミド樹脂８８重量％、ポリエチレン樹脂５重量％、ポリエチレンワックス５重量％および硫酸バリウム２重量％からなるペレットを、（２）ポリアミド樹脂８６重量％、ポリエチレン樹脂５重量％、ポリエチレンワックス７重量％および硫酸バリウム２重量％からなるペレットを、（３）ポリアミド樹脂８３重量％、ポリエチレン樹脂５重量％、ポリエチレンワックス１０重量％および硫酸バリウム２重量％からなるペレットを、それぞれ作製した。ついで、前記実施例１と同様に成形して各成分組成からなる内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００３６】
実施例９
ポリアミド樹脂（Ａ−１）４１重量％、前記実施例６と同様のポリマーアロイＡ５０重量％、炭化水素系ワックスとしてマイクロクリスタリンワックス７重量％、硫酸バリウム２重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、ポリアミド樹脂８１重量％、ポリエチレン樹脂１０重量％、マイクロクリスタリンワックス７重量％および硫酸バリウム２重量％からなるペレットを作製した。ついで、前記実施例１と同様に成形して内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００３７】
実施例１０
ポリアミド樹脂（Ａ−１）５０重量部およびポリエチレン樹脂（Ｂ−１）５０重量部の混合物を押出機で溶融混練し、ポリアミド樹脂５０重量％およびポリエチレン樹脂５０重量％からなるペレットを作製した（以下「ポリマーアロイＢ」という）。ついで、ポリアミド樹脂（Ａ−１）５１重量％、得られたポリマーアロイＢ４０重量％、炭化水素系ワックスとしてポリエチレンワックス７重量％、硫酸バリウム２重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、ポリアミド樹脂７１重量％、ポリエチレン樹脂２０重量％、ポリエチレンワックス７重量％および硫酸バリウム２重量％からなるペレットを作製した。ついで、前記実施例１と同様に成形して内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００３８】
実施例１１
ポリアミド樹脂（Ａ−２）８１重量％、ポリエチレン樹脂（Ｂ−２）１０重量％、炭化水素系ワックスとしてパラフィンワックス７重量％、硫酸バリウム２重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、ポリアミド樹脂８１重量％、ポリエチレン樹脂１０重量％、パラフィンワックス７重量％および硫酸バリウム２重量％からなるペレットを作製した。ついで、前記実施例１と同様に成形して内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００３９】
実施例１２
ポリアミド樹脂（Ａ−２）８１重量％、ポリエチレン樹脂（Ｂ−３）１０重量％、炭化水素系ワックスとしてパラフィンワックス７重量％、硫酸バリウム２重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、ポリアミド樹脂８１重量％、ポリエチレン樹脂１０重量％、パラフィンワックス７重量％および硫酸バリウム２重量％からなるペレットを作製した。ついで、前記実施例１と同様に成形して内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００４０】
実施例１３〜１６
ポリアミド樹脂（Ａ−１）２１〜３６重量％、前記実施例６と同様のポリマーアロイＡ５０重量％、炭化水素系ワックスとしてポリエチレンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂５〜２０重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、（１）ポリアミド樹脂７６重量％、ポリエチレン樹脂１０重量％、ポリエチレンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂５重量％からなるペレットを、（２）ポリアミド樹脂７１重量％、ポリエチレン樹脂１０重量％、ポリエチレンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂１０重量％からなるペレットを、（３）ポリアミド樹脂６６重量％、ポリエチレン樹脂１０重量％、ポリエチレンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂１５重量％からなるペレットを、（４）ポリアミド樹脂６１重量％、ポリエチレン樹脂１０重量％、ポリエチレンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂２０重量％からなるペレットを、それぞれ作製した。ついで、前記実施例１と同様に成形して各成分組成からなる内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００４１】
実施例１７
ポリアミド樹脂（Ａ−２）７１重量％、ポリエチレン樹脂（Ｂ−２）１０重量％、炭化水素系ワックスとしてパラフィンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂１０重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、ポリアミド樹脂７１重量％、ポリエチレン樹脂１０重量％、パラフィンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂１０重量％からなるペレットを作製した。ついで、前記実施例１と同様に成形して内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００４２】
実施例１８
ポリアミド樹脂（Ａ−２）７１重量％、ポリエチレン樹脂（Ｂ−３）１０重量％、炭化水素系ワックスとしてポリエチレンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂１０重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、ポリアミド樹脂７１重量％、ポリエチレン樹脂１０重量％、ポリエチレンワックス７重量％、硫酸バリウム２重量％およびフェノキシ樹脂１０重量％からなるペレットを作製した。ついで、前記実施例１と同様に成形して内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００４３】
比較例１
ポリマーアロイＡを成形して内径内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００４４】
比較例２
ポリアミド樹脂（Ａ−１）９５重量％および炭化水素系ワックスとしてポリエチレンワックス５重量％を混合して混合物を作製した後、この混合物を押出機で溶融混練し、ポリアミド樹脂９５重量％、ポリエチレンワックス５重量％からなるペレットを作製した。次いで、このペレットを射出成形機のホッパーに投入し、成形して内径１０ｍｍ、外径１４ｍｍ、長さ１０ｍｍの円筒状試験片（摺動部材）を作製した。
【００４５】
上述した実施例１〜１８および比較例１〜２で作製した円筒状試験片について、表２に示す試験条件でジャーナル試験を行なった。その試験結果を表３〜６に示す。摩擦係数については、試験開始から安定時に移行した段階での摩擦係数を示し、摩耗量については、試験終了後の円筒状試験片（摺動部材）の寸法変化量で示した。また、試験後の相手材表面の損傷度の評価を、損傷が認められないものを○印にて、損傷が認められるものを×印にて表示した。
【００４６】
【表２】
＜ジャーナル試験＞
すべり速度 ２０ｍ／ｍｉｎ
荷重 ５ｋｇｆ
相手材 アルミニウム合金（Ａ５０５２）
試験時間 ２４ｈｒ
潤滑 無潤滑
（以下余白）
【００４７】
【表３】
【００４８】
【表４】
【００４９】
【表５】
【００５０】
【表６】
以上の結果から、本発明のポリエチレン樹脂と炭化水素系ワックスと硫酸バリウムと残部ポリアミド樹脂からなる樹脂組成物、あるいはこれら組成にさらにフェノキシ樹脂を配合してなる樹脂組成物を成形してなる摺動部材はいずれも良好な摩擦摩耗特性を示した。また、試験後の相手材表面には何らの損傷も認められなかった。一方、比較例１の樹脂組成物を成形してなる摺動部材は、摩擦係数が高く、摩耗量も多く、摩擦摩耗特性に劣るものであり、相手材表面に引掻き傷のような損傷（摩耗痕）が認められ、本発明の目的を達成するものではなかった。さらに、比較例２の樹脂組成物を成形してなる摺動部材は、相手材との摺動において、相手材表面に損傷等を与えることなく低い摩擦係数を示したが、摩耗量が多く本発明の目的を達成するものではなかった。
【００５２】
【発明の効果】
以上説明した本発明によれば、アルミニウム合金などの軟質金属を相手材とした場合において、優れた摩擦摩耗特性を発揮する摺動部材用樹脂組成物および摺動部材が提供される。[0001]
[Technical field to which the invention belongs]
The present invention relates to a resin composition for a sliding member, and in particular, when a soft metal such as an aluminum alloy is used as a sliding counterpart material, the resin composition for a sliding member that exhibits particularly excellent frictional wear characteristics, and The present invention relates to a sliding member.
[0002]
[Prior art]
Conventionally, thermoplastic synthetic resins such as polyamide resin and polyacetal resin are widely used as mechanical elements such as bearings and gears because they are excellent in mechanical strength and wear resistance. However, these resins do not provide sufficient friction and wear characteristics with the resin alone, so that these resins may contain solid lubricants such as graphite, molybdenum disulfide, and ethylene tetrafluoride resins, and lubricating oils such as mineral oil and wax. Friction and wear characteristics are improved by adding or blending other synthetic resins having low friction properties such as polyethylene resin.
[0003]
For example, as a resin composition containing a polyethylene resin, 70 to 98% by weight of a thermoplastic resin selected from polyamide resin, polyacetal resin, polyester resin and polycarbonate resin and 2 to 30% by weight of ultrahigh molecular weight polyethylene resin powder are melted. A kneaded thermoplastic resin composition is known (Japanese Patent Publication No. 63-65232).
[0004]
On the other hand, not only a synthetic resin sliding member but also a sliding member such as a bearing is an important factor for obtaining an excellent frictional wear characteristic of a mating material such as a shaft material and surface properties. With the development of OA equipment such as copying machines in recent years, it is indispensable to use an aluminum alloy as a sliding partner material in machinery and equipment that are required to be lighter. However, good friction and wear characteristics are required.
[0005]
The sliding member made of the thermoplastic resin composition disclosed in Japanese Patent Publication No. 63-65232 described above has a problem that a sliding coefficient using an aluminum alloy is a high friction coefficient and a large amount of wear. It is hard to say that the above requirements are satisfied.
[0006]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and its object is to provide a sliding member resin composition and a sliding member that exhibit excellent frictional wear characteristics when a soft metal such as an aluminum alloy is used as a counterpart. Is to provide.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventor has obtained a resin composition containing a polyamide resin as a main component and a certain proportion of polyethylene resin, hydrocarbon wax and barium sulfate, or the resin. The knowledge that the sliding member which consists of a resin composition which mix | blended phenoxy resin with the composition can achieve the said objective was acquired.
[0008]
The present invention has been completed based on the above findings. According to the present invention, the object is 0.5 to 30% by weight of a polyethylene resin, 1 to 15% by weight of a hydrocarbon wax, 0. This is achieved by a resin composition for a sliding member comprising 1 to 5% by weight and the remaining polyamide resin.
[0009]
Moreover, according to this invention, the said objective is achieved also by the resin composition for sliding members which mix | blended 3-25 weight% of phenoxy resin further with the resin composition which consists of the said component composition.
[0010]
Furthermore, according to this invention, the said objective is achieved also by the sliding member formed by shape | molding these resin compositions for sliding members.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below. First, the resin composition for sliding members will be described. In the resin composition for a sliding member of the present invention, a polyamide resin is used as a main component, and a polyethylene resin, a hydrocarbon wax, and barium sulfate are used as blending components.
[0012]
The main component of the polyamide resin is an aliphatic polyamide resin, and specific examples include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, and the like, and one or two of these are selected and used. Is done.
[0013]
Examples of the polyethylene resin used in the present invention include a low density polyethylene resin, a linear low density polyethylene resin, a medium density polyethylene resin, and a high density polyethylene resin. Further, an ultrahigh molecular weight polyethylene resin and a high molecular weight polyethylene resin comprising an ultrahigh molecular weight polyethylene component and a low molecular weight polyethylene component can also be used.
[0014]
Copolymers of ethylene and a small amount of other α-olefins such as propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like can also be used. Furthermore, a polyethylene resin in which the ethylene homopolymer or copolymer is modified with an unsaturated carboxylic acid, a derivative thereof, a vinyl polymer, or the like can also be used. This modified polyethylene resin improves the affinity with the polyamide resin.
[0015]
Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, endocis-bicyclo [2,2,1] hept-5-ene- 2,3-dicarboxylic acid (nadic acid) and the like can be mentioned. Examples of unsaturated carboxylic acid derivatives include maleyl chloride, maleimide, acrylic acid amide, methacrylic acid amide, glycidyl methacrylate, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. . These unsaturated carboxylic acids or derivatives thereof are used alone or in combination. In particular, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid or acid anhydrides thereof are more preferable.
[0016]
Examples of the method of modifying the polyethylene resin with a carboxylic acid or a derivative thereof include a method in which a graft monomer selected from an unsaturated carboxylic acid or a derivative thereof is graft-polymerized onto the polyethylene resin. As a method for graft polymerization, a conventionally known method can be employed. For example, there is a method in which a polyethylene resin is melted and a graft monomer is added to perform graft polymerization, or a method in which the polyethylene resin is dissolved in a solvent and the graft monomer is added to perform graft polymerization. At this time, it is preferable to use a radical initiator in combination. The addition ratio of the graft monomer is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyethylene resin.
[0017]
Examples of the vinyl polymer include polystyrene, polymethyl methacrylate, acrylonitrile-styrene copolymer, and the like.
[0018]
As a method of modifying the polyethylene resin with a vinyl polymer, a suspension of the polyethylene resin in a suspension of a vinyl monomer such as styrene, a radical polymerization initiator such as benzoyl peroxide, and t-butylperoxymethacryloyloxyethyl carbonate After adding a solution comprising an organic peroxide-containing vinyl monomer and impregnating the polyethylene resin with a radical polymerization initiator, an organic peroxide-containing vinyl monomer and a vinyl monomer, Polymerizing an organic peroxide-containing vinyl monomer to produce an organic peroxide group-containing vinyl polymer, and melt-kneading the resulting resin composition or a resin composition obtained by adding a polyethylene resin A method for obtaining a polyethylene resin grafted with a vinyl polymer. That. The content of the vinyl polymer in the polyethylene resin modified with the vinyl polymer is preferably 10 to 60% by weight.
[0019]
As a commercial product of the polyethylene resin grafted with the vinyl copolymer as described above, “Modiper (trade name)” manufactured by NOF Corporation is mentioned.
[0020]
The polyethylene resin described above is preferably blended in the form of a polymer alloy with a polyamide resin. The polymer alloy is composed of 20 to 50% by weight of polyethylene resin and 80 to 50% by weight of polyamide resin.
[0021]
The moldability is improved by blending the polyethylene resin with the polyamide resin as the main component. Moreover, the friction coefficient of a sliding member is reduced, the attack property with respect to a counterpart material is eased, and the conformability is improved. The blending amount of the polyethylene resin is usually 0.5 to 30% by weight, preferably 5 to 25% by weight, and more preferably 10 to 20% by weight. When the blending amount of the polyethylene resin is less than 0.5% by weight, the above effect is not exhibited. When the blending amount exceeds 30% by weight, the wear resistance is lowered and the strength as a sliding member is increased. Reduce.
[0022]
Examples of the hydrocarbon wax used in the present invention include paraffin wax, polyethylene wax, and microcrystalline wax.
[0023]
These hydrocarbon waxes contribute to the low friction of the sliding member and significantly reduce damage to the counterpart material. The blending amount of the hydrocarbon wax is usually 1 to 15% by weight, preferably 3 to 10% by weight, and more preferably 5 to 7% by weight. When the blending amount of the hydrocarbon wax is less than 1% by weight, it does not contribute sufficiently to low friction, and when the blending amount exceeds 15% by weight, the moldability is remarkably lowered and the strength as a sliding member is lowered. Let
[0024]
Barium sulfate (BaSO 4 ) used in the present invention does not exhibit any lubricity per se, but is blended into the component composition comprising the polyamide resin, polyethylene resin and hydrocarbon wax, The effect of promoting the film-forming property of the mixed coating of polyethylene resin and hydrocarbon wax on the surface of the counterpart material, enhancing the retention of the coating on the surface of the counterpart material, and improving the durability of the coating.
[0025]
The barium sulfate preferably has an average particle diameter of 20 μm or less in order to obtain a uniform resin composition. The compounding quantity of barium sulfate is 0.1 to 5% by weight, preferably 1 to 3% by weight. When the blending amount is less than 0.1% by weight, the above-mentioned mixed coating of polyamide resin, polyethylene resin and hydrocarbon wax is formed on the surface of the counterpart material, the retention of the coating on the surface of the counterpart material, If the effect is not exerted on the durability and the amount exceeds 5% by weight, a problem occurs in the film-forming property of the mixed coating on the surface of the counterpart material, and it is difficult to form a good mixed coating on the surface of the counterpart material. As a result, the disadvantage of deteriorating the friction and wear characteristics appears.
[0026]
In the present invention, a certain proportion of phenoxy resin can be further blended with the resin composition for sliding members having the above-described component composition. The phenoxy resin used in the present invention is a linear polymer obtained by condensation of bisphenol A and epichlorohydrin, and has the following structural formula.
[0027]
[Chemical 1]
This phenoxy resin improves the wear resistance of the sliding member by being blended with the polyamide resin, polyethylene resin, hydrocarbon wax and barium sulfate at a predetermined ratio. And the compounding quantity is 3-25 weight%, Preferably 5-20 weight% is suitable. If the blending amount of this phenoxy resin is less than 3% by weight, a sufficient effect for improving the wear resistance of the sliding member cannot be obtained. There is a risk of damaging the surface, and the mechanical strength of the sliding member is lowered.
[0029]
The resin composition for a sliding member of the present invention can be obtained by mixing predetermined amounts of the above-described components with a mixer such as a Henschel mixer, a super mixer, a ball mill, or a tumbler mixer according to a conventional method. The polymer alloy can be obtained by melting and kneading each component at a predetermined ratio.
[0030]
Next, the sliding member of the present invention will be described. The sliding member of the present invention is obtained by molding the above-described resin composition for a sliding member. Molding of the resin composition for sliding members is a method of directly molding with an injection molding machine or an extrusion molding machine, and a method of molding pellets obtained from the resin composition for sliding members with an injection molding machine or an extrusion molding machine. Either may be sufficient.
[0031]
The sliding member of the present invention is particularly excellent in friction and wear characteristics when a soft metal such as an aluminum alloy is used as a sliding partner, and is a sliding bearing for office / information equipment, electrical equipment, home appliances, a sliding bearing device, It is used as a sliding member that makes sliding contact such as a sealing material.
[0032]
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the summary is exceeded. The polyamide resins and polyethylene resins used in the examples and comparative examples are shown in Table 1 below.
[0033]
[Table 1]
<Polyamide resin>
A-1: Nylon 6 [“Ube Nylon P1011F (trade name)” manufactured by Ube Industries, Ltd.]
A-2: Nylon 66 [“Amilan CM3001N (trade name)” manufactured by Toray Industries, Inc.]
<Polyethylene resin>
B-1: Modified polyethylene resin grafted with maleic anhydride [100 parts by weight of high molecular weight polyethylene resin “Lubmer L5000 (trade name)” manufactured by Mitsui Chemicals, 1 part by weight of maleic anhydride, 0.1 part by weight of benzoyl peroxide It was obtained by mixing and melt-kneading with an extruder. ]
B-2: High-density polyethylene resin [“Hi-Zex 2100JP (trade name)” manufactured by Mitsui Chemicals, Inc.]
B-3: Modified polyethylene resin obtained by grafting polystyrene onto low density polyethylene resin (70% by weight of low density polyethylene / 30% by weight of polystyrene)
[Nippon Yushi Co., Ltd. “Modiper A1100 (trade name)”]
<Phenoxy resin>
“Fenototo YP-50P (trade name)” manufactured by Toto Kasei Co., Ltd.
[0034]
Examples 1-5
Polyamide resin (A-1) 80-97.5% by weight, polyethylene resin (B-1) 0.5-10% by weight, paraffin wax 1-7% by weight as hydrocarbon wax, barium sulfate 0.5-3 A mixture was prepared by mixing wt%, and this mixture was melt kneaded with an extruder. (1) 97.5 wt% polyamide resin, 0.5 wt% polyethylene resin, 1 wt% paraffin wax and 1 barium sulfate (2) 8% by weight of polyamide resin, 5% by weight of polyethylene resin, 5% by weight of paraffin wax, and 0.5% by weight of barium sulfate. (3) 89% by weight of polyamide resin (4) Polyamide resin 8 (5) Polyamide resin 80% by weight, polyethylene resin 10% by weight, paraffin wax 7% by weight and barium sulfate 3% by weight, pellets comprising 10% by weight polyethylene resin 10% by weight, paraffin wax 7% by weight and barium sulfate 2% by weight. % Pellets were prepared. Subsequently, these pellets were put into a hopper of an injection molding machine and molded to produce a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm made of each component composition.
[0035]
Examples 6-8
A mixture of 80 parts by weight of polyamide resin (A-1) and 20 parts by weight of polyethylene resin (B-1) was melt-kneaded with an extruder to produce pellets comprising 80% by weight of polyamide resin and 20% by weight of polyethylene resin (hereinafter referred to as “the pellet”). "Polymer alloy A"). Next, a mixture was prepared by mixing 63 to 68% by weight of polyamide resin (A-1), 25% by weight of the obtained polymer alloy A, 5 to 10% by weight of polyethylene wax as a hydrocarbon wax, and 2% by weight of barium sulfate. Thereafter, this mixture was melt-kneaded with an extruder, and (1) pellets consisting of 88% by weight polyamide resin, 5% by weight polyethylene resin, 5% by weight polyethylene wax and 2% by weight barium sulfate were obtained. %, Polyethylene resin 5% by weight, polyethylene wax 7% by weight and barium sulfate 2% by weight, (3) polyamide resin 83% by weight, polyethylene resin 5% by weight, polyethylene wax 10% by weight and barium sulfate 2% by weight Each pellet was made. Next, a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm was formed by molding in the same manner as in Example 1.
[0036]
Example 9
After preparing a mixture by mixing 41% by weight of polyamide resin (A-1), 50% by weight of polymer alloy A as in Example 6 above, 7% by weight of microcrystalline wax as hydrocarbon wax, and 2% by weight of barium sulfate. The mixture was melt-kneaded with an extruder to produce pellets consisting of 81% by weight polyamide resin, 10% by weight polyethylene resin, 7% by weight microcrystalline wax and 2% by weight barium sulfate. Next, a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm was formed in the same manner as in Example 1.
[0037]
Example 10
A mixture of 50 parts by weight of polyamide resin (A-1) and 50 parts by weight of polyethylene resin (B-1) was melt-kneaded with an extruder to produce pellets consisting of 50% by weight of polyamide resin and 50% by weight of polyethylene resin (hereinafter referred to as “the pellet”). "Polymer alloy B"). Next, 51 wt% of the polyamide resin (A-1), 40 wt% of the obtained polymer alloy B, 7 wt% of polyethylene wax as a hydrocarbon wax, and 2 wt% of barium sulfate were mixed to prepare a mixture. Was melt-kneaded with an extruder to produce pellets consisting of 71% by weight polyamide resin, 20% by weight polyethylene resin, 7% by weight polyethylene wax and 2% by weight barium sulfate. Next, a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm was formed in the same manner as in Example 1.
[0038]
Example 11
A mixture was prepared by mixing 81% by weight of polyamide resin (A-2), 10% by weight of polyethylene resin (B-2), 7% by weight of paraffin wax as hydrocarbon wax, and 2% by weight of barium sulfate. Was melt-kneaded with an extruder to produce pellets consisting of 81% by weight polyamide resin, 10% by weight polyethylene resin, 7% by weight paraffin wax and 2% by weight barium sulfate. Next, a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm was formed in the same manner as in Example 1.
[0039]
Example 12
A mixture was prepared by mixing 81% by weight of polyamide resin (A-2), 10% by weight of polyethylene resin (B-3), 7% by weight of paraffin wax as hydrocarbon wax, and 2% by weight of barium sulfate. Was melt-kneaded with an extruder to produce pellets consisting of 81% by weight polyamide resin, 10% by weight polyethylene resin, 7% by weight paraffin wax and 2% by weight barium sulfate. Next, a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm was formed in the same manner as in Example 1.
[0040]
Examples 13-16
Polyamide resin (A-1) 21 to 36% by weight, polymer alloy A 50% by weight as in Example 6, 7% by weight of polyethylene wax as hydrocarbon wax, 2% by weight of barium sulfate and 5 to 20% by weight of phenoxy resin The mixture was melt-kneaded with an extruder and (1) 76% by weight polyamide resin, 10% by weight polyethylene resin, 7% by weight polyethylene wax, 2% by weight barium sulfate and phenoxy resin 5 (2) 71% by weight of polyamide resin, 10% by weight of polyethylene resin, 7% by weight of polyethylene wax, 2% by weight of barium sulfate, and 10% by weight of phenoxy resin. % By weight, polyethylene resin 10% by weight, polyethylene wax 7% by weight Pellets composed of 2% by weight of barium sulfate and 15% by weight of phenoxy resin are composed of (4) 61% by weight of polyamide resin, 10% by weight of polyethylene resin, 7% by weight of polyethylene wax, 2% by weight of barium sulfate and 20% by weight of phenoxy resin. Each pellet was made. Next, a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm was formed by molding in the same manner as in Example 1.
[0041]
Example 17
Mixing 71% by weight of polyamide resin (A-2), 10% by weight of polyethylene resin (B-2), 7% by weight of paraffin wax as hydrocarbon wax, 2% by weight of barium sulfate and 10% by weight of phenoxy resin After preparation, this mixture was melt-kneaded with an extruder to produce pellets composed of 71% by weight polyamide resin, 10% by weight polyethylene resin, 7% by weight paraffin wax, 2% by weight barium sulfate and 10% by weight phenoxy resin. Next, a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm was formed in the same manner as in Example 1.
[0042]
Example 18
Polyamide resin (A-2) 71 wt%, polyethylene resin (B-3) 10 wt%, polyethylene wax 7 wt%, barium sulfate 2 wt% and phenoxy resin 10 wt% as a hydrocarbon wax. After the preparation, this mixture was melt-kneaded with an extruder to produce pellets composed of 71% by weight polyamide resin, 10% by weight polyethylene resin, 7% by weight polyethylene wax, 2% by weight barium sulfate and 10% by weight phenoxy resin. Next, a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm was formed in the same manner as in Example 1.
[0043]
Comparative Example 1
Polymer alloy A was molded to produce a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm.
[0044]
Comparative Example 2
A mixture was prepared by mixing 95% by weight of polyamide resin (A-1) and 5% by weight of polyethylene wax as a hydrocarbon wax, and then melt-kneading the mixture with an extruder to obtain 95% by weight of polyamide resin, A pellet consisting of% by weight was prepared. Next, this pellet was put into a hopper of an injection molding machine and molded to produce a cylindrical test piece (sliding member) having an inner diameter of 10 mm, an outer diameter of 14 mm, and a length of 10 mm.
[0045]
A journal test was performed on the cylindrical test pieces prepared in Examples 1 to 18 and Comparative Examples 1 and 2 described above under the test conditions shown in Table 2. The test results are shown in Tables 3-6. As for the friction coefficient, the friction coefficient at the stage of transition from the start of the test to the stable state is shown, and the wear amount is shown as the dimensional change amount of the cylindrical test piece (sliding member) after the test. In addition, the degree of damage on the surface of the mating material after the test was indicated by a mark “◯” when no damage was observed and by a mark “X” when damage was observed.
[0046]
[Table 2]
<Journal examination>
Sliding speed 20m / min
Load 5kgf
Mating material Aluminum alloy (A5052)
Test time 24hr
Lubrication No lubrication (hereinafter blank)
[0047]
[Table 3]
[0048]
[Table 4]
[0049]
[Table 5]
[0050]
[Table 6]
From the above results, the sliding composition formed by molding the resin composition comprising the polyethylene resin, hydrocarbon wax, barium sulfate and the remainder polyamide resin of the present invention, or a resin composition obtained by further blending these compositions with a phenoxy resin. All members showed good friction and wear characteristics. Further, no damage was observed on the surface of the counterpart material after the test. On the other hand, the sliding member formed by molding the resin composition of Comparative Example 1 has a high coefficient of friction, a large amount of wear, and inferior frictional wear characteristics. A mark) was observed, and the object of the present invention was not achieved. Furthermore, the sliding member formed by molding the resin composition of Comparative Example 2 showed a low coefficient of friction without damaging the surface of the counterpart material when sliding with the counterpart material, but the amount of wear was large. The object of the invention was not achieved.
[0052]
【The invention's effect】
According to the present invention described above, there are provided a resin composition for a sliding member and a sliding member that exhibit excellent frictional wear characteristics when a soft metal such as an aluminum alloy is used as a counterpart material.
Claims (6)
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| JPS6121143A (en) * | 1984-07-10 | 1986-01-29 | Karupu Kogyo Kk | Composite resin composition |
| JPS6454038A (en) * | 1987-08-24 | 1989-03-01 | Mitsuboshi Belting Ltd | Production of polyamide molding containing lubricant |
| JP3099396B2 (en) * | 1990-03-08 | 2000-10-16 | 日本油脂株式会社 | Sliding property improving agent and sliding property improving method |
| JP3419967B2 (en) * | 1995-08-16 | 2003-06-23 | 日本ポリペンコ株式会社 | Polyamide composition |
| JP3618199B2 (en) * | 1996-07-09 | 2005-02-09 | Ｎｔｎ株式会社 | Sliding member, plain bearing device, and developing device |
| JP3611227B2 (en) * | 1996-09-30 | 2005-01-19 | 日本ジーイープラスチックス株式会社 | Polycarbonate resin composition |
| JP4183804B2 (en) * | 1998-08-03 | 2008-11-19 | 株式会社プライムポリマー | Abrasion resistant soft polyolefin resin composition |
| JP3595751B2 (en) * | 1999-12-06 | 2004-12-02 | 株式会社メイト | Thermoplastic resin composition |
| JP2001181472A (en) * | 1999-12-28 | 2001-07-03 | Nof Corp | Thermoplastic resin composition and its molded product |
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