JP4519355B2 - Underwater sliding member and manufacturing method thereof - Google Patents

Underwater sliding member and manufacturing method thereof Download PDF

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Publication number
JP4519355B2
JP4519355B2 JP2001128383A JP2001128383A JP4519355B2 JP 4519355 B2 JP4519355 B2 JP 4519355B2 JP 2001128383 A JP2001128383 A JP 2001128383A JP 2001128383 A JP2001128383 A JP 2001128383A JP 4519355 B2 JP4519355 B2 JP 4519355B2
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Prior art keywords
fiber cloth
carbon fiber
phenol resin
sliding member
resin composition
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JP2001128383A
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JP2002323038A (en
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隆 中丸
公樹 福倉
与幸 山根
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Oiles Corp
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Oiles Corp
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  • Compositions Of Macromolecular Compounds (AREA)
  • Sliding-Contact Bearings (AREA)

Description

【0001】
【発明が属する技術分野】
本発明は、軸受、すべり板、スラストワッシャー等に使用されて好適な水中用摺動部材ならびにその製造方法に関する。
【0002】
【従来の技術】
従来、綿布を補強基材とするフェノール樹脂からなる水中軸受はよく知られている。しかしながら、土砂などの異物濃度の高い環境で使用される場合は充分な性能が得られなかった。また、ポンプなどに使用される場合、起動時の短時間ではあるがドライ条件での運転となる。ところが、従来の補強基材そのものおよびフェノール樹脂自体は何ら潤滑性を有さないものであるため、起動時の摩擦が大きい、摩耗が進行するといった問題があった。
【0003】
【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、異物濃度の高い環境においても充分な耐摩耗性を有するとともに、起動時のドライ運転の条件下においても良好な摺動特性を有する水中用摺動部材ならびにその製造方法を提供することにある。
【0004】
【課題を解決するための手段】
本発明者らは、上記目的を達成すべく鋭意検討を重ねた結果、特定のフェノール樹脂組成物を含有する炭素繊維布を用いて摺動層を形成することにより、上記目的を達成し得るとの知見を得た。
【0005】
本発明は、上記知見に基づき完成されたものであり、その第一の要旨は、グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を含有した炭素繊維布の積層体からなる水中用摺動部材に存する。該積層体は円筒状であっても平板状であってもよい。
【0006】
本発明の第二の要旨は、(イ)グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を炭素繊維布に含浸せしめ乾燥して炭素繊維布プリプレグを製造する工程、(ロ)該炭素繊維布プリプレグを芯金に加熱加圧しながら所定の厚みになるまで巻きつけ円筒状積層体を形成する工程、(ハ)該円筒状積層体を芯金とともに加熱硬化処理する工程、からなる円筒状の水中用摺動部材の製造方法に存する。
【0007】
本発明の第三の要旨は、(イ)グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を炭素繊維布に含浸せしめ乾燥した後所定の寸法に裁断して炭素繊維布プリプレグを製造する工程、(ロ)該炭素繊維布プリプレグを所定の枚数重ね合わせて平板状積層体を形成する工程、(ハ)該平板状積層体を加圧しながら加熱硬化処理する工程、からなる平板状の水中用摺動部材の製造方法に存する。
【0008】
本発明の第四の要旨は、グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を含有した炭素繊維布の1層または2層以上からなる摺動層が、熱硬化性合成樹脂を含有したガラス繊維布の積層補強層に一体に接合されてなる水中用摺動部材に存する。このとき、円筒状の積層補強層の内周面に摺動層が一体に接合された構成、平板状の積層補強層上に摺動層が一体に接合された構成をとることができる。
【0009】
本発明の第五の要旨は、(イ)グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を炭素繊維布に含浸せしめ乾燥して炭素繊維布プリプレグを製造する工程、(ロ)該炭素繊維布プリプレグを芯金に加熱加圧しながら1層または2層以上巻きつけて摺動層を形成する工程、(ハ)該摺動層の外周に熱硬化性合成樹脂を含有したガラス繊維布プリプレグを加熱加圧しながら所定の厚みになるまで巻きつけ摺動層および積層補強層からなる円筒状積層体を形成する工程、(ニ)該円筒状積層体を芯金とともに加熱硬化処理する工程、からなる円筒状の水中用摺動部材の製造方法に存する。
【0010】
本発明の第六の要旨は、(イ)グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を炭素繊維布に含浸せしめ乾燥した後所定の寸法に裁断して炭素繊維布プリプレグを製造する工程、(ロ)熱硬化性合成樹脂を含有したガラス繊維布プリプレグを所定の大きさに裁断し所定の枚数重ね合わせ、その上に前記炭素繊維布プリプレグを1層または2層以上重ね合わせ平板状積層体を形成する工程、(ハ)該平板状積層体を加圧しながら加熱硬化処理する工程、からなる平板状の水中用摺動部材の製造方法に存する。
【0011】
【発明の実施の形態】
以下、本発明を説明する。先ず、炭素繊維布について説明する。本発明に用いる炭素繊維布としては従来公知の二次元織物を用いることができる。織物の形態としては、平織、斜文織、朱子織、バスケット織などが使用されるが、これらの中でも樹脂含浸性の点で平織、バスケット織が好ましい。具体的には、呉羽化学工業社製「クレカクロス(商品名)」、東レ社製「トレカクロス(商品名)」、東邦レーヨン社製「ベスファイトクロス(商品名)」等が挙げられる。
【0012】
フェノール樹脂としては、レゾール型、ノボラック型いずれであってもよいが、加熱のみによって硬化可能なレゾール型フェノール樹脂がプリプレグ作製時における取扱い性の点から好ましい。具体的には、群栄化学工業社製「レヂトップ(商品名)」、昭和高分子社製「ショウノール(商品名)」等が挙げられる。
【0013】
上記フェノール樹脂に配合される充填材としては、グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素が使用される。これらは単独または2種以上を組合わせて使用される。
【0014】
グラファイトは特に限定はされないが、鱗片状黒鉛、鱗状黒鉛、土状黒鉛等の天然黒鉛が好ましい。
【0015】
四フッ化エチレン樹脂としては、潤滑用四フッ化エチレン樹脂が好ましく、具体的には、三井デュポンフロロケミカル社製「TLP−10(商品名)」、ダイキン工業社製「ルブロンL−5(商品名)」、喜多村社製「KTL−8N(商品名)」等が挙げられる。
【0016】
無定形炭素としては、カーボンブラック、コークス粉末、炭化フェノール樹脂等が挙げられる。ここで、炭化フェノール樹脂とは、粒状のフェノール・ホルムアルデヒド樹脂を不活性雰囲気で400〜2200℃の高温焼成によって炭素化させたもので、例えば、鐘紡社製「ベルパールC−800(商品名)」、「ベルパールC−2000(商品名)」が挙げられる。
【0017】
上記充填材およびフェノール樹脂により炭素繊維布に含有させるフェノール樹脂組成物が形成されるが、フェノール樹脂組成物における充填材の配合割合は、5〜40重量%、好ましくは10〜40重量%、さらに好ましくは20〜30重量%である。5重量%より少ない場合は配合の効果が現われず、40重量%を超えて配合した場合は炭素繊維布同士の結合力が低下し摺動部材としての強度が不充分となってしまう。
【0018】
上記フェノール樹脂と充填材からなるフェノール樹脂組成物が炭素繊維布に含有されるのだが、フェノール樹脂組成物と炭素繊維布の配合比率は、重量比でフェノール樹脂組成物:炭素繊維布=80:20〜60:40である。フェノール樹脂組成物の配合割合が前記割合より多い場合は耐摩耗性が不充分となり、少ない場合は炭素繊維布同士の結合力が低下してしまう。
【0019】
積層補強層に使用されるガラス繊維布としては従来公知のものが使用され、このガラス繊維布に含有される熱硬化性合成樹脂としては、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂などが使用される。そして、この熱硬化性合成樹脂とガラス繊維布の配合割合は、熱硬化性合成樹脂:ガラス繊維布=40:60〜60:40が好ましい。熱硬化性合成樹脂の配合割合が前記割合より多い場合は補強層としての強度が不充分となり、少ない場合はガラス繊維布同士の結合力が低下し製造が困難となる。
【0020】
つぎに、上述した構成からなる摺動部材の製造方法について説明する。
【0021】
まず、グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材をフェノール樹脂ワニスと混合して、必要であればさらに溶剤を加えて混合して、固形分が50〜70重量%の含浸液を調製する。
【0022】
次にこの含浸液を基材である炭素繊維布に含浸させて、成形材料である炭素繊維布プリプレグを製造する。製造方法の一例を図1に示す。図において、ローラー5に巻きつけられた基材である炭素繊維布1が引き出され、含浸液2に浸漬された後、乾燥炉3を通して溶剤を飛ばして半硬化状態に乾燥される。こうして得られた成形材料としての炭素繊維布プリプレグ4をローラー6に巻きつける。
【0023】
得られた炭素繊維布プリプレグを用いて円筒状の摺動部材(軸受ブッシュ)を製造するには、ロールド成形法が適用される。ロールド成形法は、ローラー端面から見て、三角形を形成するように3本のローラーを平行に配設し、この3本のローラーで挟むように芯金を配し、この芯金にプリプレグを巻きつけ、芯金を一定方向に駆動回転させるとともに、芯金に接する各ローラーを芯金に従動するように回転させ、積層管を成形する方法である。ロールド成形法の概略を図2に示す。図1において得られた炭素繊維布プリプレグ4をローラー6より、予め80〜100℃に加温された加熱ローラー9、冷却ローラー10を介し、加圧ローラー8で2〜2.5kgf/mm(線圧に換算した値である)で加圧しながら、予め100〜110℃に加温された芯金7に連続的に所望の径まで巻きつけて円筒状積層体を製造する。
【0024】
得られた円筒状積層体を芯金とともに120〜180℃の雰囲気に調製された加熱炉に入れて硬化処理を行なう。この加熱硬化処理は一般には加圧することなく行なわれるが、必要に応じて加圧しながら行なってもよい。硬化処理終了後冷却して芯金を抜き取り、円筒状成形物を得る。このようにして得られた円筒状成形物は、用途に応じて適当な長さに切断し、内外径面および端面を切削加工することによって、フェノール樹脂組成物を含有する炭素繊維布の積層体からなる円筒状の摺動部材が得られる。
【0025】
外周側に熱硬化性合成樹脂を含有したガラス繊維布からなる積層補強層を設ける場合は、図3に示すように、芯金7にまず炭素繊維布プリプレグを1層または2層以上巻きつけ摺動層11を形成し、その外側に炭素繊維布プリプレグと同様の方法により得たガラス繊維布プリプレグ13を巻きつけて積層補強層12を形成する。こうして得られた円筒状積層体を加熱硬化処理した後、切削加工することにより、内周面にフェノール樹脂組成物を含有する炭素繊維布からなる摺動層を有し、外周側に熱硬化性合成樹脂を含有するガラス繊維布の積層補強層を有する円筒状の摺動部材を得ることができる。
【0026】
平板状の摺動部材(すべり板)を製造する場合は、図4に示すように、成形品形状に応じて様々な形に炭素繊維布プリプレグを裁断し、得られた板状の炭素繊維布プリプレグ21を必要な枚数だけ積み重ね、温度120〜180℃、圧力20〜40kgf/cmで加圧加熱成形を行なう。
【0027】
熱硬化性合成樹脂を含有したガラス繊維布からなる積層補強層を有するすべり板を製造する場合は、所望の寸法に裁断したガラス繊維布プリプレグを必要枚数積み重ね、その上に同様の寸法に裁断した炭素繊維布プリプレグを必要枚数積み重ねて、これを加圧加熱成形すればよい。
【0028】
【実施例】
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。
【0029】
<実施例1〜5、比較例1〜2>
固形分濃度が62重量%のフェノール樹脂ワニス(群栄化学工業社製「レヂトップPL−4222(商品名)」)および充填材を固形分組成が表1〜3に示す組成となるように混合し、この混合液にメタノールを加えて固形分濃度が60重量%の含浸液を調製した。図1に示す装置を用いて炭素繊維布に前記含浸液を含浸させた後、110〜140℃に雰囲気調整された乾燥炉を通して溶剤を飛ばし、フェノール樹脂および充填材からなるフェノール樹脂組成物が含浸された炭素繊維布プリプレグを製造した。
【0030】
この炭素繊維布プリプレグを用いて図2に示す装置によりロールド成形を行ない、得られた円筒状積層体を芯金とともに120〜180℃に雰囲気調整された加熱炉に入れて12時間程度加熱硬化処理せしめた後、冷却して芯金を抜き取り、機械加工して内径60mm、外径75mm、長さ60mmの円筒状摺動部材を得た。
【0031】
<実施例6〜7>
前述の実施例と同様にして固形分組成が表2に示す組成であるフェノール樹脂組成物が含有された炭素繊維布プリプレグを製造した。
【0032】
図2に示す装置を用いて、まず芯金の回りに前記炭素繊維布プリプレグを所定の厚さになるまで巻き付けて摺動層を形成し、その外周にエポキシ樹脂を50重量%含浸させたガラス繊維布プリプレグを巻き付けて円筒状積層体を得た。得られた円筒状積層体を芯金とともに120〜180℃に雰囲気調整された加熱炉に入れて12時間程度加熱硬化処理せしめた後、冷却して芯金を抜き取り、機械加工して内径60mm、外径75mm、長さ60mm、摺動層の厚さが2.5mm、積層補強層の厚さが5mmの円筒状摺動部材を得た。
【0033】
<比較例3>
固形分濃度が62重量%のフェノール樹脂ワニス(群栄化学工業社製「レヂトップPL−4222(商品名)」)および充填材を固形分組成が表3に示す組成となるように混合し、これに綿布の4mm角細片を加えて充分撹拌混合してフェノール樹脂組成物を綿布細布に含浸させ、加温して溶剤を飛ばして所定の縮合度に乾燥した。このようにして得られたものを成形材料として金型に入れ加熱加圧成形して内径60mm、外径75mm、長さ60mmの円筒状摺動部材を得た。
【0034】
表中、フェノール樹脂組成物の各成分の割合は重量%であり、フェノール樹脂組成物と炭素繊維布の配合比率は重量比である。また、無定形炭素としては、鐘紡社製炭化フェノール樹脂「ベルパールC−2000(商品名)」を使用した。(以下余白)
【0035】
【表1】

Figure 0004519355
(以下余白)
【0036】
【表2】
Figure 0004519355
(以下余白)
【0037】
【表3】
Figure 0004519355
【0038】
上述した実施例1〜7および比較例1〜3で作製した円筒状摺動部材について、表4に示す条件で異物の存在する水中での累積負荷試験を行なった。表5〜6に各荷重における摩擦係数および試験終了後の摩耗量を示す。摩擦係数は各荷重において終了直前の値を示し、摩耗量は摺動部材の寸法変化量で示した。
【0039】
【表4】
<ジャーナル試験1>
すべり速度:5m/sec
荷重:初期荷重5kgf/cmで30分毎に5kgf/cmずつ累積して最大15kgf/cm
相手材:タングステンカーバイド
試験時間:90分
潤滑:JIS1種ケイ砂が3000ppm含まれる水中
【0040】
【表5】
Figure 0004519355
(以下余白)
【0041】
【表6】
Figure 0004519355
【0042】
以上の結果より、本発明による摺動部材はいずれも良好な摺動特性を示した。特に摩耗量が少ないという特徴を有する。これに対して、比較例の摺動部材は、摩擦係数は本発明の摺動部材とあまり変わらぬ値を示すものの、摩耗量が多かった。
【0043】
また、ドライ条件での性能を調べるために表7に示す条件にて評価を行なった。その結果を表8〜9に示す。摩擦係数は試験開始後5分経過以降の安定後の摩擦係数を示し、摩耗量は試験終了後の摺動部材の寸法変化量で示した。
【0044】
【表7】
<ジャーナル試験2>
すべり速度:5m/sec
荷重:1kgf/cm
相手材:タングステンカーバイド
試験時間:60分
潤滑:無潤滑(ドライ)
【0045】
【表8】
Figure 0004519355
【0046】
【表9】
Figure 0004519355
【0047】
以上の結果より、本発明による摺動部材はドライ条件においても良好な摺動特性を示した。これに対して、比較例1の摺動部材は試験開始後7分で摩擦係数が0.3を超えたため試験を中止した。表の摩擦係数は摩擦係数が上昇する直前の値である。試験を途中で中止したため摩耗量は測定しなかった。比較例2の摺動部材は摩擦係数は低い値を示すものの摩耗量が多かった。比較例3の摺動部材は摩擦係数も高く、摩耗量も多かった。
【0048】
【発明の効果】
本発明の請求項1に記載された水中用摺動部材によれば、炭素繊維布を用いたことにより摺動面の表面硬度が向上するので、耐摩耗性が高められる。また、耐吸水性が向上するので、水中での使用において摺動部材の膨潤が抑えられ、膨潤に起因する寸法変化、これによる相手材への抱きつき、さらには焼付きなどの発生を防止できる。さらに、熱伝導性も向上するので、いっそう焼付きの防止に効果を発揮する。また、炭素繊維布にグラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂組成物からなるフェノール樹脂組成物を含有した構成としたので、異物濃度の高い水中においても充分な耐摩耗性を有するとともに、ドライ条件においても良好な摺動特性を示す。
【0049】
ここで、フェノール樹脂組成物と炭素繊維布の配合比率を重量比で、フェノール樹脂組成物:炭素繊維布=80:20〜60:40とした場合、積層された炭素繊維布間の結合力を向上させる。
【0050】
本発明の請求項5に記載の製造方法によれば、円筒状の水中用摺動部材を得ることができ、ロールド成形法を用いているので大口径の摺動部材も容易に得ることができる。
【0051】
本発明の請求項6に記載の製造方法によれば、平板状の水中用摺動部材が得られる。
【0052】
本発明の請求項8に記載された水中用摺動部材によれば、摺動特性に重要な摺動層のみをフェノール樹脂組成物を含有した炭素繊維布で構成し、摺動層以外を熱硬化性合成樹脂を含有したガラス繊維布で構成したので、炭素繊維布のみを使用した場合に比較して、摺動部材全体の強度が向上するとともに、寸法変化量がさらに低く抑えられる。
【0053】
本発明の請求項12に記載の製造方法によれば、円筒状の積層補強層の内周面に摺動層が一体に接合されてなる、円筒状の水中用摺動部材が得られる。
【0054】
本発明の請求項13の製造方法によれば、平板状の積層補強層の上に摺動層が一体に接合されてなる、平板状の水中用摺動部材が得られる。
【図面の簡単な説明】
【図1】本発明のプリプレグの製造方法の一例を示す図である。
【図2】本発明の円筒状の摺動部材を製造するロールド成形法の説明図である。
【図3】本発明の円筒状の積層補強層の内周面に摺動層を有する摺動部材の説明図である。
【図4】本発明の平板状の摺動部材の説明図である。
【符号の説明】
4 成形材料(炭素繊維布プリプレグ)
7 芯金
8 加圧ローラー
9 加熱ローラー
10 冷却ローラー
11 摺動層
12 積層補強層[0001]
[Technical field to which the invention belongs]
The present invention relates to an underwater sliding member suitable for use in bearings, sliding plates, thrust washers, and the like, and a method for manufacturing the same.
[0002]
[Prior art]
Conventionally, an underwater bearing made of a phenol resin using a cotton cloth as a reinforcing base material is well known. However, sufficient performance could not be obtained when used in an environment with a high foreign matter concentration such as earth and sand. Further, when used for a pump or the like, the operation is performed under dry conditions although it is a short time at the time of starting. However, since the conventional reinforcing base material itself and the phenol resin itself have no lubricity, there are problems that the friction at the time of starting is large and the wear progresses.
[0003]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and its purpose is to have sufficient wear resistance even in an environment where the concentration of foreign matter is high and to have good sliding characteristics even under conditions of dry operation at startup. An object is to provide an underwater sliding member and a method of manufacturing the same.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors can achieve the above object by forming a sliding layer using a carbon fiber cloth containing a specific phenol resin composition. I got the knowledge.
[0005]
The present invention has been completed based on the above findings, and the first gist thereof is one or more fillers 5 selected from graphite, tetrafluoroethylene resin, boron nitride, and amorphous carbon. It exists in the sliding member for water which consists of a laminated body of the carbon fiber cloth containing the phenol resin composition which consists of -40 weight% and remainder phenol resin. The laminate may be cylindrical or flat.
[0006]
The second gist of the present invention is (i) composed of 5 to 40% by weight of one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon, and the balance phenol resin. A step of impregnating a carbon fiber cloth with a phenol resin composition and drying to produce a carbon fiber cloth prepreg; (b) a cylindrical laminate in which the carbon fiber cloth prepreg is wound on a core metal to a predetermined thickness while being heated and pressed; A method for producing a cylindrical underwater sliding member comprising a step of forming a body, and (c) a step of heat-curing the cylindrical laminated body together with a cored bar.
[0007]
The third gist of the present invention consists of (i) 5 to 40% by weight of one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon, and the balance phenol resin. A step of impregnating a carbon fiber cloth with a phenol resin composition and drying, and then cutting to a predetermined size to produce a carbon fiber cloth prepreg; (b) a predetermined number of the carbon fiber cloth prepregs are stacked to form a flat laminate. The present invention resides in a method for producing a flat plate-shaped underwater sliding member comprising: a step of forming; and (c) a step of heating and curing the flat plate-like laminate while applying pressure.
[0008]
The fourth gist of the present invention is a phenol resin composition comprising 5 to 40% by weight of one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon, and the balance phenol resin. A sliding layer composed of one layer or two or more layers of a carbon fiber cloth containing an object is present in an underwater sliding member integrally joined to a laminated reinforcing layer of a glass fiber cloth containing a thermosetting synthetic resin. . At this time, a configuration in which the sliding layer is integrally joined to the inner peripheral surface of the cylindrical laminated reinforcing layer, or a configuration in which the sliding layer is integrally joined to the flat laminated reinforcing layer can be adopted.
[0009]
The fifth gist of the present invention consists of (i) 5 to 40% by weight of one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon, and the balance phenol resin. A step of impregnating a carbon fiber cloth with a phenol resin composition and drying to produce a carbon fiber cloth prepreg, (b) sliding the carbon fiber cloth prepreg while winding the carbon fiber cloth prepreg on a core metal while heating one or more layers A step of forming a layer; (c) a glass fiber cloth prepreg containing a thermosetting synthetic resin on the outer periphery of the sliding layer is wound with heating and pressurizing until it reaches a predetermined thickness, and is composed of a sliding layer and a laminated reinforcing layer The present invention resides in a method of manufacturing a cylindrical underwater sliding member comprising a step of forming a cylindrical laminate, and (d) a step of heat-curing the cylindrical laminate with a core.
[0010]
The sixth gist of the present invention consists of (a) 5 to 40% by weight of one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon, and the balance phenol resin. A step of producing a carbon fiber cloth prepreg by impregnating a carbon fiber cloth with a phenolic resin composition and drying it, and then cutting to a predetermined size; (b) a glass fiber cloth prepreg containing a thermosetting synthetic resin having a predetermined size; A step of forming a flat laminate by stacking the carbon fiber cloth prepreg on one or more layers, and (c) heat curing treatment while pressing the flat laminate. The manufacturing method of the flat member for underwater sliding which consists of a process to carry out.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described below. First, the carbon fiber cloth will be described. A conventionally known two-dimensional fabric can be used as the carbon fiber cloth used in the present invention. As the form of the woven fabric, a plain weave, a diagonal weave, a satin weave, a basket weave, and the like are used. Among these, a plain weave and a basket weave are preferable in terms of resin impregnation. Specifically, “Kureka Cloth (trade name)” manufactured by Kureha Chemical Industry Co., Ltd. “Toray Cloth (trade name)” manufactured by Toray Industries, Inc., “Beth Fight Cloth (trade name)” manufactured by Toho Rayon Co., Ltd. and the like can be mentioned.
[0012]
The phenolic resin may be either a resol type or a novolac type, but a resol type phenolic resin that can be cured only by heating is preferable from the viewpoint of handling at the time of preparing a prepreg. Specifically, “Resitop (trade name)” manufactured by Gunei Chemical Industry Co., Ltd., “Shonol (trade name)” manufactured by Showa Polymer Co., Ltd. and the like can be mentioned.
[0013]
As the filler blended with the phenol resin, graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon are used. These are used alone or in combination of two or more.
[0014]
The graphite is not particularly limited, but natural graphite such as scaly graphite, scaly graphite, and earthy graphite is preferable.
[0015]
As the tetrafluoroethylene resin, a tetrafluoroethylene resin for lubrication is preferable. Specifically, “TLP-10 (trade name)” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Lublon L-5 (commercial product) manufactured by Daikin Industries, Ltd.” Name) "," KTL-8N (trade name) "manufactured by Kitamura, and the like.
[0016]
Examples of amorphous carbon include carbon black, coke powder, and carbonized phenol resin. Here, the carbonized phenol resin is obtained by carbonizing granular phenol / formaldehyde resin by high-temperature firing at 400 to 2200 ° C. in an inert atmosphere. For example, “Bell Pearl C-800 (trade name)” manufactured by Kanebo Co., Ltd. , “Bellepearl C-2000 (trade name)”.
[0017]
The phenol resin composition to be contained in the carbon fiber cloth is formed by the filler and the phenol resin, but the blending ratio of the filler in the phenol resin composition is 5 to 40% by weight, preferably 10 to 40% by weight, Preferably it is 20-30 weight%. When the amount is less than 5% by weight, the effect of blending does not appear. When the amount exceeds 40% by weight, the bonding strength between the carbon fiber cloths is lowered, and the strength as a sliding member becomes insufficient.
[0018]
The phenol resin composition composed of the phenol resin and the filler is contained in the carbon fiber cloth. The mixing ratio of the phenol resin composition and the carbon fiber cloth is phenol resin composition: carbon fiber cloth = 80 by weight ratio. 20-60: 40. When the blending ratio of the phenol resin composition is larger than the above ratio, the wear resistance is insufficient, and when it is small, the bonding strength between the carbon fiber cloths is lowered.
[0019]
As the glass fiber cloth used for the laminated reinforcing layer, conventionally known ones are used, and as the thermosetting synthetic resin contained in the glass fiber cloth, phenol resin, epoxy resin, unsaturated polyester resin, etc. are used. The And as for the mixture ratio of this thermosetting synthetic resin and glass fiber cloth, thermosetting synthetic resin: glass fiber cloth = 40: 60-60: 40 is preferable. When the blending ratio of the thermosetting synthetic resin is larger than the above ratio, the strength as the reinforcing layer is insufficient, and when the blending ratio is small, the bonding strength between the glass fiber cloths is lowered and the production becomes difficult.
[0020]
Below, the manufacturing method of the sliding member which consists of the structure mentioned above is demonstrated.
[0021]
First, one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon are mixed with a phenol resin varnish, and if necessary, a solvent is added and mixed. An impregnating solution having a solid content of 50 to 70% by weight is prepared.
[0022]
Next, the impregnating liquid is impregnated into a carbon fiber cloth as a base material to produce a carbon fiber cloth prepreg as a molding material. An example of the manufacturing method is shown in FIG. In the figure, the carbon fiber cloth 1 which is a base material wound around a roller 5 is drawn out and immersed in the impregnating liquid 2, and then the solvent is blown off through a drying furnace 3 to be dried in a semi-cured state. A carbon fiber cloth prepreg 4 as a molding material thus obtained is wound around a roller 6.
[0023]
In order to manufacture a cylindrical sliding member (bearing bush) using the obtained carbon fiber cloth prepreg, a rolled molding method is applied. In the rolled molding method, three rollers are arranged in parallel so as to form a triangle when viewed from the roller end face, and a core metal is arranged so as to be sandwiched between the three rollers, and a prepreg is wound around the core metal. In this method, the cored bar is driven and rotated in a certain direction, and each roller in contact with the cored bar is rotated so as to follow the cored bar, thereby forming a laminated tube. An outline of the rolled forming method is shown in FIG. The carbon fiber cloth prepreg 4 obtained in FIG. 1 is heated by a pressure roller 8 through a heating roller 9 and a cooling roller 10 that are preheated to 80 to 100 ° C. from a roller 6 and 2 to 2.5 kgf / mm (line A cylindrical laminated body is manufactured by continuously winding a cored bar 7 preliminarily heated to 100 to 110 ° C. to a desired diameter while pressurizing at a predetermined pressure.
[0024]
The obtained cylindrical laminate is put together with a cored bar in a heating furnace prepared in an atmosphere of 120 to 180 ° C. to perform a curing process. This heat-curing treatment is generally performed without applying pressure, but may be performed while applying pressure as necessary. After completion of the curing process, the core is removed by cooling to obtain a cylindrical molded product. The cylindrical molded product thus obtained is cut into an appropriate length according to the application, and the inner and outer diameter surfaces and the end surface are cut to form a laminate of a carbon fiber cloth containing a phenol resin composition. A cylindrical sliding member is obtained.
[0025]
When a laminated reinforcing layer made of glass fiber cloth containing a thermosetting synthetic resin is provided on the outer peripheral side, as shown in FIG. 3, first, one or more layers of carbon fiber cloth prepreg are wound around the core metal 7 A dynamic layer 11 is formed, and a glass fiber cloth prepreg 13 obtained by the same method as that of the carbon fiber cloth prepreg is wound around the outside to form a laminated reinforcing layer 12. The cylindrical laminate thus obtained is heat-cured and then cut to have a sliding layer made of a carbon fiber cloth containing a phenolic resin composition on the inner peripheral surface and thermosetting on the outer peripheral side. A cylindrical sliding member having a laminated reinforcing layer of glass fiber cloth containing a synthetic resin can be obtained.
[0026]
When producing a flat sliding member (sliding plate), as shown in FIG. 4, the carbon fiber cloth prepreg is cut into various shapes according to the shape of the molded product, and the obtained plate-like carbon fiber cloth is obtained. The required number of prepregs 21 are stacked, and pressure heating molding is performed at a temperature of 120 to 180 ° C. and a pressure of 20 to 40 kgf / cm 2 .
[0027]
When manufacturing a sliding plate having a laminated reinforcing layer made of glass fiber cloth containing a thermosetting synthetic resin, a necessary number of glass fiber cloth prepregs cut to a desired size are stacked, and then cut to the same size. A necessary number of carbon fiber cloth prepregs may be stacked, and this may be pressure-heat-molded.
[0028]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the summary is exceeded.
[0029]
<Examples 1-5, Comparative Examples 1-2>
A phenol resin varnish (“Resitop PL-4222 (trade name)” manufactured by Gunei Chemical Industry Co., Ltd.) having a solid content concentration of 62% by weight and a filler were mixed so that the solid content composition was as shown in Tables 1 to 3. Then, methanol was added to the mixed solution to prepare an impregnating solution having a solid concentration of 60% by weight. After impregnating the carbon fiber cloth with the impregnation liquid using the apparatus shown in FIG. 1, the solvent is blown through a drying furnace whose atmosphere is adjusted to 110 to 140 ° C., and the phenol resin composition comprising the phenol resin and the filler is impregnated. A carbon fiber cloth prepreg was produced.
[0030]
Using this carbon fiber cloth prepreg, roll forming is performed by the apparatus shown in FIG. 2, and the obtained cylindrical laminate is put together with a cored bar in a heating furnace whose atmosphere is adjusted to 120 to 180 ° C. for about 12 hours. After caulking, the metal core was removed by cooling and machined to obtain a cylindrical sliding member having an inner diameter of 60 mm, an outer diameter of 75 mm, and a length of 60 mm.
[0031]
<Examples 6 to 7>
A carbon fiber cloth prepreg containing a phenol resin composition having a solid content composition shown in Table 2 was produced in the same manner as in the above-described Examples.
[0032]
Using the apparatus shown in FIG. 2, first, a glass fiber cloth prepreg is wound around a metal core to a predetermined thickness to form a sliding layer, and the outer periphery is impregnated with 50% by weight of epoxy resin. A fiber cloth prepreg was wound to obtain a cylindrical laminate. The obtained cylindrical laminated body was put together with a cored bar in a heating furnace whose atmosphere was adjusted to 120 to 180 ° C. and heat-cured for about 12 hours, then cooled and extracted, and machined to have an inner diameter of 60 mm, A cylindrical sliding member having an outer diameter of 75 mm, a length of 60 mm, a sliding layer thickness of 2.5 mm, and a laminated reinforcing layer thickness of 5 mm was obtained.
[0033]
<Comparative Example 3>
A phenol resin varnish (“Resitop PL-4222 (trade name)” manufactured by Gunei Chemical Industry Co., Ltd.) having a solid content concentration of 62% by weight and a filler were mixed so that the solid content composition was as shown in Table 3. A 4 mm square strip of cotton cloth was added to the mixture, and the mixture was sufficiently stirred and impregnated to impregnate the cotton resin cloth with a phenol resin composition, heated to remove the solvent and dried to a predetermined degree of condensation. The product thus obtained was placed in a mold as a molding material and heated and pressed to obtain a cylindrical sliding member having an inner diameter of 60 mm, an outer diameter of 75 mm, and a length of 60 mm.
[0034]
In the table, the proportion of each component of the phenol resin composition is wt%, and the blending ratio of the phenol resin composition and the carbon fiber cloth is a weight ratio. In addition, as amorphous carbon, a carbonized phenol resin “Bellpearl C-2000 (trade name)” manufactured by Kanebo Co., Ltd. was used. (The following margin)
[0035]
[Table 1]
Figure 0004519355
(The following margin)
[0036]
[Table 2]
Figure 0004519355
(The following margin)
[0037]
[Table 3]
Figure 0004519355
[0038]
The cylindrical sliding members produced in Examples 1 to 7 and Comparative Examples 1 to 3 described above were subjected to a cumulative load test in water where foreign substances existed under the conditions shown in Table 4. Tables 5 to 6 show the friction coefficient at each load and the wear amount after the test. The coefficient of friction indicates the value immediately before the end of each load, and the amount of wear is indicated by the dimensional change of the sliding member.
[0039]
[Table 4]
<Journal Exam 1>
Sliding speed: 5m / sec
Load: Maximum cumulative with initial load 5 kgf / cm 2 every 30 minutes by 5kgf / cm 2 15kgf / cm 2
Counterpart material: Tungsten carbide Test time: 90 minutes Lubrication: Underwater containing 3000 ppm of JIS class 1 silica sand
[Table 5]
Figure 0004519355
(The following margin)
[0041]
[Table 6]
Figure 0004519355
[0042]
From the above results, all the sliding members according to the present invention showed good sliding characteristics. In particular, the amount of wear is small. In contrast, the sliding member of the comparative example had a large amount of wear although the coefficient of friction was not much different from that of the sliding member of the present invention.
[0043]
Moreover, in order to investigate the performance under dry conditions, evaluation was performed under the conditions shown in Table 7. The results are shown in Tables 8-9. The coefficient of friction indicates the coefficient of friction after stabilization 5 minutes after the start of the test, and the amount of wear is indicated by the dimensional change of the sliding member after the end of the test.
[0044]
[Table 7]
<Journal Exam 2>
Sliding speed: 5m / sec
Load: 1 kgf / cm 2
Counterpart material: Tungsten carbide Test time: 60 minutes Lubrication: No lubrication (dry)
[0045]
[Table 8]
Figure 0004519355
[0046]
[Table 9]
Figure 0004519355
[0047]
From the above results, the sliding member according to the present invention showed good sliding characteristics even under dry conditions. In contrast, the sliding member of Comparative Example 1 was stopped because the coefficient of friction exceeded 0.3 after 7 minutes from the start of the test. The friction coefficient in the table is the value immediately before the friction coefficient increases. The amount of wear was not measured because the test was stopped midway. Although the sliding member of Comparative Example 2 showed a low friction coefficient, the amount of wear was large. The sliding member of Comparative Example 3 had a high coefficient of friction and a large amount of wear.
[0048]
【The invention's effect】
According to the underwater sliding member described in claim 1 of the present invention, since the surface hardness of the sliding surface is improved by using the carbon fiber cloth, the wear resistance is enhanced. In addition, since the water absorption resistance is improved, the sliding member can be prevented from swelling when used in water, and dimensional change due to swelling, hugging to a counterpart material, and further seizure can be prevented. Furthermore, since the thermal conductivity is improved, it is more effective in preventing seizure. Also, a phenol resin composition comprising 5 to 40% by weight of one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon on the carbon fiber cloth and the remainder phenol resin composition. Therefore, it has sufficient wear resistance even in water with a high concentration of foreign matter, and exhibits good sliding characteristics even under dry conditions.
[0049]
Here, when the blending ratio of the phenol resin composition and the carbon fiber cloth is weight ratio, and the phenol resin composition: carbon fiber cloth = 80: 20 to 60:40, the bonding strength between the laminated carbon fiber cloths is Improve.
[0050]
According to the manufacturing method of the fifth aspect of the present invention, a cylindrical underwater sliding member can be obtained, and since a rolled molding method is used, a large-diameter sliding member can be easily obtained. .
[0051]
According to the manufacturing method of the sixth aspect of the present invention, a flat underwater sliding member is obtained.
[0052]
According to the underwater sliding member described in claim 8 of the present invention, only the sliding layer important for the sliding characteristics is composed of the carbon fiber cloth containing the phenol resin composition, and the rest of the sliding layer is heated. Since it comprised with the glass fiber cloth containing curable synthetic resin, compared with the case where only a carbon fiber cloth is used, while the intensity | strength of the whole sliding member improves, a dimensional change amount is further suppressed low.
[0053]
According to the manufacturing method of the twelfth aspect of the present invention, a cylindrical underwater sliding member is obtained in which the sliding layer is integrally joined to the inner peripheral surface of the cylindrical laminated reinforcing layer.
[0054]
According to the manufacturing method of the thirteenth aspect of the present invention, a flat plate-like underwater sliding member is obtained in which a sliding layer is integrally joined on a flat plate-like laminated reinforcing layer.
[Brief description of the drawings]
FIG. 1 is a diagram showing an example of a method for producing a prepreg of the present invention.
FIG. 2 is an explanatory view of a rolled forming method for producing a cylindrical sliding member of the present invention.
FIG. 3 is an explanatory view of a sliding member having a sliding layer on the inner peripheral surface of the cylindrical laminated reinforcing layer of the present invention.
FIG. 4 is an explanatory diagram of a flat sliding member of the present invention.
[Explanation of symbols]
4 Molding material (carbon fiber cloth prepreg)
7 Core Bar 8 Pressure Roller 9 Heating Roller 10 Cooling Roller 11 Sliding Layer 12 Laminated Reinforcement Layer

Claims (7)

グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を含有した炭素繊維布の1層または2層以上からなる摺動層が、熱硬化性合成樹脂を含有したガラス繊維布の積層補強層に一体に接合されてなることを特徴とする水中用摺動部材。1 of the carbon fiber cloth containing the phenol resin composition which consists of 5 to 40 weight% of 1 type, or 2 or more types of fillers selected from graphite, tetrafluoroethylene resin, boron nitride, and amorphous carbon, and the remainder phenol resin. A sliding member for underwater, wherein a sliding layer comprising two or more layers is integrally joined to a laminated reinforcing layer of glass fiber cloth containing a thermosetting synthetic resin. 円筒状の積層補強層の内周面に摺動層が一体に接合されてなる請求項に記載の水中用摺動部材。Underwater sliding member according to claim 1, the sliding layer on the inner peripheral surface of the cylindrical laminated reinforcing layer are bonded together. 平板状の積層補強層上に摺動層が一体に接合されてなる請求項に記載の水中用摺動部材。Underwater sliding member according to claim 1, the sliding layer are integrally joined to the plate-shaped laminated reinforcing layer. フェノール樹脂組成物と炭素繊維布の配合比率が、重量比でフェノール樹脂組成物:炭素繊維布=80:20〜60:40である請求項1〜3のいずれか一項に記載の水中用摺動部材。The underwater slide according to any one of claims 1 to 3 , wherein a mixing ratio of the phenol resin composition and the carbon fiber cloth is phenol resin composition: carbon fiber cloth = 80: 20 to 60:40 by weight ratio. A moving member. (イ)グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を炭素繊維布に含浸せしめ乾燥して炭素繊維布プリプレグを製造する工程、
(ロ)該炭素繊維布プリプレグを芯金に加熱加圧しながら1層または2層以上巻きつけて摺動層を形成する工程、
(ハ)該摺動層の外周に熱硬化性合成樹脂を含有したガラス繊維布プリプレグを加熱加圧しながら所定の厚みになるまで巻きつけ摺動層および積層補強層からなる円筒状積層体を形成する工程、
(ニ)該円筒状積層体を芯金とともに加熱硬化処理する工程、
からなることを特徴とする円筒状の水中用摺動部材の製造方法。
(I) A carbon fiber cloth is formed of a phenol resin composition comprising 5 to 40% by weight of one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon, and the remaining phenol resin. Impregnating and drying to produce a carbon fiber cloth prepreg,
(B) A step of forming a sliding layer by winding the carbon fiber cloth prepreg on one or more layers while heating and pressing the core metal.
(C) A glass fiber cloth prepreg containing a thermosetting synthetic resin is wound around the outer periphery of the sliding layer while being heated and pressurized to a predetermined thickness to form a cylindrical laminate composed of a sliding layer and a laminated reinforcing layer. The process of
(D) a step of heat-curing the cylindrical laminate together with a cored bar,
A method for producing a cylindrical underwater sliding member, comprising:
(イ)グラファイト、四フッ化エチレン樹脂、窒化ホウ素および無定形炭素から選択される1種または2種以上の充填材5〜40重量%と残部フェノール樹脂からなるフェノール樹脂組成物を炭素繊維布に含浸せしめ乾燥した後所定の寸法に裁断して炭素繊維布プリプレグを製造する工程、
(ロ)熱硬化性合成樹脂を含有したガラス繊維布プリプレグを所定の大きさに裁断し所定の枚数重ね合わせ、その上に前記炭素繊維布プリプレグを1層または2層以上重ね合わせ平板状積層体を形成する工程、
(ハ)該平板状積層体を加圧しながら加熱硬化処理する工程、
からなることを特徴とする平板状の水中用摺動部材の製造方法。
(I) A carbon fiber cloth is formed of a phenol resin composition comprising 5 to 40% by weight of one or more fillers selected from graphite, tetrafluoroethylene resin, boron nitride and amorphous carbon, and the remaining phenol resin. A step of producing a carbon fiber cloth prepreg by impregnating and drying and then cutting to a predetermined size;
(B) A glass fiber cloth prepreg containing a thermosetting synthetic resin is cut into a predetermined size and a predetermined number of sheets are stacked, and one or more carbon fiber cloth prepregs are stacked thereon to form a flat laminate. Forming a process,
(C) a step of heat-curing while pressing the flat laminate,
A method for producing a flat underwater sliding member, comprising:
フェノール樹脂組成物と炭素繊維布の配合比率が、重量比でフェノール樹脂組成物:炭素繊維布=80:20〜60:40である請求項またはに記載の水中用摺動部材の製造方法。The method for producing an underwater sliding member according to claim 5 or 6 , wherein a mixing ratio of the phenol resin composition and the carbon fiber cloth is phenol resin composition: carbon fiber cloth = 80: 20 to 60:40 in weight ratio. .
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