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JP3527093B2 - グリース組成物 - Google Patents

グリース組成物

Info

Publication number
JP3527093B2
JP3527093B2 JP08413398A JP8413398A JP3527093B2 JP 3527093 B2 JP3527093 B2 JP 3527093B2 JP 08413398 A JP08413398 A JP 08413398A JP 8413398 A JP8413398 A JP 8413398A JP 3527093 B2 JP3527093 B2 JP 3527093B2
Authority
JP
Japan
Prior art keywords
fatty acid
grease composition
ester
grease
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP08413398A
Other languages
English (en)
Other versions
JPH11279578A (ja
Inventor
秀樹 小泉
敦 横内
賢一 磯
道治 中
敏明 遠藤
淳 柴山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NSK Ltd
Kyodo Yushi Co Ltd
Original Assignee
NSK Ltd
Kyodo Yushi Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NSK Ltd, Kyodo Yushi Co Ltd filed Critical NSK Ltd
Priority to JP08413398A priority Critical patent/JP3527093B2/ja
Priority to US09/280,678 priority patent/US6251841B1/en
Priority to DE19914498A priority patent/DE19914498B4/de
Publication of JPH11279578A publication Critical patent/JPH11279578A/ja
Application granted granted Critical
Publication of JP3527093B2 publication Critical patent/JP3527093B2/ja
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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Description

【発明の詳細な説明】
【０００１】
【発明の属する技術分野】本発明はグリース組成物に関
し、特に錆止め性能の改善を図ったグリース組成物に関
するものである。より詳しくは、自動車電装部品のよう
に走行中における、路上の水、塩水或いは海水などの侵
入により、また製鉄産業では、冷却水の侵入により、錆
の発生が問題となる転がり軸受などの潤滑部に使用され
るグリース組成物に関するものである。
【０００２】
【従来の技術】錆の発生が問題となる転がり軸受など
は、適当なシールやその他機構上の対策によって、錆の
原因となる物質の侵入を防いでいる。例えば自動車にお
いては、軸受を直接泥水がかからない位置に配置した
り、泥よけ等を取り付けたりの対策が行われている。さ
らに防塵性を付与したシール板の採用により、軸受内部
への侵入を防いでいる。しかしながら、転がり軸受は、
その機構上完全な密封化は不可能であるため、錆止め性
能が付与された潤滑グリースを使用することが通常であ
る。
【０００３】錆止め性能の付与には、通常、グリースに
錆止め剤と呼ばれる物質を添加することが行われる。錆
止め剤としては、クロム酸塩や亜硝酸塩、モリブデン酸
塩、タングステン酸塩等、特にこれらのナトリウム塩か
らなる無機不働態化剤が、その性能の高さから広く使用
されている。とりわけ、亜硝酸ナトリウムは最も効果的
であり、主流となっている。また、無機不働態化剤は水
溶性であり、グリースのように油系のものには分散し難
いことから、界面活性剤を併用させたグリースも市販さ
れている。また、有機系の錆止め剤も使用されており、
これらは親油性有機インヒビターとも呼ばれている。例
えば、スルホン酸塩やカルボン酸塩等が親油性有機イン
ヒビターとして代表的である。しかし、この親油性有機
インヒビターは、それ単独での錆止め性能は無機不働態
化剤ほど強力ではなく、特に塩水条件下では不十分であ
ることから、無機不働態化剤との併用、更には界面活性
剤を併用したグリースもある。この油溶性有機インヒビ
ターと無機不働態化剤、更には界面活性剤を併用したグ
リースは、無機不働態化剤を単独使用したグリースより
も優れた錆止め性能を有する。
【０００４】
【発明が解決しようとする課題】しかしながら、無機不
働態化剤として代表的な亜硝酸ナトリウムは、優れた錆
止め性能を有する一方で、使用条件によっては動植物に
影響を与える可能もあり、出来ればその使用を避けた方
が望ましいとされている。
【０００５】一方において、グリースに対する錆止め性
能の要求は近年、特に厳しさを増している。例えば、自
動車では、海岸での走行や、路面凍結防止のために食塩
を散布した道路での走行等、使用の多様化に伴ってグリ
ースに対する錆止め性能の要求が強くなってきている。
また、製鉄産業においても、連続鋳造設備で使用される
モールディングパウダーの変遷によって、冷却水中にそ
の成分の一部が溶解し、圧延ローラに組み込まれた軸受
の発錆を促進させていることから、グリースに対する錆
止め性能の向上が同様に求められている。
【０００６】以上のように、近年では錆止め性能ととも
に安全性も求められる傾向にあるが、これらを同時に満
足するようなグリースは無いのが現状であり、本発明は
これを解決することを目的とする。
【０００７】
【課題を解決するための手段】本発明は、上記課題を解
決すべく鋭意検討した結果達成されたものであり、潤滑
基油及び増ちょう剤からなるグリース組成物に、Ａ）カ
ルボン酸、カルボン酸塩、スルホン酸塩、アミンまたは
これらを組み合わせた混合物からなる親油性有機インヒ
ビターと、Ｂ）ドデカン酸、セバシン酸及びホウ酸の少
なくとも１種とジエタノールアミン、アミノテトラゾー
ル及びジエチルアミノエタノールの少なくとも１種との
塩、ラノリン脂肪酸ポリエチレングリコールエステル、
ラノリン脂肪酸アミンエステル、ラノリン脂肪酸アルカ
ノールアマイド、またはこれらを組み合わせた混合物か
らなる親水性有機インヒビターと、Ｃ）非イオン系界面
活性剤とを、各々該グリース組成物全量の０．１〜１０
重量％となるように配合したことを特徴とするグリース
組成物に関するものである。即ち、本発明は、特定の親
水性有機インヒビターを親油性有機インヒビター及び非
イオン系界面活性剤と併用することで、従来より特に錆
止め性能に優れているとされている亜硝酸ナトリウムを
含むグリース組成物と同等以上の錆止め性能を有するグ
リース組成物を得たものである。
【０００８】本発明のグリース組成物における親油性有
機インヒビター、親水性有機インヒビター、界面活性剤
の組み合わせは、各々の持つ錆止め能力以上の効果を発
揮する。いわゆる相乗効果と呼ばれるものだが、これ
は、各々の成分が持っている錆止め能力に加え、他の成
分が効果的に働ける作用を示すものと考えられる。本発
明に使用した界面活性剤は、発錆の原因となる水をグリ
ース基油中に、エマルジョンとして取り込み、親油性有
機インヒビターと水に含まれる腐食物質の金属表面上で
の交換を妨げる。また、そのエマルジョン中に親水性有
機インヒビターも取り込んでおり、さらに発錆を抑制す
ることができる。従って、本発明による親油性有機イン
ヒビター、親水性有機インヒビター、界面活性剤の組み
合わせによって、単独の使用で考えられるよりはるかに
大きく、無機不働態化剤と同等以上の錆止め性能を有す
るグリースを提供することができる。
【０００９】
【発明の実施の形態】以下、本発明のグリース組成物に
関して詳細に説明する。本発明のグリース組成物では、
錆止め剤として親油性有機インヒビターと親水性有機イ
ンヒビターとを併用する。親油性有機インヒビターとし
て、カルボン酸、カルボン酸塩、スルホン酸塩、アミン
を用いる。この親油性有機インヒビターは、極性基を金
属表面（例えば、軸受の内輪や外輪、転動体）に向けて
配列した状態で吸着することにより防錆被膜を形成する
とされている。本発明においては、中でも有機スルホン
酸塩を好適に使用する。この有機スルホン酸塩は一般式
「ＲＳＯ3 ・Ｍ」で表されるもので、酸側のＲＳＯ3 と
しては、例えば、石油スルホン酸、ジノリルナフタレン
スルホン酸等が挙げられ、アルカリ側のＭとしては、Ｂ
ａ，Ｃａ，Ｚｎ，Ｐｂ，Ｎａ，Ｌｉ等の金属及びＮ
Ｈ4、Ｈ2 Ｎ（ＣＨ2 ）2 ＮＨ2 等のアミンが挙げられ
る。これらの親油性有機インヒビターは、単独でも、適
宜組み合わせて使用してもよい。
【００１０】親水性有機インヒビターは、エマルジョン
中に取り込まれることを特徴とするもので、本発明にお
いては、ドデカン酸、セバシン酸及びホウ酸の少なくと
も１種とジエタノールアミン、アミノテトラゾール及び
ジエチルアミノエタノールの少なくとも１種との塩、ラ
ノリン脂肪酸ポリエチレングリコールエステル、ラノリ
ン脂肪酸アミンエステル、ラノリン脂肪酸アルカノール
アマイド、またはこれらを組み合わせた混合物を用い
る。
【００１１】本発明は、上記親油性有機インヒビターと
上記親水性有機インヒビターとを使用した上で、さらに
非イオン系界面活性剤を併用することに特徴を有する。
非イオン系界面活性剤としては、親水性親油性バランス
（ＨＬＢ）が１．５〜９の範囲にあるものが望ましく、
具体的にはグリセリン脂肪酸エステル、ポリグリセリン
脂肪酸エステル、ソルビタン脂肪酸エステル、ペンタエ
リスリトール脂肪酸エステル、ポリオキシエチレン脂肪
酸エステル等のエステル化合物、ポリオキシエチレンア
ルキルフェニルエーテル等のエーテル化合物が挙げられ
る。この非イオン系界面活性剤は、有機インヒビターの
一種として数えられることもあるが、その単独使用での
錆止め性能は上記２種よりも非常に小さく、ここでは主
に上記２種の有機インヒビターのグリース中での分散性
の向上に寄与する。また、非イオン系のものを選択した
ことにより、電気的に中性を維持できる。
【００１２】上記した親油性有機インヒビター、親水性
有機インヒビター及び非イオン系界面活性剤の添加量
は、グリース組成物全量に対して各々０．１〜１０重量
％となるように配合される。各々の配合量が０．１重量
％未満では、錆止め能力が不足しており、１０重量％よ
りも多いと、グリースの耐熱性やせん断安定性等の物性
に影響を与え、長時間の使用に耐え得ないグリースとな
る。また、上記の範囲内であれば各々の配合比率は特に
制限されるものではないが、本発明においては相乗効果
により錆止め性能が高まるものと考えられることから、
各々当量ずつとするのが最も効果的である。
【００１３】また、本発明は、潤滑基油と増ちょう剤の
種類を問わず適用可能である。例えば潤滑基油として
は、鉱油、ジエステル、ポリオールエステルに代表され
るエステル系合成油、ポリαオレフィンに代表される合
成炭化水素油、アルキルジフェニルエーテルに代表され
るエーテル系合成油が挙げられる。増ちょう剤として
は、Ｌｉ石けんに代表される石けん系増ちょう剤、ジウ
レアに代表されるウレア系増ちょう剤、ベントナイトに
代表される無機系増ちょう剤、ポリテトラフルオロエチ
レン（ＰＴＦＥ）に代表される有機系増ちょう剤等が挙
げられるが、ウレア系が最も好ましい。この理由とし
て、石けん系は軸受回転（せん断）を受けた時にグリー
スが軟化する傾向があり好ましくなく、また無機系（ベ
ントナイト）有機系（ＰＴＦＥ）は元々音響特性が良く
ない。これに対してウレア系はせん断安定性に優れ、ち
ょう度変化が少なく、音響特性にも優れている。
【００１４】
〔基グリースＡ〕
・増ちょう剤：トリレンジイソシアネートとパラトルイ
ジン、オクチルアミンとからなるジウレア化合物 ・基 油 ：４０℃の動粘度が７７ｃＳｔであるアル
キルジフェニルエーテル油とペンタエリスリトールエス
テル油との混合物 ・ちょう度 ：ＮＬＧＩ Ｎｏ．２グレード 〔基グリースＢ〕 ・増ちょう剤：リチウム石けん ・基 油 ：４０℃の動粘度が２６ｃＳｔであるペン
タエリスリトールエステル油とジエステル油との混合物 ・ちょう度 ：ＮＬＧＩ Ｎｏ．２グレード
【００１５】また、使用した添加剤として、スルホネー
ト類は、全て市販のジノリルナフタレンスルホネートの
各種金属塩を使用した。アルカノールアミン塩におい
て、同塩Ａはドデカン２酸、セバシン酸、ホウ酸とジエ
タノールアミンとの塩であり、同塩Ｂはドデカン２酸、
セバシン酸とアミノテトラゾール、ジエタノールアミ
ン、ジエチルアミノエタノールとの塩である。ラノリン
脂肪酸誘導体としては、ラノリン脂肪酸ポリエチレング
リコールエステル、ラノリン脂肪酸アミンエステル、ラ
ノリン脂肪酸アルカノールアマイドを使用した。更に、
参考例として親水性インヒビターとして無機不働態化剤
である亜硝酸ナトリウムを、親油性有機インヒビター及
び親水性有機インヒビターとともに基グリースＡに配合
した試験グリースを作製した。
【００１６】上記の各試験グリースに関して、防錆試験
を行った。試験方法は下記の通りである。 〔防錆試験方法〕ゴムシール付き密封深溝玉軸受（＃６
３０３）内に２．４ｇの試験グリースを封入し、１８０
０ｒｐｍ、３０秒間ならし回転した。その後、軸受内に
３重量％の塩水を０．５ｃｃ注入し、再び１８００ｒｐ
ｍ、３０秒間ならし回転した。次いで、軸受を５２℃、
１００％ＲＨに保持した恒温恒湿槽内に２４時間放置し
た後分解し、軸受軌道面の錆状況を観察した。評価並び
に判定基準は以下のとおりであり、表１〜３に示した。 評 価（肉眼） ＃１・・・・錆なし ＃２・・・・小錆３点以内 ＃３・・・・＃２より発錆の大きい、或いは多いもの
【００１７】
【表１】
【００１８】
【表２】
【００１９】
【表３】
【００２０】比較例に示されるように、親油性有機イン
ヒビター、親水性有機インヒビター及び界面活性剤の組
み合わせのうち、１種を含まないだけで錆止め性能が著
しく劣るようになる。また、各実施例の試験グリースは
参考例の試験グリースと比較しても同等の錆止め性能を
有することが判る。
【００２１】
【発明の効果】以上説明したように、本発明によれば、
親油性有機インヒビター、特定の親水性有機インヒビタ
ー及び非イオン系界面活性剤を組み合わせることによ
り、無機不働態化剤を含むグリース組成物と同等以上の
錆止め性能が得られ、錆止め性能とともに安全性を兼ね
備えたグリース組成物が得られる。
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ１０Ｍ 129:74 Ｃ１０Ｍ 133:04 133:04 133:08 133:08 133:16 133:16 133:44 133:44 135:10 135:10 145:36 145:36 145:38 145:38） Ｃ１０Ｎ 10:04 Ｃ１０Ｎ 10:04 30:12 30:12 40:02 40:02 50:10 50:10 (72)発明者 横内 敦 神奈川県藤沢市鵠沼神明一丁目５番50号 日本精工株式会社内 (72)発明者 磯 賢一 神奈川県藤沢市鵠沼神明一丁目５番50号 日本精工株式会社内 (72)発明者 中 道治 神奈川県藤沢市鵠沼神明一丁目５番50号 日本精工株式会社内 (72)発明者 遠藤 敏明 神奈川県藤沢市辻堂神台一丁目４番６号 協同油脂株式会社内 (72)発明者 柴山 淳 神奈川県藤沢市辻堂神台一丁目４番６号 協同油脂株式会社内 (56)参考文献 特開 平３−79698（ＪＰ，Ａ) 特開 平３−200898（ＪＰ，Ａ) 特開 平９−279368（ＪＰ，Ａ) 特開 昭53−34062（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C10M 141/06 - 141/08 C10M 129/00 - 129/95 C10M 133/00 - 135/36 C10M 145/24 - 145/38 C10M 159/08 C10M 159/12 C10M 161/00 - 163/00 C10N 10:04 C10N 30:12 C10N 40:02 C10N 50:10

Claims (3)

    (57)【特許請求の範囲】
  1. 【請求項１】 潤滑基油及び増ちょう剤からなるグリー
    ス組成物に、Ａ）カルボン酸、カルボン酸塩、スルホン酸塩、アミン
    またはこれらを組み合わせた混合物からなる親油性有機
    インヒビターと、 Ｂ）ドデカン酸、セバシン酸及びホウ酸の少なくとも１
    種とジエタノールアミン、アミノテトラゾール及びジエ
    チルアミノエタノールの少なくとも１種との塩、ラノリ
    ン脂肪酸ポリエチレングリコールエステル、ラノリン脂
    肪酸アミンエステル、ラノリン脂肪酸アルカノールアマ
    イド、またはこれらを組み合わせた混合物からなる親水
    性有機インヒビターと、 Ｃ）非イオン系界面活性剤と を、 各々該グリース組成物全量の０．１〜１０重量％となる
    ように配合したことを特徴とするグリース組成物。
  2. 【請求項２】 非イオン系界面活性剤が、親水性親油性
    バランス（ＨＬＢ）が１．５〜９であり、かつ、グリセ
    リン脂肪酸エステル、ポリグリセリン脂肪酸エステル、
    ソルビタン脂肪酸エステル、ペンタエリスリトール脂肪
    酸エステル、ポリオキシエチレン脂肪酸エステルまたは
    ポリオキシエチレンアルキルフェニルエーテルであるこ
    とを特徴とする請求項１に記載のグリース組成物。
  3. 【請求項３】 親油性有機インヒビターが、バリウムま
    たは亜鉛の有機スルホン酸塩であり、かつ、グリース全
    量の０．１〜２重量％配合されることを特徴とする請求
    項１または２記載のグリース組成物。
JP08413398A 1998-03-30 1998-03-30 グリース組成物 Expired - Fee Related JP3527093B2 (ja)

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US09/280,678 US6251841B1 (en) 1998-03-30 1999-03-29 Grease composition
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US6673750B2 (en) * 2001-02-22 2004-01-06 Ntn Corporation Lubricating composition
US7196042B2 (en) * 2002-03-07 2007-03-27 Nsk Ltd. Grease composition and rolling apparatus
JP4883743B2 (ja) * 2002-08-02 2012-02-22 Ｎｔｎ株式会社 グリース組成物および該グリース組成物封入軸受
JP2005105238A (ja) * 2003-01-06 2005-04-21 Nsk Ltd 自動車電装補機用グリース組成物及び前記グリース組成物を封入した転がり軸受
US8188016B2 (en) 2003-07-08 2012-05-29 Ntn Corporation Lubricant composition and bearing using same
JP4653969B2 (ja) * 2004-05-12 2011-03-16 Ｎｔｎ株式会社 モータ用グリース封入軸受
JP2005290278A (ja) * 2004-04-02 2005-10-20 Ntn Corp 耐防錆グリース組成物、グリース封入軸受および錆止め剤
EP1806391A1 (en) * 2004-10-18 2007-07-11 NSK Ltd. Waterproof grease composition and roller bearing for wheel support
JP5664890B2 (ja) * 2009-10-15 2015-02-04 協同油脂株式会社 風力発電機軸受用グリース組成物
JP5727276B2 (ja) * 2011-03-04 2015-06-03 協同油脂株式会社 グリース組成物及びグリース封入転がり軸受
CN102199473B (zh) * 2011-04-21 2013-10-16 常州曙光化工厂 置换型防锈油的制备方法
CN105408647B (zh) 2013-07-19 2018-12-04 Ntn株式会社 滚动轴承
JP6777457B2 (ja) 2016-08-18 2020-10-28 出光興産株式会社 潤滑油組成物

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US4201681A (en) * 1977-10-03 1980-05-06 Exxon Research & Engineering Co. Metalworking corrosion inhibition/drawing lubricant
US4897210A (en) * 1988-07-12 1990-01-30 Pennzoil Products Company Lithium complex grease thickener and high dropping point thickened grease
JPH07796B2 (ja) * 1989-08-22 1995-01-11 日本精工株式会社 高速ころがり軸受用グリース組成物
JP3601634B2 (ja) * 1996-04-12 2004-12-15 新日本石油株式会社 さび止め剤組成物

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