JP4634585B2 - 防錆性および耐摩耗性が改良されたグリース組成物 - Google Patents

防錆性および耐摩耗性が改良されたグリース組成物 Download PDF

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Publication number
JP4634585B2
JP4634585B2 JP2000242911A JP2000242911A JP4634585B2 JP 4634585 B2 JP4634585 B2 JP 4634585B2 JP 2000242911 A JP2000242911 A JP 2000242911A JP 2000242911 A JP2000242911 A JP 2000242911A JP 4634585 B2 JP4634585 B2 JP 4634585B2
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Japan
Prior art keywords
grease composition
grease
wear resistance
benzotriazole
rust
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JP2000242911A
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JP2002053889A (ja
Inventor
幸洋 尾崎
憲明 篠田
貢一 中沢
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Showa Shell Sekiyu KK
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Showa Shell Sekiyu KK
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Application filed by Showa Shell Sekiyu KK filed Critical Showa Shell Sekiyu KK
Priority to JP2000242911A priority Critical patent/JP4634585B2/ja
Priority to ARP010103788A priority patent/AR032630A1/es
Priority to BRPI0113118-4A priority patent/BR0113118B1/pt
Priority to HU0302687A priority patent/HUP0302687A3/hu
Priority to CNB018139086A priority patent/CN1191341C/zh
Priority to PL01363179A priority patent/PL194360B1/pl
Priority to US10/344,494 priority patent/US6800595B2/en
Priority to CZ2003373A priority patent/CZ295732B6/cs
Priority to KR1020037001912A priority patent/KR100787403B1/ko
Priority to PCT/EP2001/009347 priority patent/WO2002012418A2/en
Priority to EP01958070A priority patent/EP1307532B1/en
Priority to JP2002561248A priority patent/JP2004518014A/ja
Priority to RU2003106404/04A priority patent/RU2263137C2/ru
Priority to CA002418850A priority patent/CA2418850A1/en
Priority to AU2001279815A priority patent/AU2001279815B2/en
Priority to DE60121341T priority patent/DE60121341T2/de
Priority to AU7981501A priority patent/AU7981501A/xx
Publication of JP2002053889A publication Critical patent/JP2002053889A/ja
Priority to ZA200300993A priority patent/ZA200300993B/en
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Description

【０００１】
【発明の属する技術分野】
本発明は、チオ硫酸ソーダを含有する防錆性および耐摩耗性が改良されたグリース組成物に関する。
【０００２】
【従来技術】
自動車、鉄鋼、鉄道、その他諸工業の機械装置の軸受、歯車などには、耐摩耗性や耐荷重性に優れた極圧グリースが多く使用されている。
【０００３】
極圧グリース組成物として一般的なものとしては、各種グリースに硫化オレフィン、硫化油脂、硫黄−リン系極圧剤、二硫化モリブデン、有機モリブデン化合物、鉛化合物、ジチオリン酸亜鉛などの添加剤を含有したものが代表的極圧グリース組成物である。
【０００４】
最近の技術としては、特開平３−１３１６９０号公報、特開平１１−３５９６５号公報およびＵＳＰ４，９２３，６２５号明細書にチオ硫酸ソーダを含有した極圧性に優れるグリース組成物が開示されている。
【０００５】
しかしながら、これらの技術では耐摩耗性が充分でなく、またチオ硫酸ソーダが吸湿性を有することから錆を誘発する可能性があった。特に、鉄鋼設備や食品機械の軸受、歯車などは多量の水と接触した条件下で潤滑されるため錆の発生が促進され、潤滑上の問題を生じやすい。
【０００６】
【発明が解決しようとする課題】
本発明の目的は、チオ硫酸ソーダを含有するグリース組成物の極圧性を十分に維持しつつ、錆の発生を抑制するとともに耐摩耗性をも向上させたグリース組成物を提供する点にある。
【０００７】
【課題を解決するための手段】
本発明者等は、チオ硫酸ソーダを含有する各種グリースに添加剤を加え、防錆試験や四球試験を行い、限定した添加剤が錆の発生防止および耐摩耗性の向上に顕著な効果があることを見出し、本発明を完成するに至った。
【０００８】
すなわち、本発明の第一は、チオ硫酸ソーダを０．０５〜３０重量％含有したグリース組成物において、（Ａ）カルシウムサリシレート、マグネシウムサリシレート、およびカルシウムフェネートよりなる群から選ばれた少なくとも１種類の添加剤を全組成物に対し０．１〜５重量％配合したことを特徴とするグリース組成物に関する。
【０００９】
本発明の第二は、さらに（Ｂ）ベンゾトリアゾール系化合物を全組成物に対し０．１〜５重量％配合した請求項１記載のグリース組成物に関する。
【００１０】
本発明のグリース組成物には、増ちょう剤としてウレア系化合物、リチウム石けん、リチウム複合石けんおよびアルミニウム複合石けんのいずれのものも単独または混合して使用できる。なお、ウレア系化合物としては、ウレア結合をもつ化合物のほか、ウレア結合とウレタン結合の両方を含む化合物であってもよいことは当然である。
【００１１】
本発明に用いる基油としては、植物油、鉱油およびエステル油、エーテル油、炭化水素油等の合成油またはそれらの混合油を用いることができる。
【００１２】
本発明に使用するチオ硫酸ソーダとしては、Ｎａ２Ｓ２Ｏ３（無水）、Ｎａ２Ｓ２Ｏ３・５Ｈ２Ｏ（五水和物）またはそれらの混合物を使用できる。また、チオ硫酸ソーダを含む市販の添加剤（たとえばＤｅｓｉｌｕｂｅ８８，Ｄｅｓｉｌｕｂｅ Ｔｅｃｈｎｏｌｏｇｙ，Ｉｎｃ．ＵＳＡ）も使用できる。
【００１３】
【作用】
本発明は、チオ硫酸ソーダ中の硫黄が高温において金属中の鉄と反応し、化学結合によって生成した層がグリースの金属接触を防ぎ、また同時に上述したこれらの添加剤の相乗効果によって金属表面により強く吸着して、強固な皮膜を形成し、錆発生や摩耗を防止していると推測される。
【００１４】
前記（Ａ）のカルシウムサリシレート、マグネシウムサリシレート、カルシウムフェネートよりなる群から選ばれた少なくとも１種類の添加剤、および前記（Ｂ）のベンゾトリアゾール系化合物の添加量は、全グリース組成物に対してそれぞれ０．１〜５重量％、好ましくは０．２〜３重量％である。前記（Ａ）の添加剤が、０．１重量％未満の場合には、錆抑制効果が不十分であり、前記（Ｂ）の添加剤が、０．１重量％未満の場合には、耐摩耗性の向上効果が不十分である。またこれらの添加剤が、それぞれ５重量％を超えても効果の一層の増大はない。
【００１５】
前記（Ｂ）のベンゾトリアゾール系化合物の例としては、１，２，３−ベンゾトリアゾール、２−（２′−ヒドロキシ−５′−メチルフェニル）−ベンゾトリアゾール、２−〔２′−ヒドロキシ−３′−（３″，４″，５″，６″−テトラヒドロフタルイミドメチル）−５′−メチルフェニル〕−ベンゾトリアゾール、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−ブチルフェニル）−ベンゾトリアゾール、２−（２′−ヒドロキシ−５′−ｔ−オクチルフェニル）−ベンゾトリアゾール、２−（２′−ヒドロキシ−３′，５′−ジ−ｔ−アミルフェニル）−ベンゾトリアゾール、２−〔２−ヒドロキシ−３，５−ビス（α，α−ジメチルベンジル）フェニル〕−２Ｈ−ベンゾトリアゾール、２−（２′−ヒドロキシ−３′−ウンデシル−５′−メチルフェニル）ベンゾトリアゾールなどを挙げることができる。
【００１６】
また本発明においては、アミン系やフェノール系などの酸化防止剤、硫化オレフィンや硫化油脂などの極圧添加剤、フォスファイトやフォスフエートなどの極圧／耐摩耗剤、ポリブデンやポリメタクリレートなどの増粘剤、二硫化モリブデンや窒化ホウ素などの固体潤滑剤、あるいはその他の各種添加剤を配合することができる。
【００１７】
【実施例】
以下に実施例および比較例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものではない。
【００１８】
表１〜表１８に示す処方により、基グリースに前記（Ａ）および（Ｂ）に相当する添加剤あるいはその他の添加剤を加え、三本ロールミルで処理し、実施例と比較例のグリースを得た。基グリースの組成は、次に示すとおりである。
【００１９】
Ｉ．ウレア系基グリース
１００℃の動粘度が約１５ｍｍ２／ｓの精製鉱油（５４００ｇ）中でジフェニルメタン−４，４′−ジイソシアネート（２９５．２ｇ）とオクチルアミン（３０４．８ｇ）を反応させ、生成したウレア系化合物を均一に分散して、ちょう度（２５℃、６０Ｗ）２８９、滴点２６３℃のウレア系基グリースを得た。ウレア系化合物の含有量は、１０重量％である。
【００２０】
II．リチウム石けん系基グリース
１００℃の動粘度が約１５ｍｍ２／ｓの精製鉱油（５４００ｇ）中で１２−ヒドロキシステアリン酸リチウム（６００ｇ）を溶解し、均一に分散することにより、ちょう度（２５℃、６０Ｗ）２６８、滴点１９９℃の性状を有するリチウム石けん系基グリースを得た。リチウム石けんの含有量は、１０重量％である。
【００２１】
III．リチウム複合石けん系基グリース
１００℃の動粘度が約１１ｍｍ２／ｓの精製鉱油（４１６５ｇ）中で１２−ヒドロキシステアリン酸３５０ｇを水酸化リチウム５０．５ｇと反応させた後、アゼライン酸１２０．６５ｇを水酸化リチウム５９．０ｇと反応させ、均一に分散処理することにより、ちょう度（２５℃、６０Ｗ）２８１、滴点２５９℃の性状を有するリチウム複合石けん系基グリースを得た。リチウム複合石けんの含有量は、１０．４重量％である。
【００２２】
IV．アルミニウム複合石けん系基グリース
１００℃の動粘度が約１１ｍｍ２／ｓの精製鉱油（４２７２ｇ）中に安息香酸１５８．２２ｇとステアリン酸３３４．８ｇを溶解し、その後市販の環状アルミニウムオキサイドプロピレート潤滑液〔商品名：川研ファインケミカル（株）製アルゴマー〕を加えて反応を行い、生成した石けんを均一に分散処理して、ちょう度（２５℃、６０Ｗ）２７９、滴点２５８℃のアルミニウム複合石けん系基グリースを得た。アルミニウム複合石けんの含有量は、１１重量％となるようにした。また、安息香酸（ＢＡ）とステアリン酸（ＦＡ）のモル比をＢＡ／ＦＡ＝１．１および安息香酸とステアリン酸に対するアルミニウム（Ａｌ）のモル比を（ＢＡ＋ＦＡ）／Ａｌ＝１．９とした。
【００２３】
得られたグリースについて防錆試験（湿潤試験）、四球試験（ＥＰ試験および耐摩耗試験）を行い、防錆性、極圧性および耐摩耗性を確認した。
【００２４】
湿潤試験
ＪＩＳ Ｋ２２２０ ５．１７の湿潤試験に従い、規定される試験片に片面の塗布量が０．３０±０．０５ｇになるように試験片全面に試料を均一に塗布した。グリースを塗布した鋼板を、温度４９℃、相対湿度９５％以上の湿潤箱内につり下げ、２週間後の錆発生度をＪＩＳ Ｋ２２４６の等級で表示した。
等級 錆発生度％
Ａ級 ０
Ｂ級 １〜１０
Ｃ級 １１〜２５
Ｄ級 ２６〜５０
Ｅ級 ５１〜１００
【００２５】
ＥＰ試験
ＡＳＴＭ Ｄ２５９６に従い、四球試験によって融着荷重（Ｎ）を調べた。
Figure 0004634585
【００２６】
耐摩耗試験
ＡＳＴＭ Ｄ２２６６に従い、四球試験によってボールの摩耗痕径（ｍｍ）を測定した。
Figure 0004634585
【００２７】
試験結果を纏めて表１〜表１８に示す。
また、表中、＊１〜＊１０は下記のとおりである。
【００２８】
Ｄｅｓｉｌｕｂｅ８８＊１はＤｅｓｉｌｕｂｅ Ｔｅｃｈｎｏｌｏｇｙ，Ｉｎｃ．の商品名であり、チオ硫酸ソーダを含んだ無機のＳ−Ｐ系添加剤である。
【００２９】
以下は本発明の前記（Ａ）相当品またはカルシウムスルフォネートである。
ＳＡＰ００１＊２はＩｎｆｅｎｅｕｍ Ｌｔｄ．の商品名であり、カルシウムサリシレートのことである。
ＳＡＰ００７＊３はＩｎｆｅｎｅｕｍ Ｌｔｄ．の商品名であり、マグネシウムサリシレートのことである。
ＯＬＯＡ２１９＊４はオロナイト ジャパン（株）の商品名であり、カルシウムフェネートのことである。
ＮＡ−ＳＵＬ７２９＊５はＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ，ＩＮＣ．の商品名であり、カルシウムスルフォネートのことである。
【００３０】
以下は本発明の前記（Ｂ）相当品である。
ＢＴ−１２０＊６は城北化学（株）の商品名であり、１，２，３−ベンゾトリアゾールのことである。
【００３１】
以下は前記（Ａ）（Ｂ）以外の添加剤である。
ＮＡ−ＳＵＬ ＺＳ＊７はＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ，ＩＮＣ．の商品名であり、ジンクスルフォネートのことである。
Ｄａｉｌｕｂｅ Ｚ−５００＊８は大日本インキ化学工業（株）の商品名であり、ナフテン酸亜鉛のことである。
ＮＡ−ＳＵＬ ＳＳ＊９はＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ，ＩＮＣ．の商品名であり、ナトリウムスルフォネートのことである。
ＮＡ−ＳＵＬ ７０７＊１０はＫＩＮＧ ＩＮＤＵＳＴＲＩＥＳ，ＩＮＣ．の商品名であり、リチウムスルフォネートのことである。
【００３２】
【表１】
Figure 0004634585
【００３３】
【表２】
Figure 0004634585
【００３４】
【表３】
Figure 0004634585
【００３５】
【表４】
Figure 0004634585
【００３６】
【表５】
Figure 0004634585
【００３７】
【表６】
Figure 0004634585
【００３８】
【表７】
Figure 0004634585
【００３９】
【表８】
Figure 0004634585
【００４０】
【表９】
Figure 0004634585
【００４１】
【表１０】
Figure 0004634585
【００４２】
【表１１】
Figure 0004634585
【００４３】
【表１２】
Figure 0004634585
【００４４】
【表１３】
Figure 0004634585
【００４５】
【表１４】
Figure 0004634585
【００４６】
【表１５】
Figure 0004634585
【００４７】
【表１６】
Figure 0004634585
【００４８】
【表１７】
Figure 0004634585
【００４９】
【表１８】
Figure 0004634585
【００５０】
【発明の効果】
本発明は表１〜１０の実施例と表１１〜１８の比較例から明らかなように、チオ硫酸ソーダを配合したグリース組成物に前記（Ａ）の添加剤を添加したグリース組成物は優れた極圧性を有しており、かつ錆止め性能が大幅に向上している。またチオ硫酸ソーダを配合したグリース組成物に前記（Ａ）の添加剤と前記（Ｂ）のベンゾトリアゾール系化合物を添加したグリース組成物は優れた極圧性、防錆性に加えて優れた耐磨耗性を有する。特にウレアグリース、リチウム石けんグリースおよびリチウム複合石けんグリースにおいては耐摩耗性の向上が顕著である。また、チオ硫酸ソーダは食品添加剤として古くから認められているほか、万能の解毒剤としても知られているものであるから、人体にやさしく、ひいては地球環境にもやさしい添加物である。したがって、本発明は、環境への適合性に極めて優れたグリース組成物である。

Claims (5)

  1. チオ硫酸ソーダを０．０５〜３０重量％含有したグリース組成物において、（Ａ）カルシウムサリシレート、マグネシウムサリシレート、およびカルシウムフェネートよりなる群から選ばれた少なくとも１種類の添加剤を全組成物に対し０．１〜５重量％配合したことを特徴とするグリース組成物。
  2. さらに（Ｂ）ベンゾトリアゾール系化合物を全組成物に対し０．１〜５重量％配合した請求項１記載のグリース組成物。
  3. 増ちょう剤がウレア系化合物である請求項１または２記載のグリース組成物。
  4. 増ちょう剤がリチウム石けんまたはリチウム複合石けんである請求項１または２記載のグリース組成物。
  5. 増ちょう剤がアルミニウム複合石けんである請求項１または２記載のグリース組成物。
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HUP0302687A2 (hu) 2003-11-28
AU7981501A (en) 2002-02-18
PL194360B1 (pl) 2007-05-31
HUP0302687A3 (en) 2005-11-28
AR032630A1 (es) 2003-11-19
WO2002012418A2 (en) 2002-02-14
RU2263137C2 (ru) 2005-10-27
DE60121341D1 (de) 2006-08-17
CN1446251A (zh) 2003-10-01
EP1307532A2 (en) 2003-05-07
ZA200300993B (en) 2004-04-01
DE60121341T2 (de) 2007-07-26
BR0113118B1 (pt) 2011-07-12
US20030176295A1 (en) 2003-09-18
JP2004518014A (ja) 2004-06-17
BR0113118A (pt) 2003-06-10
AU2001279815B2 (en) 2004-06-03
KR100787403B1 (ko) 2007-12-21
PL363179A1 (en) 2004-11-15
CN1191341C (zh) 2005-03-02

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