JP3812995B2 - Grease composition for constant velocity joints - Google Patents

Grease composition for constant velocity joints Download PDF

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Publication number
JP3812995B2
JP3812995B2 JP21417197A JP21417197A JP3812995B2 JP 3812995 B2 JP3812995 B2 JP 3812995B2 JP 21417197 A JP21417197 A JP 21417197A JP 21417197 A JP21417197 A JP 21417197A JP 3812995 B2 JP3812995 B2 JP 3812995B2
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Japan
Prior art keywords
grease
cvj
constant velocity
flaking
urea
Prior art date
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Expired - Fee Related
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JP21417197A
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Japanese (ja)
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JPH1135965A (en
Inventor
幸洋 尾崎
智郎 宗像
強 吉田
隆一 益森
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Showa Shell Sekiyu KK
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Showa Shell Sekiyu KK
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Priority to JP21417197A priority Critical patent/JP3812995B2/en
Priority to CN98806285A priority patent/CN1097630C/en
Priority to PCT/EP1998/004983 priority patent/WO1999005240A1/en
Priority to KR10-2000-7000688A priority patent/KR100503108B1/en
Priority to EP98945164A priority patent/EP0998544B1/en
Priority to DE69816085T priority patent/DE69816085T2/en
Publication of JPH1135965A publication Critical patent/JPH1135965A/en
Application granted granted Critical
Publication of JP3812995B2 publication Critical patent/JP3812995B2/en
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Description

【０００１】
【発明の属する技術分野】
本発明は、自動車の等速ジョイント〔Ｃｏｎｓｔａｎｔ Ｖｅｌｏｃｉｔｙ Ｊｏｉｎｔ，以下ＣＶＪと略する〕用グリースに関する。ＣＶＪのグリース潤滑は、往復動の転がりと滑りが混在した高面圧下の摩擦条件下で行なわれるため極めて苛酷である。本発明は、この潤滑箇所に適用してＣＶＪの異常摩耗やフレーキングの発生を防止し、極めて長寿命な耐久性を有した等速ジョイント用グリース組成物に関するものである。
【０００２】
【従来の技術】
自動車のＣＶＪは、ＦＦ車（前輪駆動車）や４ＷＤ（四輪駆動車）およびＦＲ車（後輪駆動車）に採用され、需要は増加の傾向にある。自動車の高速化、高出力化、軽量化に伴い、ＣＶＪも小型化、高トルク化、高速仕様化になってきているためＣＶＪのグリース潤滑は、一段と厳しくなっている。ＣＶＪは、その機構により固定型ジョイント（Ｆｉｘｅｄ Ｊｏｉｎｔ）とプランジング型ジョイント（Ｐｌｕｎｇｉｎｇ Ｊｏｉｎｔ）に区分される。このＣＶＪの中で特に固定型ジョイントは、一般にホイール側に用いられ高角度かつ高面圧下で使用されるため非常に苛酷である。
【０００３】
ＣＶＪ用グリースとして一般的なものは、増ちょう剤にリチウム石けんを用い、硫黄−リン系極圧剤、二硫化モリブデン等の添加剤を含有したものが多く使用されている。最近では、耐熱性に優れたウレア系グリースに各種の極圧剤を添加したものも増えてきている。
【０００４】
代表的な技術としては、ウレアグリースに（Ａ）硫化ジアルキルジチオカルバミン酸モリブデンと、（Ｂ）特定のジチオリン酸亜鉛化合物からなる極圧添加剤と、（Ｃ）エポキシ化脂肪酸エステルまたはエポキシ化脂肪酸グリセライドが必須成分として含有された等速ジョイント用グリース組成物が特開平６−５７２８４号公報に開示されている。
【０００５】
また、ウレアグリースに関するその他の技術は特公平４−３４５９０号、特開平６−５７２８３号、特開平６−１００８７８号、特開平７−１９７０７２号および特開平８−４１４８５号公報、ＵＳＰ４，８４０，７４０号、ＵＳＰ５，１６０，６４５号、ＵＳＰ５，４４９，４７１号明細書等に示されている。これらの技術は、いずれも基グリースに有機モリブデン化合物を加え、さらに他の添加剤（例えば、ジチオリン酸亜鉛）と併用して摩擦摩耗を低減し、その効果によってフレーキングの発生を防止した技術と言える。
【０００６】
しかしながら、これらの技術では摩擦や摩耗低減効果が認められるが、ＣＶＪ機構内において、内外輪みぞと玉およびケージと玉との複雑な往復動の転がり滑り摩擦に基因する金属表面の疲労からくるフレーキングに対しては、余り防止機能を果していないのが実状である。
【０００７】
そこで、ＣＶＪの製造メーカーやグリース供給メーカーは高性能なＣＶＪ用グリースを選定するのにチムケン試験、四球式ＥＰ試験、ファレックス試験、ＳＲＶ試験およびハフナーフレッチング試験などの一般の摩擦摩耗試験を用いてＣＶＪのフレーキング寿命を把握しようと努力している。そして、これらの試験機を用いて低摩擦係数のグリースを得ることでプランジングジョイントに要求される振動は一応低減することができる。しかし、ＣＶＪの耐久性に関しては、潤滑条件が複雑なため、前述した試験機では適性グリースを選定できないため実際のＣＶＪを使った台上試験機を用いてフレーキング寿命や摩耗の状態などの性能評価を行っている現状にある。
【０００８】
従って、一般の摩擦摩耗試験で優れた結果を示すものが必ずしもＣＶＪのフレーキングを防止し、耐久性が長いとは限らないという点がＣＶＪのフレーキング防止技術の開発を困難なものとしている。
【０００９】
【発明が解決しようとする課題】
本発明の目的は、ＣＶＪのフレーキングを防止できる新規な等速ジョイント用グリース組成物を提供する点にある。
【００１０】
【課題を解決するための手段】
本発明者等は、グリースに添加すると四球式ＥＰ試験で極めて高い融着荷重を示すチオ硫酸ソーダに着眼し、実際のＣＶＪを用いて試験を行い、従来グリースよりも優れたフレーキングの発生防止の効果を認知し、本発明を達成するに至った。すなわち本発明は、基油とウレア系増ちょう剤に対してチオ硫酸ソーダ０．０５〜３０重量％を含有させたことを特徴とする等速ジョイント用グリース組成物に関する。
【００１１】
本発明に用いる基油としては、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】
ウレア系増ちょう剤としては、ウレア系増ちょう剤であればいずれのものも使用できる。ウレア系増ちょう剤の例としては、ジウレア、トリウレア、テトラウレア等を挙げることができる。また、ウレア・ウレタン化合物およびウレア・イミド化合物のようにウレア化合物を含む種々の増ちょう剤を用いることができる。
【００１３】
本発明に使用するチオ硫酸ソーダは、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（Ｄｅｓｉｌｕｂｅ８８，Ｄｅｓｉｌｕｂｅ Ｔｅｃｈｎｏｌｏｇｙ，Ｉｎｃ．ＵＳＡ）も使用できる。
【００１４】
【作用】
本発明のチオ硫酸ソーダを配合したウレア系グリースがＣＶＪのフレーキングを防止し、耐久性を向上させるという効果については、チオ硫酸ソーダ中のイオウが高温において金属中の鉄と反応し、化学結合により生成した層が金属接触を防ぎ、高面圧下において摩耗を抑制していると考えられる。
また、この添加剤はウレア系グリースのみに有効に作用し、ＣＶＪのフレーキングを防止することから、増ちょう剤であるウレア化合物が金属表面に吸着し、摩耗を防止して耐久性を向上していると推測される。
【００１５】
チオ硫酸ソーダの添加量は、ウレア系グリース中に０．０５〜３０重量％、好ましくは０．２〜２０重量％である。０．０５重量％未満の場合については、フレーキング防止効果が不十分であり、また３０重量％を越えても効果の一層の増大はない。
【００１６】
また本発明の組成物には、フェノール系やアミン系の酸化防止剤、有機モリブデン化合物、二硫化モリブデン、硫化油脂、硫化オレフィン、ポリサルファイド、フォスフェート、フォスファイト、チオフォスフェート、ジチオリン酸亜鉛等の極圧／耐摩耗剤、ポリブデン、ポリメタクリレート等の増粘剤など、公知の各種添加剤を配合することができる。
【００１７】
【実施例】
本発明を実施例および比較例を挙げて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および表２に示す配合で、基グリースに添加剤を加え、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、次に示す通りである。なお、基油は１００℃の粘度が約１５ｍｍ2／Ｓ の精製鉱油を用いた。
【００１９】
Ｉ．ジウレアグリース
基油（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、生成したウレア化合物を均一に分散してグリースを得た。ウレア化合物の含有量は、１０重量％である。
【００２０】
II．テトラウレアグリース
基油（５２８０ｇ）中でジフェニルメタン−４，４′−ジイソシアネート（３３４．２ｇ）とステアリルアミン（３４５．６ｇ）およびエチレンジアミン（４０．２ｇ）を反応させ、生成したウレア化合物を均一に分散してグリースを得た。ウレア化合物の含有量は、１２重量％である。
【００２１】
III．リチウム石けんグリース
基油（５４６０ｇ）中で１２−ヒドロキシステアリン酸リチウム（５４０ｇ）を溶解し、均一に分散することによりグリースを得た。リチウム石けんの含有量は、９重量％である。
【００２２】
得られたグリースについて、実際のＣＶＪを用いて台上耐久試験を行い、フレーキングの発生度合を確認した。
〔試験条件〕
回転数 １４００ｒｐｍ
負荷トルク ２９４Ｎ・ｍ
ジョイント角度 ６ｄｅｇ
ジョイントタイプ バーフィールドジョイント
また、ＡＳＴＭ Ｄ２５９６に規定する四球式ＥＰ試験で融着荷重（Ｎ）を求めた。これらの結果を表１〜４に併記する。
【００２３】
なお、表中、＊１〜７および＊＊は下記のとおりである。
＊１ Ｄｅｓｉｌｕｂｅ８８（Ｄｅｓｉｌｕｂｅ Ｔｅｃｈｎｏｌｏｇｙ，Ｉｎｃ．製、商品名）はチオ硫酸ソーダを含んだ無機のＳ−Ｐ系添加剤である。
＊２ モリバンＡ（Ｖａｎｄｅｒｂｉｌｔ社製、商品名）は、Ｍｏ−ＤＴＣ（モリブデンジチオカーバメート）である。
＊３ サクラルーブ６００（旭電化製、商品名）は、Ｍｏ−ＤＴＣである。
＊４ サクラルーブ３００（旭電化製、商品名）は、Ｍｏ−ＤＴＰ（モリブデンジチオホスフェート）である。
＊５ ルーブリゾール１３９５（Ｌｕｂｒｉｚｏｌ社製、商品名）は、Ｚｎ−ＤＴＰ（ジンクジチオホスフェート）である。
＊６ アングラモル３３（Ｌｕｂｒｉｚｏｌ社製、商品名）は、硫化オレフィンである。
＊７ イルガルーブＴＰＰＴ（ＣＩＢＡ−ＧＥＩＧＹ社製、商品名）は、トリフェニルホスホロチオネートである。
＊＊ フレーキング発生度合は、ＣＶＪを１２６０万回転した後の状態と、２５２０万回転した後の状態を観察し、つぎのように評価したものである。
◎ フレーキング発生なし
○ 微少フレーキングあり
△ 中フレーキングあり
× 大フレーキングあり
【００２４】
【表１】

Figure 0003812995
【００２５】
【表２】
Figure 0003812995
【００２６】
【表３】
Figure 0003812995
【００２７】
【表４】
Figure 0003812995
【００２８】
【発明の効果】
表１〜４に示す結果から明らかなように、本発明の等速ジョイント用グリース組成物は、著しい極圧性を有しており、従来グリースよりも有効なフレーキング防止性を与える。その結果、等速ジョイントの耐久性を向上できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a grease for a constant velocity joint (constant velocity joint, hereinafter abbreviated as CVJ) of an automobile. CVJ grease lubrication is extremely severe because it is carried out under high surface pressure friction conditions in which reciprocating rolling and sliding are mixed. The present invention relates to a grease composition for a constant velocity joint, which is applied to this lubricated portion to prevent the occurrence of abnormal wear and flaking of CVJ and has a very long durability.
[0002]
[Prior art]
The CVJ for automobiles is used in FF vehicles (front-wheel drive vehicles), 4WD (four-wheel drive vehicles), and FR vehicles (rear-wheel drive vehicles), and demand is increasing. As CVJs have become smaller, higher torque, and higher speed specifications with the increase in speed, output, and weight of automobiles, grease lubrication of CVJ has become more severe. The CVJ is classified into a fixed joint and a plunging joint according to the mechanism. Among these CVJs, the fixed joint is particularly severe because it is generally used on the wheel side and is used at a high angle and high surface pressure.
[0003]
As a general grease for CVJ, lithium soap is used as a thickener, and a lot of additives containing sulfur-phosphorus extreme pressure agent, molybdenum disulfide and the like are used. Recently, an increasing number of urea-based greases with excellent heat resistance and various extreme pressure agents have been added.
[0004]
As a typical technique, urea grease contains (A) molybdenum dialkyldithiocarbamate disulfide and (B) an extreme pressure additive comprising a specific zinc dithiophosphate compound, and (C) epoxidized fatty acid ester or epoxidized fatty acid glyceride. A grease composition for a constant velocity joint contained as an essential component is disclosed in JP-A-6-57284.
[0005]
Other technologies relating to urea grease are disclosed in JP-B-4-34590, JP-A-6-57283, JP-A-6-1000087, JP-A-7-197072 and JP-A-8-41485, USP 4,840,740. No., USP 5,160,645, USP 5,449,471 and the like. All of these technologies add organomolybdenum compounds to the base grease, and further use in combination with other additives (for example, zinc dithiophosphate) to reduce frictional wear and prevent the occurrence of flaking due to its effect. I can say that.
[0006]
However, although these techniques have the effect of reducing friction and wear, in the CVJ mechanism, there is a frame caused by fatigue on the metal surface due to the rolling and sliding friction of the complicated reciprocating motion between the inner and outer ring grooves and balls and the cage and balls. The reality is that King does not perform much of the prevention function.
[0007]
Therefore, CVJ manufacturers and grease suppliers use general friction and wear tests such as the Timken test, four-ball EP test, Falex test, SRV test and Huffner fretting test to select high-performance CVJ grease. Efforts are being made to understand the flaking life of CVJ. The vibration required for the plunging joint can be reduced temporarily by obtaining grease having a low coefficient of friction using these test machines. However, regarding the durability of CVJ, since the lubrication conditions are complex, the appropriate grease cannot be selected with the above-mentioned testing machine, so the performance such as the flaking life and the state of wear using the bench testing machine using the actual CVJ. It is in the current state of evaluating.
[0008]
Therefore, it is difficult to develop a CVJ anti-flaking technique in that an excellent result in a general friction and wear test does not necessarily prevent CVJ flaking and does not necessarily have long durability.
[0009]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel grease composition for a constant velocity joint that can prevent flaking of CVJ.
[0010]
[Means for Solving the Problems]
The inventors have focused on sodium thiosulfate, which shows an extremely high fusing load in the four-ball EP test when added to grease, and conducted tests using actual CVJ to prevent the occurrence of flaking superior to conventional grease. The present invention has been achieved. That is, the present invention relates to a grease composition for a constant velocity joint characterized by containing 0.05 to 30% by weight of sodium thiosulfate with respect to a base oil and a urea-based thickener.
[0011]
As the base oil used in the present invention, mineral oils, synthetic oils such as ester oils, ether oils, hydrocarbon oils, or mixed oils thereof can be used.
[0012]
Any urea thickener can be used as long as it is a urea thickener. Examples of urea-based thickeners include diurea, triurea, and tetraurea. Further, various thickeners containing a urea compound such as a urea / urethane compound and a urea / imide compound can be used.
[0013]
As the sodium thiosulfate used in the present invention, Na 2 S 2 O 3 (anhydrous), Na 2 S 2 O 3 .5H 2 O (pentahydrate) or a mixture thereof can be used. Commercially available additives containing sodium thiosulfate (Desirube 88, Desilube Technology, Inc. USA) can also be used.
[0014]
[Action]
The urea-based grease containing sodium thiosulfate of the present invention prevents CVJ flaking and improves durability. Regarding the effect that sulfur in sodium thiosulfate reacts with iron in metal at high temperature, chemical bonding It is considered that the layer formed by the above prevents metal contact and suppresses wear under high surface pressure.
In addition, this additive works effectively only on urea-based grease and prevents CVJ flaking, so the urea compound as a thickener is adsorbed on the metal surface, preventing wear and improving durability. I guess that.
[0015]
The amount of sodium thiosulfate added is 0.05 to 30% by weight, preferably 0.2 to 20% by weight, in the urea grease. When it is less than 0.05% by weight, the anti-flaking effect is insufficient, and when it exceeds 30% by weight, the effect is not further increased.
[0016]
In addition, the composition of the present invention includes phenolic and amine antioxidants, organic molybdenum compounds, molybdenum disulfide, sulfurized fats and oils, sulfurized olefins, polysulfide, phosphate, phosphite, thiophosphate, zinc dithiophosphate, and the like. Various known additives such as pressure / antiwear agents, thickeners such as polybutene and polymethacrylate can be blended.
[0017]
【Example】
The present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto.
[0018]
In the formulations shown in Tables 1 and 2, an additive was added to the base grease and treated with a three-roll mill to obtain greases of Examples and Comparative Examples. The composition of the base grease is as shown below. As the base oil, a refined mineral oil having a viscosity at 100 ° C. of about 15 mm 2 / S was used.
[0019]
I. Diphenylmethane-4,4′-diisocyanate (295.2 g) and octylamine (304.8 g) were reacted in diurea grease base oil (5400 g), and the resulting urea compound was uniformly dispersed to obtain a grease. The urea compound content is 10% by weight.
[0020]
II. Diphenylmethane-4,4'-diisocyanate (334.2 g) is reacted with stearylamine (345.6 g) and ethylenediamine (40.2 g) in a tetraurea grease base oil (5280 g), and the resulting urea compound is uniformly dispersed. To obtain grease. The urea compound content is 12% by weight.
[0021]
III. Lithium soap grease base oil (5460 g) was dissolved in lithium 12-hydroxystearate (540 g) and dispersed uniformly to obtain a grease. The content of lithium soap is 9% by weight.
[0022]
The obtained grease was subjected to a bench durability test using an actual CVJ, and the occurrence of flaking was confirmed.
〔Test conditions〕
Rotation speed 1400rpm
Load torque 294N ・ m
Joint angle 6deg
Joint type Barfield joint Also, the fusion load (N) was determined by the four-ball EP test specified in ASTM D2596. These results are also shown in Tables 1-4.
[0023]
In the table, * 1 to 7 and ** are as follows.
* 1 Desirube 88 (manufactured by Desirube Technology, Inc., trade name) is an inorganic SP-based additive containing sodium thiosulfate.
* 2 Moriban A (trade name, manufactured by Vanderbilt) is Mo-DTC (molybdenum dithiocarbamate).
* 3 Sakura Lube 600 (trade name, manufactured by Asahi Denka) is Mo-DTC.
* 4 SakuraLube 300 (trade name, manufactured by Asahi Denka) is Mo-DTP (molybdenum dithiophosphate).
* 5 Lubrizol 1395 (manufactured by Lubrizol, trade name) is Zn-DTP (zinc dithiophosphate).
* 6 Angolamol 33 (trade name, manufactured by Lubrizol) is a sulfurized olefin.
* 7 Ilgarve TPPT (trade name, manufactured by CIBA-GEIGY) is triphenyl phosphorothioate.
** The degree of occurrence of flaking was evaluated as follows by observing the state after 12.6 million rotations of CVJ and the state after 25.2 million rotations.
◎ No flaking occurred ○ Minor flaking △ Medium flaking x Large flaking [0024]
[Table 1]
Figure 0003812995
[0025]
[Table 2]
Figure 0003812995
[0026]
[Table 3]
Figure 0003812995
[0027]
[Table 4]
Figure 0003812995
[0028]
【The invention's effect】
As is apparent from the results shown in Tables 1 to 4, the grease composition for constant velocity joints of the present invention has a remarkably extreme pressure property and provides more effective anti-flaking properties than conventional greases. As a result, the durability of the constant velocity joint can be improved.

Claims (1)

基油とウレア系増ちょう剤に対してチオ硫酸ソーダ０．０５〜３０重量％を含有させたことを特徴とする等速ジョイント用グリース組成物。A grease composition for a constant velocity joint, comprising 0.05 to 30% by weight of sodium thiosulfate based on a base oil and a urea-based thickener.
JP21417197A 1997-07-24 1997-07-24 Grease composition for constant velocity joints Expired - Fee Related JP3812995B2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP21417197A JP3812995B2 (en) 1997-07-24 1997-07-24 Grease composition for constant velocity joints
CN98806285A CN1097630C (en) 1997-07-24 1998-07-23 Grease composition for constant velocity joint
PCT/EP1998/004983 WO1999005240A1 (en) 1997-07-24 1998-07-23 Grease composition for a constant velocity joint
KR10-2000-7000688A KR100503108B1 (en) 1997-07-24 1998-07-23 Grease composition for a constant velocity joint
EP98945164A EP0998544B1 (en) 1997-07-24 1998-07-23 Grease composition for a constant velocity joint
DE69816085T DE69816085T2 (en) 1997-07-24 1998-07-23 LUBRICATING GREASE COMPOSITION FOR HOMOKINETIC CLUTCH

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP21417197A JP3812995B2 (en) 1997-07-24 1997-07-24 Grease composition for constant velocity joints

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JPH1135965A JPH1135965A (en) 1999-02-09
JP3812995B2 true JP3812995B2 (en) 2006-08-23

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EP (1) EP0998544B1 (en)
JP (1) JP3812995B2 (en)
KR (1) KR100503108B1 (en)
CN (1) CN1097630C (en)
DE (1) DE69816085T2 (en)
WO (1) WO1999005240A1 (en)

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JP4634585B2 (en) * 2000-08-10 2011-02-16 昭和シェル石油株式会社 Grease composition with improved rust and wear resistance
US8153053B2 (en) 2002-11-21 2012-04-10 Diamet Corporation Method for forming compact from powder and sintered product
JP4769456B2 (en) * 2004-12-27 2011-09-07 昭和シェル石油株式会社 Urea-based lubricating grease composition, rolling bearing and electric power steering device
JP5225354B2 (en) * 2010-10-18 2013-07-03 昭和シェル石油株式会社 Grease composition with improved rust and wear resistance

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US3505223A (en) * 1967-03-30 1970-04-07 Ethyl Corp Lubricant compositions
US4986923A (en) * 1989-06-27 1991-01-22 Amoco Corporation Front-wheel drive grease with synergistic sulfate and carbonate additive system
US4923625A (en) * 1989-09-28 1990-05-08 Desilube Technology, Inc. Lubricant compositions
US5354485A (en) * 1993-03-26 1994-10-11 The Lubrizol Corporation Lubricating compositions, greases, aqueous fluids containing organic ammonium thiosulfates

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Publication number Publication date
KR100503108B1 (en) 2005-07-25
JPH1135965A (en) 1999-02-09
CN1260825A (en) 2000-07-19
DE69816085T2 (en) 2004-05-19
EP0998544B1 (en) 2003-07-02
CN1097630C (en) 2003-01-01
DE69816085D1 (en) 2003-08-07
EP0998544A1 (en) 2000-05-10
KR20010022118A (en) 2001-03-15
WO1999005240A1 (en) 1999-02-04

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