JPH05263091A - Greased rolling bearing for alternator - Google Patents

Greased rolling bearing for alternator

Info

Publication number
JPH05263091A
JPH05263091A JP4173093A JP17309392A JPH05263091A JP H05263091 A JPH05263091 A JP H05263091A JP 4173093 A JP4173093 A JP 4173093A JP 17309392 A JP17309392 A JP 17309392A JP H05263091 A JPH05263091 A JP H05263091A
Authority
JP
Japan
Prior art keywords
oil
grease
bearing
base oil
alternator
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.)
Granted
Application number
JP4173093A
Other languages
Japanese (ja)
Other versions
JP2557597B2 (en
Inventor
Mitsunari Aso
光成 麻生
Osamu Hirano
修 平野
Eishin Mikami
英信 三上
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.)
NTN Corp
Original Assignee
NTN Corp
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 NTN Corp filed Critical NTN Corp
Priority to ITMI930056A priority Critical patent/IT1263745B/en
Priority to KR1019930000657A priority patent/KR970002552B1/en
Priority to DE4301438A priority patent/DE4301438C2/en
Priority to FR9300520A priority patent/FR2686348B1/en
Priority to US08/006,796 priority patent/US5301923A/en
Priority to GB9301158A priority patent/GB2263482B/en
Publication of JPH05263091A publication Critical patent/JPH05263091A/en
Application granted granted Critical
Publication of JP2557597B2 publication Critical patent/JP2557597B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16CSHAFTS; FLEXIBLE SHAFTS; ELEMENTS OR CRANKSHAFT MECHANISMS; ROTARY BODIES OTHER THAN GEARING ELEMENTS; BEARINGS
    • F16C33/00Parts of bearings; Special methods for making bearings or parts thereof
    • F16C33/30Parts of ball or roller bearings
    • F16C33/66Special parts or details in view of lubrication
    • F16C33/6603Special parts or details in view of lubrication with grease as lubricant
    • F16C33/6633Grease properties or compositions, e.g. rheological properties
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/18Ethers, e.g. epoxides
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    • C10M107/00Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/02Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation
    • C10M107/10Hydrocarbon polymers; Hydrocarbon polymers modified by oxidation containing aliphatic monomer having more than 4 carbon atoms
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    • C10M115/00Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof
    • C10M115/08Lubricating compositions characterised by the thickener being a non-macromolecular organic compound other than a carboxylic acid or salt thereof containing nitrogen
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    • C10M125/00Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/20Compounds containing nitrogen
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    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10Sulfonic acids or derivatives thereof
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    • C10M169/00Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/02Mixtures of base-materials and thickeners
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/028Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • C10M2205/0285Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04Ethers; Acetals; Ortho-esters; Ortho-carbonates
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/10Amides of carbonic or haloformic acids
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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

PURPOSE:To obtain the subject bearing which does not suffer abnormal peeling due to hydrogen enbrittlement on its rolling face even under conditions of a high rotational speed and a high load and is durable. CONSTITUTION:A rolling bearing 2 of an alternator is sealed with a grease composition prepared by adding 5-40wt.% thickener comprising an aromatic diurea compound containing two urea bonds (NHC0NH) in the molecule or an aromatic urea/urethane compound containing both a urea bond and a urethane bond (NHCOO)in the molecule to a base oil prepared by mixing an alkyldiphenyl ether oil with a poly-alpha-olefin oil in a weight ratio of 20:80 to 80:20 and adding a passivating oxidizing agent such as sodium nitrite and an organic sulfonate such as barium sulfonate or zinc sulfonate.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】この発明は、自動車等のオルタネ
ータの回転軸を支持するオルタネータ用グリース封入転
がり軸受に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a grease-filled rolling bearing for an alternator which supports a rotating shaft of an alternator for an automobile or the like.

【0002】[0002]

【従来の技術】近年、自動車の小型化、軽量化および静
粛性向上の要求に伴ない、その電装部品や補機部品の小
型化、軽量化およびエンジンルーム内の密閉化が図られ
ているが、その一方、装置の性能自体には高出力・高効
率化の要求が増大し、オルタネータにおいては、小型化
に伴って生じる出力の低下を高速回転することで補なう
手法が採られている。
2. Description of the Related Art In recent years, along with the demands for downsizing, weight reduction and quietness of automobiles, electric components and auxiliary parts thereof have been downsized, reduced in weight and sealed in the engine room. On the other hand, there is an increasing demand for higher output and higher efficiency in the performance of the device itself, and in alternators, a method has been adopted to compensate for the decrease in output that occurs with miniaturization by rotating at high speed. ..

【0003】図1は、高速回転の使用を目的とした自動
車用オルタネータのプーリ部分の構造を示しており、プ
ーリ1を支持する転がり軸受2は、高速回転時の潤滑性
を保持するため、軸受内部にグリースを封入したグリー
ス封入軸受が使用されている。
FIG. 1 shows a structure of a pulley portion of an alternator for an automobile intended for use at high speed rotation. A rolling bearing 2 supporting the pulley 1 retains lubricity at high speed rotation. A grease-filled bearing with grease filled inside is used.

【0004】上記の構造では、プーリ1を小型化したこ
とに伴う伝動効率の低下を防ぐため、プーリ1に伝動ベ
ルトの係合溝3を多数形成し、かつベルトの張力を大き
くとる方法がとられており、このため、上記軸受2には
高温条件での高速回転と高荷重が共に加わることにな
る。
In the above structure, in order to prevent the reduction of the transmission efficiency due to the downsizing of the pulley 1, a method of forming a large number of engaging grooves 3 of the transmission belt on the pulley 1 and increasing the tension of the belt is adopted. Therefore, the bearing 2 is subjected to both high speed rotation and high load under high temperature conditions.

【0005】[0005]

【発明が解決しようとする課題】しかし、上記のような
高速化・高荷重化を伴なう従来のグリースを使用したオ
ルタネータ用軸受では、転走面に生じる剥離(フレーキ
ング)によって、これら軸受が早期に寿命に至る事例が
数多く報告されるようになった。この早期寿命を引き起
こす剥離は、金属疲労により生じる通常の転走面表面な
いし表層の剥離とは違い、相当内部の深い部分から突然
に生じる特異な破壊現象(以下、異常剥離という)であ
って、この異常剥離から生じる軸受寿命は、通常のグリ
ース封入軸受の計算寿命に比べて短寿命を示す。
However, in the bearings for alternators using the conventional grease accompanied with the above-mentioned high speed and high load, the bearings (flaking) generated on the rolling surface cause these bearings. Many cases have been reported that lead to early life. The peeling that causes this early life is a peculiar fracture phenomenon (hereinafter referred to as abnormal peeling) that suddenly occurs from a deep portion inside, unlike normal peeling of the raceway surface or surface layer caused by metal fatigue. The bearing life resulting from this abnormal peeling is shorter than the calculated life of a normal grease-filled bearing.

【0006】上記異常剥離の原因については、この発明
者らは、高速化による振動が転走面の鏡面摩耗を引き起
こし、それによる新生面の形成が触媒作用となってグリ
ースが分解し、その際に発生した水素が鋼中に侵入し脆
化する現象(以下、水素脆性現象という)によることを
解明し、これを防止するために、鋼の表面にいわゆる黒
染処理等の不活性化処理を行なう技術を開示した(特開
平2−190615号)。
Regarding the cause of the above-mentioned abnormal peeling, the inventors of the present invention have found that the vibration due to the increase in speed causes the mirror surface of the rolling contact surface to wear, and the resulting new surface acts as a catalyst to decompose the grease. It is clarified that the generated hydrogen penetrates into the steel and becomes brittle (hereinafter referred to as the hydrogen embrittlement phenomenon), and in order to prevent this, the surface of the steel is subjected to an inactivation treatment such as so-called black dyeing treatment. The technology has been disclosed (Japanese Patent Laid-Open No. 2-190615).

【0007】また、他の解決策として、特開平3−25
0094号では、水素との結合力の強いフェニルエーテ
ルを基油とするグリースを開示した。
Further, as another solution, Japanese Patent Laid-Open No. 3-25
Japanese Patent No. 0094 discloses a grease based on phenyl ether, which has a strong bonding force with hydrogen, as a base oil.

【0008】しかし、上記フェニルエーテル油を基油と
するグリースは、粘度特性に劣るので、軸受転走面に充
分に供給され難い。従って、このようなグリースを封入
した転がり軸受は、特に軸受保持器端面からシールまで
の距離の設定条件により、高速回転かつ高荷重条件下で
は焼付現象を起こし易くなる。
However, since the grease using the above phenyl ether oil as a base oil is inferior in viscosity characteristics, it is difficult to sufficiently supply it to the bearing rolling surface. Therefore, such a rolling bearing in which grease is filled is apt to cause a seizure phenomenon under high-speed rotation and high-load conditions, particularly depending on the setting condition of the distance from the end surface of the bearing cage to the seal.

【0009】また、フェニルエーテルを基油とした上記
のグリースでは、前記した水素脆性現象の発生を確実に
抑えることは難しかった。さらにまた、多様な使用条件
が想定されるオルタネータ用の転がり軸受は、泥水等が
侵入しても発錆を充分に抑える特性も要求される。
Further, with the above grease using phenyl ether as a base oil, it was difficult to reliably suppress the occurrence of the hydrogen embrittlement phenomenon. Furthermore, rolling bearings for alternators, which are expected to be used under various conditions, are required to have the property of sufficiently suppressing rusting even when muddy water enters.

【0010】そこで、この発明は、上記した問題点を解
決し、高速回転かつ高荷重条件下においても水素脆性現
象を起こさず耐久性があり、また防錆性にも優れたオル
タネータ用グリース封入転がり軸受とすることを課題と
している。
In view of the above, the present invention solves the above-mentioned problems, does not cause hydrogen embrittlement even under high-speed rotation and high-load conditions, has durability, and is excellent in rust prevention. The challenge is to make it a bearing.

【0011】[0011]

【課題を解決するための手段】上記の課題を解決するた
めに、この発明は、アルキルジフェニルエーテル油とポ
リαオレフィン油を20:80から80:20の重量比
で配合した基油に、増稠剤として芳香族ジウレア化合物
または芳香族ウレア・ウレタン化合物を5〜40重量%
配合し、さらに不動態化酸化剤および有機スルホン酸塩
を添加したグリース組成物をオルタネータ用転がり軸受
内に封入したのである。以下、その詳細を述べる。
In order to solve the above-mentioned problems, the present invention provides a base oil prepared by blending an alkyl diphenyl ether oil and a poly-α-olefin oil in a weight ratio of 20:80 to 80:20. 5-40% by weight of aromatic diurea compound or aromatic urea-urethane compound as an agent
The grease composition in which the passivation oxidant and the organic sulfonate were blended and further added was enclosed in the rolling bearing for the alternator. The details will be described below.

【0012】この発明に用いるアルキルジフェニルエー
テル油は、ジフェニルエーテル1モルと炭素数10〜2
2のαオレフィン1〜3モルの付加反応によって得られ
るものである。アルキルジフェニルエーテル油の一例を
下記〔化1〕の式に示す。
The alkyl diphenyl ether oil used in the present invention comprises 1 mol of diphenyl ether and 10 to 2 carbon atoms.
It is obtained by the addition reaction of 1 to 3 mol of the α-olefin of 2. An example of the alkyl diphenyl ether oil is shown in the formula of the following [Chemical formula 1].

【0013】[0013]

【化1】 [Chemical 1]

【0014】この発明に用いるポリαオレフィン油は、
αオレフィンを低重合し、その末端二重結合に水素を添
加した構造であり、下記〔化2〕の(I)、(II)、
(III)、(IV)の式にそれぞれ示すものが例示でき
る。
The poly-α-olefin oil used in the present invention is
It has a structure in which an α-olefin is low-polymerized, and hydrogen is added to the terminal double bond, and (I), (II) in the following [Chemical formula 2]
The compounds represented by the formulas (III) and (IV) can be exemplified.

【0015】[0015]

【化2】 [Chemical 2]

【0016】この発明の基油におけるアルキルジフェニ
ルエーテル油とポリαオレフィン油との配合重量比は2
0:80から80:20である。なぜなら基油中のポリ
αオレフィン油が上記範囲未満では、低温下での性能が
劣り、上記範囲を越えると、耐熱性が充分に得られなく
なって好ましくないからである。また、グリースの分解
による水素発生量を可及的に少なくするため、アルキル
ジフェニルエーテル油のポリαオレフィン油に対する特
に好ましい配合量比は、50:50以上である。
The blending weight ratio of the alkyl diphenyl ether oil and the poly-α-olefin oil in the base oil of the present invention is 2
It is from 0:80 to 80:20. This is because if the amount of poly-α-olefin oil in the base oil is less than the above range, the performance at low temperature is poor, and if it exceeds the above range, heat resistance cannot be sufficiently obtained, which is not preferable. Further, in order to reduce the amount of hydrogen generated due to the decomposition of grease as much as possible, the particularly preferable compounding ratio of the alkyl diphenyl ether oil to the poly α-olefin oil is 50:50 or more.

【0017】つぎに、この発明において増稠剤として使
用する芳香族ジウレア化合物は、分子中にウレア結合
(−NHCONH−)を2個有する下記〔化3〕の式で
示されるような化合物であって、グリース製造工程にお
いては、基油を溶媒としてモノアミンと芳香族ジイソシ
アネートを配合し、基油中に細かく析出させて得られ
る。
Next, the aromatic diurea compound used as the thickener in the present invention is a compound having two urea bonds (-NHCONH-) in the molecule and represented by the formula [Chemical Formula 3] below. In the grease production process, the base oil is used as a solvent to blend the monoamine and the aromatic diisocyanate, and finely precipitated in the base oil.

【0018】[0018]

【化3】 [Chemical 3]

【0019】増稠剤として他方の芳香族ウレア・ウレタ
ン化合物は、分子中にウレア結合(−NHCONH−)
およびウレタン結合(−NHCOO−)の両方を有する
下記〔化4〕の式で示されるような化合物であって、イ
ソシアネートとアルコール、アミンをトルエンまたは基
油を溶媒として反応させ、基油またはトルエン中に析出
させて得られる。
The other aromatic urea-urethane compound as a thickener has a urea bond (-NHCONH-) in the molecule.
And a urethane bond (-NHCOO-), which is a compound represented by the following formula [Chemical Formula 4], wherein isocyanate and alcohol, amine are reacted with toluene or base oil as a solvent, It is obtained by precipitating.

【0020】[0020]

【化4】 [Chemical 4]

【0021】このような芳香族ジウレア化合物または芳
香族ウレア・ウレタン化合物の前記基油に対する添加量
は、5〜40重量%である。なぜなら、5重量%未満の
少量の芳香族ジウレア化合物または芳香族ウレア・ウレ
タン化合物を添加して得たグリースは、粘性の乏しい液
状となり、40重量%を越える多量では固体状となっ
て、不適となるからである。
The amount of such an aromatic diurea compound or aromatic urea-urethane compound added to the base oil is 5 to 40% by weight. This is because the grease obtained by adding a small amount of an aromatic diurea compound or an aromatic urea-urethane compound of less than 5% by weight becomes a liquid having a low viscosity, and a large amount of more than 40% by weight becomes a solid state, which is unsuitable. Because it will be.

【0022】つぎに、この発明に用いる不動態化酸化剤
は、オルタネータ用転がり軸受を構成する鋼などの金属
表面に対して不動態化を起こさせる酸化剤であり、たと
えば亜硝酸塩、硝酸塩、クロム酸塩、リン酸塩、モリブ
デン酸塩、タングステン酸塩等のカソード復極型の無機
腐食抑制剤を使用する。
Next, the passivating oxidant used in the present invention is an oxidant that causes passivation to the metal surface such as steel constituting the rolling bearing for the alternator, and examples thereof include nitrite, nitrate and chromium. Cathode depolarizing inorganic corrosion inhibitors such as acid salts, phosphates, molybdates, and tungstates are used.

【0023】また、この発明に用いる有機スルホン酸塩
とは、一般式RSO3 Mで示される化合物であって、こ
のものは、分子内に、極性基(SO3 2-)を有する有機
スルホン酸(RSO3 )と、Ba、Zn、Ca等のアル
カリ土類金属、もしくは金属類としてPb、Na、Li
等またはアミン類からなる親油基Mとを有する油溶性界
面活性剤型の化合物である。有機スルホン酸としては、
石油スルホン酸、アルキルベンゼンスルホン酸、ジノニ
ルナフタレンスルホン酸が挙げられる。
The organic sulfonate used in the present invention is a compound represented by the general formula RSO 3 M, which is an organic sulfonic acid having a polar group (SO 3 2− ) in the molecule. (RSO 3 ) and alkaline earth metals such as Ba, Zn and Ca, or Pb, Na and Li as metals.
And a lipophilic group M composed of an amine or the like and an oil-soluble surfactant type compound. As organic sulfonic acid,
Examples include petroleum sulfonic acid, alkylbenzene sulfonic acid, and dinonylnaphthalene sulfonic acid.

【0024】なお、この発明に用いるグリース組成物の
耐圧性を高める場合には、ジチオリン酸亜鉛等の極圧添
加剤を0.1〜5重量%配合すれば適当である。
In order to improve the pressure resistance of the grease composition used in the present invention, it is suitable to add 0.1 to 5% by weight of an extreme pressure additive such as zinc dithiophosphate.

【0025】[0025]

【作用】高速回転、高荷重の条件で使用される軸受にお
いて、転走面に生じる現象を考えると、転走面には、回
転中の振動とその表面を高速度で擦過摺接する転動体に
より絶えず鏡面摩耗が引き起こされると想定される。
In a bearing used under conditions of high speed rotation and high load, considering the phenomenon that occurs on the rolling contact surface, the rolling contact surface is formed by the vibration during rotation and the rolling element that makes rubbing sliding contact on the surface at high speed. It is assumed that there will be constant mirror wear.

【0026】このような摩耗が生じると、その摩耗によ
って引き起こされる新生面の形成が触媒作用をしてグリ
ースが化学分解し、このグリースの分解により多量の水
素が新生面の形成領域に発生する。
When such abrasion occurs, the formation of a new surface caused by the abrasion acts as a catalyst to chemically decompose the grease, and a large amount of hydrogen is generated in the area where the new surface is formed by the decomposition of the grease.

【0027】そして、この発生した水素は、鋼の内部に
容易に侵入することができ、さらに引張り応力が集中し
ている箇所に拡散移動するので、応力が集中する金属面
の奥側に水素分子形成による高圧が発生し、これが亀裂
を生じさせて破壊を生じさせることが判明した。
The generated hydrogen can easily penetrate into the inside of the steel, and diffusely moves to a place where the tensile stress is concentrated, so that hydrogen molecules are deep inside the metal surface where the stress is concentrated. It has been found that high pressures are generated by the formation, which cause cracking and destruction.

【0028】そこで、この発明の軸受の基材表面の水素
脆性発生防止機構について、以下に図2を参照しつつ説
明する。
Therefore, the mechanism for preventing hydrogen embrittlement on the surface of the base material of the bearing of the present invention will be described below with reference to FIG.

【0029】転がり軸受の基材4表面は、不動態化酸化
剤によって酸化された金属酸化物からなる不動態膜5で
被覆され、この上に有機スルホン酸塩6のスルホン酸基
6aが単分子層状に強く吸着する。不動態膜5は、分極
した構造を持つため、極性のあるスルホン酸基6aと相
互作用を持ちやすいからである。そして、有機スルホン
酸塩6は、親油基6bを外側に向けて配向するので、親
油基6bのさらに外側には基油の油膜7が安定して形成
されることとなる。
The surface of the base material 4 of the rolling bearing is covered with a passivation film 5 made of a metal oxide oxidized by a passivating oxidizer, and a sulfonic acid group 6a of an organic sulfonate 6 is unimolecular on the surface. Strongly adsorbs in layers. This is because the passivation film 5 has a polarized structure and is likely to interact with the polar sulfonic acid group 6a. Since the organic sulfonate 6 is oriented with the lipophilic group 6b facing outward, the oil film 7 of the base oil is stably formed further outside the lipophilic group 6b.

【0030】このような基材4表面の油膜構造による
と、図外の転動体がこの表面に擦過摺接した際、油膜7
が除去されても不動態膜5が新生面8の露出を防止し、
さらに不動態膜5が剥離して新生面8が露出した場合で
も、基油に配合されたアルキルジフェニルエーテル油の
物性により、水素の発生量は極力抑制される。アルキル
ジフェニルエーテルは、エステルに比べてC−H、C−
C、C−Oの結合解離エネルギーが高く、分解され難い
からである。
According to such an oil film structure on the surface of the base material 4, when the rolling element (not shown) makes sliding contact with this surface, the oil film 7 is formed.
Even if the film is removed, the passive film 5 prevents the new surface 8 from being exposed,
Further, even when the passivation film 5 is peeled off and the new surface 8 is exposed, the amount of hydrogen generated is suppressed as much as possible due to the physical properties of the alkyldiphenyl ether oil blended in the base oil. Alkyl diphenyl ether has C-H, C-, as compared with ester.
This is because the bond dissociation energy of C and C—O is high and it is difficult to decompose.

【0031】なお、前記した不動態膜5上の有機スルホ
ン酸塩6は、油膜7切れを速やかに回復させるので、水
素脆性の発生は一層抑制されると考えられる。
Since the organic sulfonate 6 on the passivation film 5 promptly recovers the breakage of the oil film 7, it is considered that the occurrence of hydrogen embrittlement is further suppressed.

【0032】[0032]

【実施例】【Example】

〔実施例1および2〕アルキルジフェニルエーテル油と
ポリαオレフィン油の混成油からなる基油を表1に示す
配合割合で調製し、この基油の半量に1molの4,
4’−ジフェニルメタンジイソシアネートを溶かし、残
りの半量の基油に2molのモノアミン(パラトルイジ
ン)を溶かして前記半量の基油に撹拌しながら加えた
後、100〜120℃で30分間撹拌を続けて反応させ
てジウレア化合物(芳香族ジウレア化合物)を基油に折
出した。これに酸化防止剤としてフェノチアジンを0.5
重量%を加えて、さらに100〜120℃で10分間撹
拌した。その後冷却し、添加剤であるジンクスルホネー
トを1重量%と多価アルコールエステルを1重量%と亜
硝酸ナトリウム0.5重量%を添加混合してから、三本
ロールで均質化し、グリース組成物を得た。このグリー
ス組成物の稠度、滴点、摩擦係数を測定すると共に、転
がり軸受に封入してオルタネータ実機耐久試験および錆
試験を以下のように行ない、この結果を表1中に併記し
た。
[Examples 1 and 2] A base oil composed of a mixed oil of an alkyl diphenyl ether oil and a poly-α-olefin oil was prepared at a blending ratio shown in Table 1, and 1 mol of 4, 4
4'-diphenylmethane diisocyanate was dissolved, 2 mol of monoamine (paratoluidine) was dissolved in the remaining half amount of the base oil, and the mixture was added to the half amount of the base oil while stirring, and then the reaction was continued by stirring at 100 to 120 ° C for 30 minutes. Then, the diurea compound (aromatic diurea compound) was deposited on the base oil. Phenothiazine was added to this as an antioxidant at 0.5.
Weight% was added and the mixture was further stirred at 100 to 120 ° C. for 10 minutes. After cooling, 1% by weight of zinc sulfonate as an additive, 1% by weight of polyhydric alcohol ester and 0.5% by weight of sodium nitrite were added and mixed, and then homogenized with a three-roll mill to prepare a grease composition. Obtained. The consistency, dropping point, and coefficient of friction of this grease composition were measured, and the grease composition was sealed in a rolling bearing and subjected to an alternator actual machine durability test and a rust test as follows, and the results are also shown in Table 1.

【0033】稠 度:JIS K2220 5.3に
より測定した。
Consistency: Measured according to JIS K2220 5.3.

【0034】滴 点:グリースが融解して自重で落下
し始める温度(℃)をグリース類滴点試験法JIS K
2220 5.4により測定した。
Drop point: The temperature (° C.) at which grease melts and begins to fall by its own weight is the grease drop point test method JIS K
2220 5.4.

【0035】摩擦係数:図3に示すように、モータ軸9
に固定したリング10(直径40mm、肉厚4mm、SUJ
2)の下部にサンプルであるグリースを塗布したフェル
ト11を摺接するよう取付け、1000rpmで回転す
るリング10の上端にプレート12に固定したボール1
3(直径6.35mm、SUJ2)を圧接した。この際、
摩擦力にて発生する力Fを下記測定条件で測定し、摩擦
係数を算出した。
Friction coefficient: As shown in FIG.
Fixed to the ring 10 (diameter 40 mm, wall thickness 4 mm, SUJ
The ball 11 fixed to the plate 12 is attached to the lower part of 2) so that the felt 11 coated with grease is slidably contacted and the upper end of the ring 10 rotating at 1000 rpm.
3 (diameter 6.35 mm, SUJ2) was pressed. On this occasion,
The force F generated by the frictional force was measured under the following measurement conditions, and the friction coefficient was calculated.

【0036】記 測定時間 回転開始5分後、荷重P 1.2kgf、温度
室温。
Measurement time 5 minutes after the start of rotation, load P 1.2 kgf, temperature room temperature.

【0037】錆 試 験:ASTM D 1743の錆
試験法をさらに厳しくした方法で、軸受6302に試料
グリースを1.6〜1.9g封入してからゴム製シール
をし、アキシャル荷重を39.2N加えて毎分1800
回転で1分間慣らし運転した。次に、3%食塩水を0.
5ml軸受内部へ注入した後、再びアキシャル荷重を3
9.2N加えて毎分1800回転で3分間回転した。こ
の軸受をデシケータに入れ40℃で100時間放置した
後、発錆状況を調べた。発錆状況は内輪レースを周方向
に22等分、外輪レースを周方向に30等分して錆のあ
った区間を数え、試験回数n=4回の平均を錆評点とし
た。
Rust test: According to the method of rust test of ASTM D 1743, the bearing 6302 was filled with 1.6 to 1.9 g of sample grease and sealed with a rubber, and the axial load was set to 39.2N. Plus 1800 per minute
It was run-in for 1 minute by rotation. Next, add 3% saline to 0.
After injecting into the 5ml bearing, apply an axial load of 3 again.
9.2 N was added and the rotation was performed at 1800 rpm for 3 minutes. After placing this bearing in a desiccator and leaving it at 40 ° C. for 100 hours, the rusting condition was examined. Regarding the rusting condition, the inner ring race was divided into 22 equal parts in the circumferential direction and the outer ring race was equally divided into 30 parts in the circumferential direction, and the rusted section was counted.

【0038】オルタネータ実機耐久試験:図1に示すオ
ルタネータにおけるプーリ1側の転がり軸受2を使用
し、実機により寿命試験(n:試験回数)を行なった。
テストの軸受回転数は18,000rpmで設定し、プ
ーリ1に対する負荷荷重を330kgで行なった。そし
て、軸受内に剥離が発生し、振動検出器の振動が設定値
以上になって発電機が停止する時間を異常剥離寿命と
し、試験回数nの平均を求めた。また、軸受内グリース
が劣化したことによって軸受の回転トルクが過大にな
り、このオルタネータを駆動している電動機の入力電流
が制限電流を超過するまでの時間を焼付寿命とし試験回
数nの平均を求めた。
Alternator actual machine endurance test: Using the rolling bearing 2 on the pulley 1 side of the alternator shown in FIG. 1, a life test (n: number of tests) was carried out by an actual machine.
The bearing rotation speed in the test was set at 18,000 rpm, and the load applied to the pulley 1 was 330 kg. Then, the time during which the peeling occurred in the bearing, the vibration of the vibration detector exceeded the set value and the generator stopped, was taken as the abnormal peeling life, and the average of the number of tests n was calculated. Also, the rotational torque of the bearing becomes excessive due to the deterioration of the grease in the bearing, and the time until the input current of the motor driving this alternator exceeds the limit current is taken as the seizure life and the average of the number of tests n is calculated. It was

【0039】[0039]

【表1】 [Table 1]

【0040】また、基油の配合割合と摩擦係数との関係
を調べるため、以下のような実験を行なった。すなわ
ち、表2に示す割合でアルキルジフェニルエーテルとポ
リαオレフィン油を混合し、その摩擦係数を前記した図
3に示す装置を用い、前記と全く同様の測定条件で調べ
た。この結果を表2中に併記した。
Further, in order to investigate the relationship between the blending ratio of the base oil and the friction coefficient, the following experiment was conducted. That is, alkyl diphenyl ether and poly α-olefin oil were mixed in the proportions shown in Table 2, and the friction coefficient thereof was examined using the apparatus shown in FIG. 3 and under the same measurement conditions as above. The results are also shown in Table 2.

【0041】[0041]

【表2】 [Table 2]

【0042】〔実施例3〕極圧添加剤としてジチオリン
酸亜鉛を1重量%配合する以外は実施例1と全く同様に
してグリース組成物を調製し、前記各試験を行なった結
果を表1中に併記した。
Example 3 A grease composition was prepared in the same manner as in Example 1 except that 1% by weight of zinc dithiophosphate was blended as an extreme pressure additive, and the results of the above-mentioned tests are shown in Table 1. Also described in.

【0043】〔実施例4〕アルキルジフェニルエーテル
油とポリαオレフィン油の混成油からなる基油を表1に
示す配合割合で調製し、この基油の半量に1molの
4,4’−ジフェニルメタンジイソシアネートを溶か
し、残りの半量の基油に2molのモノアミン(パラト
ルイジン)を溶かして前記半量の基油に撹拌しながら加
えた後、100〜120℃で30分間撹拌を続けて反応
させてジウレア化合物(芳香族ジウレア化合物)を基油
に配合した。これに酸化防止剤としてフェノチアジンを
0.5重量%を加えて、さらに100〜120℃で10分
間撹拌した。その後冷却し、添加剤であるバリウムスル
ホネートを3重量%添加混合してから、三本ロールで均
質化し、グリース組成物を得た。得られたグリース組成
物およびこれを封入した転がり軸受について、実施例1
と全く同様に試験を行い、この結果を表1中に併記し
た。
Example 4 A base oil composed of a mixed oil of an alkyl diphenyl ether oil and a poly-α-olefin oil was prepared in a blending ratio shown in Table 1, and 1 mol of 4,4′-diphenylmethane diisocyanate was added to half the base oil. After being dissolved, 2 mol of monoamine (paratoluidine) was dissolved in the remaining half amount of the base oil and added to the half amount of the base oil while stirring, and then the reaction was continued by stirring at 100 to 120 ° C. for 30 minutes to react the diurea compound (aromatic Group diurea compound) was added to the base oil. Phenothiazine (0.5% by weight) as an antioxidant was added thereto, and the mixture was further stirred at 100 to 120 ° C for 10 minutes. After cooling, 3% by weight of barium sulfonate as an additive was added and mixed, and then homogenized with a triple roll to obtain a grease composition. About the obtained grease composition and the rolling bearing in which the grease composition is enclosed, Example 1
A test was conducted in exactly the same manner as above, and the results are also shown in Table 1.

【0044】〔実施例5および6〕1molのハイドロ
キノンをトルエンに分散させ、2molの2,4−トリ
レンジイソシアネートを滴下し、約50℃に保持したま
ま60分間攪拌した。この時の反応触媒としてはトリエ
チルアミンを用いた。さらに、1molのアニリンを加
え、約80℃に保持したまま60分間攪拌し、1mol
のラウリルアミン飽和トルエン溶液を加えて、180分
間攪拌させ、ウレア・ウレタン化合物の増稠剤を調整し
た。そして、表1に示したアルキルジフェニルエーテル
油とポリαオレフィン油の混成油からなる基油と酸化防
止剤であるフェノチアジンを加え、30分間攪拌し、こ
の液をホーロー製バットにあけ、一夜室温に放置した
後、150℃に設定したマッフル炉に30分間入れて脱
ソルベントを行なった。その後、三本ロールで均質化し
てグリース組成物を得た。得られたグリース組成物およ
び、これを封入した転がり軸受について、実施例1と全
く同様に試験を行ない、この結果を表1中に併記した。
[Examples 5 and 6] 1 mol of hydroquinone was dispersed in toluene, 2 mol of 2,4-tolylene diisocyanate was added dropwise, and the mixture was stirred for 60 minutes while maintaining it at about 50 ° C. Triethylamine was used as the reaction catalyst at this time. Further, 1 mol of aniline was added, and the mixture was stirred for 60 minutes while maintaining it at about 80 ° C.
The laurylamine saturated toluene solution of was added and stirred for 180 minutes to prepare a thickening agent for the urea-urethane compound. Then, a base oil consisting of a mixed oil of an alkyl diphenyl ether oil and a poly-α-olefin oil shown in Table 1 and phenothiazine as an antioxidant were added and stirred for 30 minutes, and this liquid was placed in a enamel vat and left overnight at room temperature. After that, it was placed in a muffle furnace set at 150 ° C. for 30 minutes for desolventization. Then, it homogenized with a triple roll to obtain a grease composition. The obtained grease composition and the rolling bearing in which the grease composition was enclosed were tested in exactly the same manner as in Example 1, and the results are also shown in Table 1.

【0045】〔比較例1〕アルキルジフェニルエーテル
油の単独成分を基油とし、1molの4,4’−ジフェ
ニルメタンジイソシアネートを基油(重量%)の半量に
溶かした液に、残りの半量の基油に2molのモノアミ
ン(パラトルイジン)を溶かして撹拌しながら加えた
後、100〜120℃で30分間撹拌を続けて反応させ
てジウレア化合物(芳香族ジウレア化合物)を基油に配
合した。これに酸化防止剤としてフェノチアジンを0.
5重量%を加えて、さらに100〜120℃で10分間
撹拌した。その後冷却し、亜硝酸ナトリウムを0.5重
量%加えてから、三本ロールで均質化し、グリース組成
物を得た。得られたグリース組成物およびこれを封入し
た転がり軸受について実施例1と全く同様の試験を行な
い、この結果を表3中に併記した。
Comparative Example 1 Using a single component of an alkyldiphenyl ether oil as a base oil, 1 mol of 4,4′-diphenylmethane diisocyanate was dissolved in half of the base oil (% by weight), and the remaining half of the base oil was added. 2 mol of monoamine (paratoluidine) was melted and added with stirring, and then the mixture was continuously stirred for 30 minutes at 100 to 120 ° C. to react to blend a diurea compound (aromatic diurea compound) into the base oil. Phenothiazine was added to this as an antioxidant.
5% by weight was added, and the mixture was further stirred at 100 to 120 ° C. for 10 minutes. Then, the mixture was cooled, 0.5% by weight of sodium nitrite was added, and then homogenized with a triple roll to obtain a grease composition. The same test as in Example 1 was performed on the obtained grease composition and the rolling bearing in which the grease composition was enclosed, and the results are also shown in Table 3.

【0046】〔比較例2〕ポリαオレフィン油の単独成
分を基油とし、1molの4,4’−ジフェニルメタン
ジイソシアネートを基油(重量%)の半量に溶かした液
に、残りの半量の基油に2molのモノアミン(シクロ
ヘキシルアミン)を溶かして撹拌しながら加えた後、1
00〜120℃で30分間撹拌を続けて反応させてジウ
レア化合物(脂環族ジウレア化合物)を基油に配合し
た。これに酸化防止剤としてフェノチアジンを0.5重
量%を加えて、さらに100〜120℃で10分間撹拌
した。
Comparative Example 2 Using a single component of poly-α-olefin oil as a base oil, 1 mol of 4,4′-diphenylmethane diisocyanate was dissolved in half of the base oil (% by weight), and the remaining half of the base oil was added. 2 mol of monoamine (cyclohexylamine) was dissolved in and added with stirring, and then 1
Stirring was continued for 30 minutes at 00 to 120 ° C. to cause reaction, and the diurea compound (alicyclic diurea compound) was blended with the base oil. To this, 0.5% by weight of phenothiazine as an antioxidant was added, and the mixture was further stirred at 100 to 120 ° C for 10 minutes.

【0047】その後冷却ししてから、三本ロールで均質
化し、グリース組成物を得た。得られたグリース組成物
およびこれを封入した転がり軸受について実施例1と全
く同様の試験を行ない、この結果を表3中に併記した。
After cooling, the mixture was homogenized with a three-roll mill to obtain a grease composition. The same test as in Example 1 was performed on the obtained grease composition and the rolling bearing in which the grease composition was enclosed, and the results are also shown in Table 3.

【0048】〔比較例3および4〕アルキルジフェニル
エーテル油と鉱油またはポリオールエステル油からなる
基油および増稠剤を表3に示す配合割合で比較例1と同
様に調製し、均質化してグリース組成物を得た。
[Comparative Examples 3 and 4] A base oil comprising an alkyl diphenyl ether oil and a mineral oil or a polyol ester oil and a thickener were prepared in the same proportion as in Comparative Example 1 and homogenized to prepare a grease composition. Got

【0049】これらグリース組成物を転がり軸受に封入
して、前記した錆試験およびオルタネータ実機耐久試験
を以下のように行ない、この結果を表3中に併記した。
These grease compositions were enclosed in rolling bearings, and the above-mentioned rust test and alternator actual machine durability test were conducted as follows, and the results are also shown in Table 3.

【0050】[0050]

【表3】 [Table 3]

【0051】表1および表3に示す試験結果から明らか
なように、基油としてアルキルジフェニルエーテル油と
ポリαオレフィン油を前記の所定範囲内で配合しなかっ
たグリースを用いた比較例1および2、または不動態化
酸化剤を使用しなかった比較例2〜4は、摩擦係数、錆
評点、オルタネータ実機耐久性の一以上の項目で劣って
いた。一方、所定の基油、増稠剤、不動態化酸化剤およ
び有機スルホン酸塩を所定の配合割合で調製した実施例
1〜6では、全ての試験項目で満足し得る結果が得ら
れ、特に、実施例3において総合的に最も優れた結果が
得られた。
As is clear from the test results shown in Tables 1 and 3, Comparative Examples 1 and 2 using the grease in which the alkyl diphenyl ether oil and the poly α-olefin oil were not blended within the above-mentioned predetermined range as the base oil, Alternatively, Comparative Examples 2 to 4 in which the passivating oxidant was not used were inferior in one or more items of the friction coefficient, the rust rating, and the alternator actual machine durability. On the other hand, in Examples 1 to 6 in which predetermined base oils, thickeners, passivating oxidizers and organic sulfonates were prepared in predetermined mixing ratios, satisfactory results were obtained in all test items, and particularly, In Example 3, the best overall results were obtained.

【0052】[0052]

【効果】この発明のオルタネータ用グリース封入転がり
軸受は、以上のように構成したので、高速回転かつ高荷
重条件下においても軸受転走面に水素脆性現象に伴う異
常剥離を起こさず耐久性があり、また上記利点と共に防
錆性にも優れたものとなって一層長寿命であり、特にオ
ルタネータの軸受として優れたものであるという利点が
ある。
[Effect] Since the rolling bearing with grease filled for the alternator of the present invention is configured as described above, it is durable and does not cause abnormal peeling due to the hydrogen embrittlement phenomenon on the rolling surface of the bearing even under conditions of high speed rotation and high load. Further, in addition to the above advantages, there is an advantage that the rust prevention property is excellent and the life is further longer, and particularly, the bearing is excellent as an alternator bearing.

【図面の簡単な説明】[Brief description of drawings]

【図1】オルタネータおよびその軸受の一部切り欠き縦
断面図
FIG. 1 is a partially cutaway vertical sectional view of an alternator and its bearing.

【図2】軸受の基材表面の水素脆性発生防止機構を説明
する模式図
FIG. 2 is a schematic diagram illustrating a mechanism for preventing hydrogen embrittlement from occurring on the surface of a bearing base material.

【図3】摩擦係数の測定装置を模式化して示す説明図FIG. 3 is an explanatory view schematically showing a friction coefficient measuring device.

【符号の説明】[Explanation of symbols]

1 プーリ 2 軸受 3 伝動ベルトの係合溝 4 基材 5 不動態膜 6 有機スルホン酸塩 7 油膜 1 Pulley 2 Bearing 3 Engagement groove of transmission belt 4 Base material 5 Passive film 6 Organic sulfonate 7 Oil film

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C10M 135:10 125:20 7419−4H 125:24 125:22) C10N 10:02 10:04 30:00 Z 8217−4H 30:12 40:02 50:10 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C10M 135: 10 125: 20 7419-4H 125: 24 125: 22) C10N 10:02 10:04 30 : 00 Z 8217-4H 30:12 40:02 50:10

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 アルキルジフェニルエーテル油とポリα
オレフィン油を20:80から80:20の重量比で配
合した基油に、増稠剤として芳香族ジウレア化合物また
は芳香族ウレア・ウレタン化合物を5〜40重量%配合
し、さらに不動態化酸化剤および有機スルホン酸塩を添
加したグリース組成物を転がり軸受内に封入してなるオ
ルタネータ用グリース封入転がり軸受。
1. Alkyl diphenyl ether oil and poly α
5 to 40% by weight of an aromatic diurea compound or an aromatic urea-urethane compound as a thickener is added to a base oil in which an olefin oil is added in a weight ratio of 20:80 to 80:20, and a passivating oxidant is further added. A grease-filled rolling bearing for an alternator in which a grease composition containing an organic sulfonate is filled in the rolling bearing.
JP4173093A 1992-01-22 1992-06-30 Rolling bearing with grease for alternator Expired - Lifetime JP2557597B2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ITMI930056A IT1263745B (en) 1992-01-22 1993-01-18 CONTACT ROLLING BEARING CLOSED WITH GREASE
KR1019930000657A KR970002552B1 (en) 1992-01-22 1993-01-20 Grease-sealed rolling contact bearing
DE4301438A DE4301438C2 (en) 1992-01-22 1993-01-20 Lubricant and its use
FR9300520A FR2686348B1 (en) 1992-01-22 1993-01-20 GREASE COMPOSITION FOR A SEALLESS LUBRICATING BEARING.
US08/006,796 US5301923A (en) 1992-01-22 1993-01-21 Grease-sealed rolling contact bearing
GB9301158A GB2263482B (en) 1992-01-22 1993-01-21 A grease composition and a grease-sealed rolling bearing incorporating the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP932992 1992-01-22
JP4-9329 1992-01-22

Publications (2)

Publication Number Publication Date
JPH05263091A true JPH05263091A (en) 1993-10-12
JP2557597B2 JP2557597B2 (en) 1996-11-27

Family

ID=11717436

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4173093A Expired - Lifetime JP2557597B2 (en) 1992-01-22 1992-06-30 Rolling bearing with grease for alternator

Country Status (2)

Country Link
JP (1) JP2557597B2 (en)
KR (1) KR970002552B1 (en)

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JP2003105366A (en) * 2001-09-27 2003-04-09 Ntn Corp Grease composition and bearing with sealed grease
JP2006002018A (en) * 2004-06-17 2006-01-05 Ntn Corp Torque limiter
JP2006071104A (en) * 1997-07-02 2006-03-16 Nsk Ltd Rolling bearing
JP2007132520A (en) * 1997-07-02 2007-05-31 Nsk Ltd Rolling bearing
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US7438477B2 (en) 2001-11-29 2008-10-21 Ntn Corporation Bearing part, heat treatment method thereof, and rolling bearing
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US7744283B2 (en) 2003-03-14 2010-06-29 Ntn Corporation Bearing for alternator and bearing for pulley
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JP2006071104A (en) * 1997-07-02 2006-03-16 Nsk Ltd Rolling bearing
JP2007132520A (en) * 1997-07-02 2007-05-31 Nsk Ltd Rolling bearing
JP2003105366A (en) * 2001-09-27 2003-04-09 Ntn Corp Grease composition and bearing with sealed grease
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US7438477B2 (en) 2001-11-29 2008-10-21 Ntn Corporation Bearing part, heat treatment method thereof, and rolling bearing
US7490583B2 (en) 2002-10-17 2009-02-17 Ntn Corporation Full-type rolling bearing and roller cam follower for engine
US7334943B2 (en) 2003-02-28 2008-02-26 Ntn Corporation Differential support structure, differential's component, method of manufacturing differential support structure, and method of manufacturing differential's component
US7682087B2 (en) 2003-02-28 2010-03-23 Ntn Corporation Transmission component, method of manufacturing the same, and tapered roller bearing
US7744283B2 (en) 2003-03-14 2010-06-29 Ntn Corporation Bearing for alternator and bearing for pulley
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US9376644B2 (en) 2006-03-29 2016-06-28 Kyodo Yushi Co., Ltd. Lubricant composition
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US9719045B2 (en) 2012-10-26 2017-08-01 Kyodo Yushi Co., Ltd. Grease composition
WO2015016376A1 (en) 2013-08-02 2015-02-05 協同油脂株式会社 Grease composition
US10077411B2 (en) 2013-08-02 2018-09-18 Kyodo Yushi Co., Ltd. Grease composition
EP3666860A1 (en) 2018-11-06 2020-06-17 Kyodo Yushi Co., Ltd. Anti-flaking agent and lubricant composition comprising the same
JP2021123605A (en) * 2020-01-31 2021-08-30 Ntn株式会社 Grease composition, and grease-sealed bearing
CN116113683A (en) * 2020-08-12 2023-05-12 株式会社捷太格特 Grease composition and rolling bearing
US12037561B2 (en) 2020-08-12 2024-07-16 Jtekt Corporation Grease composition, and rolling bearing

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KR970002552B1 (en) 1997-03-06
JP2557597B2 (en) 1996-11-27
KR930016680A (en) 1993-08-26

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