JP4979744B2 - Rolling bearings for automotive electrical equipment and accessories - Google Patents
Rolling bearings for automotive electrical equipment and accessories Download PDFInfo
- Publication number
- JP4979744B2 JP4979744B2 JP2009171488A JP2009171488A JP4979744B2 JP 4979744 B2 JP4979744 B2 JP 4979744B2 JP 2009171488 A JP2009171488 A JP 2009171488A JP 2009171488 A JP2009171488 A JP 2009171488A JP 4979744 B2 JP4979744 B2 JP 4979744B2
- Authority
- JP
- Japan
- Prior art keywords
- electrical equipment
- molybdate
- rolling bearing
- rolling
- acid
- 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 - Lifetime
Links
- 238000005096 rolling process Methods 0.000 title claims description 75
- 239000004519 grease Substances 0.000 claims description 47
- -1 organic acid salt Chemical class 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 31
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- 239000003921 oil Substances 0.000 claims description 23
- 239000002199 base oil Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000002562 thickening agent Substances 0.000 claims description 13
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
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Images
Description
本発明は自動車電装・補機用転がり軸受に関し、特にファンカップリング装置、オルタネータ、アイドラプーリ、カーエアコン用電磁クラッチ、電動ファンモータ等の自動車電装部品、補機用の転がり軸受に関する。 TECHNICAL FIELD The present invention relates to rolling bearings for automobile electrical equipment and auxiliary equipment, and more particularly to fan electrical coupling equipment, alternators, idler pulleys, electromagnetic clutches for car air conditioners, electric fan motors and other automotive electrical components, and rolling bearings for auxiliary equipment.
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、エンジンルーム内の電装補機においては、小型化に伴なって生じる出力の低下を高速回転させることで補う手法が採られている。
以下に、自動車電装・補機用転がり軸受の例として、ファンカップリング装置用転がり軸受、自動車用オルタネータ用転がり軸受およびアイドラプーリ用転がり軸受について概要を説明する。
In recent years, along with demands for miniaturization, weight reduction and quietness improvement of automobiles, miniaturization, weight reduction and sealing of engine compartments have been attempted for the electrical parts and auxiliary parts. The demand for high output and high efficiency is increasing in the performance of the engine itself, and in the electrical equipment in the engine room, a method is used to compensate for the decrease in output caused by downsizing by rotating at high speed. .
Hereinafter, outlines of a rolling bearing for a fan coupling device, a rolling bearing for an alternator for an automobile, and a rolling bearing for an idler pulley will be described as examples of the rolling bearing for an electric vehicle / auxiliary machine.
自動車用ファンカップリング装置は、内部に粘性流体を封入し、外周面に送風用のファンが取り付けられたハウジングを、軸受を介してエンジンに直結するロータに連結され、雰囲気温度に感応して増減する粘性流体の剪断抵抗を利用して、エンジンからの駆動トルク伝達量およびファンの回転数を制御することにより、エンジン温度に対応した最適な送風を行なう装置である。
このため、ファンカップリング装置用転がり軸受は、エンジン温度の変動に伴い回転数が 1000 rpm から 10000 rpm まで変動する回転ムラの他に、夏場の高速運転時には 180 ℃以上の高温下で、回転数 10000 rpm 以上の高速回転という極めて過酷な環境に耐えられる耐熱性、グリースシール性、耐久性が要求される。
A fan coupling device for automobiles has a housing in which viscous fluid is sealed inside and a fan for blowing air on the outer peripheral surface is connected to a rotor directly connected to the engine via a bearing, and increases or decreases in response to the ambient temperature. It is a device that performs optimum ventilation corresponding to the engine temperature by controlling the amount of drive torque transmitted from the engine and the rotational speed of the fan using the shearing resistance of the viscous fluid.
For this reason, the rolling bearings for fan coupling devices have a rotational speed of 180 ° C or higher during high-speed operation in summer, in addition to uneven rotation where the rotational speed varies from 1000 rpm to 10000 rpm as the engine temperature varies. Heat resistance, grease sealability, and durability that can withstand extremely harsh environments of high speed rotation of 10,000 rpm or higher are required.
自動車用オルタネータは、エンジンの回転をベルトで受けて発電し、車両の電気負荷に電力を供給するとともに、バッテリーを充電する機能を有する。このためオルタネータ用転がり軸受は、 180 ℃以上の高温下で、回転数 10000 rpm 以上の高速回転という極めて過酷な環境に耐えられる耐熱性、グリースシール性、耐久性が要求される。
耐熱、耐久性が求められるシール部材の弾性体としてフッ化ビニリデン−テトラフルオロエチレン−プロピレンの３元共重合体、またはテトラフルオロエチレン−プロピレン２元共重合体を採用することにより、ウレア系グリースとの組み合わせにおいて、転がり軸受の耐久性を向上させる方法が知られている（特許文献１）。
The alternator for automobiles has a function of generating power by receiving rotation of an engine with a belt, supplying electric power to an electric load of the vehicle, and charging a battery. For this reason, rolling bearings for alternators are required to have heat resistance, grease sealability and durability that can withstand extremely harsh environments such as high-speed rotations of 10,000 rpm or higher at high temperatures of 180 ° C or higher.
By adopting a terpolymer of vinylidene fluoride-tetrafluoroethylene-propylene or a tetrafluoroethylene-propylene binary copolymer as an elastic body of a seal member that requires heat resistance and durability, In this combination, a method for improving the durability of the rolling bearing is known (Patent Document 1).
また、本出願人は、ファンカップリング装置用転がり軸受およびオルタネータ用転がり軸受として、ウレア化合物を含有するグリースを用い、このグリースを封止するためのシール部材に、少なくとも該グリースに接触するゴム成形体を有し、該ゴム成形体がテトラフルオロエチレンと、プロピレンと、水素原子の一部がフッ素原子で置換された炭素数２〜４の不飽和炭化水素からなる架橋用単量体とを含む共重合体からなる加硫可能なフッ素ゴム組成物の成形体を用いた転がり軸受に関して出願している（特願２００４−７０８４および特願２００４−６７０９２）。 Further, the applicant of the present invention uses a grease containing a urea compound as a rolling bearing for a fan coupling device and a rolling bearing for an alternator, and a rubber molding that contacts at least the grease is used as a seal member for sealing the grease. The rubber molded body contains tetrafluoroethylene, propylene, and a crosslinking monomer composed of an unsaturated hydrocarbon having 2 to 4 carbon atoms in which a part of hydrogen atoms are substituted with fluorine atoms. An application has been filed for rolling bearings using a vulcanizable fluororubber composition formed of a copolymer (Japanese Patent Application Nos. 2004-7084 and 2004-67092).
自動車用アイドラプーリは、エンジンの回転を自動車の補機に伝える駆動ベルトのベルトテンショナーとして使用されるものであり、軸間距離が固定されているような場合のベルトにテンショナーとして張力を与えるためのプーリとしての機能と、ベルトの走行方向を変えるため、または障害物を避けるために用いてエンジン室内容積の減少を図るアイドラーとしての機能とを合わせもつものである。
このため、アイドラプーリ用転がり軸受は、 180 ℃以上の高温下で、回転数 10000 rpm 以上の高速回転という極めて過酷な環境に耐えられる耐熱性、グリースシール性、耐久性が要求される。
高温、高速回転で使用される転がり軸受に好適なグリース組成物として、基油に対する酸化防止能を有する融点 80 ℃以上のアミド系ワックスをグリース組成物に 0.5 〜 10 重量％配合し、かつ 40 ℃における動粘度が 20 〜 150 mm2/s の基油を用い、グリース組成物の増ちょう剤がウレア系増ちょう剤であリ、グリース組成物全体に対して 5 〜30 重量％配合されたグリース組成物が知られている（特許文献２）。
The idler pulley for automobiles is used as a belt tensioner for a drive belt that transmits engine rotation to the auxiliary equipment of the automobile, and is used to apply tension as a tensioner to the belt when the center distance is fixed. The function as a pulley is combined with the function as an idler that is used to change the running direction of the belt or to avoid an obstacle to reduce the volume of the engine compartment.
For this reason, idler pulley rolling bearings are required to have heat resistance, grease sealability, and durability that can withstand extremely harsh environments such as high-speed rotations of 10,000 rpm or higher at high temperatures of 180 ° C or higher.
As a grease composition suitable for rolling bearings used at high temperature and high speed, an amide wax having a melting point of 80 ° C or higher, which has an antioxidant ability for base oil, is blended in the grease composition at 0.5-10% by weight, and 40 ° C. Grease formulated with a base oil having a kinematic viscosity of 20 to 150 mm 2 / s and a thickener in the grease composition is a urea thickener, and 5 to 30% by weight based on the total grease composition A composition is known (Patent Document 2).
ところが、使用条件が過酷になることで、転がり軸受の転走面に白色組織変化を伴った特異的な剥離が早期に生じ、問題になっている。
この特異的な剥離は、通常の金属疲労により生じる転走面内部からの剥離と異なり、転走面表面の比較的浅いところから生じる破壊現象で、水素が原因の水素脆性と考えられている。
このような早期に発生する白色組織変化を伴った特異な剥離現象を防ぐ方法として、例えばグリース組成物に不動態化剤を添加する方法が知られている（特許文献３）。
しかしながら、近年の自動車電装・補機に用いられる転がり軸受の使用条件の過酷化に伴い、不動態化剤を添加する方法では充分な対策ができなくなってきている。
However, due to severe usage conditions, specific peeling accompanied with white structure change occurs early on the rolling surface of the rolling bearing, which is a problem.
This specific exfoliation is different from the exfoliation from the inside of the rolling contact surface caused by normal metal fatigue, and is a fracture phenomenon that occurs from a relatively shallow portion of the surface of the rolling contact surface and is considered to be hydrogen embrittlement caused by hydrogen.
As a method for preventing such a specific peeling phenomenon accompanied by a white tissue change that occurs at an early stage, for example, a method of adding a passivating agent to a grease composition is known (Patent Document 3).
However, with the recent increase in the usage conditions of rolling bearings used in automobile electrical equipment and accessories, it has become impossible to take sufficient measures with the method of adding a passivating agent.
本発明はこのような問題に対処するためになされたものであり、水素脆性による転走面での剥離を効果的に防止できる自動車電装・補機用転がり軸受の提供を目的とする。 The present invention has been made to cope with such problems, and an object of the present invention is to provide a rolling bearing for automobile electrical equipment and auxiliary equipment that can effectively prevent peeling on a rolling surface due to hydrogen embrittlement.
本発明の自動車電装・補機用転がり軸受は、180 ℃以上の高温、回転数 10000 rpm 以上の高速回転で、かつ、急加減速を伴う使用環境下において、エンジン出力で回転駆動される回転軸を静止部材に回転自在に支持する自動車電装・補機用転がり軸受であって、上記転がり軸受は、内輪および外輪と、この内輪および外輪間に介在する複数の転動体と、この転動体の周囲にグリース組成物を封止するためのシール部材を上記内輪および外輪の軸方向両端開口部に設けてなり、上記グリース組成物は、基油に、増ちょう剤と添加剤とを配合してなるグリース組成物であって、上記添加剤は少なくともモリブデン酸塩および有機酸塩を含むことを特徴とする。
また、上記モリブデン酸塩がモリブデン酸ナトリウム、モリブデン酸カリウムおよびモリブデン酸リチウムから選ばれた少なくとも一つのモリブデン酸塩であることを特徴とする。
また、上記有機酸塩が炭素数 1 から炭素数 20 の有機酸のナトリウム塩であることを特徴とする。特に有機酸が、安息香酸、セバシン酸、またはコハク酸であることを特徴とする。
各成分の配合割合は、グリース組成物全体に対して、上記モリブデン酸塩が 0.01 〜 5 重量％、該モリブデン酸塩の添加量に対して、上記有機酸塩が 5 〜 70 重量％配合されてなることを特徴とする。
また、上記増ちょう剤がウレア系増ちょう剤であることを特徴とする。
The rolling bearing for automobile electrical equipment / auxiliary machine according to the present invention is a rotating shaft that is driven to rotate at an engine output under a high temperature of 180 ° C. or higher, a high-speed rotation of 10000 rpm or more, and in a use environment with sudden acceleration / deceleration. A rolling bearing for automotive electrical equipment and auxiliary equipment that rotatably supports a stationary member. The rolling bearing includes an inner ring and an outer ring, a plurality of rolling elements interposed between the inner ring and the outer ring, and a periphery of the rolling element. A seal member for sealing the grease composition is provided at both ends of the inner ring and the outer ring in the axial direction, and the grease composition comprises a base oil and a thickener and an additive. A grease composition, wherein the additive contains at least a molybdate and an organic acid salt.
The molybdate is at least one molybdate selected from sodium molybdate, potassium molybdate and lithium molybdate.
The organic acid salt is a sodium salt of an organic acid having 1 to 20 carbon atoms. In particular, the organic acid is benzoic acid, sebacic acid or succinic acid.
The blending ratio of each component is 0.01 to 5% by weight of the molybdate with respect to the entire grease composition, and 5 to 70% by weight of the organic acid salt with respect to the addition amount of the molybdate. It is characterized by becoming.
The thickener is a urea-based thickener.
本発明の自動車電装・補機用転がり軸受は、エンジン出力で回転駆動される回転軸を静止部材に回転自在に支持する自動車電装・補機用転がり軸受であって、前記転がり軸受に封入されるグリース組成物が、軸受部における摩擦摩耗面または摩耗により露出した鉄系金属新生面において酸化鉄とともにモリブデン化合物を含有する膜を形成できるモリブデン酸塩と該膜の形成を促進する有機酸塩とを含有することを特徴とする。
また、上記自動車電装・補機用転がり軸受は、上記内輪および上記外輪の転走面において、水素脆性による剥離の発生を防止できることを特徴とする。
An automotive electrical equipment / auxiliary rolling bearing according to the present invention is an automotive electrical equipment / auxiliary rolling bearing that rotatably supports a rotating shaft driven by an engine output on a stationary member, and is enclosed in the rolling bearing. The grease composition contains a molybdate capable of forming a film containing a molybdenum compound together with iron oxide on a frictional wear surface or a new surface of a ferrous metal exposed by wear in the bearing portion, and an organic acid salt that promotes the formation of the film It is characterized by doing.
In addition, the rolling bearing for automobile electrical equipment / auxiliary equipment can prevent the occurrence of separation due to hydrogen embrittlement on the rolling surfaces of the inner ring and the outer ring.
自動車電装・補機用転がり軸受に封入するグリース組成物は、基油と増ちょう剤とからなるグリースにモリブデン酸塩および有機酸塩を配合してなるので、自動車や産業機械に使用される軸受で見られる水素脆性による特異な剥離の発生を抑制することができ、自動車電装・補機用転がり軸受の長寿命化が図れる。 The grease composition enclosed in rolling bearings for automotive electrical equipment and auxiliary machinery is made by blending molybdate and organic acid salt with grease consisting of base oil and thickener. The occurrence of peculiar delamination due to hydrogen embrittlement, which can be seen in, can be suppressed, and the life of rolling bearings for automobile electrical equipment and auxiliary equipment can be extended.
エンジン出力で回転駆動される回転軸を静止部材に回転自在に支持する自動車電装・補機用転がり軸受の一例を図１に示す。図１はグリース組成物が封入されている深溝玉軸受の断面図である。
深溝玉軸受１は、外周面に内輪転走面２ａを有する内輪２と内周面に外輪転走面３ａを有する外輪３とが同心に配置され、内輪転走面２ａと外輪転走面３ａとの間に複数個の転動体４が配置される。この複数個の転動体４を保持する保持器５および外輪３等に固定されるシール部材６が内輪２および外輪３の軸方向両端開口部８ａ、８ｂにそれぞれ設けられている。少なくとも転動体４の周囲にグリース組成物７が封入される。
FIG. 1 shows an example of a rolling bearing for automobile electrical equipment and auxiliary equipment that rotatably supports a rotating shaft that is driven to rotate by engine output on a stationary member. FIG. 1 is a cross-sectional view of a deep groove ball bearing in which a grease composition is enclosed.
In the deep groove ball bearing 1, an
自動車電装・補機の一例を図２に示す。図２はファンカップリング装置の構造の断面図である。ファンカップリング装置は、冷却用ファン９を支持するケース１０内にシリコーンオイル等の粘性流体が充填されたオイル室１１とドライブディスク１８が組込まれた撹拌室１２とを設け、両室１１、１２間に設けられた仕切板１３にポート１４を形成し、そのポート１４を開閉するスプリング１５の端部を上記仕切板１３に固定している。
また、ケース１０の前面にバイメタル１６を取付け、そのバイメタル１６にスプリング１５のピストン１７を設けている。バイメタル１６はラジエータを通過した空気の温度が設定温度、例えば 60 ℃以下の場合、扁平の状態となり、ピストン１７はスプリング１５を押圧し、スプリング１５はポート１４を閉じる。また、上記空気の温度が設定温度をこえると、バイメタル１６は図２（ｂ）に示すように、外方向にわん曲し、ピストン１７はスプリング１５の押圧を解除し、スプリング１５は弾性変形してポート１４を開放する。
上記の構成からなるファンカップリング装置の運転状態において、ラジエータを通過した空気の温度がバイメタル１６の設定温度より低い場合、ポート１４はスプリング１５によって閉じられているため、オイル室１１内の粘性流体は撹拌室１２内に流れず、その撹拌室１２内の粘性流体は、ドライブディスク１８の回転により仕切板１３に設けた流通穴１９からオイル室１１内に送られる。
このため、撹拌室１２内の粘性流体の量はわずかになり、ドライブディスク１８の回転による剪断抵抗は小さくなるので、ケース１０への伝達トルクは減少し、ファン９は低速回転する。
ラジエータを通過した空気の温度がバイメタル１６の設定温度をこえると、図２（ｂ）に示すように、バイメタル１６は外方向にわん曲し、ピストン１７はスプリング１５の押圧を解除する。このとき、スプリング１５は仕切板１３から離れる方向に弾性変形するため、ポート１４は開放し、オイル室１１内の粘性流体はポート１４から撹拌室１２内に流れる。
このため、ドライブディスク１８の回転による粘性流体の剪断抵抗が大きくなり、ケース１０への回転トルクが増大し、転がり軸受に支持されているファン９が高速回転する。
ファンカップリング装置は温度の変化に応じてファン９の回転速度が変化するため、ウォーミングアップを早めると共に、冷却水の過冷却を防止し、エンジンを効果的に冷却することができる。エンジン温度が低いとファン９はドライブ軸２０と切り離されているに等しく、高温の場合は連結されているに等しい。このように、転がり軸受１は低温から高温まで広い温度範囲および広い回転範囲で使用される。
An example of an automobile electrical equipment / auxiliary machine is shown in FIG. FIG. 2 is a cross-sectional view of the structure of the fan coupling device. The fan coupling device includes an
A
When the temperature of the air that has passed through the radiator is lower than the set temperature of the
For this reason, the amount of viscous fluid in the stirring
When the temperature of the air that has passed through the radiator exceeds the set temperature of the
For this reason, the shear resistance of the viscous fluid due to the rotation of the
In the fan coupling device, the rotation speed of the
自動車電装・補機のオルタネータの一例を図３に示す。図３はオルタネータの構造の断面図である。オルタネータは、静止部材であるハウジングを形成する一対のフレーム２１ａに、ロータ２２を装着されたロータ回転軸２３が、一対の玉軸受１で回転自在に支持されている。ロータ２２にはロータコイル２４が取り付けられ、ロータ２２の外周に配置されたステータ２５には、１２０°の位相で３巻のステータコイル２６が取り付けられている。
ロータ回転軸２３は、その先端に取り付けられたプーリ２７にベルト（図示省略）で伝達される回転トルクで回転駆動されている。プーリ２７は片持ち状態でロータ回転軸２３に取り付けられており、ロータ回転軸２３の高速回転に伴って振動も発生するため、特にプーリ２７側を支持する玉軸受１は、苛酷な負荷を受ける。
An example of an alternator for automobile electrical equipment and auxiliary equipment is shown in FIG. FIG. 3 is a sectional view of the structure of the alternator. The alternator includes a pair of
The
自動車の補機駆動ベルトのベルトテンショナーとして使用されるアイドラプーリの一例を図４に示す。図４はアイドラプーリの構造の断面図である。
このプーリは、鋼板プレス製のプーリ本体２８と、プーリ本体２８の内径に嵌合された単列の深溝玉軸受１とで構成される。プーリ本体２８は、内径円筒部２８ａ、内径円筒部２８ａの一端から外径側に延びたフランジ部２８ｂ、フランジ部２８ｂから軸方向に延びた外径円筒部２８ｃ、内径円筒部２８ａの他端から内径側に延びた鍔部２８ｄからなる環体である。内径円筒部２８ａの内径には、玉軸受１の外輪３が嵌合され、外径円筒部２８ｃの外径にはエンジンによって駆動されるベルトと接触するプーリ周面２８ｅが設けられている。このプーリ周面２８ｅをベルトに接触させることにより、プーリがアイドラとしての役割を果たす。
An example of an idler pulley used as a belt tensioner for an automobile accessory drive belt is shown in FIG. FIG. 4 is a sectional view of the structure of the idler pulley.
The pulley includes a
玉軸受１はプーリ本体２８の内径円筒部２８ａの内径に嵌合された外輪３、図示されていない固定軸に嵌合される内輪２、内・外輪２、３の転走面２ａ、３ａ間に組み込まれた複数の転動体４、転動体４を円周等間隔に保持する保持器５、グリースを密封する一対のシール部材６で構成され、内輪２および外輪３はそれぞれ一体に形成されている。
The
モリブデン酸塩および有機酸塩を配合することにより、摩擦摩耗面または摩耗により露出した金属新生面でモリブデン酸塩が分解・反応し、酸化鉄とともにモリブデン化合物被膜が軸受転走面に生成される。さらにモリブデン酸塩と有機酸塩とを併用することにより、モリブデン酸塩のみを配合した場合に比較して、酸化膜が厚く、モリブデン含有量が多いことが表面分析の結果分かった。よって、有機酸塩は、酸化鉄およびモリブデン化合物被膜の軸受転走面への生成を助長する作用があるものと考えられる。軸受転走面に生成した酸化鉄およびモリブデン化合物被膜は、グリースの分解による水素の発生を抑制して、水素ぜい性による特異な剥離を防止できる。 By blending molybdate and organic acid salt, the molybdate decomposes and reacts on the frictional wear surface or the new metal surface exposed by wear, and a molybdenum compound film is formed on the bearing rolling surface along with iron oxide. Furthermore, by using both molybdate and organic acid salt, as a result of surface analysis, it was found that the oxide film was thicker and the molybdenum content was higher than when only molybdate was blended. Therefore, it is considered that the organic acid salt has an effect of promoting the generation of the iron oxide and molybdenum compound coating on the bearing rolling surface. The iron oxide and molybdenum compound coating formed on the rolling surface of the bearing can suppress the generation of hydrogen due to the decomposition of the grease and prevent unique peeling due to hydrogen embrittlement.
本発明に使用できるモリブデン酸塩は、金属塩であることが好ましい。金属塩を構成する金属としては、ナトリウム、カリウム、リチウム、マグネシウム、カルシウム、銅、亜鉛、バリウム等が例示できる。
軸受部における摩擦摩耗面または摩耗により露出した鉄系金属新生面において反応して、酸化鉄とともにモリブデン化合物を含有する膜を形成しやすい金属としてはアルカリ金属であることから、本発明においては、モリブデン酸塩のアルカリ金属塩が好ましい。好適なアルカリ金属のモリブデン酸塩はモリブデン酸リチウム、モリブデン酸ナトリウムまたはモリブデン酸カリウムが挙げられ、これらは単独でも混合物としても使用できる。
The molybdate that can be used in the present invention is preferably a metal salt. Examples of the metal constituting the metal salt include sodium, potassium, lithium, magnesium, calcium, copper, zinc, barium and the like.
In the present invention, the metal that easily forms a film containing a molybdenum compound together with iron oxide reacts on the frictional wear surface or the newly formed iron-based metal surface exposed by wear in the bearing portion. Alkali metal salts of the salts are preferred. Suitable alkali metal molybdates include lithium molybdate, sodium molybdate or potassium molybdate, which can be used alone or as a mixture.
本発明に使用できる有機酸塩は、芳香族系有機酸、脂肪族系有機酸、または脂環族系有機酸等の塩であればいずれも使用できる。また、有機酸としては一塩基性、多塩基性有機酸を使用できる。これらの中で特に炭素数 1 から炭素数 20 を有する化学構造の有機酸がモリブデン化合物を含有する膜生成を助長するので好ましい。 The organic acid salt that can be used in the present invention can be any salt such as an aromatic organic acid, an aliphatic organic acid, or an alicyclic organic acid. As the organic acid, monobasic or polybasic organic acids can be used. Among these, an organic acid having a chemical structure having 1 to 20 carbon atoms is particularly preferable because it promotes formation of a film containing a molybdenum compound.
有機酸の具体例を例示すれば、蟻酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、ヘプタン酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、ステアリン酸、ノナデシル酸、アラキン酸等の１価飽和脂肪酸、アクリル酸、クロトン酸、ウンデシレン酸、オレイン酸、ガドレイン酸等の１価不飽和脂肪酸、マロン酸、メチルマロン酸、コハク酸、メチルコハク酸、ジメチルマロン酸、エチルマロン酸、グルタル酸、アジピン酸、ジメチルコハク酸、ピメリン酸、テトラメチルコハク酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸等の２価飽和脂肪酸、フマル酸、マレイン酸、オレイン酸等の２価不飽和脂肪酸、酒石酸、クエン酸等の脂肪酸誘導体、安息香酸、フタル酸、トリメリット酸、ピロメリット酸等の芳香族有機酸が挙げられる。 Specific examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecyl Monovalent saturated fatty acids such as acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid and arachidic acid, monounsaturated fatty acids such as acrylic acid, crotonic acid, undecylenic acid, oleic acid and gadoleic acid, malonic acid and methylmalon Divalent saturation such as acid, succinic acid, methyl succinic acid, dimethyl malonic acid, ethyl malonic acid, glutaric acid, adipic acid, dimethyl succinic acid, pimelic acid, tetramethyl succinic acid, suberic acid, azelaic acid, sebacic acid, brassic acid Divalent unsaturated fatty acids such as fatty acids, fumaric acid, maleic acid, oleic acid, tartaric acid, Fatty acid derivatives such as phosphate, benzoic acid, phthalic acid, trimellitic acid, and aromatic organic acids such as pyromellitic acid.
有機酸はその金属塩であることが好ましく、金属塩の中でもナトリウム塩が好ましい。好ましい有機酸の金属塩としては、安息香酸ナトリウム、セバシン酸一ナトリウム塩、セバシン酸二ナトリウム塩、コハク酸一ナトリウム塩、コハク酸二ナトリウム塩が挙げられる。 The organic acid is preferably a metal salt thereof, and a sodium salt is preferable among the metal salts. Preferred metal salts of organic acids include sodium benzoate, monosodium sebacate, disodium sebacate, monosodium succinate, and disodium succinate.
本発明に使用できる基油は、スピンドル油、冷凍機油、タービン油、マシン油、ダイナモ油等の鉱油、高精製度鉱油、流動パラフィン、フィッシャー・トロプシュ法により合成されたＧＴＬ油、ポリブテン、ポリαオレフィン、アルキルナフタレン、脂環式化合物等の炭化水素系合成油、または、天然油脂、ポリオールエステル油、リン酸エステル油、ポリマーエステル油、芳香族エステル油、炭酸エステル油、ジエステル油、ポリグリコール油、シリコーン油、ポリフェニルエーテル油、アルキルジフェニルエーテル油、アルキルベンゼン油、フッ素化油等の非炭化水素系合成油等を使用できる。 Base oils that can be used in the present invention are mineral oils such as spindle oil, refrigerator oil, turbine oil, machine oil, dynamo oil, highly refined mineral oil, liquid paraffin, GTL oil synthesized by the Fischer-Tropsch method, polybutene, poly α Hydrocarbon synthetic oils such as olefins, alkylnaphthalenes and alicyclic compounds, or natural oils, polyol ester oils, phosphate ester oils, polymer ester oils, aromatic ester oils, carbonate ester oils, diester oils, polyglycol oils Non-hydrocarbon synthetic oils such as silicone oil, polyphenyl ether oil, alkyldiphenyl ether oil, alkylbenzene oil, and fluorinated oil can be used.
本発明に使用できる増ちょう剤としては、ベントン、シリカゲル、フッ素化合物、リチウム石けん、リチウムコンプレックス石けん、力ルシウム石けん、カルシウムコンプレックス石けん、アルミニウム石けん、アルミニウムコンプレックス石けん等の石けん類、ジウレア化合物、ポリウレア化合物等のウレア系化合物が挙げられる。耐熱性、コスト等を考慮するとウレア系化合物が望ましい。 Thickeners that can be used in the present invention include benton, silica gel, fluorine compound, lithium soap, lithium complex soap, strong lucium soap, calcium complex soap, aluminum soap, aluminum complex soap, and other soaps, diurea compounds, polyurea compounds, etc. These urea compounds are mentioned. In consideration of heat resistance, cost, and the like, a urea compound is desirable.
ウレア系化合物は、例えば、ジウレア化合物、ポリウレア化合物が挙げられる。ジウレア化合物は、例えば、ジイソシアネートとモノアミンの反応で得られる。ジイソシアネートとしては、フェニレンジイソシアネート、トリレンジイソシアネート、ジフェニルジイソシアネート、ジフェニルメタンジイソシアネート、オクタデカンジイソシアネート、デカンジイソシアネート、ヘキサンジイソシアネー卜等が挙げられ、モノアミンとしては、オクチルアミン、ドデシルアミン、ヘキサデシルアミン、ステアリルアミン、オレイルアミン、アニリン、ｐ−トルイジン、シクロヘキシルアミン等が挙げられる。ポリウレア化合物は、例えば、ジイソシアネートとモノアミン、ジアミンとの反応で得られる。ジイソシアネート、モノアミンとしては、ジウレア化合物の生成に用いられるものと同様のものが挙げられ、ジアミンとしては、エチレンジアミン、プロパンジアミン、ブタンジアミン、ヘキサンジアミン、オクタンジアミン、フェニレンジアミン、トリレンジアミン、キシレンジアミン、ジアミノジフェニルメタン等が挙げられる。 Examples of the urea compound include a diurea compound and a polyurea compound. A diurea compound is obtained by reaction of diisocyanate and a monoamine, for example. Examples of the diisocyanate include phenylene diisocyanate, tolylene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, octadecane diisocyanate, decane diisocyanate, hexane diisocyanate, etc., and monoamines include octylamine, dodecylamine, hexadecylamine, stearylamine, Examples include oleylamine, aniline, p-toluidine, cyclohexylamine and the like. The polyurea compound can be obtained, for example, by reacting diisocyanate with a monoamine or diamine. Examples of the diisocyanate and monoamine include those similar to those used for the production of the diurea compound. Examples of the diamine include ethylenediamine, propanediamine, butanediamine, hexanediamine, octanediamine, phenylenediamine, tolylenediamine, xylenediamine, And diaminodiphenylmethane.
ウレア化合物は、イソシアネート化合物とアミン化合物を反応させることにより得られる。反応性のある遊離基を残さないため、イソシアネート化合物のイソシアネート基とアミン化合物のアミノ基とは略当量となるように配合することが好ましい。
基油にウレア化合物を配合して各種配合剤を配合するためのベースグリースが得られる。ベースグリースは、基油中でイソシアネート化合物とアミン化合物とを反応させて作製する。
A urea compound is obtained by reacting an isocyanate compound and an amine compound. In order not to leave a reactive free radical, the isocyanate group of the isocyanate compound and the amino group of the amine compound are preferably blended so as to be approximately equivalent.
Base grease for blending various compounding agents by blending a urea compound with a base oil can be obtained. The base grease is produced by reacting an isocyanate compound and an amine compound in a base oil.
ベースグリースに対する増ちょう剤の配合割合は、ベースグリース全体に対して増ちょう剤が 1 〜 40 重量％、好ましくは 3 〜 25 重量％配合される。増ちょう剤の含有量が 1 重量％未満では、増ちょう効果が少なくなり、グリース化が困難となり、 40 重量％をこえると得られたベースグリースが硬くなりすぎ、所期の効果が得られ難くなる。 The blending ratio of the thickener to the base grease is 1 to 40% by weight, preferably 3 to 25% by weight, based on the whole base grease. If the content of the thickener is less than 1% by weight, the thickening effect is reduced, making it difficult to make grease. If the content exceeds 40% by weight, the obtained base grease becomes too hard and the desired effect is difficult to obtain. Become.
モリブデン酸塩および有機酸塩の配合割合は、上記ベースグリースと各種配合剤から構成されるグリース組成物全体に対して、上記モリブデン酸塩が 0.01 〜 5 重量％、該モリブデン酸塩の添加量に対して、上記有機酸塩が 5 〜 70 重量％配合される。モリブデン酸塩および有機酸塩の配合割合が上記配合範囲未満だと水素脆性による転走面での剥離を効果的に防止できない。また上記範囲をこえても剥離防止効果がそれ以上に向上しない。 The blending ratio of molybdate and organic acid salt is 0.01-5% by weight of molybdate and the amount of molybdate added to the entire grease composition composed of the base grease and various compounding agents. On the other hand, the organic acid salt is blended in an amount of 5 to 70% by weight. If the blending ratio of molybdate and organic acid salt is less than the above blending range, peeling on the rolling surface due to hydrogen embrittlement cannot be effectively prevented. Moreover, even if it exceeds the said range, the peeling prevention effect does not improve any more.
また、モリブデン酸塩および有機酸塩の混合配合剤とともに、必要に応じて公知のグリース用添加剤を含有させることができる。この添加剤として、例えば、有機亜鉛化合物、アミン系、フェノール系、イオウ系等の酸化防止剤、ベンゾトリアゾールなどの金属不活性剤、ポリメタクリレート、ポリスチレン等の粘度指数向上剤、二硫化モリブデン、グラファイト等の固体潤滑剤、金属スルホネート、多価アルコールエステルなどの防錆剤、有機モリブデンなどの摩擦低減剤、エステル、アルコールなどの油性剤、リン系などの摩耗防止剤等が挙げられる。これらを単独または 2 種類以上組み合せて添加できる。 In addition to a mixed compounding agent of molybdate and organic acid salt, a known additive for grease can be contained as necessary. Examples of the additives include organic zinc compounds, amine-based, phenol-based, sulfur-based antioxidants, metal deactivators such as benzotriazole, polymethacrylate, polystyrene and other viscosity index improvers, molybdenum disulfide, graphite. Examples thereof include solid lubricants such as metal sulfonates, rust preventives such as polyhydric alcohol esters, friction reducing agents such as organic molybdenum, oily agents such as esters and alcohols, and phosphorus-based antiwear agents. These can be added alone or in combination of two or more.
本発明に使用できるグリース組成物は、水素脆性による特異な剥離の発生を抑制することができるので、グリース封入軸受の寿命を向上させることができる。このため、玉軸受、円筒ころ軸受、円すいころ軸受、自動調心ころ軸受、針状ころ軸受、スラスト円筒ころ軸受、スラスト円すいころ軸受、スラスト針状ころ軸受、スラスト自動調心ころ軸受等の封入グリースとして使用できる。 Since the grease composition that can be used in the present invention can suppress the occurrence of peculiar peeling due to hydrogen embrittlement, the life of the grease-sealed bearing can be improved. For this reason, ball bearings, cylindrical roller bearings, tapered roller bearings, spherical roller bearings, needle roller bearings, thrust cylindrical roller bearings, thrust tapered roller bearings, thrust needle roller bearings, thrust spherical roller bearings, etc. Can be used as grease.
実施例１〜実施例１３
表１および表２に示した基油の半量に、４，４−ジフェニルメタンジイソシアナート（ＭＤＩ）を表１および表２に示す割合で溶解し、残りの半量の基油に４，４−ジフェニルメタンジイソシアナートの２倍当量となるモノアミンを溶解した。それぞれの配合割合および種類は表１および表２の通りである。
４，４−ジフェニルメタンジイソシアナートを溶解した溶液を撹拌しながらモノアミンを溶解した溶液を加えた後、100 〜 120 ℃で 30 分間撹拌を続けて反応させて、ジウレア化合物を基油中に生成させた。
これにモリブデン酸塩、有機酸塩および酸化防止剤を表１および表２に示す配合割合で加えてさらに 100 〜 120 ℃で 10 分間撹拌した。その後冷却し、三本ロールで均質化し、グリース組成物を得た。
Examples 1 to 13
4,4-Diphenylmethane diisocyanate (MDI) is dissolved in half of the base oil shown in Table 1 and Table 2 in the proportions shown in Table 1 and Table 2, and 4,4-diphenylmethane is dissolved in the remaining half of the base oil. A monoamine that was twice the equivalent of diisocyanate was dissolved. The respective blending ratios and types are as shown in Tables 1 and 2.
A solution in which monoamine is dissolved is added while stirring the solution in which 4,4-diphenylmethane diisocyanate is dissolved, and then the reaction is continued for 30 minutes at 100 to 120 ° C. to form a diurea compound in the base oil. It was.
To this, molybdate, organic acid salt and antioxidant were added at the blending ratios shown in Tables 1 and 2, and the mixture was further stirred at 100 to 120 ° C. for 10 minutes. Thereafter, the mixture was cooled and homogenized with three rolls to obtain a grease composition.
表１および表２において、基油として用いたアルキルジフェニルエーテル油は松村石油社製商品名のＬＢ１００を、合成炭化水素油は新日鉄化学社商品名のシンフルード６０１を、ポリオールエステルは花王社商品名のカオルーブ２６８をそれぞれ用いた。また鉱油は動粘度 30.7 mm2/s（ 40 ℃）のパラフィン系鉱油を用いた。
酸化防止剤はアルキル化ジフェニルアミンを用いた。
In Tables 1 and 2, the alkyl diphenyl ether oil used as the base oil is LB100 under the trade name of Matsumura Oil Co., Ltd., synthetic hydrocarbon oil is Shinflud 601 under the trade name of Nippon Steel Chemical Co., and polyol ester is the trade name of Kao Corporation. Kaolube 268 was used respectively. As the mineral oil, a paraffinic mineral oil having a kinematic viscosity of 30.7 mm 2 / s (40 ° C.) was used.
As the antioxidant, alkylated diphenylamine was used.
得られたグリース組成物の高温高速試験、急加減速試験、日本工業規格による混和ちょう度測定を行なった。試験方法および試験条件を以下に示す。また、結果を表１および表２に示す。 The obtained grease composition was subjected to a high-temperature high-speed test, a rapid acceleration / deceleration test, and a blending penetration measurement according to Japanese Industrial Standards. Test methods and test conditions are shown below. The results are shown in Tables 1 and 2.
高温高速試験
転がり軸受（６２０４）に各実施例で得られたグリース組成物をそれぞれ 1.8 g 封入し、軸受外輪外径部温度 180 ℃、ラジアル荷重 67 N 、アキシャル荷重 67 N の下で、 10000 rpm の回転数で回転させ、焼きつきに至るまでの時間を測定した。
High-temperature, high-speed test Rolling bearing (6204) was filled with 1.8 g of the grease composition obtained in each example, and the bearing outer ring outer diameter was 180 ° C, radial load was 67 N, and axial load was 67 N, 10000 rpm It was rotated at the number of revolutions, and the time until burn-in was measured.
急加減速試験
電装補機の一例であるオルタネータの回転軸を支持する内輸回転の転がり軸受において、急加減速試験を行なった。急加減速試験条件は、回転軸先端に取り付けたプーリに対する負荷荷重を 3234 N 、回転速度は 0 〜 18000 rpm で運転条件を設定した。そして、軸受内に異常剥離が発生し、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計測した。
Rapid Acceleration / Deceleration Test A rapid acceleration / deceleration test was performed on a rolling bearing with internal rotation that supports the rotating shaft of an alternator, which is an example of an electrical accessory. The rapid acceleration / deceleration test conditions were set such that the load applied to the pulley attached to the tip of the rotating shaft was 3234 N and the rotation speed was 0 to 18000 rpm. Then, abnormal peeling occurred in the bearing, and the time when the generator stopped when the vibration of the vibration detector exceeded the set value was measured.
比較例１〜比較例６
実施例１に準じる方法で、表２に示す配合割合で、増ちょう剤、基油を選択してベースグリ一スを調整し、さらに添加剤を配合してグリース組成物を得た。得られたグリース組成物を実施例１と同様の試験を行なって評価した。結果を表２に示す。
Comparative Examples 1 to 6
By the method according to Example 1, the thickener and base oil were selected at the blending ratios shown in Table 2 to adjust the base grease, and further additives were blended to obtain a grease composition. The obtained grease composition was evaluated by performing the same test as in Example 1. The results are shown in Table 2.
表１および表２に示すように、各実施例は転走面で生じる白色組織変化を伴った特異的な剥離を効果的に防止できるので、高温高速試験および急加減速試験に優れている。各実施例の急加減速試験は全て 300 時間以上を示した。 As shown in Table 1 and Table 2, each example can effectively prevent specific peeling accompanied with a white texture change occurring on the rolling surface, and thus is excellent in a high-temperature high-speed test and a rapid acceleration / deceleration test. All the rapid acceleration / deceleration tests in each example showed 300 hours or more.
本発明の自動車電装・補機用転がり軸受は、転がり軸受に封入するグリース組成物が、転がり軸受の転走面で生じる白色組織変化を伴った特異的な剥離を効果的に防止でき軸受寿命に優れるのでカーエアコン用電磁クラッチ、電動ファンモータ等の自動車電装部品、補機等の転がり軸受、モータ用軸受に利用できる。 According to the rolling bearing for automotive electrical equipment and auxiliary equipment of the present invention, the grease composition enclosed in the rolling bearing can effectively prevent specific peeling accompanied by white structure change occurring on the rolling surface of the rolling bearing, and the bearing life can be improved. Since it is excellent, it can be used for automobile electric parts such as electromagnetic clutches for car air conditioners and electric fan motors, rolling bearings for auxiliary machines, and motor bearings.
１ グリース封入軸受
２ 内輪
３ 外輪
４ 転動体
５ 保持器
６ シール部材
７ グリース組成物
DESCRIPTION OF
Claims (8)
前記グリース組成物は、基油に、増ちょう剤と添加剤とを配合してなるグリース組成物であって、前記添加剤は、少なくともモリブデン酸塩と、有機酸塩とを含み、
前記有機酸塩が、炭素数 2 から炭素数 20 のカルボン酸のナトリウム塩であることを特徴とする自動車電装・補機用転がり軸受。 Automotive electrical equipment / complement that rotatably supports a rotating shaft that is driven to rotate by engine output under a high temperature of 180 ° C or higher, high-speed rotation of 10,000 rpm or higher, and sudden acceleration / deceleration. A rolling bearing for a machine, wherein the rolling bearing includes an inner ring and an outer ring, a plurality of rolling elements interposed between the inner ring and the outer ring, and a seal member for sealing a grease composition around the rolling element. Provided in the axially both ends opening of the inner ring and the outer ring,
The grease composition, a base oil, a grease composition obtained by blending an additive and thickener, wherein the additive is seen containing at least molybdate and an organic acid salt,
A rolling bearing for automobile electrical equipment and accessories , wherein the organic acid salt is a sodium salt of a carboxylic acid having 2 to 20 carbon atoms .
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| JP5738712B2 (en) * | 2011-08-03 | 2015-06-24 | 協同油脂株式会社 | Grease composition |
| JP6534816B2 (en) * | 2015-01-16 | 2019-06-26 | Ntn株式会社 | Rolling bearing |
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| JP2878749B2 (en) * | 1990-01-16 | 1999-04-05 | エヌティエヌ株式会社 | Grease-filled rolling bearings for alternators |
| JP2557597B2 (en) * | 1992-01-22 | 1996-11-27 | エヌティエヌ株式会社 | Rolling bearing with grease for alternator |
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| JP2003013973A (en) * | 2001-06-28 | 2003-01-15 | Ntn Corp | Heat-resistant, high speed, and high-loaded rolling bearing and grease composition |
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