CN103429721A - 润滑脂组合物 - Google Patents

润滑脂组合物 Download PDF

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CN103429721A
CN103429721A CN2012800129327A CN201280012932A CN103429721A CN 103429721 A CN103429721 A CN 103429721A CN 2012800129327 A CN2012800129327 A CN 2012800129327A CN 201280012932 A CN201280012932 A CN 201280012932A CN 103429721 A CN103429721 A CN 103429721A
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grease composition
alkyl
formula
oil
rolling bearing
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今井裕
相田亮
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Kyodo Yushi Co Ltd
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Abstract

根据本发明，提供一种用于汽车电器设备用或汽车辅助设备用滚动轴承的润滑脂组合物，其特征在于，含有以烷基二苯基醚油作为必需成分的基础油，含有下述式(1)所表示的二脲化合物作为增稠剂，并且含有有机磺酸盐系防锈剂和耐负荷添加剂作为抗剥离添加剂。式中，R2表示二苯基甲烷基。R1和R3相同或者不同，表示碳原子数为6～12的芳香族系烃基。本发明的润滑脂组合物被封入汽车电器设备用或辅助用滚动轴承，所述汽车电器设备用或辅助用滚动轴承即使在高温环境下也轴承润滑寿命长，且耐剥离性优异。

Description

润滑脂组合物
技术领域
本发明涉及汽车电器设备用或汽车辅助设备用滚动轴承中所使用的润滑脂组合物。
背景技术
对应汽车的小型轻量化、使用空间扩大化的需求，需要减小引擎室空间，伴随这种需求，发电机、张紧轮等电器、辅助部件也需要小型轻量化。此外，为了静音性，引擎室被密闭化，使用环境变为高温，因而，需要能够耐高温的润滑脂。
此外，由于滑轮的小径化、传动扭矩的增大、皮带耐久性提高，从20世纪80年代中期开始，已由以往的V型皮带转变为采用多Ｖ型皮带，从那时起，就有了在滚动轴承的滚动面上，发生伴随白色组织变化的特异的早期异常剥离的问题。
这样一来，在电器、辅助部件的轴承中，就需要具有高温耐久性和耐氢脆剥离性两种性能的润滑脂。
作为用于滚动轴承的润滑脂，使用以作为廉价的矿物油的锂皂润滑脂、二脲润滑脂以及合成油作为基础油的锂皂润滑脂、二脲润滑脂等。在汽车电器设备、辅助用滚动轴承中所使用的润滑脂中，特别是从高温耐久性的观点出发，往往使用合成油二脲润滑脂。
在专利文献1中，提出了具有下述特征的润滑脂：在含有超过50质量%的量的醚系合成油的基础油中，作为必需成分，含有由下述通式：
R2-NHCONH-R1-NHCONH-R3
所表示的二脲化合物的至少1种组成的凝胶化剂。式中，R1表示碳原子数为6～15的2价芳香族烃基，R2和R3为相同或不同的基团，表示环己基、碳原子数为7～12的环己基衍生物基或碳原子数为8～20的烷基，且环己基或其衍生物基团的含有率，即(环己基或其衍生物基团的数目)/(环己基或其衍生物基的数目＋烷基的数目)×100为50～100%。
此外，在专利文献2中，提出了具有下述特征的脲基脂：以下面的通式：
R1NHCONHR2NHCONHR3
所表示的脲化合物为增稠剂，将其在作为基础油的润滑油中配合3～15重量%。式中的R1和R3表示以十八烷基为必需成分且进一步还含有辛基、十二烷基中的任1种或两种的基团；R2表示碳原子数为6～15的2价烃基，并且，R1和R3的基团所拥有的十八烷基、辛基、十二烷基中，十八烷基的比例以摩尔比率计为20～80摩尔%。
可是，以环己胺、烷基胺为单胺的脲润滑脂与以芳香族胺为单胺的脲润滑脂相比，从高温耐久性的观点出发并不是优选的物质。
在汽车的电器、辅助滚动轴承领域，从以往开始氢脆就成为问题，通过对所使用的润滑脂的性质进行改善来应对。例如，为了抑制由于磨耗而产生的新生面的催化剂作用，已提出在润滑脂中添加钝化氧化剂，使金属表面氧化来抑制表面的催化剂活性，从而抑制由于润滑剂的分解而产生氢(例如专利文献3)。此外，为了抑制由于润滑剂的分解而产生氢，提出了使用苯基醚系合成油作为润滑脂的基础油(例如专利文献4)。作为在摩擦学(トライボロジー)金属材料、各种部件以及水容易侵入的部位所使用的轴承中封入的润滑脂，提出了添加吸收氢的偶氮化合物(例如专利文献5)。作为即使遭受水的浸入也不会发生由氢脆引起的剥离的、用于长寿命的滚动轴承的润滑脂组合物，提出了在基础油中添加有氟化聚合物油、在增稠剂中添加有聚四氟乙烯且含有导电性物质的润滑脂组合物(例如专利文献6)。
可是，这些均为已经产生氢后的作用，也就是说，并不是防止氢向金属内部的侵入的方法，不是能够应对氢脆的方法。
现有技术文献
专利文献
专利文献1:日本专利第2979274号公报
专利文献2:日本特开平1-268793号公报
专利文献3:日本特开平3-210394号公报
专利文献4:日本特开平3-250094号公报
专利文献5:日本特开2002-130301号公报
专利文献6:日本特开2002-250351号公报
发明内容
发明所要解决的课题
本发明所要解决的课题是提供即使在高温环境下也轴承润滑寿命长且耐氢脆剥离性优异的封入汽车电器设备用或辅助用滚动轴承的润滑脂组合物。
本发明的另一个课题是提供封入有前述润滑脂组合物的滚动轴承。
用于解决课题的方法
本发明人等针对上述在高温环境下的轴承润滑寿命和耐氢脆剥离性的课题，通过选择适当的基础油、增稠剂和添加剂，从而使其得到改善。即，根据本发明，提供以下的润滑脂组合物。
1.一种用于汽车电器设备用或汽车辅助设备用滚动轴承的润滑脂组合物，其特征在于，含有以烷基二苯基醚油作为必需成分的基础油，含有下述式(1)所表示的二脲化合物作为增稠剂，并且含有有机磺酸盐系防锈剂和耐负荷添加剂作为抗剥离添加剂。
Figure BDA0000380817520000031
式中，R2表示二苯基甲烷基。R1和R3相同或者不同，表示碳原子数为6～12的芳香族系烃基。
2.根据前述1所述的用于滚动轴承的润滑脂组合物，有机磺酸盐系防锈剂由下述式(2)表示。
[R4-SO3]nM···式(2)
式中，R4表示烷基、烯基、烷基萘基、二烷基萘基、烷基苯基或石油高沸点馏分残基。前述烷基或烯基为直链或支链，碳原子数为2～22。M表示碱金属、碱土金属、锌或铵离子。n表示M的价数。
3.根据前述1或2所述的润滑脂组合物，有机磺酸盐系防锈剂为选自由锌盐和钙盐组成的组中的至少一种。
4.根据前述1～3中任一项所述的润滑脂组合物，耐负荷添加剂为选自由硫代氨基甲酸盐、硫代磷酸盐、环烷酸盐、羧酸盐和有机磷酸酯组成的组中的至少1种。
5.根据前述1～4中任一项所述的润滑脂组合物，耐负荷添加剂为选自由硫代氨基甲酸盐和硫代磷酸盐组成的组中的至少一种。
6.根据前述1～5中任一项所述的润滑脂组合物，其进一步含有胺系抗氧化剂和苯酚系抗氧化剂作为抗氧化剂。
7.汽车电器设备用或辅助用滚动轴承，其封入有前述1～6中任一项所述的润滑脂组合物。
发明效果
本发明的润滑脂组合物即使在高温环境下也轴承润滑寿命长，且耐氢脆剥离性优异。
具体实施方式
增稠剂
使用下述式(1)所表示的二脲化合物作为增稠剂：
Figure BDA0000380817520000041
式中，R2表示二苯基甲烷基。R1和R3相同或者不同，表示碳原子数为6～12的芳香族系烃基。作为R1和R3的具体例子，可以列举苯胺、苄基胺、甲苯胺、氯苯胺等。其中，优选甲苯胺。
通过在基础油中含有式(1)的增稠剂，能够获得即使在高温下也耐热性优异的润滑脂。
前述增稠剂可以通过例如使单胺与二异氰酸酯在10～150℃下进行反应而得到，但其反应方法没有特殊限制，可以通过公知的方法来实施。此时可以使用挥发性的溶剂，但如果将基础油作为溶剂来使用，就可以直接配合于本发明的组合物中。作为可以具体使用的二异氰酸酯，可以列举例如二苯基甲烷-4,4’-二异氰酸酯。
从耐泄漏性的观点出发，本发明的组合物中前述增稠剂的量优选为10～30质量%，更优选为15～25质量%。
这里，作为润滑脂所使用的增稠剂，一般而言，虽然号称可以使用包含Li、Na等的金属皂类、膨润土(ベントン)、硅胶、二脲化合物、聚四氟乙烯所代表的氟系增稠剂等非皂类等，但金属皂类、膨润土、硅胶并不是满足耐热性、即在高温下的轴承润滑寿命的增稠剂。此外，氟系增稠剂虽然满足耐热性，但非常昂贵，缺乏通用性。
基础油
基础油以在高温下耐热性优异的烷基二苯基醚油为必需成分。烷基可以为支链，也可以为直链，但优选为直链。烷基的碳原子数优选为10～20，优选为12～14。烷基二苯基醚油可以单独使用一种，也可以并用二种以上。
在烷基二苯基醚油与其他基础油并用的情况下，该基础油的种类没有特殊限定。可以使用例如二酯、多元醇酯所代表的酯系合成油，聚α-烯烃、聚丁烯所代表的合成烃油、硅胶系合成油、氟系合成油等。
在并用烷基二苯基醚油与其他基础油的情况下，基础油中的烷基二苯基醚油的含量没有特殊限定，但从耐热性的观点出发，优选以基础油的全部质量为基准优选含有50质量%以上。
关于40℃时的基础油的运动粘度没有特殊限定，但优选为30～300mm2/s。更优选为50～200mm2/s，进一步优选为50～150mm2/s。
如果40℃时的基础油的运动粘度比300mm2/s高，则变得不能满足低温流动性。如果40℃时的基础油的运动粘度比30mm2/s低，则会蒸发，耐热性方面是不优选的。
添加剂
本发明的润滑脂组合物含有以有机磺酸盐系防锈剂和耐负荷添加剂为必需成分的抗剥离添加剂。通过并用这些物质，即使在严格的润滑条件下，也可以提高剥离寿命。
作为有机磺酸盐系防锈剂，可以适当使用下述式(2)所表示的化合物：
[R4-SO3]nM···式(2)
式中，R4表示烷基、烯基、烷基萘基、二烷基萘基、烷基苯基或石油高沸点馏分残基。前述烷基或烯基为直链或支链，碳原子数为2～22。作为R4，优选烷基的碳原子数优选为6～18、更优选为8～12、特别优选为9的二烷基萘基。
M表示碱金属、碱土金属、锌或铵离子。优选为碱土金属和锌。作为碱土金属，优选钙。
n表示M的价数。
有机磺酸盐系防锈剂优选为选自由锌盐和钙盐组成的组中的至少一种。有机磺酸盐系防锈剂特别优选为二壬基萘磺酸锌盐和/或二壬基萘磺酸钙盐。
本发明的润滑脂组合物中有机磺酸盐系防锈剂的量优选为0.1～10质量%，更优选为0.2～5质量%。
作为耐负荷添加剂，可以使用二烷基二硫代氨基甲酸锌盐(ZnDTP)等硫代氨基甲酸盐，二烷基二硫代磷酸锌盐等硫代磷酸盐，环烷酸锌、环烷酸钙等环烷酸盐，烷基羧酸锌等羧酸盐和三辛基磷酸酯、三苯基硫代磷酸酯等有机磷酸酯等。
耐负荷添加剂优选为选自由硫代氨基甲酸盐、硫代磷酸盐、环烷酸盐、羧酸盐和有机磷酸酯组成的组中的至少1种，更优选为选自由硫代氨基甲酸盐和硫代磷酸盐组成的组中的至少一种。
耐负荷添加剂可以为碱金属盐、碱土金属盐、锌盐或铵盐。优选为锌盐。
作为耐负荷添加剂，特别优选硫代氨基甲酸锌盐、硫代磷酸锌盐，最优选二烷基二硫代氨基甲酸锌盐、二烷基二硫代磷酸锌盐。
本发明的组合物中耐负荷添加剂的含量优选为0.1～10质量%，更优选为0.2～5质量%。
本发明的组合物中抗剥离添加剂的量优选为0.1～10质量%，更优选为0.2～8质量%。
此外，根据需要，本发明的润滑脂组合物可以含有任何添加剂。作为例子，可以列举胺系、苯酚系等抗氧化剂。特别优选作为初始(一次)抗氧化剂的胺系、苯酚系抗氧化剂。为了在广阔的温度范围进行使用，与单独使用这些物质相比，更优选进行并用。以本发明的润滑脂组合物的全部质量为基准，胺系抗氧化剂的添加量优选为0.1～5质量%，更优选为0.5～4质量%。苯酚系抗氧化剂的添加量也同样地优选为0.1～5质量%，更优选为0.5～4质量%。并用胺系与苯酚系时的总添加量优选为0.5～6质量%，更优选为1～5质量%。
此外，作为其他添加剂的例子，可以列举胺系、苯酚系以外的抗氧化剂，例如喹啉系等，亚硝酸钠等无机钝化剂，胺系、羧酸盐等前述有机磺酸系防锈剂以外的防锈剂，苯并三唑等金属腐蚀防止剂，脂肪酸、脂肪酸酯、磷酸酯等油性剂，前述耐负荷添加剂以外的磷系、硫系、有机金属系等耐磨耗剂、极压剂，氧化金属盐、二硫化钼等固体润滑剂等。以本发明的润滑脂组合物的全部质量为基准，这些任意的添加剂的量通常为0.5～5质量%。
本发明的组合物的工作锥入度(混和ちょう度)可以适当调整，优选为200～400，更优选为250～350。
对于作为本发明润滑脂组合物的用途的汽车电器设备或汽车辅助设备用滚动轴承，可以列举发电机、汽车空调用电磁离合器、中间皮带轮(中間プーリ)、惰轮(アイドラプーリ)、张紧轮等滚动轴承。
实施例
试验润滑脂的调整
在下述基础油中，使二苯基甲烷二异氰酸酯1摩尔和单胺(环己胺、辛基胺、对甲苯胺)进行反应而升温、冷却后，得到基础油脂。在基础油脂中加入下述添加剂和基础油，用3联辊研磨后，使工作锥入度为350，得到实施例1～6和比较例1～8的润滑脂组合物。
基础油
○烷基二苯基醚油
·C12～C14烷基二苯基醚油：40℃的运动粘度＝97mm2/s
○多元醇酯油
·二季戊四醇酯油：40℃的运动粘度＝76.9mm2/s
○合成烃油
·聚α-烯烃油：40℃的运动粘度＝68.0mm2/s
抗剥离添加剂
防锈剂
○磺酸Zn
·二壬基萘磺酸酸Zn盐
○磺酸Ca
·二壬基萘磺酸Ca盐
耐负荷添加剂
○ZnDTP
·二烷基二硫代磷酸Zn
○ZnDTC
·二烷基二硫代氨基甲酸Zn
抗氧化剂
○胺系抗氧化剂
·烷基二苯基胺
○苯酚系抗氧化剂
·受阻酚
试验方法
(1)轴承润滑寿命试验(遵从ASTM D3336)
本试验是对高温下的轴承润滑寿命进行评价的内圈旋转试验。使滚动轴承在下述条件下运转，将直至马达产生过电流(4安培)或直至轴承温度上升+15℃的时间作为润滑寿命。将结果示于表1和表2。
轴承形式：6204金属密封
试验温度：180℃
转数：10000rpm
试验负荷：轴向负荷66.7N    径向负荷66.7N
(2)4球滚动试验
试验方法的概要
准备3个φ15mm的轴承用钢球，配置于内径40mm、高度14mm的容器内，填充约20g试验润滑脂。使1个φ5/8英寸的轴承用钢球接触于该3个钢球上。
施加负荷，旋转4小时进行磨合后，在试验部导入氢气。如果以规定的转速旋转，则下侧的3个钢球一边自转一边公转。使其连续旋转直至钢球面上产生剥离。将寿命设为产生剥离的时间点的上钢球相对于下钢球的接触次数。这里，剥离产生于表面压力最高的球-球之间。
使用实施例和比较例的润滑脂组合物作为试验润滑脂进行上述试验。
将结果示于表1和表2。
试验条件
试验钢球：φ5/8in轴承用钢球(旋转球)、φ15mm轴承用钢球(从动球)
试验负荷：100kgf(4.1GPa)
旋转速度：1500rpm
氢导入量：15mL/分钟
氢纯度：99.99%
试验部气压：0.96气压(由于减压排气)
试验重复数：5(平均寿命：n＝5的平均)
评价
轴承润滑寿命试验   400小时以上···○(合格)
不到400小时···×(不合格)
4球滚动试验试验   20×106次以上···○(合格)
不到20×106次···×(不合格)
综合评价
轴承润滑寿命试验、4球滚动试验均合格···○(合格)
轴承润滑寿命试验、4球滚动试验中任1个不合格···×(不合格)
表1
Figure BDA0000380817520000091
表2
Figure BDA0000380817520000101
增稠剂为芳香族二脲(由二苯基甲烷二异氰酸酯和对甲基苯胺形成)、基础油含有烷基二苯基醚油、含有规定的添加剂的实施例1～6的润滑脂组合物的轴承润滑寿命和4球滚动试验均合格。
另一方面，不含有任一种的比较例1～8的润滑脂组合物轴承润滑寿命和4球滚动试验均不合格。

Claims (7)

1.一种润滑脂组合物，是用于汽车电器设备用或汽车辅助设备用滚动轴承的润滑脂组合物，其特征在于，
含有以烷基二苯基醚油作为必需成分的基础油，
含有下述式(1)所表示的二脲化合物作为增稠剂，并且
含有有机磺酸盐系防锈剂和耐负荷添加剂作为抗剥离添加剂；
Figure FDA0000380817510000011
式中，R2表示二苯基甲烷基；R1和R3相同或者不同，表示碳原子数为6～12的芳香族系烃基。
2.根据权利要求1所述的用于滚动轴承的润滑脂组合物，有机磺酸盐系防锈剂由下述式(2)表示，
[R4-SO3]nM···式(2)，
式中，R4表示烷基、烯基、烷基萘基、二烷基萘基、烷基苯基或石油高沸点馏分残基；所述烷基或烯基为直链或支链，碳原子数为2～22；M表示碱金属、碱土金属、锌或铵离子；n表示M的价数。
3.根据权利要求1或2所述的润滑脂组合物，有机磺酸盐系防锈剂为选自由锌盐和钙盐组成的组中的至少一种。
4.根据权利要求1～3中任一项所述的润滑脂组合物，耐负荷添加剂为选自由硫代氨基甲酸盐、硫代磷酸盐、环烷酸盐、羧酸盐和有机磷酸酯组成的组中的至少1种。
5.根据权利要求1～4中任一项所述的润滑脂组合物，耐负荷添加剂为选自由硫代氨基甲酸盐和硫代磷酸盐组成的组中的至少一种。
6.根据权利要求1～5中任一项所述的润滑脂组合物，其进一步含有胺系抗氧化剂和苯酚系抗氧化剂来作为抗氧化剂。
7.汽车电器设备用或辅助用滚动轴承，其封入有权利要求1～6中任一项所述的润滑脂组合物。
CN2012800129327A 2011-03-17 2012-03-19 润滑脂组合物 Pending CN103429721A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115867632A (zh) * 2020-07-06 2023-03-28 株式会社捷太格特 润滑脂组合物和滚动轴承
CN116113683A (zh) * 2020-08-12 2023-05-12 株式会社捷太格特 润滑脂组合物和滚动轴承

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009270058A (ja) * 2008-05-09 2009-11-19 Kyodo Yushi Co Ltd 等速ジョイント用グリース組成物及び等速ジョイント
CN103097504B (zh) * 2011-08-26 2014-06-18 日本精工株式会社 润滑脂组合物和滚动装置
JP6041202B2 (ja) 2012-10-26 2016-12-07 協同油脂株式会社 グリース組成物
US10266787B2 (en) 2012-11-16 2019-04-23 Idemitsu Kosan Co., Ltd. Grease composition
JP6292569B2 (ja) * 2013-12-04 2018-03-14 協同油脂株式会社 等速ジョイント用グリース組成物及びそのグリース組成物を封入した等速ジョイント
US10611765B2 (en) 2014-11-06 2020-04-07 Ohio State Innovation Foundation Pyrrolopyrimidine derivatives as Mps1/TTK kinase inhibitors
JP6744708B2 (ja) * 2015-01-21 2020-08-19 セイコーインスツル株式会社 転がり軸受用グリース、転がり軸受、転がり軸受装置及び情報記録再生装置
MY173662A (en) * 2015-02-09 2020-02-14 Moresco Corp Lubricant composition, use thereof, and aliphatic ether compound
JP6845633B2 (ja) * 2016-08-04 2021-03-17 協同油脂株式会社 グリース組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2263482A (en) * 1992-01-22 1993-07-28 Ntn Toyo Bearing Co Ltd Grease composition for rolling contact bearing
JPH05194979A (ja) * 1992-01-22 1993-08-03 Ntn Corp 軸受封入用グリース組成物
CN101910386A (zh) * 2008-01-23 2010-12-08 协同油脂株式会社 润滑油组合物以及机械部件

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2706169B1 (fr) * 1991-10-04 1996-09-27 Nsk Ltd Composition de graisse pour paliers soumis à des conditions élevées de température, de vitesse et de charge.
JP3519417B2 (ja) * 1991-10-04 2004-04-12 協同油脂株式会社 高温・高速・高荷重印加用の低起動トルク性に優れる軸受用グリース組成物
JP2557597B2 (ja) * 1992-01-22 1996-11-27 エヌティエヌ株式会社 オルタネータ用グリース封入転がり軸受
JP2979274B2 (ja) 1992-06-29 1999-11-15 日本精工株式会社 高速ころがり軸受用グリース組成物
JP3464063B2 (ja) * 1994-12-27 2003-11-05 Ｎｔｎ株式会社 転がり軸受封入用グリース組成物
US6417143B1 (en) * 1998-10-30 2002-07-09 Ntn Corporation Rolling bearings and greases for the same
JP2002130301A (ja) 2000-10-17 2002-05-09 Nsk Ltd 転がり軸受
JP2002250351A (ja) 2001-02-20 2002-09-06 Nsk Ltd 転がり軸受
JP4883743B2 (ja) * 2002-08-02 2012-02-22 Ｎｔｎ株式会社 グリース組成物および該グリース組成物封入軸受
JP4102627B2 (ja) * 2002-09-13 2008-06-18 株式会社ジェイテクト 転がり軸受
JP2005290278A (ja) * 2004-04-02 2005-10-20 Ntn Corp 耐防錆グリース組成物、グリース封入軸受および錆止め剤
JP5634035B2 (ja) * 2009-05-29 2014-12-03 協同油脂株式会社 グリース組成物及び機械部品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2263482A (en) * 1992-01-22 1993-07-28 Ntn Toyo Bearing Co Ltd Grease composition for rolling contact bearing
JPH05194979A (ja) * 1992-01-22 1993-08-03 Ntn Corp 軸受封入用グリース組成物
CN101910386A (zh) * 2008-01-23 2010-12-08 协同油脂株式会社 润滑油组合物以及机械部件

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115867632A (zh) * 2020-07-06 2023-03-28 株式会社捷太格特 润滑脂组合物和滚动轴承
CN115867632B (zh) * 2020-07-06 2024-05-17 株式会社捷太格特 润滑脂组合物和滚动轴承
CN116113683A (zh) * 2020-08-12 2023-05-12 株式会社捷太格特 润滑脂组合物和滚动轴承
CN116113683B (zh) * 2020-08-12 2024-10-15 株式会社捷太格特 润滑脂组合物和滚动轴承

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JP2012193298A (ja) 2012-10-11
US20130345101A1 (en) 2013-12-26
EP2687584B1 (en) 2020-09-09
EP2687584A1 (en) 2014-01-22
JP5774881B2 (ja) 2015-09-09

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