CN101484558B - 润滑脂组合物及轴承 - Google Patents

润滑脂组合物及轴承 Download PDF

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CN101484558B
CN101484558B CN2007800253516A CN200780025351A CN101484558B CN 101484558 B CN101484558 B CN 101484558B CN 2007800253516 A CN2007800253516 A CN 2007800253516A CN 200780025351 A CN200780025351 A CN 200780025351A CN 101484558 B CN101484558 B CN 101484558B
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grease composition
rust
fluorine
quality
alkali metal
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CN101484558A (zh
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松原宪一郎
大贯裕次
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Kyodo Yushi Co Ltd
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Abstract

本发明提供一种润滑脂组合物以及封入有该润滑脂组合物的轴承，该润滑脂组合物为基础油包含氟系合成油的润滑脂组合物，其特征在于，含有0.1质量％以上且小于1.0质量％的用通式(1)((CH2)n(COO)2Mm；式中，n表示1～19的整数，M表示碱金属或碱土金属，m在M为碱金属时表示2、在M为碱土金属时表示1)表示的脂肪族二元酸盐作为防锈剂。前述组合物是适于高温条件下的滚动轴承、具有优异的防锈性、且降低环境负荷的氟系润滑脂组合物。

Description

润滑脂组合物及轴承
技术领域
本发明涉及润滑脂组合物及轴承。更详细地，涉及适于在处于高温条件下的滚动轴承中所使用的、蒸发损失量少的、具有优异的防锈性的氟系润滑脂组合物及封入有该组合物的轴承。
背景技术
在高温条件下，为提高润滑脂组合物的润滑寿命而对于润滑脂组合物所要求的性能，是低蒸发损失量、高氧化稳定性、优异的防锈性和优异的润滑性等。至今，人们提出了各种涉及提高润滑脂组合物的防锈性和润滑寿命的方案。
例如，有人提出了这样的润滑脂的方案：关于作为温度函数的运动粘度稳定性和低蒸气压和极限条件下的良好的润滑特性，以非官能性全氟聚醚为基础的润滑脂可保持良好的性能，通过使用包含这样的全氟聚醚或氟聚醚衍生物的具有分子末端官能团的含氟油，在像高速下操作这样的用途中显示出优秀的润滑性，此外，还具有高耐腐蚀性(例如，参照专利文献1)。
此外，还有人提出了这样的润滑脂组合物的方案：通过向全氟聚醚基础油中添加作为增稠剂的脂肪族二羧酸金属盐、单酰胺单羧酸金属盐或单酯羧酸金属盐中的至少一种，使得对于对象材料在耐磨耗性、耐泄漏性、洗涤性等方面优异，而且也可满足成本要求(例如，参照专利文献2)。
为了给予润滑脂组合物防锈性能，通常添加防锈剂。作为高温用滚动轴承用氟系润滑脂的防锈剂的成分，多使用无机钝化剂，尤其是亚硝酸钠作为最有效的防锈剂至今还被广泛使用。但是，已知亚硝酸钠与仲胺在酸性条件下反应而生成N-亚硝胺。亚硝胺是对环境有害的物质，因此正在寻求代替亚硝酸钠的防锈剂。
专利文献1：日本特开平1-272696
专利文献2：日本特开2001-354986
发明内容
本发明的目的是提供一种氟系润滑脂组合物及封入有该组合物的轴承，该氟系润滑脂组合物适合于高温条件下的滚动轴承，且长时间地显示出优异的防锈性和稳定的润滑性，此外还考虑到了降低环境负荷。即，提供一种在高温条件下蒸发损失量少、具有优异的防锈性的低环境负荷型氟系润滑脂组合物及封入有该组合物的轴承。
本发明人等为实现上述目的进行了深入的研究，结果完成了如下所述的润滑脂组合物：通过使用含有氟系合成油的基础油、作为低环境负荷型防锈剂的二元酸盐，该组合物具有优异的防锈性，此外，通过添加特定量的该二元酸盐，该组合物在高温条件下的蒸发损失量优异，适合于高温下的滚动轴承，而且还考虑了降低环境负荷。
本发明提供以下所述的氟系润滑脂组合物及轴承。
1.一种润滑脂组合物，其特征在于，其为基础油包含氟系合成油的润滑脂组合物，作为防锈剂，含有0.1质量％以上且小于1.0质量％的用通式(1)表示的脂肪族二元酸盐。
(CH2)n(COO)2Mm    (1)
(式中，n表示1～19的整数，M表示碱金属或碱土金属，m在M为碱金属时表示2、在M为碱土金属时表示1。)
2.根据上述1所述的润滑脂组合物，其中，氟系合成油是全氟烷基聚醚油。
3.根据上述1或2所述的润滑脂组合物，其中，脂肪族二元酸盐是碱金属盐。
4.一种封入有上述1～3的任一项所述的润滑脂组合物的轴承。
本发明的考虑了降低环境负荷的氟系润滑脂组合物，由于蒸发损失量少、防锈性优异、适合于在高温条件下的滚动轴承中使用、而且长时间地显示出稳定的润滑性，因而是非常有用的。特别是，使用癸二酸钠、壬二酸钠、辛二酸钠等二元酸盐作为防锈剂时，与亚硝酸钠不同，不会对人体和环境产生不良影响，可发挥优异的防锈性，通过添加特定量的二元酸盐，具有即使在高温条件下蒸发损失量也少的优异特性。
本发明基于如下认识而得到：使用氟系合成油作为基础油，作为防锈剂，添加特定量的特定的低环境负荷型二元酸盐系防锈剂，由此得到的润滑脂组合物具有与使用亚硝酸钠作为防锈剂的润滑脂组合物同等的优异的防锈性，即使在高温条件下蒸发损失量也少，不损失耐热性。
具体实施方式
以下，对本发明进行详细说明。
就本发明的氟系润滑脂组合物而言，作为基础油而使用的氟系合成油，只要在其分子中含有氟，并且耐热性优异，可用作润滑油的氟系合成油，就完全可以使用。特别优选惰性的、蒸气压低的全氟烷基聚醚油。作为全氟烷基聚醚油，运动粘度(動粘度)(40℃)优选为5～1500mm2/s，进一步优选为50～1000mm2/s，特别优选为70～800mm2/s。运动粘度(40℃)小于5mm2/s的全氟烷基聚醚油，其流动点低，但蒸发量增多，另一方面，当运动粘度(40℃)超过1500mm2/s时，蒸发量低，但是流动点趋于增高。当蒸发量增多时，耐热性有损失，当流动点增高时，不能在低温下使用。
基础油相对于本发明的润滑脂组合物中的基础油、增稠剂和防锈剂的合计量的比例，优选为50～98质量％，进一步优选为65～85质量％。
作为本发明的润滑脂组合物中所使用的增稠剂，只要是分散于氟系合成油中，形成润滑脂状(半固体状)的固体，就完全可以使用。可举出例如以聚四氟乙烯、聚三氟乙烯为代表的氟树脂，以Li皂、Ca皂、Al皂为代表的金属皂，以Li复合皂、Ca复合皂、Al复合皂为代表的复合皂，尿素化合物、聚氨酯化合物、膨润土、硅化合物、对苯二甲酸钠、氰尿酸三聚氰胺、炭黑等。特别优选耐热性优异的聚四氟乙烯、二氧化硅、氰尿酸三聚氰胺、炭黑等。
本发明的润滑脂组合物中的增稠剂的比例，优选为1～49质量％，更优选额外10～40质量％。这是因为，当增稠剂量小于1质量％时，流动性增高，当增稠剂量超过49质量％时，变得过硬，不论是哪种情况，都难以用作润滑脂。
本发明的润滑脂组合物的特征为，作为防锈剂，配合0.1质量％以上且小于1.0质量％的用通式(1)表示的脂肪族二元酸金属盐。当小于0.1质量％时，没有防锈效果，当为1.0质量％以上时，与小于1.0质量％的情况相比，蒸发量增多，耐热性有损失。
(CH2)n(COO)2Mm    (1)
(式中，n表示1～19的整数，M表示碱金属或碱土金属，m在M为碱金属时表示2、在M为碱土金属时表示1。)
作为脂肪族二元酸金属盐的具体例子，有癸二酸钠、癸二酸锂、己二酸钠、己二酸锂、壬二酸钠、壬二酸锂等，癸二酸钠尤其有效。
以下，例示实施例对本发明进行具体说明。
使用表格中所示的成分来制备试验润滑脂。
作为增稠剂，使用聚四氟乙烯(PTFE)、二氧化硅、氰尿酸三聚氰胺(MCA)和PTFE的混合物、碳黑这4种。
作为基础油，使用运动粘度(40℃)为420mm2/s、80mm2/s、700mm2/s的3种全氟烷基聚醚油。
作为防锈剂，使用0.2质量％、0.5质量％、0.8质量％、2.0质量％的癸二酸钠，各0.5质量％的磺酸钡(二壬基萘磺酸钡)、琥珀酸酐、硬脂酸锌、硬脂酸钠。
<试验方法>
·防锈性：Emcor防锈试验(IP220)
评价基准
0：无锈
4：外圈面的5～10％的范围上产生锈
5：外圈面的10％以上的范围上产生锈
·蒸发损失量：
(试验条件)
将试验润滑脂以约2mm的厚度均匀地涂布于60×80×1mm的SPCC钢板上，在规定温度的恒温空气浴中放置规定时间，测定重量的减少(即，蒸发损失量)。
规定温度：230℃
规定时间：1200h
※蒸发损失量在10％以上为不良。
结果
配合了0.2～0.8质量％的癸二酸钠的实施例1～8中，防锈性都良好。配合了0.5质量％的癸二酸钠以外的二元酸盐的实施例9～11中，防锈性都良好。
不含癸二酸钠的比较例1、包含二元酸盐以外的防锈剂的比较例2～5中，防锈性差。
另外，从使癸二酸钠的配合量变化的实施例1～3、比较例1和比较例6来看，在包含0.1质量％以上且小于1.0质量％的癸二酸钠的实施例1～3中，防锈性优异，并且，蒸发损失量也在10％以下，耐热性优异，但是，在不含癸二酸钠的比较例1中，防锈性差，在包含2.0质量％的癸二酸钠的比较例6中，蒸发损失量超过10％，耐热性差。
表1
  实施例1   实施例2 实施例3 实施例4 实施例5   实施例6
增稠剂(配合量％) PTFE(25.0) PTFE(25.0) PTFE(25.0) 二氧化硅(10.0)   MCA(20.0)PTFE(5.0) 碳(10.0)
  基础油运动粘度(配合量％)   PFAE420(74.5)   PFAE420(74.8)   PFAE420(74.2)   PFAE420(89.5)   PFAE420(74.5)   PFAE420(89.5)
  防锈剂(配合量％)   癸二酸钠(0.5)   癸二酸钠(0.2)   癸二酸钠(0.8) 癸二酸钠(0.5)   癸二酸钠(0.5)   癸二酸钠(0.5)
  防锈性   0   0   0   0   0   0
  蒸发损失量(质量％) 8.0 7.5 8.4 - - -
表2
  实施例7   实施例8   实施例9   实施例10   实施例11
  增稠剂(配合量％)   PTFE(25.0)   PTFE(25.0)   PTFE(25.0)   PTFE(25.0)   PTFE(25.0)
  基础油(运动粘度)(配合量％)   PFAE80(74.5)   PFAE700(74.5)   PFAE420(74.5)   PFAE420(74.5)   PFAE420(74.5)
  防锈剂(配合量％)   癸二酸钠(0.5)   癸二酸钠(0.5)   癸二酸锂(0.5)   己二酸钠(0.5)   壬二酸钠(0.5)
  防锈性   0   0   0   0   0
表3
  比较例1   比较例2   比较例3   比较例4 比较例5 比较例6
  增稠剂(配合量％)   PTFE(25.0)   PTFE(25.0)   PTFE(25.0)   PTFE(25.0)   PTFE(25.0)   PTFE(25.0)
  基础油运动粘度(配合量％)   PFAE420(75.0)   PFAE420(74.5)   PFAE420(74.5)   PFAE420(74.5)   PFAE420(74.5)   PFAE420(73.0)
  防锈剂(配合量％)   不添加(0.0)   磺酸钡(0.5)   琥珀酸酐(0.5)   硬脂酸锌(0.5)   硬脂酸钠(0.5)   癸二酸钠(2.0)
  防锈性   5   4   4   4   4   0
  蒸发损失量(质量％) 7.4 - - - - 14.6
表中，蒸发损失量一行的“-”表示未测定。

Claims (3)

1.一种润滑脂组合物，其特征在于，其为基础油包含氟系合成油的润滑脂组合物，所述氟系合成油是全氟烷基聚醚油，含有0.1质量％以上且小于1.0质量％的用通式(1)表示的脂肪族二元酸盐作为防锈剂，
(CH2)n(COO)2Mm    (1)
式中，n表示1～19的整数，M表示碱金属或碱土金属，m在M为碱金属时表示2、m在M为碱土金属时表示1。
2.根据权利要求1所述的润滑脂组合物，其中，脂肪族二元酸盐是碱金属盐。
3.一种轴承，其特征在于，封入有权利要求1或2所述的润滑脂组合物。
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