CN109477024B - 润滑脂组合物 - Google Patents

润滑脂组合物 Download PDF

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CN109477024B
CN109477024B CN201780046083.XA CN201780046083A CN109477024B CN 109477024 B CN109477024 B CN 109477024B CN 201780046083 A CN201780046083 A CN 201780046083A CN 109477024 B CN109477024 B CN 109477024B
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acid
grease composition
zinc
bearing
ester
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CN109477024A (zh
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斋藤绫祐
佐藤雄太
广冈岩树
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Kyodo Yushi Co Ltd
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Abstract

一种润滑脂组合物，含有增稠剂、基油和摩擦调节剂，前述摩擦调节剂含有选自由脂肪酸、脂肪酸金属盐、磷酸酯、硫代磷酸酯和二硫代磷酸锌组成的组中的至少1种、以及多元醇酯。

Description

润滑脂组合物
技术领域
本发明涉及适合用于滚动轴承、尤其是4点接触轴承的润滑脂组合物。
背景技术
近年来，从减少消耗能量的观点出发，对各产业中使用的机械部件要求高效率化，正在进行部件的轻量化、小型化、结构改良等各种研究。可是，随着部件的小型化，存在下述问题：由于旋转变动时的速度差变大，因而不仅发生滚动运动，还会发生滚动滑动运动；为了提高传输效率，导致对于包括旋转体的机械部件的荷重变高；或者，滚动、滚动滑动运动中的轴承的扭矩变高。
从部件的小型化的观点出发，在从两个方向施加轴向荷重的用途中，逐渐应用4点接触轴承代替以往的双列角接触球轴承。4点接触轴承具有即使是与单列球轴承同等的主尺寸也能够从两个方向承受轴向荷重的特征，一般在纯轴向荷重或者轴向荷重大的使用条件下，以2点接触状态使用。此外，通过将轴向方向的内部间隙设为负值(即赋予了预负荷的状态)，能够抑制由内部间隙导致的噪音、令人不愉快的振动的产生，能够适应要求高精度的部件。
可是，在径向荷重相对于轴向荷重大的使用条件下、滚动速度非常慢的使用条件下，存在如下问题：由于从2点接触状态变为4点接触状态，导致在接触部发生大的滑动运动，发生扭矩增大、爬行(stick slip)。
以往，作为降低滚动轴承的扭矩的方法，有下述方法：为了降低滚动粘性阻力，尽可能使基油的运动粘度降低；为了降低搅拌阻力，使润滑脂的表观粘度减小；或者，减少在机械构件中使用时的润滑脂的量。例如在专利文献1中提出了一种润滑脂组合物，其使用了含有40℃时的运动粘度为10mm2/s以上的酯油的基油。例如在专利文献2中提出为了降低搅拌阻力而使用脂环式脂肪族二脲作为增稠剂的润滑脂组合物。
可是，上述方法无法抑制因滑动运动导致的扭矩增大。专利文献1、2中公开的轴承并非4点接触轴承。
现有技术文献
专利文献
专利文献1：日本特开2000－198993号公报
专利文献2：日本特开2012－172066号公报
发明内容
发明所要解决的课题
因此，本发明所要解决的课题是，提供能够有效地降低扭矩的润滑脂组合物。
用于解决课题的方案
针对上述课题，本发明人等通过选定适当的添加剂来解决。即，根据本发明，提供以下的润滑脂组合物。
1.一种润滑脂组合物，含有增稠剂、基油和摩擦调节剂，
所述摩擦调节剂含有选自由脂肪酸、脂肪酸金属盐、磷酸酯、硫代磷酸酯和二硫代磷酸锌组成的组中的至少1种、以及多元醇酯。
2.前述第1项所述的润滑脂组合物，所述摩擦调节剂为磷酸酯和多元醇酯。
3.前述第1或第2项所述的润滑脂组合物，所述磷酸酯为选***磷酸酯、酸性磷酸酯和酸性磷酸酯胺盐组成的组中的至少1种。
4.前述第1～3中任一项所述的润滑脂组合物，其用于滚动轴承。
5.前述第4项所述的润滑脂组合物，滚动轴承为进行滚动滑动运动的轴承。
6.所述第4或第5项所述的润滑脂组合物，滚动轴承为4点接触轴承。
发明的效果
根据本发明的润滑脂组合物能够有效降低扭矩。如果将本发明的润滑脂组合物应用于进行滚动滑动运动的滚动轴承，则能够降低该轴承滑动时的摩擦。
具体实施方式
〔增稠剂〕
作为本发明中能够使用的增稠剂，可列举锂皂、复合锂皂所代表的皂系增稠剂；二脲所代表的脲系增稠剂；有机黏土、二氧化硅所代表的无机系增稠剂；PTFE所代表的有机系增稠剂等。
优选为皂系增稠剂，更优选为锂皂或者复合锂皂。作为锂皂，优选硬脂酸锂或12-羟基硬脂酸锂，更优选12-羟基硬脂酸锂。作为复合锂皂，优选硬脂酸、12-羟基硬脂酸等脂肪族羧酸的锂盐与二元酸锂盐的复合物等。作为二元酸，优选琥珀酸、丙二酸、己二酸、庚二酸、壬二酸、癸二酸等，更优选壬二酸、癸二酸。特别优选作为壬二酸与氢氧化锂的盐和12-羟基硬脂酸与氢氧化锂的盐的混合物的复合锂皂。
锂皂和复合锂皂的润滑性良好，因此尤其在滑动大的滚动滑动环境下，降低扭矩的效果大。此外，缺点少且价格不高，因此是具有实用性的增稠剂。进而，复合锂皂的耐热性优异，因此即使在高温环境下，寿命也优异。
相对于本发明的润滑脂组合物的质量，增稠剂的含量优选为3～20质量％，进一步优选为5～15质量％。如果增稠剂的含量在这样的范围内，则润滑脂具有适当的硬度，发生泄露的情况少，流动性也良好，因此低温性也优异。
〔基油〕
本发明中能够使用的基油没有特别限定。可以使用矿物油、合成油或它们的混合物。作为合成油，可列举二酯、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、烷基二苯基醚、聚丙二醇所代表的醚系合成油、有机硅油、氟化油等各种合成油等。
作为本发明的基油，优选矿物油、聚α-烯烃、多元醇酯、烷基二苯基醚，进一步优选多元醇酯、烷基二苯基醚。特别优选聚α-烯烃。
以本发明的润滑脂组合物的总质量为基准，基油的含量优选至少为50质量％。更优选为80～90质量％。进一步优选为85～90质量％。
40℃时的基油的运动粘度没有特别限定，优选为15～200mm2/s。更优选为30～100mm2/s，特别优选为40～80mm2/s。如果40℃时的基油的运动粘度为这样的范围内，则能够在确保可以满足的低温流动性的同时具有良好的耐热性。
〔摩擦调节剂〕
本发明的摩擦调节剂含有选自脂肪酸、脂肪酸金属盐、磷酸酯、硫代磷酸酯、二硫代磷酸锌中的至少1种与多元醇酯的组合。
作为脂肪酸，可列举例如丁酸、戊酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸、肉豆蔻酸、十五烷酸、棕榈酸、十七烷酸、硬脂酸、花生酸、二十一烷酸、山嵛酸、木焦油酸、蜡酸、褐煤酸、蜂花酸等饱和脂肪酸、巴豆酸、肉豆蔻脑酸、棕榈油酸、6-十六碳烯酸(sapienicacid)、油酸、反油酸、异油酸、鳕油酸、二十碳烯酸、芥酸、羧酸(ルボン酸)、亚油酸、二十碳二烯酸、二十二碳二烯酸、亚麻酸、松油酸(pinolenic acid)、桐酸、米德酸(mead acid)、二高-γ-亚麻酸、二十碳三烯酸、十八碳四烯酸、花生四烯酸、二十碳四烯酸、肾上腺酸(adrenic acid)、5,8,10,12,14-十八碳五烯酸(bosseopentaenoic acid)、二十碳五烯酸、4,7,10,13,16-二十二碳五烯酸(osbond Acid)、鰶鱼酸(clupanodonic acid)、二十四碳五烯酸、二十二碳六烯酸、二十四碳六烯酸(nisinic acid)等不饱和脂肪酸和它们的混合物。作为脂肪酸，优选辛酸、癸酸、月桂酸、肉豆蔻酸(ミスチリン酸)、棕榈酸、硬脂酸、油酸、亚油酸，进一步优选油酸。
作为脂肪酸金属盐，可列举例如碳原子数优选为6～24、进一步优选为12～18的脂肪酸的金属皂和它们的混合物。作为脂肪酸的优选具体例子，可列举硬脂酸、棕榈酸等。作为金属皂，可列举钠、钾等碱金属皂、镁、钙等碱土金属皂、锌皂、铝皂、锂皂和它们的混合物。作为脂肪酸金属盐，优选硬脂酸金属皂，特别优选硬脂酸的锂皂。
作为磷酸酯，可列举例如磷酸酯、亚磷酸酯、次磷酸酯、酸性磷酸酯的胺盐、酸性亚磷酸酯的胺盐、酸性次磷酸酯的胺盐和它们的混合物。
作为磷酸酯，优选磷酸酯、亚磷酸酯、酸性磷酸酯、酸性磷酸酯的胺盐。更优选磷酸三甲苯酯(TCP)、磷酸三辛酯(TOP)。
作为亚磷酸酯，优选亚磷酸三苯酯、亚磷酸三乙酯。
作为酸性磷酸酯，优选二苯基氢亚磷酸酯、二乙基氢亚磷酸酯。
作为酸性磷酸酯的胺盐，优选为酸性磷酸酯由式(1)表示的化合物的胺盐。
R15OAPO(OH)3-A (1)
(式中，R15表示碳数1～30的直链或支链烷基，优选表示碳数1～18的直链或支链烷基，进一步优选表示碳数1～8的烷基，特别优选表示碳数1～4的烷基。A表示1或2，优选表示2。)作为酸性磷酸酯的胺盐，特别优选叔烷基胺-磷酸二甲酯。
作为硫代磷酸酯，可列举乙基-3-[[双(1-甲基乙氧基)硫膦基]硫代]丙酸酯、三苯基硫代磷酸酯与叔丁基苯基衍生物的混合物、3-(二异丁氧基-硫代磷酰巯基)-2-甲基-丙酸、三[(2或4)-异烷基苯酚]硫代磷酸酯、硫代磷酸三苯酯。作为硫代磷酸酯，优选硫代磷酸三苯酯。
作为二硫代磷酸锌，可列举二丁基二硫代磷酸锌、二戊基二硫代磷酸锌、二己基二硫代磷酸锌、二庚基二硫代磷酸锌、二辛基二硫代磷酸锌、二壬基二硫代磷酸锌、二癸基二硫代磷酸锌、二(十一烷基)二硫代磷酸锌、二(十二烷基)二硫代磷酸锌、硫化二丁基二硫代磷酸锌、硫化二戊基二硫代磷酸锌、硫化二己基二硫代磷酸锌、硫化二庚基二硫代磷酸锌、硫化二辛基二硫代磷酸锌、硫化二壬基二硫代磷酸锌、硫化二癸基二硫代磷酸锌、硫化二(十一烷基)二硫代磷酸锌、硫化二(十二烷基)二硫代磷酸锌、和它们的混合物等。作为二硫代磷酸锌，优选二丁基二硫代磷酸锌和二戊基二硫代磷酸锌的混合物。
作为多元醇酯系摩擦调节剂，可列举：甘油脂肪酸酯，脱水山梨糖醇三油酸酯、脱水山梨糖醇单油酸酯等脱水山梨糖醇脂肪酸酯。作为多元醇酯系摩擦调节剂，优选脱水山梨糖醇三油酸酯、脱水山梨糖醇单油酸酯，更优选脱水山梨糖醇三油酸酯。
作为本发明的摩擦调节剂，优选并用磷酸酯和多元醇酯。更优选本发明的摩擦调节剂仅包含选自脂肪酸、脂肪酸金属盐、磷酸酯、硫代磷酸酯、二硫代磷酸锌中的至少1种与多元醇酯的组合。更优选本发明的摩擦调节剂为磷酸酯和多元醇酯。更优选作为选***磷酸酯、酸性磷酸酯和酸性磷酸酯胺盐组成的组中的至少1种的磷酸酯与多元醇酯的组合。其中，优选为选自由油酸、叔烷基胺-磷酸二甲酯、硫代磷酸三苯酯和二烷基二硫代磷酸锌组成的组中的至少1种与脱水山梨糖醇三油酸酯的组合。特别是，优选为叔烷基胺-磷酸二甲酯与脱水山梨糖醇三油酸酯的组合。
以本发明的润滑脂组合物的总质量为基准，本发明的摩擦调节剂的含量优选为0.2～10质量％，更优选为0.5～5质量％，进一步优选为1～3质量％。本发明的润滑脂组合物含有上述预定的摩擦调节剂以外的摩擦调节剂的情况下，相对于100质量份摩擦调节剂，本申请规定的摩擦调节剂的含量优选为5质量份。
〔添加剂〕
除了摩擦调节剂以外，本发明的润滑脂组合物还可以进一步含有各种润滑油、润滑脂中通常使用的添加剂。作为这样的添加剂，可列举抗氧化剂、防锈剂、耐荷重添加剂、金属腐蚀抑制剂、油性剂、固体润滑剂、其他摩擦调节剂等。其中，优选含有抗氧化剂、防锈剂或金属腐蚀抑制剂。
相对于本发明的润滑脂组合物的总质量，这些任选添加剂的含量通常为0.2～25质量％。
作为抗氧化剂，可列举胺系抗氧化剂和酚系抗氧化剂等。
作为胺系抗氧化剂，可列举N-正丁基-对氨基苯酚、4,4’-四甲基-二氨基二苯基甲烷、α-萘胺、N-苯基-α-萘胺、吩噻嗪、烷基二苯基胺等。其中，优选烷基二苯基胺。
作为酚系抗氧化剂，可列举2,6-二叔丁基-对甲酚(BHT)、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、4,4’-亚丁基双(3-甲基-6-叔丁基苯酚)、2,6-二叔丁基-苯酚、2,4-二甲基-6-叔丁基苯酚、叔丁基羟基苯甲醚(BHA)、4,4’-亚丁基双(3-甲基-6-叔丁基苯酚)、4,4’-亚甲基双(2,3-二叔丁基苯酚)、4,4’-硫代双(3-甲基-6-叔丁基苯酚)、十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯等。其中，优选十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯。
优选含有胺系抗氧化剂和酚系抗氧化剂作为抗氧化剂。特别优选含有烷基二苯基胺和十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯。
相对于本发明的润滑脂组合物的总质量，抗氧化剂的含量优选为0.5～6质量％。
作为防锈剂，可列举无机系防锈剂和有机系防锈剂。作为无机系防锈剂，可列举硅酸Na、碳酸Li、碳酸K、氧化Zn等无机金属盐。优选氧化锌。作为有机系防锈剂，可列举：磺酸锌盐、磺酸Ca盐等有机磺酸盐；苯甲酸Na、苯甲酸Li等苯甲酸盐；癸二酸Na等羧酸盐；琥珀酸、琥珀酸酐、琥珀酸半酯等琥珀酸衍生物；脱水山梨糖醇单油酸酯、脱水山梨糖醇三油酸酯等脱水山梨糖醇酯；包含饱和或不饱和的碳数4～22的脂肪酸(优选为包含饱和或不饱和的碳数8～18的脂肪酸)与饱和或不饱和的碳数1～42的胺(优选饱和或不饱和的碳数4～22的胺)的脂肪酸胺盐等。优选琥珀酸衍生物；有机磺酸盐；脂肪酸胺盐，特别优选琥珀酸半酯；磺酸锌盐(尤其是二壬基萘磺酸锌)；含有碳数8的脂肪酸与碳数12的胺的盐、和碳数18的脂肪酸与碳数12～20的(混合)胺的盐的混合物。
以本发明的润滑脂组合物的总质量为基准，防锈剂的含量优选为0.2～10质量％。
作为金属钝化剂，可列举苯并***、苯并咪唑、吲哚、甲基苯并***等***化合物。其中，更优选苯并***。
以本发明的润滑脂组合物的总质量为基准，金属钝化剂的含量优选为0.01～5质量％。
〔工作锥入度〕
本发明的润滑脂组合物的60次工作锥入度优选为200～350。如果工作锥入度在该范围内，则因高速旋转导致的泄露变少，能够满足润滑寿命，另一方面，润滑脂的流动性也良好，能够满足润滑寿命。
〔轴承〕
封入本发明的润滑脂组合物的轴承优选为进行滚动滑动运动的滚动轴承。优选为进行滑动大的滚动滑动运动的滚动轴承，作为种类，可列举4点接触轴承。
实施例
·试验润滑脂的调制
关于含有锂皂作为增稠剂的润滑脂组合物，在基油中投入12羟基硬脂酸，加温后，添加氢氧化锂水溶液，再次加热后骤冷，将由此得到的物质作为基体润滑脂，在其中加入基油和添加剂，以工作锥入度成为300(JIS K2220，60次工作锥入度)的方式进行磨机处理，调制润滑脂。
关于含有复合锂皂作为增稠剂的润滑脂组合物，在基油中投入壬二酸和12羟基硬脂酸，加温后，添加氢氧化锂水溶液，再次加热后骤冷，将由此得到的物质作为基体润滑脂，在其中加入基油和添加剂，以工作锥入度成为300(JIS K2220，60次工作锥入度)的方式进行磨机处理，调制润滑脂。
＜增稠剂＞
·锂皂：由12羟基硬脂酸和氢氧化锂合成的皂
·复合锂皂：由壬二酸和12羟基硬脂酸以及氢氧化锂合成的复合皂
＜基油＞
·聚α-烯烃(运动粘度：48.5mm2/s@40℃)
按照JIS K 2220 23.测定基油在40℃时的运动粘度。
＜摩擦调节剂＞
·脂肪酸：油酸(LUNAC O-P，花王株式会社制)
·脂肪酸金属盐：硬脂酸锂(胜田化工株式会社制)
·磷酸酯：叔烷基胺－磷酸二甲酯(Vanlube672，R.T.Vanderbilt公司制)
·硫代磷酸酯：硫代磷酸三苯酯(IRGALUBE TPPT，BASF公司制)
·二硫代磷酸锌：二烷基二硫代磷酸锌(Lubrizol1395，Lubrizol公司制)
·多元醇酯：脱水山梨糖醇三油酸酯(Nonion OP-85R，日油株式会社制)
＜其他添加剂＞
·胺系抗氧化剂(烷基二苯基胺)
·酚系抗氧化剂(十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)
·烯基琥珀酸酐(防锈剂)
·苯并***(金属钝化剂)
＜试验方法＞
·轴承扭矩试验
本试验是评价轴承扭矩的试验。使滚动轴承在下述条件下运动，使安装于轴承壳体的杆与固定于支架的负载传感器接触，测定扭矩。
轴承形式：QJ205(4点接触轴承)
试验温度：25℃
转速：1rpm
试验荷重：径向荷重500N，轴向荷重50N
评价：作为以比较例1的测定值为基准的轴承扭矩降低率来表示。
将结果示于表1和表2。
[表1]
Figure BDA0001956417530000091
[表2]
Figure BDA0001956417530000101

Claims (5)

1.一种润滑脂组合物，
含有增稠剂、基油和摩擦调节剂，
所述摩擦调节剂为叔烷基胺-磷酸二甲酯和脱水山梨糖醇三油酸酯的组合，
所述基油选自聚α-烯烃、多元醇酯和烷基二苯基醚组成的组中的至少一种。
2.根据权利要求1所述的润滑脂组合物，其用于滚动轴承。
3.根据权利要求2所述的润滑脂组合物，滚动轴承为进行滚动滑动运动的轴承。
4.根据权利要求2所述的润滑脂组合物，滚动轴承为4点接触轴承。
5.根据权利要求3所述的润滑脂组合物，滚动轴承为4点接触轴承。
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