CN109312248B - 等速接头用润滑脂组合物和封入有该润滑脂组合物的等速接头 - Google Patents

等速接头用润滑脂组合物和封入有该润滑脂组合物的等速接头 Download PDF

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CN109312248B
CN109312248B CN201780038051.5A CN201780038051A CN109312248B CN 109312248 B CN109312248 B CN 109312248B CN 201780038051 A CN201780038051 A CN 201780038051A CN 109312248 B CN109312248 B CN 109312248B
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constant velocity
oil
grease composition
mass
content
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CN109312248A (zh
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荒井孝
德毛泰叶
石岛实
此本武美
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Jxtg Energy Corp
NTN Corp
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NTN Corp
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D3/00—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive
    • F16D3/16—Universal joints in which flexibility is produced by means of pivots or sliding or rolling connecting parts
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Abstract

本发明提供一种等速接头用润滑脂组合物，其含有：润滑油基础油、由含氮化合物形成的增稠剂、甘油三酯、二酯、和氮化硼，甘油三酯和二酯的总计的含量以润滑脂组合物总量基准计为1～5质量％，甘油三酯的含量相对于二酯的含量的质量比(甘油三酯/二酯)为0.3～1.5。

Description

等速接头用润滑脂组合物和封入有该润滑脂组合物的等速 接头
技术领域
本发明涉及等速接头用润滑脂组合物和封入有该润滑脂组合物的等速接头。特别是涉及适合于汽车用驱动轴中应用的等速接头的润滑脂组合物和封入有该润滑脂组合物的等速接头。
背景技术
等速接头是指，在交叉的二轴间的任意的交叉角中，其角速度以等速旋转，而传递转矩的万向接头，被广泛用于汽车、产业机械等。汽车用途中，被用于从汽车的差速齿轮向驱动轮传递动力的驱动轴、向FR车、4WD车的差速齿轮传递动力的螺旋桨轴。
等速接头中，封入有作为润滑剂的润滑脂。作为等速接头用润滑脂，使用的是，在由润滑油基础油和锂皂、脲系增稠剂形成的基础润滑脂中配混有二硫化钼等添加剂而得到的物质(例如参照专利文献1)。
另外，为了防止封入于内部的润滑脂向外部的泄漏，在等速接头上安装保护罩。该保护罩由氯丁橡胶、有机硅橡胶、氯化聚乙烯橡胶等橡胶材料、或热塑性弹性体等树脂材料构成，期望润滑脂对保护罩材料的影响小，即，在保护罩材料与润滑脂接触的状态下保护罩材料的物性变化小。
进而，为了降低润滑脂成本而减量较昂贵的二硫化钼、有机钼等添加剂的情况下，本申请人提出了一种润滑脂组合物，其中，通过配混甘油三酯等也可以使等速接头长寿命化、低振动化，同时将对保护罩材料的影响限制为较少(例如参照专利文献2)。
现有技术文献
专利文献
专利文献1：日本特开2007-056139号公报
专利文献2：日本特开2014-043526号公报
发明内容
发明要解决的问题
然而，例如在汽车的特殊的运转条件下，等速接头进行复杂的滑动运动，对金属接触的润滑部重复施加应力，因此，对于润滑脂组合物要求严苛的润滑条件下的耐久性提高。
因此，本发明的课题在于，提供：能实现严苛的润滑条件下的耐久性提高的等速接头用润滑脂组合物和封入有该润滑脂组合物的等速接头。
用于解决问题的方案
本发明为了解决上述课题而提供下述[1]～[5]所示的润滑脂组合物和下述[6]所示的等速接头。
[1]一种等速接头用润滑脂组合物，其含有：润滑油基础油、由含氮化合物形成的增稠剂、甘油三酯、二酯、和氮化硼，甘油三酯和二酯的总计的含量以润滑脂组合物总量基准计为1～5质量％，甘油三酯的含量相对于二酯的含量的质量比(甘油三酯/二酯)为0.3～1.5。
[2]根据[1]所述的等速接头用润滑脂组合物，其中，还含有：有机钼、二硫代磷酸锌和多硫化物。
[3]根据[2]所述的等速接头用润滑脂组合物，其中，
以润滑脂组合物总量基准计，
有机钼的含量按照钼元素换算计为0.05～0.5质量％，
有机钼、二硫代磷酸锌和多硫化物的总计的含量为2～5质量％。
[4]根据[1]～[3]中任一项所述的等速接头用润滑脂组合物，其中，
前述氮化硼的含量以润滑脂组合物总量基准计为0.05～1质量％。
[5]根据[1]～[4]中任一项所述的等速接头用润滑脂组合物，其用于汽车用驱动轴中应用的等速接头的润滑。
[6]一种等速接头，其封入有[1]～[4]中任一项所述的等速接头用润滑脂组合物。
发明的效果
根据本发明的润滑脂组合物，能实现严苛的润滑条件下的耐久性提高。
附图说明
图1为示出固定式等速接头的一例的示意剖视图。
图2为示出固定式等速接头的另一例的示意剖视图。
图3为示出汽车用驱动轴的一例的示意剖视图。
具体实施方式
[第1实施方式：等速接头用润滑脂组合物]
本发明的第1实施方式的等速接头用润滑脂组合物含有：(a)润滑油基础油、(b)由含氮化合物形成的增稠剂、(c)甘油三酯、(d)二酯、和(h)氮化硼。该润滑脂组合物中，甘油三酯和二酯的总计的含量以润滑脂组合物总量基准计为1～5质量％，甘油三酯的含量相对于二酯的含量的质量比(甘油三酯/二酯)为0.3～1.5。
润滑脂组合物优选还含有：(e)有机钼、(f)二硫代磷酸锌和(g)多硫化物。上述情况下，优选的是，有机钼的含量按照钼元素换算计为0.05～0.5质量％，有机钼、二硫代磷酸锌和多硫化物的总计的含量为2～5质量％。氮化硼的含量优选0.1～1质量％。润滑脂组合物优选用于汽车用驱动轴中应用的固定式等速接头的润滑。
作为(a)润滑油基础油，可以使用矿物油和/或合成油。
作为矿物油，可以使用：通过石油纯化业的润滑油制造工艺中通常进行的方法得到的矿物油。例如可以举出如下得到的链烷烃系或环烷烃系等矿物油：对于将原油进行常压蒸馏和减压蒸馏而得到的润滑油馏分，适宜组合溶剂脱沥青、溶剂萃取、加氢裂化、溶剂脱蜡、催化脱蜡、加氢精制、硫酸清洗、白土处理等中的1种或2种以上的精制手段而得到。
作为合成油，例如可以举出聚烯烃油、烷基苯油、烷基萘油、联苯油、二苯基烷烃油、二(烷基苯基)烷烃油、酯油、聚二醇油、聚苯醚油、全氟聚醚、氟化聚烯烃等氟化合物、硅油等。
作为润滑油基础油，优选矿物油、以聚烯烃油为代表的烃化合物，特别优选由链烷烃系烃化合物形成的基础油、或混合有链烷烃系烃化合物与环烷烃系烃化合物的基础油。
润滑油基础油的100℃下的运动粘度优选1～200mm2/s、更优选5～50mm2/s。润滑油基础油的含量以润滑脂组合物总量基准计、优选为60质量％以上、更优选70质量％以上。运动粘度和润滑油基础油的含量为该范围内时，容易简便地制备具有期望的稠度的润滑脂组合物。
作为(b)由含氮化合物形成的增稠剂，可以使用选自脲系增稠剂、氨基甲酸酯系增稠剂和脲/氨基甲酸酯系增稠剂中的至少1种。通过使用这些增稠剂，可以得到充分的耐热性。
作为脲系增稠剂，例如可以举出缩二脲化合物、缩三脲化合物、缩四脲化合物、聚脲化合物(除缩二脲化合物、缩三脲化合物、缩四脲化合物之外)等脲化合物、脲/氨基甲酸酯化合物、二氨基甲酸酯等氨基甲酸酯化合物或它们的混合物等，其中，优选缩二脲化合物、脲/氨基甲酸酯化合物、二氨基甲酸酯化合物或它们的混合物。
作为脲系增稠剂的优选例，可以举出通式(1)所示的缩二脲化合物。
A-NH-(C＝O)-NH-R1-NH-(C＝O)-NH-B (1)
通式(1)中，R1表示2价的有机基团，优选表示2价的烃基。作为上述2价的烃基，具体而言，可以举出直链或支链状的亚烷基、直链或支链状的亚烯基、环亚烷基、亚芳基、烷基亚芳基、芳基亚烷基等。另外，A、B表示1价的有机基团，优选表示1价的烃基。作为上述1价的烃基，具体而言，可以举出直链或支链状的烷基、直链或支链状的烯基、环烷基、芳基、烷基芳基、芳基烷基等。
作为脲/氨基甲酸酯系增稠剂的优选例，可以举出通式(2)所示的脲/氨基甲酸酯化合物。
A-NH-(C＝O)-NH-R1-NH-(C＝O)-O-B (2)
通式(2)中，R1表示2价的有机基团，优选表示2价的烃基。作为上述2价的烃基，具体而言，可以举出直链或支链状的亚烷基、直链或支链状的亚烯基、环亚烷基、亚芳基、烷基亚芳基、芳基亚烷基等。另外，A、B表示1价的有机基团，优选表示1价的烃基。作为上述1价的烃基，具体而言，可以举出直链或支链状的烷基、直链或支链状的烯基、环烷基、芳基、烷基芳基、芳基烷基等。
(b)增稠剂的含量以润滑脂组合物总量基准计、优选为2～20质量％、更优选5～15质量％。
(c)甘油三酯例如为甘油与一元羧酸的三酯。一元羧酸优选碳数8～24、更优选10～20的脂肪酸。作为这样的甘油三酯，可以使用以油脂的形式市售的产品，例如可以使用：牛油、猪油、向日葵油、大豆油、菜籽油、米糠油、椰子油、棕榈油、棕榈仁油。
(c)甘油三酯的含量以润滑脂组合物总量基准计、优选为0.5～5质量％、更优选0.5～3质量％、进一步优选0.5～1.5质量％。
(d)二酯例如为二羧酸与一元醇的酯。作为二羧酸，可以举出脂肪族烃的2个氢原子被羧基取代而成的化合物，优选脂肪族烃的两末端的氢原子被羧基取代而成的化合物。二羧酸的碳数优选2～18、更优选4～10。一元醇优选脂肪族醇、更优选支链饱和脂肪族醇。一元醇的碳数优选2～18、更优选4～10。二酯的碳数优选15～30、更优选20～25。
(d)二酯的含量以润滑脂组合物总量基准计，优选为0.2～10质量％、更优选0.5～5质量％、进一步优选0.5～3质量％。
(c)甘油三酯的含量相对于(d)二酯的含量的质量比((c)甘油三酯/(d)二酯)为0.3～1.5、优选0.3～1.2、更优选0.3～0.9、进一步优选0.3～0.6。(c)甘油三酯和(d)二酯的总计的含量为1～5质量％、优选2～5质量％、更优选2～4质量％、进一步优选2～3质量％。
作为(e)有机钼，可以使用二硫代氨基甲酸钼和/或二硫代磷酸钼。
作为二硫代氨基甲酸钼，可以使用以润滑油添加剂的形式市售的产品，例如可以使用下述通式(3)所示的化合物。
Figure BDA0001911426840000061
通式(3)中，R2和R3任选彼此相同或不同，分别表示碳数1以上的烃基，X任选相同或不同，分别表示氧原子或硫原子，a、b、c分别表示1～6的整数。作为通式(3)中的R2和R3所示的烃基，例如可以举出碳数1～24的烷基、碳数5～7的环烷基、碳数6～11的烷基环烷基、碳数6～18的芳基、碳数7～24的烷基芳基和碳数7～12的芳基烷基。
二硫代氨基甲酸钼中的钼元素含量以二硫代氨基甲酸钼总量基准计、优选10～40质量％、更优选10～30质量％。二硫代氨基甲酸钼中的硫元素含量以二硫代氨基甲酸钼总量基准计、优选10～40质量％、更优选20～35质量％。
作为二硫代磷酸钼，可以使用以润滑油添加剂的形式市售的产品。作为优选的二硫代磷酸钼的例子，可以举出下述通式(4)所示的化合物。
Figure BDA0001911426840000062
通式(4)中，R4和R5任选彼此相同或不同，分别表示碳数1以上的烃基，X1、X2、X3、X4和X5任选相同或不同，分别表示氧原子或硫原子，a、b、c分别表示1～6的整数。作为通式(4)中的R4和R5所示的烃基，例如可以举出碳数1～24的烷基、碳数5～7的环烷基、碳数6～11的烷基环烷基、碳数6～18的芳基、碳数7～24的烷基芳基和碳数7～12的芳基烷基。
二硫代磷酸钼中的钼元素含量以二硫代磷酸钼总量基准计、优选2～20质量％、更优选5～15质量％。二硫代磷酸钼中的磷元素含量以二硫代磷酸钼总量基准计、优选1～20质量％、更优选3～10质量％。二硫代磷酸钼中的硫元素含量以二硫代磷酸钼总量基准计、优选5～25质量％、更优选10～20质量％。
将润滑脂组合物总量设为基准，按照钼元素换算计，(e)有机钼的含量优选0.05～0.5质量％、更优选0.05～0.4质量％。
作为(f)二硫代磷酸锌，可以使用以润滑油添加剂的形式市售的产品，例如可以使用下述通式(5)所示的化合物。
Figure BDA0001911426840000071
通式(5)中，R6～R9任选彼此相同或不同，分别表示烃基。通式(5)中，作为R6～R9所示的烃基，例如可以举出碳数1～24的烷基、碳数5～7的环烷基、碳数6～11的烷基环烷基、碳数6～18的芳基、碳数7～24的烷芳基或碳数7～12的芳烷基，优选碳数2～10的烷基、特别优选仲型的支链烷基。
二硫代磷酸锌中的锌元素含量以二硫代磷酸锌总量基准计、优选2～20质量％、更优选5～15质量％。二硫代磷酸锌中的磷元素含量以二硫代磷酸锌总量基准计、优选2～25质量％、更优选4～15质量％。二硫代磷酸锌中的硫元素含量以二硫代磷酸锌总量基准计、优选10～30质量％、更优选15～25质量％。
将润滑脂组合物总量设为基准，(f)二硫代磷酸锌的含量优选0.2～2质量％、更优选0.3～1质量％。
作为(g)多硫化物，可以使用以润滑油添加剂的形式市售的产品，例如可以使用下述通式(6)所示的化合物。
R10-Sx-R11 (6)
通式(6)中，R10和R11任选彼此相同或不同，分别表示碳数3～20的直链状或支链状的烷基、碳数6～20的芳基、碳数6～20的烷芳基或碳数6～20的芳烷基，x表示2～6的整数、优选2～5的整数。
多硫化物中的硫元素含量以多硫化物总量基准计、优选20～55质量％、更优选35～50质量％。多硫化物的含量以润滑脂组合物总量基准计、优选0.1～2质量％、更优选0.2～1.8质量％。
(e)有机钼、(f)二硫代磷酸锌和(g)多硫化物的总计含量以润滑脂组合物总量基准计、优选2～5质量％、更优选2～4质量％。
作为(h)氮化硼，只要为一般用作固体润滑剂的物质就没有特别限定。
氮化硼的颗粒直径优选0.2～50μm、更优选1～10μm。(h)氮化硼的含量以润滑脂组合物总量基准计、优选0.05～1质量％、更优选0.05～0.5质量％。
第1实施方式的润滑脂组合物除上述(a)～(h)成分以外，可以根据需要还含有：一般用于润滑油、润滑脂的添加剂。作为上述添加剂，例如可以举出清洁剂、分散剂、抗磨剂、粘度指数改进剂、抗氧化剂、极压剂、防锈剂、防腐蚀剂等。
上述第1实施方式的润滑脂组合物封入于等速接头而使用。作为等速接头，可以使用固定式等速接头、滑动式等速接头的结构。固定式等速接头中可以举出滚动体为滚珠者，滑动式等速接头中可以举出滚动体为滚珠或滚柱者。这样的等速接头可以用于汽车用驱动轴。
[第2实施方式：固定式等速接头]
本发明的第2实施方式的等速接头是封入有上述第1实施方式的等速接头用润滑脂组合物的等速接头。作为等速接头，可以使用固定式等速接头、滑动式等速接头的结构。固定式等速接头中可以举出滚动体为滚珠者，滑动式等速接头中可以举出滚动体为滚珠或滚柱者。
滚动体为滚珠的固定式等速接头的一例如图1所示的被称为球笼型固定式等速接头10。如图1所示那样，球笼型固定式等速接头10具备：在球面状的内周面11a形成有多条轨道11b的外侧接头构件11；在球面状的外周面12a形成有与外侧接头构件11的轨道11b成对的多条轨道12b的内侧接头构件12；和，夹设于外侧接头构件11的轨道11b与内侧接头构件12的轨道12b之间的作为滚动体的滚珠13，且具有夹设有笼14的结构，所述笼14用于将滚珠13保持在外侧接头构件11与内侧接头构件12之间。滚珠13的个数优选3～10个中的任意者。球笼型固定式等速接头中，也包含图2所示的无底切型固定式等速接头20。另外，为了防止封入于内部的润滑脂向外部的泄漏、为了防止异物对内部的侵入，等速接头上安装有保护罩(未做图示)。
上述等速接头10、20可以用于汽车用驱动轴。图3为示出汽车用驱动轴的一例的示意剖视图。汽车用驱动轴60中，分别地在驱动轮侧WS上具备固定式等速接头10(20)，在差速齿轮侧GS上具备滑动式等速接头30，具有用轴61连接这些等速接头10(20)、30彼此的构成。为了防止封入于内部的润滑脂向外部的泄漏、为了防止异物对内部的侵入，等速接头10(20)、30具备安装于外侧接头构件11与轴61之间的保护罩62、63。
实施例
以下，基于实施例和比较例对本发明进一步进行具体说明，但本发明不受以下的实施例的任何限定。
[实施例1～6、比较例1]
将实施例和比较例中的润滑脂组合物的组成示于表1。表1中的各成分如以下所述。
(a)润滑油基础油：
实施例1～6：
以质量比45：45：10混合有链烷烃矿物油1(100℃下的运动粘度：10.7mm2/s、40℃下的运动粘度：93.9mm2/s、15℃下的密度：0.8858g/cm3)与链烷烃矿物油2(100℃下的运动粘度：31.7mm2/s、40℃下的运动粘度：500mm2/s、15℃下的密度：0.9008g/cm3)与环烷烃矿物油(100℃下的运动粘度：2.2mm2/s、40℃下的运动粘度：8.0mm2/s、15℃下的密度：0.9115g/cm3)的润滑油基础油(100℃下的运动粘度：13.1mm2/s、40℃下的运动粘度：129.9mm2/s)。
比较例1：
以质量比45：45：10混合有链烷烃矿物油1(100℃下的运动粘度：10.7mm2/s、40℃下的运动粘度：93.9mm2/s、15℃下的密度：0.8858g/cm3)与链烷烃矿物油2(100℃下的运动粘度：31.7mm2/s、40℃下的运动粘度：500mm2/s、15℃下的密度：0.9008g/cm3)与环烷烃矿物油(100℃下的运动粘度：6.5mm2/s、40℃下的运动粘度：68.3mm2/s、15℃下的密度：0.9292g/cm3)的润滑油基础油(100℃下的运动粘度：15.7mm2/s、40℃下的运动粘度：179.2mm2/s)。
(b)脲/氨基甲酸酯系增稠剂：由二苯基甲烷-4,4’-二异氰酸酯、环己基胺和十八烷基醇的反应生成的脲/氨基甲酸酯系化合物。
(c)甘油三酯：猪油。
(d)二酯：己二酸二辛酯(己二酸与2-乙基己醇的二酯)。
(e)二硫代氨基甲酸钼(MoDTC)：以二硫代氨基甲酸钼总量基准计、钼元素含量为29质量％、硫元素含量为28质量％的、通式(3)所示的二硫代氨基甲酸钼。
(f)二硫代磷酸锌(ZnDTP)：通式(5)的R6～R9为碳数3～8的仲型结构的烷基，以二硫代磷酸锌总量基准计、锌元素含量为10质量％、磷元素含量为9质量％、硫元素含量为18质量％的二硫代磷酸锌。
(g)多硫化物：硫元素含量以多硫化物基准计为42质量％的、通式(6)所示的多硫化物。
(h)氮化硼：平均粒径为2μm的六方晶系氮化硼粉体。
(i)胺系抗氧化剂和防锈剂(金属磺酸酯)。
实施例1～6和比较例1中，润滑油基础油中，使二苯基甲烷-4,4’-二异氰酸酯、环己基胺和十八烷基醇反应，使生成的脲/氨基甲酸酯系化合物均匀分散后，在其中进一步配混其他成分，进行辊磨机混炼，制备润滑脂。
实施例和比较例中的润滑脂组合物的性状(稠度)和特性如下进行评价。将结果分别示于表1。
[稠度]
依据JIS K2220，测定60W下的稠度。
[低温转矩]
依据JIS K2220，在轴承6204C3中封入润滑脂，在-30℃的条件下测定旋转转矩。将旋转初始的转矩为300mNm以下的情况评价为“A”、超过300mNm且400mNm以下的情况评价为“B”、超过400mNm的情况评价为“C”。之后，封入于等速接头的试验中也得到了同样的结果。
[摩擦试验]
依据ASTM D5707，在100N、30Hz、±1mm、30分钟、滚珠/板的条件下测定摩擦系数。摩擦系数为0.08以下的情况评价为“A”、超过0.08且0.09以下的情况评价为“B”、超过0.09的情况评价为“C”。摩擦试验中，之后，封入于等速接头的试验中也得到了同样的结果。
[表1]
Figure BDA0001911426840000121
实施例1～6为组合并使用了(c)甘油三酯和(d)二酯的润滑脂组合物，在低温转矩和摩擦特性这两方面优异，即，为能提高严苛的润滑条件下的耐久性的润滑脂组合物。
另一方面，比较例1为除(d)二酯之外的润滑脂组合物，为严苛的润滑条件下的耐久性差的润滑脂组合物。
产业上的可利用性
本发明的润滑脂组合物在等速接头中能提高严苛的润滑条件下的耐久性。
附图标记说明
10…球笼型固定式等速接头、11…外侧接头构件、11a…内周面、11b…轨道、12…内侧接头构件、12a…外周面、12b…轨道、13…滚珠、14…笼、20…无底切型固定式等速接头、60…汽车用驱动轴、61…轴、62、63…保护罩。

Claims (6)

1.一种等速接头用润滑脂组合物，其含有：
润滑油基础油、
由含氮化合物形成的增稠剂、
甘油三酯、
作为二羧酸与一元醇的酯的二酯、和
氮化硼，
所述甘油三酯和所述二酯的总计的含量以润滑脂组合物总量基准计为1~5质量%，所述甘油三酯的含量相对于所述二酯的含量的质量比，即甘油三酯/二酯为0.3~0.9，
所述润滑油基础油为矿物油和/或合成油，
所述合成油为选自聚烯烃油、烷基苯油、烷基萘油、联苯油、二苯基烷烃油、二（烷基苯基）烷烃油、聚二醇油、聚苯醚油、全氟聚醚、氟化聚烯烃以及硅油中的至少一种。
2.根据权利要求1所述的等速接头用润滑脂组合物，其中，还含有：有机钼、二硫代磷酸锌和多硫化物。
3.根据权利要求2所述的等速接头用润滑脂组合物，其中，
以润滑脂组合物总量基准计，
所述有机钼的含量按照钼元素换算计为0.05~0.5质量%，
所述有机钼、所述二硫代磷酸锌和所述多硫化物的总计的含量为2~5质量%。
4.根据权利要求1~3中任一项所述的等速接头用润滑脂组合物，其中，
所述氮化硼的含量以润滑脂组合物总量基准计为0.05~1质量%。
5.根据权利要求1所述的等速接头用润滑脂组合物，其用于汽车用驱动轴中应用的等速接头的润滑。
6.一种等速接头，其封入有权利要求1~4中任一项所述的等速接头用润滑脂组合物。
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