CN1656200A - 润滑脂组合物和转动轴承 - Google Patents
润滑脂组合物和转动轴承 Download PDFInfo
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Abstract
润滑脂组合物,其含有润滑油基础油、通式(1)~(3)所示双脲化合物中的至少1种、环烷酸盐和琥珀酸或其衍生物,其中通式(1)~(3)所示双脲化合物各自的含有比例满足式(4)和式(5)所示的条件,并且以润滑脂组合物总量为基准环烷酸盐和琥珀酸或其衍生物的含有比例分别为0.1~ 10质量%,式(1)~(3)中,R1表示C7~12的含芳香族环的烃基,R2表示C6~15的2价烃基,R3表示环己基或C7~12的烷基环己基,5≤W1+W2+W3≤35(4),0≤(W1+0.5×W2)/(W1+W2+W3)≤0.55(5)。式(4)、(5)中,W1、W2和W3分别表示通式(1)~(3)所示的双脲化合物以润滑脂组合物总量为基准的含有比例(质量%)。
Description
技术领域
本发明涉及润滑脂组合物和轴承,特别涉及适宜在汽车的电装零件、作为发动机副机的交流发电机和中间皮带轮、汽车空调用电磁离合器等的高温高速高负荷条件下使用,剥离寿命和高温下的烧结寿命优异的润滑脂组合物以及使用该润滑脂组合物的转动轴承。
背景技术
在汽车发动机的各种动力装置的旋转处,例如交流发电机、汽车空调用电磁离合器、中间皮带轮等汽车电装零件、发动机副机中一般使用转动轴承,其润滑主要使用润滑脂。
由于以汽车小型轻量化为目的的FF车的普及,以及希望扩大移动空间,希望发动机运转空间减小,在上述电装零件、发动机副机中小型轻量化进一步发展。此外,对于这些零件等日益要求其高性能、高功率化。但是,小型化产生的功率降低是不可避免的,例如在交流发电机和汽车空调用电磁离合器中通过高速化补偿功率的降低部分,但与此相伴,空转轮也同样地高速化。此外,由于希望提高肃静性,发动机运转空间的密闭化在发展,促进了发动机运转空间内的高温化,因此作为上述零件等的特性,耐高温性也成为必须。
伴随着该高速化、高性能化,与氢脆性产生的白色组织变化相伴,在上述零件等的轴承中产生剥离的问题明显化,防止其发生成为新的重要课题。此外,由于在上述零件等中在高温区域(例如170~180℃)中使用,因此高温下的耐烧结性也成为了重要的要求性能。此外,在用于这些轴承的润滑脂中,其必须为与其他各处使用的润滑脂的防锈性能更优异的润滑脂。
在该背景下,提出了用于提高润滑脂特性的各种添加剂处方。例如在特开平3-210394号公报中公开了分别添加了油溶性有机防锈剂(磺酸金属盐等)、水溶性无机非动态化剂(亚硝酸钠等)和非离子表面活性剂的润滑脂,该添加剂处方使防锈性能得到改善。此外,特开平9-3466号公报中公开了使用双脲化合物作为增稠剂的润滑脂组合物。
发明内容
但是,即使是使用了上述公报中记载的润滑脂组合物,在高温、高速、高负荷的苛酷条件下,获得足够的剥离寿命和烧结寿命是非常困难的。例如,即使如特开平3-210394号公报等中公开的润滑脂组合物那样使用磺酸盐等作为防锈剂,在维持防锈性能的同时获得足够的剥离寿命也未必容易。此外,在特开平9-3466号公报中公开的润滑脂组合物的情况下,在高速条件下的耐烧结性比较良好,但尚未获得能够将该耐烧结性维持到高温区域(例如160℃以上)的润滑脂。
本发明鉴于上述以往技术所具有的课题而提出,目的在于提供即使在高温、高速和高负荷条件下使用时,也能实现足够的剥离寿命和高温烧结寿命的润滑脂组合物和使用其的轴承。
为了解决上述课题,本发明的润滑脂组合物的特征在于:其含有润滑油基础油、下述通式(1)~(3)所示双脲化合物中的至少1种、环烷酸盐和琥珀酸或其衍生物,其中下述通式(1)~(3)所示双脲化合物各自的含有比例满足式(4)和式(5)所示的条件,并且以润滑脂组合物总量为基准环烷酸盐和琥珀酸或其衍生物的含有比例分别为0.1~10质量%,
式(1)~(3)中,R1表示C7~12的含芳香族环的烃基,R2表示C6~15的2价烃基,R3表示环己基或C7~12的烷基环己基,
5≤W1+W2+W3≤35 (4)
0≤(W1+0.5×W2)/(W1+W2+W3)≤0.55 (5)
式(4)、(5)中,W1、W2和W3分别表示通式(1)~(3)所示的双脲化合物以润滑脂组合物总量为基准的含有比例(质量%)。
以润滑脂组合物总量为基准,本发明的润滑脂组合物优选还含有0.1~10质量%的下述通式(6)~(11)所示的有机金属盐中的至少一种,
式(6)、(7)中,R4表示C1~18的烃基,M表示金属原子,n表示2~4的整数,x和y分别表示0~4的整数,z表示1~4的整数,
式(8)~(10)中,R5表示氢原子或C1~18的烃基,
式(11)中,R6表示C1~18的烃基。
此外,本发明的润滑脂组合物优选不含有磺酸盐。
此外,本发明的转动轴承,其特征在于:其通过内轮和外轮之间的保持器以大致等间隔转动自由地保持多个转动体,在内轮、外轮和转动体形成的轴承空间内封入上述本发明的润滑脂组合物。
附图说明
图1为表示本发明转动轴承优选一实施形态的模式截面图。
图2表示实施例中制备的(W1+0.5×W2)/(W1+W2+W3)和烧结寿命的关系。
图3表示实施例中制备的环烷酸锌的添加量和剥离发生率及锈评价点的关系。
图4表示实施例中制备的琥珀酸酯的添加量和剥离发生率及锈评价点的关系。
图5表示实施例中制备的ZnDTC的添加量和剥离发生率及烧结寿命的关系。
具体实施方式
以下对本发明优选的实施方式进行详细说明。
[润滑油基础油]
本发明中使用的润滑油基础油并无特别限制,可以使用通常润滑油的基础油。此外,为了避免低温流动性不足所产生的低温起动时的异音产生和高温下油膜形成不足而产生的烧结,优选40℃的运动粘度为10~400mm2/sec、更优选为20~250mm2/sec、进一步优选为40~150mm2/sec的基础油。
作为润滑油基础油的具体例,可以列举矿物油类、合成油类或天然油类润滑油等。作为矿物油类润滑油,可以使用将减压蒸馏、油剂脱除、溶剂抽提、氢化分解、溶剂脱蜡、硫酸洗涤、白土精制、氢化精制等适当组合对矿物油进行精制后的矿物油类润滑剂。作为合成油类润滑油基础油,可以列举烃类油、芳香族类油、酯类油、醚类油等。作为烃类油,可以列举正链烷烃、异链烷烃、聚丁烯、聚异丁烯、1-癸烯低聚物、1-癸烯和乙烯共聚低聚物等聚-α-烯烃或它们的氢化物等。作为芳香族类油,可以列举单烷基苯、二烷基苯等烷基苯,或单烷基萘、二烷基萘、多烷基萘等烷基萘等,作为酯类油,可以列举癸二酸二丁酯、二-2-乙基己基癸二酸酯、己二酸二辛酯、己二酸二异癸酯、己二酸二(十三烷基)酯、戊二酸二(十三烷基)酯、メチル·ァセチルシノレ一ト等二酯油,偏苯三酸三辛酯、偏苯三酸三癸酯、均苯四酸四辛酯等芳香族酯油,三羟甲基丙烷癸酸酯、三羟甲基丙烷壬酸酯、季戊四醇-2-乙基己酸酯、季戊四醇壬酸酯等多元醇酯油,为多元醇和二元酸、一元酸的混合脂肪酸的酯类低聚物的复合酯油等。作为醚类油,可以列举聚乙二醇、聚丙二醇、聚乙二醇单醚、聚丙二醇单醚等聚二元醇,单烷基三苯基醚、烷基二苯基醚、二烷基二苯基醚、五苯基醚、四苯基醚、单烷基四苯基醚、二烷基四苯基醚等苯基醚油等。作为其他合成润滑基础油,可以列举磷酸三甲苯酯、硅油、全氟烷基醚等。作为天然油类润滑基础油,可以列举牛脂、猪脂、大豆油、菜籽油、米糠油、椰子油、棕榈油、棕榈仁油等油脂类油或它们的氢化物。这些基础油可以单独使用1种,也可以使用2种以上的混合物。
[双脲化合物]
在本发明中,在上述润滑油基础油中添加下述通式(1)~(3)所示的双脲化合物作为增稠剂。
通式(1)、(2)中,R1表示C7~12的含芳香族环的烃基。作为该含芳香族环的烃基,具体可以列举甲苯基、二甲苯基、β-フェンシル基、叔丁基苯基、十二烷基苯基、苄基、甲基苄基等。
此外,通式(1)~(3)中的R2表示C6~15的2价烃基。作为该烃基,可以列举直链状或分支状的亚烷基、直链状或分支状的亚链烯基、亚环烷基、芳香族基团等。
此外,通式(2)、(3)中,R3表示环己基或C7~12的烷基环己基。具体可以列举甲基环己基、二甲基环己基、乙基环己基、二乙基环己基、丙基环己基、异丙基环己基、1-甲基-3-丙基环己基、丁基环己基、戊基环己基、戊基甲基环己基、己基环己基等。
通式(1)~(3)所示的双脲化合物各自的含有比例需要满足下式(4)和(5)所示的条件,
5≤W1+W2+W3≤35 (4)
0≤(W1+0.5×W2)/(W1+W2+W3)≤0.55 (5)
式(4)、(5)中,W1、W2和W3分别表示通式(1)~(3)所示的双脲化合物以润滑脂组合物总量为基准的含有比例(单位均为质量%)。
如式(4)所示,通式(1)~(3)所示的双脲化合物的含有比例的总和W1+W2+W3以润滑脂组合物总量为基准为5~35质量%。当W1+W2+W3不足5质量%时,由于作为增稠剂的效果小,因此不能成为充分的润滑脂状,或者润滑脂从轴承上渗漏多。出于同样的理由,优选W1+W2+W3为10质量%以上,更优选为13质量%以上。此外,如果W1+W2+W3超过35质量%,作为润滑脂其变得过硬,不能充分发挥润滑性能,出于同样的理由,优选W1+W2+W3为30质量%以下,更优选为25质量%以下。
此外,如果式(5)中的(W1+0.5×W2)/(W1+W2+W3)超过0.55,高温下的烧结寿命缩短。出于同样的理由,优选(W1+0.5×W2)/(W1+W2+W3)为0.4以下,更优选为0.3以下。此外,出于同样的理由,优选(W1+0.5×W2)/(W1+W2+W3)为0.1以上,更优选为0.2以上。
[添加剂]
本发明的润滑脂组合物含有后述的环烷酸盐和琥珀酸或其衍生物的两者。本发明的润滑脂组合物可以含有磺酸盐,也可以不含有磺酸盐,从可以进一步防止氢脆性剥离出发,优选不含有磺酸盐。
(环烷酸盐)
本发明中使用的环烷酸盐如果为具有环烷核的羧酸盐,并无特别限制,该羧酸可以为饱和、不饱和的任一种,但优选为具有环烷核的饱和羧酸盐。作为该环烷酸盐的具体例,可以列举饱和单环羧酸盐(CnH2n-1COOM)、饱和多环羧酸盐(CnH2n-3COOM)及它们的衍生物。例如,作为单环的羧酸盐,优选使用下式(12)、(13)所示的化合物。
式(12)、(13)中,R表示烃基。作为该烃基,可以列举烷基、链烯基、芳基、烷芳基、芳烷基等。此外,M表示金属元素,具体可以列举Co、Mn、Zn、Al、Ca、Ba、Li、Mg、Cu、Ni等。这些环烷酸盐可以单独使用1种,也可以将2种以上适当组合使用。
(琥珀酸或其衍生物)
作为本发明中使用的琥珀酸或其衍生物,可以列举琥珀酸、烷基琥珀酸、烷基琥珀酸半酯、链烯基琥珀酸、链烯基琥珀酸半酯、琥珀酰亚胺等。这些琥珀酸或其衍生物可以单独使用1种,也可以将2种以上适当组合使用。
以润滑脂组合物总量为基准,环烷酸盐、琥珀酸或其衍生物的含有比例分别为0.1~10质量%。如果该添加量不足0.1质量%,不能具有足够的防锈性。此外,如果该添加量超过10质量%,润滑脂软化,有可能产生润滑脂渗漏。此外,以润滑脂组合物总量为基准,各自的添加量如果在0.25~5质量%的范围内,在防锈性能进一步提高的同时,可以确实地防止润滑脂渗漏产生的烧结,因此优选。
(有机金属盐)
此外,为了使剥离寿命和高温下的烧结寿命提高,优选还含有下述式(6)~(11)所示的有机金属盐中的至少1种。
通式(6)所示的有机金属盐为二烷基二硫代氨基甲酸(DTC)系化合物,通式(7)所示的有机金属盐为二烷基二硫代磷酸(DTP)系化合物。
这里,M表示金属原子,具体可以列举Sb、Bi、Sn、Ni、Te、Se、Fe、Cu、Mo、Zn等。此外,R4表示C1~18的烃基,同一分子中的R4可以相同,也可以不同。作为R4所示的烃基,可以列举烷基、环烷基、链烯基、芳基、烷基芳基、芳基烷基等,其中优选1,1,3,3-四甲基丁基、1,1,3,3-四甲基己基、1,1,3-三甲基己基、1,3-二甲基丁基、1-甲基十一烷基、1-甲基己基、1-甲基戊基、2-乙基丁基、2-乙基己基、2-甲基环己基、3-庚基、4-甲基环己基、正丁基、异丁基、异丙基、异庚基、异戊基、十一烷基、二十烷基、乙基、十八烷基、辛基、环辛基、环十二烷基、环戊基、二甲基环己基、癸基、十四烷基、二十二烷基、十二烷基、十三烷基、三甲基环己基、壬基、丙基、十六烷基、己基、二十一烷基、十七烷基、庚基、十五烷基、戊基、甲基、叔丁基环己基、叔丁基、2-己烯基、2-甲基烯丙基、烯丙基、十一碳烯基、油基、癸烯基、乙烯基、丁烯基、己烯基、十七碳烯基、甲苯基、乙基苯基、异丙基苯基、叔丁基苯基、仲戊基苯基、正己基苯基、叔辛基苯基、异壬基苯基、正十二烷基苯基、苯基、苄基、1-苯基甲基、2-苯基乙基、3-苯基丙基、1,1-二甲基苄基、2-苯基异丙基、3-苯基己基、二苯甲基、联苯基。这些基团可以具有醚键。
通式(8)~(10)所示的有机金属盐为有机锌化合物。
其中,R5表示氢原子或C1~18的烃基。同一分子中的R5可以相同,也可以不同。
在上述有机锌化合物中,优选式(8)中的R5均为氢原子的メチルカプト苯并噻唑锌、式(9)中的R5均为氢原子的苯并酰胺基苯硫酚锌、和式(10)中的R5均为氢原子的巯基苯并咪唑锌。
通式(11)所示的有机金属盐为烷基黄原酸锌。
式中,R6表C1~18的烃基。
上述通式(6)~(11)所示的有机金属盐,可以各自单独使用1种,或2种以上组合使用。
这些有机金属盐的含有比例优选为0.1~10质量%,更优选为0.5~10质量%。如果该含有比例不足0.1质量%,存在无法获得剥离寿命和高温下的烧结寿命充分提高的效果。另一方面,如果该含有比例超过10质量%,有机金属盐有可能与轴承材料反应,此外,这些有机金属盐价格比较高,容易成为成本高的主要原因,而且高温下的烧结寿命有可能缩短。
为了进一步提高其性能,根据需要可以使本发明的润滑脂组合物含有公知的添加剂。作为该添加剂,可以列举例如金属皂、膨润土、二氧化硅凝胶等胶凝剂;胺系、酚系、硫系等的抗氧剂;氯系、硫系等的极压剂;脂肪酸、动植物油等油性剂;脱水山梨糖醇酯等防锈剂;苯并三唑、亚硝酸钠等金属钝化剂;聚甲基丙烯酸酯、聚异丁烯、聚苯乙烯等粘度指数提高剂等,它们可以单独使用或2种以上组合使用。此时,这些添加剂的含有比例只要能达成本发明的目的,并无特别限定,但以润滑脂组合物总量为基准,含有比例的总和优选20质量%以下。
[制法]
为了调制本发明的润滑脂组合物,可以采用在润滑油基础油中将通式(1)~(3)所示的双脲化合物、环烷酸盐和琥珀酸或其衍生物,或进一步根据需要的有机金属盐等均匀混合的方法制备。此外,当以一阶段的反应调制通式(1)~(3)所示的双脲化合物的混合物时,即使通过使用润滑油基础油作为溶剂,进而在反应后的混合物中加入环烷酸盐和琥珀酸或其衍生物等的方法,也可以制备本发明的润滑脂组合物。
[轴承]
本发明的旋转轴承,其特征在于:其通过内轮和外轮之间的保持器以大致等间隔转动自由地保持多个转动体,在内轮、外轮和转动体形成的轴承空间内封入上述本发明的润滑脂组合物。
图1为表示本发明转动轴承的实施形态所涉及的滚珠轴承的模式截面图,用含有其旋转轴的平面将滚珠轴承1切断。
在图1所示的滚珠轴承1中,在内轮10和外轮11之间的空间中通过保持器12以大致等间隔保持着多个作为转动体的滚珠13,在内轮10、外轮11、保持器12和滚珠13形成的轴承空间(润滑脂封入部分S)中填充有本发明的润滑脂组合物。在该润滑脂封入部S的两侧露出面上配置有环状的密封垫片14从而将该露出面覆盖,在密封垫片14的内径侧端部形成的配合唇15与内轮10相接,将润滑脂封入部S密封,防止润滑脂渗漏以及水分和异物从外部混入到润滑脂封入部S。
在上述实施形态中,通过在润滑脂封入部S中封入本发明的润滑脂组合物,即使在高温、高速和高负荷条件下使用,也能实现足够的剥离寿命和高温烧结寿命。因此,适宜在汽车的电装零件、作为发动机副机的交流发电机和中间皮带轮、汽车空调用电磁离合器等的高温高速高负荷条件使用。
本发明的转动轴承并不限于上述的实施形态。例如,图1表示滚珠轴承,但本发明的转动轴承可以为圆筒滚动轴承、圆锥滚动轴承、针状滚动轴承等滚动轴承。
[实施例]
以下根据实施例和比较例对本发明进行更为具体的说明,但本发明并不限于以下的实施例。
实施例1~28、比较例1~8
按以下的顺序,分别调制具有表1~6所示组成的实施例1~28和比较例1~8的润滑脂组合物。
即,将混合了甲烷二异氰酸酯的润滑油基础油和混合了胺的润滑油基础油混合,以使甲烷二异氰酸酯和胺达到所定的摩尔比并且其合计量达到所定量,进行加热搅拌使其反应。在制备的半固体状物中,加入预先溶解于润滑油基础油中的各种添加剂,充分通过搅拌器、轧制机,得到目的润滑脂组合物。使用组分如下所示。
基础油
PAO:聚-α-烯烃氢化物(40℃的运动粘度:47mm2/s)
醚:二烷基二苯基醚(40℃的运动粘度:100mm2/s)
酯:季戊四醇四酯(40℃的运动粘度:33mm2/s)
添加剂
环烷酸锌(Zn含量:10%)
琥珀酸酯:链烯基琥珀酸半酯(总酸值:155mgKOH/g)
ZnDTC:二烷基二硫代氨基甲酸锌
ZnDTP:二烷基二硫代磷酸锌
NiDTC:二烷基二硫代磷酸镍
磺酸钡(总酸值:30mgKOH/g)
然后,对于实施例1~28和比较例1~8的各润滑脂组合物进行以下试验。
(烧结寿命试验)
在内径φ17mm、外径φ52mm、宽16mm的带有接触橡胶密封垫片的深槽滚珠轴承中封入2.3g润滑脂,在内轮旋转速度20000min-1、轴承温度170℃、径向负荷98N的条件下使轴承连续旋转。当产生烧结,轴承外轮温度达到180℃时,使试验停止。进行4例该试验,到该试验结束时的时间的平均值为1000小时以上则为合格。得到的结果示于表1~6。
(急加减速试验)
使用发动机使组装到交流发电机中的轴承急加减速,对剥离寿命进行评价。即,将封入了2.36g润滑脂组合物的单列深槽滚珠轴承(内径φ17mm、外径φ47mm、宽14mm)组装到交流发电机中,反复发动机旋转速度1000~6000min-1(轴承旋转速度2400~13300min-1),在室温气氛下、皮带轮负荷1570N的条件下使轴承连续旋转。试验结束是当试验时间经过1000小时时,或轴承外轮旋转面上产生剥离而产生振动时。进行10例该试验,根据下式:
剥离发生率=(剥离发生数/试验数)×100
求出剥离发生率。得到的结果示于表1~6。
(防锈试验)
在内径φ17mm、外径φ47mm、宽14mm的带有接触橡胶密封垫片的深槽滚珠轴承中封入2.3g润滑脂,在1800min-1下使轴承旋转1分钟。旋转停止后,向轴承内注入浓度0.5质量%的盐水0.5cc,再在1800min-1下使轴承旋转1分钟。在52℃、100%RH的条件下放置48小时后,以如下所示的基准对试验轴承的内外轮轨道面的锈的发生状态进行评价。得到的结果示于表1~6。
<锈评价点>
1:无锈
2:小锈3点以下
3:小锈4点以上。
此外,将上述试验中得到的(W1+0.5×W2)/(W1+W2+W3)和烧结寿命的关系、环烷酸锌的添加量和剥离发生率及锈评价点的关系、琥珀酸酯的添加量和剥离发生率及锈评价点的关系、ZnDTC的添加量和剥离发生率及烧结寿命的关系分别示于图2、图3、图4和图5。
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 | 二异氰酸酯(mol) | 1 | 5 | 2 | 1 | 2 | 2 | |
单胺(mol) | 对甲苯胺 | 0 | 1 | 1 | 1 | 1 | 1 | |
环己胺 | 2 | 9 | 3 | 1 | 3 | 3 | ||
W1+W2+W3(质量%) | 18 | 18 | 18 | 18 | 18 | 18 | ||
(W1+0.5×W2)/(W1+W2+W3) | 0 | 0.1 | 0.25 | 0.5 | 0.25 | 0.25 | ||
基础油 | PAO(质量%) | 80.0 | 80.0 | 80.0 | 80.0 | 79.0 | 79.0 | |
醚(质量%) | - | - | - | - | - | - | ||
酯(质量%) | - | - | - | - | - | - | ||
添加剂 | 环烷酸锌(质量%) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
琥珀酸酯(质量%) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | ||
ZnDTC(质量%) | - | - | - | - | 1 | - | ||
ZnDTP(质量%) | - | - | - | - | - | 1 | ||
NiDTC(质量%) | - | - | - | - | - | - | ||
磺酸钡(质量%) | - | - | - | - | - | - | ||
烧结寿命时间(h) | 1400 | 1550 | 1600 | 1450 | 1900 | 1850 | ||
剥离发生率(%) | 0 | 0 | 0 | 0 | 0 | 0 | ||
锈评价点 | 2 | 2 | 2 | 2 | 2 | 2 |
表2
实施例7 | 实施例8 | 实施例9 | 实施例10 | 实施例11 | 实施例12 | |||
增稠剂 | 二异氰酸酯(mol) | 2 | 2 | 2 | 2 | 2 | 2 | |
单胺(mol) | 对甲苯胺 | 1 | 1 | 1 | 1 | 1 | 1 | |
环己胺 | 3 | 3 | 3 | 3 | 3 | 3 | ||
W1+W2+W3(质量%) | 18 | 18 | 18 | 18 | 18 | 18 | ||
(W1+0.5×W2)/(W1+W2+W3) | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | ||
基础油 | PAO(质量%) | 79.0 | 72.0 | - | - | - | - | |
醚(质量%) | - | - | 80.0 | 79.0 | - | - | ||
酯(质量%) | - | - | - | - | 80.0 | 79.0 | ||
添加剂 | 环烷酸锌(质量%) | 1 | 5 | 1 | 1 | 1 | 1 | |
琥珀酸酯(质量%) | 1 | 5 | 1 | 1 | 1 | 1 | ||
ZnDTC(质量%) | - | - | - | 1 | - | 1 | ||
ZnDTP(质量%) | - | - | - | - | - | - | ||
NiDTC(质量%) | 1 | - | - | - | - | - | ||
磺酸钡(质量%) | - | - | - | - | - | - | ||
烧结寿命时间(h) | 1850 | 1300 | 1600 | 1850 | 1500 | 1750 | ||
剥离发生率(%) | 0 | 0 | 0 | 0 | 0 | 0 | ||
锈评价点 | 1 | 2 | 2 | 2 | 2 | 2 |
表3
实施例13 | 实施例14 | 实施例15 | 实施例16 | 实施例17 | 实施例18 | |||
增稠剂 | 二异氰酸酯(mol) | 2 | 2 | 2 | 2 | 2 | 2 | |
单胺(mol) | 对甲苯胺 | 1 | 1 | 1 | 1 | 1 | 1 | |
环己胺 | 3 | 3 | 3 | 3 | 3 | 3 | ||
W1+W2+W3(质量%) | 18 | 18 | 18 | 18 | 18 | 18 | ||
(W1+0.5×W2)/(W1+W2+W3) | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | ||
基础油 | PAO(质量%) | 80.9 | 90.5 | 78.0 | 76.0 | 71.0 | 80.9 | |
醚(质量%) | - | - | - | - | - | - | ||
酯(质量%) | - | - | - | - | - | - | ||
添加剂 | 环烷酸锌(质量%) | 0.1 | 0.5 | 3.0 | 5.0 | 10.0 | 1.0 | |
琥珀酸酯(质量%) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 0.1 | ||
ZnDTC(质量%) | - | - | - | - | - | - | ||
ZnDTP(质量%) | - | - | - | - | - | - | ||
NiDTC(质量%) | - | - | - | - | - | - | ||
磺酸钡(质量%) | - | - | - | - | - | - | ||
烧结寿命时间(h) | 1800 | 1700 | 1500 | 1400 | 1100 | 1850 | ||
剥离发生率(%) | 0 | 0 | 0 | 0 | 0 | 0 | ||
锈评价点 | 2 | 2 | 2 | 2 | 2 | 1 |
表4
实施例19 | 实施例20 | 实施例21 | 实施例22 | 实施例23 | 实施例24 | |||
增稠剂 | 二异氰酸酯(mol) | 2 | 2 | 2 | 2 | 2 | 2 | |
单胺(mol) | 对甲苯胺 | 1 | 1 | 1 | 1 | 1 | 1 | |
环己胺 | 3 | 3 | 3 | 3 | 3 | 3 | ||
W1+W2+W3(质量%) | 18 | 18 | 18 | 18 | 18 | 18 | ||
(W1+0.5×W2)/(W1+W2+W3) | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | ||
基础油 | PAO(质量%) | 80.5 | 78.0 | 76.0 | 71.0 | 79.9 | 79.5 | |
醚(质量%) | - | - | - | - | - | - | ||
酯(质量%) | - | - | - | - | - | - | ||
添加剂 | 环烷酸锌(质量%) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
琥珀酸酯(质量%) | 0.5 | 3.0 | 5.0 | 10.0 | 1.0 | 1.0 | ||
ZnDTC(质量%) | - | - | - | - | 0.1 | 0.5 | ||
ZnDTP(质量%) | - | - | - | - | - | - | ||
NiDTC(质量%) | - | - | - | - | - | - | ||
磺酸钡(质量%) | - | - | - | - | - | - | ||
烧结寿命时间(h) | 1800 | 1600 | 1450 | 1150 | 1700 | 1800 | ||
剥离发生率(%) | 0 | 0 | 0 | 0 | 0 | 0 | ||
锈评价点 | 2 | 2 | 2 | 1 | 2 | 2 |
表5
实施例25 | 实施例26 | 实施例27 | 实施例28 | |||
增稠剂 | 二异氰酸酯(mol) | 2 | 2 | 2 | 2 | |
单胺(mol) | 对甲苯胺 | 1 | 1 | 1 | 1 | |
环己胺 | 3 | 3 | 3 | 3 | ||
W1+W2+W3(质量%) | 18 | 18 | 18 | 18 | ||
(W1+0.5×W2)/(W1+W2+W3) | 0.25 | 0.25 | 0.25 | 0.25 | ||
基础油 | PAO(质量%) | 77.0 | 75.0 | 70.0 | 68.0 | |
醚(质量%) | - | - | - | - | ||
酯(质量%) | - | - | - | - | ||
添加剂 | 环烷酸锌(质量%) | 1.0 | 1.0 | 1.0 | 1.0 | |
琥珀酸酯(质量%) | 1.0 | 1.0 | 1.0 | 1.0 | ||
ZnDTC(质量%) | 3.0 | 5.0 | 10.0 | 12.0 | ||
ZnDTP(质量%) | - | - | - | - | ||
NiDTC(质量%) | - | - | - | - | ||
磺酸钡(质量%) | - | - | - | - | ||
烧结寿命时间(h) | 1950 | 1750 | 1650 | 1500 | ||
剥离发生率(%) | 0 | 0 | 0 | 0 | ||
锈评价点 | 2 | 2 | 2 | 2 |
表6
比较例1 | 比较例2 | 比较例3 | 比较例4 | 比较例5 | 比较例6 | 比较例7 | 比较例8 | |||
增稠剂 | 二异氰酸酯(mol) | 2 | 1 | 2 | 2 | 2 | 2 | 2 | 2 | |
单胺(mol) | 对甲苯胺 | 3 | 2 | 1 | 1 | 1 | 1 | 1 | 1 | |
环己胺 | 1 | 0 | 3 | 3 | 3 | 3 | 3 | 3 | ||
W1+W2+W3(质量%) | 18 | 20 | 18 | 18 | 18 | 18 | 18 | 18 | ||
(W1+0.5×W2)/(W1+W2+W3) | 0.75 | 1 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | 0.25 | ||
基础油 | PAO(质量%) | 80.0 | 78.0 | 79.95 | 79.95 | 69.0 | 69.0 | 80.0 | 79.0 | |
醚(质量%) | - | - | - | - | - | - | - | - | ||
酯(质量%) | - | - | - | - | - | - | - | - | ||
添加剂 | 环烷酸锌(质量%) | 1.0 | 1.0 | 0.05 | 1.0 | 12.0 | 1.0 | - | - | |
琥珀酸酯(质量%) | 1.0 | 1.0 | 1.0 | 0.05 | 1.0 | 12.0 | - | - | ||
ZnDTC(质量%) | - | - | - | - | - | - | - | 1 | ||
ZnDTP(质量%) | - | - | - | - | - | - | - | - | ||
NiDTC(质量%) | - | - | - | - | - | - | - | - | ||
磺酸钡(质量%) | - | - | - | - | - | - | 2 | 2 | ||
烧结寿命时间(h) | 750 | 600 | 1600 | 1550 | 700 | 600 | 800 | 850 | ||
剥离发生率(%) | 0 | 10 | 0 | 0 | 10 | 10 | 40 | 30 | ||
锈评价点 | 2 | 2 | 3 | 3 | 1 | 1 | 2 | 2 |
如上所述,根据本发明,可以得到剥离寿命、高温烧结寿命极其优异的润滑脂组合物和使用其的转动轴承。因此,本发明在交流发电机、汽车空调用电磁离合器、中间皮带轮、电动风扇马达、水泵等的汽车电装零件、发动机副机的转动轴承方面特别有用。
Claims (4)
1、润滑脂组合物,其含有润滑油基础油、通式(1)~(3)所示双脲化合物中的至少1种、环烷酸盐和琥珀酸或其衍生物,其中通式(1)~(3)所示双脲化合物各自的含有比例满足式(4)和式(5)所示的条件,并且以润滑脂组合物总量为基准环烷酸盐和琥珀酸或其衍生物的含有比例分别为0.1~10质量%,
式(1)~(3)中,R1表示C7~12的含芳香族环的烃基,R2表示C6~15的2价烃基,R3表示环己基或C7~12的烷基环己基,
5≤W1+W2+W3≤35 (4)
0≤(W1+0.5×W2)/(W1+W2+W3)≤0.55 (5)
式(4)、(5)中,W1、W2和W3分别表示通式(1)~(3)所示的双脲化合物以润滑脂组合物总量为基准的含有比例(质量%)。
3、权利要求1所述的润滑脂组合物,其不含有磺酸盐。
4、转动轴承,其通过内轮和外轮之间的保持器以大致等间隔转动自由地保持多个转动体,在上述内轮、上述外轮和上述转动体所形成的轴承空间内封入权利要求1所述的润滑脂组合物。
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JP6700074B2 (ja) | 2016-03-11 | 2020-05-27 | 株式会社デンソー | グリース組成物、機械部材及びスタータオーバーランニングクラッチ |
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JP2018162372A (ja) * | 2017-03-24 | 2018-10-18 | Ntn株式会社 | グリース組成物、転がり軸受、およびハブベアリング |
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US20050207687A1 (en) * | 2002-01-21 | 2005-09-22 | Nsk Ltd. | Rolling bearing |
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- 2002-05-29 JP JP2002156339A patent/JP2003342593A/ja active Pending
-
2003
- 2003-05-28 EP EP03755287A patent/EP1510569A4/en not_active Withdrawn
- 2003-05-28 CN CNB038123509A patent/CN1330740C/zh not_active Expired - Fee Related
- 2003-05-28 WO PCT/JP2003/006703 patent/WO2003099973A1/ja active Application Filing
- 2003-05-28 US US10/515,837 patent/US20050250653A1/en not_active Abandoned
- 2003-05-28 AU AU2003235450A patent/AU2003235450A1/en not_active Abandoned
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CN104350136A (zh) * | 2012-03-23 | 2015-02-11 | 松下电器产业株式会社 | 润滑脂组合物、转动轴承及变频电机 |
CN104350136B (zh) * | 2012-03-23 | 2019-06-04 | 松下电器产业株式会社 | 润滑脂组合物、转动轴承及变频电机 |
CN105181403A (zh) * | 2015-06-04 | 2015-12-23 | 中国兵器工业集团第五三研究所 | 单元素标准油及其制备方法 |
CN105181403B (zh) * | 2015-06-04 | 2018-02-09 | 中国兵器工业集团第五三研究所 | 单元素标准油及其制备方法 |
CN107057807A (zh) * | 2015-11-10 | 2017-08-18 | 美蓓亚株式会社 | 润滑脂组合物、滚动轴承和马达 |
CN107057807B (zh) * | 2015-11-10 | 2021-07-23 | 美蓓亚株式会社 | 润滑脂组合物、滚动轴承和马达 |
CN108473909A (zh) * | 2016-01-22 | 2018-08-31 | 国际壳牌研究有限公司 | 润滑脂组合物 |
CN111073732A (zh) * | 2019-12-27 | 2020-04-28 | 辽宁海华科技股份有限公司 | 一种抗碱水润滑脂及其制备方法 |
CN111073732B (zh) * | 2019-12-27 | 2021-12-10 | 辽宁海华科技股份有限公司 | 一种抗碱水润滑脂及其制备方法 |
Also Published As
Publication number | Publication date |
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EP1510569A1 (en) | 2005-03-02 |
AU2003235450A1 (en) | 2003-12-12 |
CN1330740C (zh) | 2007-08-08 |
JP2003342593A (ja) | 2003-12-03 |
US20050250653A1 (en) | 2005-11-10 |
AU2003235450A8 (en) | 2003-12-12 |
WO2003099973A1 (fr) | 2003-12-04 |
EP1510569A4 (en) | 2006-03-08 |
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