CN106661495A - 润滑剂组合物及封入润滑剂组合物的轴承 - Google Patents

润滑剂组合物及封入润滑剂组合物的轴承 Download PDF

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CN106661495A
CN106661495A CN201580035402.8A CN201580035402A CN106661495A CN 106661495 A CN106661495 A CN 106661495A CN 201580035402 A CN201580035402 A CN 201580035402A CN 106661495 A CN106661495 A CN 106661495A
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lubricant compositions
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近藤凉太
川村隆之
三上英信
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Abstract

本发明提供可作为转动部件的润滑剂使用,即使在180℃以上的高温条件下也可长期地保持高润滑性能的润滑剂组合物、以及封入该润滑剂组合物而成的滚动轴承。封入润滑剂组合物的轴承(1),把润滑剂组合物(7)封入转动体(4)的周围而成,该润滑剂组合物(7)含有基油与抗氧化剂,上述基油为烷基二苯基醚油、和选自聚‑α‑烯烃油及酯油的至少1种油的混合油,并且,烷基二苯基醚油相对于基油总体含有50重量％以上,上述抗氧化剂为2,2,4‑三甲基‑1,2‑二氢喹啉或其聚合物,相对于润滑剂组合物总体含有0.1～10重量％。

Description

润滑剂组合物及封入润滑剂组合物的轴承
技术领域
本发明涉及润滑剂组合物,特别是涉及供给在高温(例如,180℃以上)的条件下使用的轴承等转动部件润滑的润滑剂组合物。另外,涉及封入该润滑剂组合物的滚动轴承。
背景技术
从前,在产业界中，为了谋求在滚动轴承等转动部件中使用的润滑剂高性能化,尝试往润滑剂中配合各种的添加剂。当滚动轴承等在高温条件下使用时,封入的润滑油或润滑脂发生氧化老化,润滑膜易发生破裂等,润滑寿命有变短的担心。特别是在高温且高速条件下,润滑膜的破裂易于产生,或者当破裂时,转动部件之间发生金属接触,发热、摩擦摩耗增大等不良情况发生。因此,滚动轴承等中使用的润滑油或润滑脂,为了提高高温耐久性,作为抗氧化剂,可单独或多种组合使用胺系抗氧化剂、苯酚系抗氧化剂、有机锌化合物等。
例如,提出了在轴承用润滑剂中,采用2,2′-亚甲基双(6-叔丁基-4-甲基苯酚)等苯酚系抗氧化剂、以及辛基化二苯胺等胺系抗氧化剂、吩噻嗪等硫系抗氧化剂等(参照专利文献1)。另外,在电动机用滚动轴承中使用的润滑脂组合物中,为了谋求其低转矩化及静音化,提出了以低粘度的酯油作为基油,以金属皂作为增稠剂,作为抗氧化剂并用液体的受阻胺及硫代磷酸三苯酯(参照专利文献2)。
现有技术文献
专利文献
专利文献1:特开2005-188557号公报
专利文献2:特开2012-162657号公报
发明内容
本发明拟解决的课题
然而,采用专利文献1及专利文献2那样的抗氧化剂时,依据组合的基油种类、以及润滑时的温度条件等,对于高温耐久性有时得不到充分的性能。例如,作为润滑剂的基油一种的苯基醚系合成油,热稳定性及氧化稳定性优良,但在180℃以上那样的高温条件下使用时,依据抗氧化剂的种类,有无法赋予充分的高温充久性的担心。
本发明是针对这样的问题提出的,目的是提供：可作为转动部件的润滑剂使用,即使在180℃以上那样的高温条件下也可得到跨长期地保持高润滑性能的润滑剂组合物,以及封入该润滑剂组合物的滚动轴承。
用于解决课题的手段
本发明的润滑剂组合物,是用于转动部件的润滑、含有基油与抗氧化剂的润滑剂组合物,其特征在于,上述基油是烷基二苯基醚油、和选自聚-α-烯烃(以下也称“PAO”)油及酯油的至少1种油的混合油,并且,上述烷基二苯基醚油相对于上述基油总体含有50重量％以上；上述抗氧化剂是由下式(1)表示的化合物或其聚合物,相对于上述润滑剂组合物总体含有0.1～10重量％。
[化1]
其特征在于,作为上述基油,上述烷基二苯基醚油相对于上述基油总体含有70～90重量％。另外,其特征在于，上述基油为上述烷基二苯基醚油与上述聚-α-烯烃油的混合油。其特征在于，上述烷基二苯基醚油的运动粘度在40℃为60～120mm2/s。
上述润滑剂组合物,其特征在于,其是含有脲化合物作为增稠剂的润滑脂。
上述润滑剂组合物,其特征在于,其能够在180℃以上的高温条件下使用。
封入本发明的润滑剂组合物的轴承,其特征在于,将上述本发明的润滑剂组合物封入润滑对象部位而成。
发明的效果
本发明的润滑剂组合物,在规定的以苯基醚系合成油作为主成分的混合基油中,作为抗氧化剂配合规定的喹啉系抗氧化剂而成,在达到180℃以上的高温条件下使用时,与对相同基油采用其它的抗氧化剂时相比,能够跨长期地抑制氧化老化,延长润滑寿命。此结果能够谋求封入该润滑剂组合物的轴承等转动部件的长寿命。
附图说明
[图1]封入本发明的润滑剂组合物的轴承之一例的深槽式滚珠轴承的截面图。
[图2]表示高温放置试验结果图。
[图3]表示高温放置试验结果图。
[图4]表示高温放置试验结果图。
具体实施方式
本发明的润滑剂组合物,可用于转动部件的润滑。具体的是,在滚动轴承或齿轮、及这些的构成部件中,在其润滑对象部位封入等后而使用。在该润滑剂组合物中设定的使用温度,例如,150℃以上,特别是180℃以上,上限为200℃左右。即,作为使用温度范围,例如150～200℃,特别是180～200℃的范围。
本发明的润滑剂组合物的形态,有如下2种:(A)以含有规定的基油、和规定的喹啉系抗氧化剂作为必须构成的润滑油；以及(B)以含有规定的基油、增稠剂、和规定的喹啉系抗氧化剂作为必须构成的润滑脂等。
本发明中使用的喹啉系抗氧化剂为式(1)表示化合物的2,2,4-三甲基-1,2-二氢喹啉、或其二聚体以上的缩合物(聚合物)。另外,也可使用该化合物与聚合物的混合物。
[化2]
该聚合物相当于JIS K 6211的抗老化剂“TMDQ”,作为其物性,可以举出软化点80～110℃、比重1.06～1.11、灰分0.5％以下。作为本发明中使用的市售品,可以举出Vanderbilt社制:VANLUBE RD、大内新兴化学工业社制:Norac(注册商标)224等。
上述润滑剂组合物作为润滑油使用时,喹啉系抗氧化剂的配合比例,相对于润滑剂组合物总体设为0.1～10重量％。当不足0.1重量％时,无法得到高温耐久性的充分提高。另外,当超过10重量％时,不仅性能无法提高,而且因抗氧化剂的老化物变蒸发等,高温耐久性有变差的担心。优选的是0.3～10重量％,更优选的是0.3～5重量％,尤其优选的是0.3～2重量％。
上述润滑剂组合物作为润滑脂使用时,喹啉系抗氧化剂的配合比例,相对于基油与增稠剂的合计量100重量份设为0.1～10重量份。当不足0.1重量份时,高温耐久性得不到充分提高。另外,当超过10重量份时,不仅性能不能提高,而且因抗氧化剂的老化物变蒸发等,高温耐久性有变差的担心。优选的是0.3～10重量份,更优选的是0.3～5重量份,尤其优选的是0.3～2重量份。
本发明的润滑剂组合物,是(X)作为必须成分的烷基二苯基醚油、与(Y)选自PAO油及酯油的至少1种油的混合油,且烷基二苯基醚油相对于上述基油总体含有50重量％以上的油。作为混合基油中的(X)与(Y)的重量比,X﹕Y＝6﹕4～9﹕1是优选的、X﹕Y＝7﹕3～9﹕1是更优选的、X﹕Y＝7.5﹕2.5～8.5﹕1.5是特优选的。X﹕Y＝7﹕3～9﹕1,即烷基二苯基醚油相对于基油总体含有70重量％以上时,特别容易得到上述喹啉系抗氧化剂带来高温耐久性的提高效果。
作为必须成分的烷基二苯基醚油,可以举出下式(2)表示的单烷基二苯基醚油、下式(3)表示的二烷基二苯基醚油、或聚烷基二苯基醚等。
[化3]
[化4]
式中的R1、R2、及R3分别为碳原子数8～20的烷基,分别结合于一个苯环上、或结合于二个苯环上。这些之中,当考虑耐热性等,具有R2及R3的二烷基二苯基醚油是优选的。
PAO油(合成烃油)为α-烯烃或异构化的α-烯烃的低聚物或聚合物的混合物。作为α-烯烃的具体例子,可以举出1-辛烯、1-壬烯、1-癸烯、1-十二碳烯、1-十三碳烯、1-十四碳烯、1-十五碳烯、1-十六碳烯、1-十七碳烯、1-十八碳烯、1-十九碳烯、1-二十碳烯、1-二十二碳烯、1-二十四碳烯等,通常使用这些的混合物。
作为酯油,可以举出癸二酸二丁酯、二-2-乙基已基癸二酸酯、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、甲基·乙酰基蓖麻醇酸酯等的二酯油,偏苯三酸三辛酯、偏苯三酸三癸酯、均苯四甲酸四辛酯等芳香族酯油,三羟甲基丙烷辛酸酯、三羟甲基丙烷壬酸酯、季戊四醇-2-乙基己酸酯、季戊四醇辛酸酯等多元醇酯油,碳酸酯油、磷酸酯油等。
本发明的润滑剂组合物的基油中,烷基二苯基醚油的运动粘度,在40℃时50～200mm2/s是优选的、60～120mm2/s是更优选的。作为全部基油(混合油)的运动粘度,在40℃时30～200mm2/s是优选的,考虑低温性及耐热性,60～100mm2/s是更优选的。
本发明的润滑剂组合物用作润滑脂时,还配合增稠剂。作为增稠剂,从耐热耐久性优良、对滑动部位的介入性与附着性也优良考虑,使用脲化合物是优选的。
脲化合物,由多异氰酸酯成分与单胺成分进行反应得到。作为多异氰酸酯成分,可以举出亚苯基二异氰酸酯、亚甲苯基二异氰酸酯、二苯基二异氰酸酯、二苯基甲烷二异氰酸酯、八癸烷二异氰酸酯、癸烷二异氰酸酯、已烷二异氰酸酯等。另外,单胺成分,可以采用脂肪族单胺、脂环族单胺及芳香族单胺。作为脂肪族单胺,可以举出已胺、辛胺、十二烷胺、十六烷胺、十八烷胺、硬脂酰胺、油胺等。作为脂环族单胺,可以举出环已胺等。作为芳香族单胺,可以举出苯胺、p-甲苯胺等。
在基油中配合脲化合物等增稠剂,可得到基础润滑脂。以脲化合物作为增稠剂的基础润滑脂,是在基油中使上述多异氰酸酯成分与单胺成分进行反应来制造的。在基础润滑脂中所占增稠剂的配合比例,1～40重量％是优选的,3～25重量％是更优选的。当增稠剂的含量不足1重量％时,增稠效果变少,润滑脂化变得困难,当超过40重量％时,得到的基础润滑脂变得过硬,难以得到期望的效果。
采用上述润滑脂时,其混合稠度(JIS K 2220)处于200～350的范围是优选的。当稠度不足200时,油分离小,有润滑变得不良的担心。另一方面,当稠度超过350时,润滑脂为软质,易从封入部位流出,是不优选的。
上述润滑剂组合物,在不损伤本发明目的的范围内,可根据需要含有上述喹啉系抗氧化剂以外的公知的添加剂。作为添加剂,例如,可以举出苯并三唑等金属钝化剂,聚甲基丙烯酸酯、聚苯乙烯等粘度指数提高剂,二硫化钼、石墨等固体润滑剂,金属磺酸盐、多元醇酯等的防锈剂,酯、醇等的油性剂,其他的防摩耗剂等。这些可以单独添加,或2种以上组合添加。
本发明中,相对上述的规定基油,采用规定的喹啉系抗氧化剂,与单独使用其他的抗氧化剂的场合相比,高温耐久性能够得到优先地提高。另外,可根据需要,作为其他的抗氧化剂,可并用芳香族胺系抗氧化剂或苯酚系抗氧化剂等。
对封入本发明的润滑剂组合物而成的润滑剂组合物封入轴承(滚动轴承),按照图1进行说明。图1为深槽式滚珠轴承的截面图。滚动轴承1,在外周面同心配置了具有内轮转动面2a的内轮2与在内周面具有外轮转动面3a的外轮3,在内轮转动面2a与外轮转动面3a之间配置多个转动体4。该转动体4由保持器5来保持。另外,内·外轮的轴向两端开口部8a、8b由密封构件6来密封,至少在转动体4的周围封入上述润滑剂组合物7。内轮2、外轮3及转动体4由作为铁系金属的轴承钢构成,作为润滑脂的润滑剂组合物7,介于与转动体4的转动面上进行润滑。
图1示出作为轴承的滚珠轴承,本发明的滚动轴承,也可以使用上述以外的圆筒滚动轴承、圆锥滚动轴承、自动调心滚动轴承、针状滚动轴承、推力圆筒滚动轴承、推力圆锥滚动轴承、推力针状滚动轴承、推力自动调心滚动轴承等。
本发明的润滑剂组合物封入轴承,由于封入了上述润滑剂组合物,即使在达到180℃以上的高温且高速条件下使用时,也可长时间地抑制润滑剂的氧化老化,达到长寿命。
实施例
本发明通过实施例及比较例具体地进行说明,但本发明不受这些例子的任何限定。
实施例1、比较例1～比较例6
关于表1中的润滑剂组合物,其高温耐久性通过高温放置时的重量减少率的测定进行评价。表1中的基油,任何一种均为烷基二苯基醚油与聚-α-烯烃油的混合油,其混合比率以重量比为8:2。供试润滑剂组合物于180℃及120℃的恒温槽中,在空气氛围气下放置,在达到0、200、400、600、800、1000小时(120℃时至600小时)的时点,从恒温槽取出,分别测定重量,依下式求重量减少率。结果一并示于表1。另外,180℃的高温放置试验结果示于图2,120℃的高温放置试验结果示于图3。各图中,横轴为测定时间(h),纵轴为重量减少率(重量％)。
重量减少率(重量％)＝100×(恒温槽放置前的润滑剂组合物的重量(g)-恒温槽放置后的润滑剂组合物的重量(g))/恒温槽放置前的润滑剂组合物的重量(g)
[表1]
1)：松村石油研究所制Moresco High Lube LB100 40℃时运动粘度97mm2/s
2)：新日铁化学社制Shin-fluid801 40℃时运动粘度46mm2/s
3)：2,2,4-三甲基-1,2-二氢喹啉聚合物
4)：辛基化二苯胺
5)：2，2＇-亚甲基双(6-叔丁基-4-甲基苯酚)
实施例2、实施例3、比较例7、及比较例8
关于表2中润滑剂组合物,其高温耐久性通过高温放置时的重量减少率测定进行评价。表2中的基油为烷基二苯基醚油与聚-α-烯烃油或酯油的混合油,其混合比率(重量比)如表中所示。另外,表2中的上角标1)～3)与表1中相同。供试润滑剂组合物在180℃的恒温槽中,空气氛围气下放置,达到0、200、400小时的时点从恒温槽取出,测定各自的重量,依上式求出重量减少率。结果一并记在表2中。另外,与实施例1等同样,高温放置试验结果示于图4。
[表2]
6)：花王社制KAOLUBE26240℃时运动粘度33.5mm2/s
如表1、2、及图2～4所示,以烷基二苯基醚油作为主成分的混合基油中,配合作为抗氧化剂的规定的喹啉系抗氧化剂的各实施例,与相对相同基油配合其它抗氧化剂时比较,已确认高温放置试验中的重量减少率小,能够抑制长时间的氧化老化。
产业上的利用可能性
本发明的润滑剂组合物,作为供作高温(例如、180℃以上)条件下使用的轴承等转动部件润滑的润滑剂组合物,能够适合地利用。
符号的说明
1滚动轴承
2内轮
3外轮
4转动体
5保持器
6密封构件
7润滑剂组合物
8a、8b开口部

Claims (7)

1.润滑剂组合物,其是用于转动部件的润滑、含有基油与抗氧化剂的润滑剂组合物,其特征在于,上述基油是含有烷基二苯基醚油、和选自聚-α-烯烃油及酯油的至少1种油的混合油,且上述烷基二苯基醚油相对于上述基油总体含有50重量％以上,上述抗氧化剂为由下式(1)表示的化合物或其聚合物,相对于上述润滑剂组合物总体,含有0.1～10重量％:
[化1]
2.按照权利要求1所述的润滑剂组合物,其特征在于,作为上述基油，上述烷基二苯基醚油相对于上述基油总体含有70～90重量％。
3.按照权利要求2所述的润滑剂组合物,其特征在于,上述基油为上述烷基二苯基醚油与上述聚-α-烯烃油的混合油。
4.按照权利要求1所述的润滑剂组合物,其特征在于,上述烷基二苯基醚油的运动粘度在40℃为60～120mm2/s。
5.按照权利要求1所述的润滑剂组合物,其特征在于,上述润滑剂组合物是含有脲化合物作为增稠剂的润滑脂。
6.按照权利要求1所述的润滑剂组合物,其特征在于,上述润滑剂组合物能够在180℃以上的高温条件下使用。
7.封入润滑剂组合物的轴承,其特征在于,封入权利要求1所述的润滑剂组合物而成。
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