CN109477025A - 润滑油组合物及其制造方法 - Google Patents
润滑油组合物及其制造方法 Download PDFInfo
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- CN109477025A CN109477025A CN201780044795.8A CN201780044795A CN109477025A CN 109477025 A CN109477025 A CN 109477025A CN 201780044795 A CN201780044795 A CN 201780044795A CN 109477025 A CN109477025 A CN 109477025A
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Abstract
本发明提供尽管硫酸灰分少清洁性也良好、且即使劣化后也具有良好的减摩擦作用的润滑油组合物。润滑油组合物,其含有基础油(A)、不含金属的硫系抗氧化剂(B)和分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C),以上述润滑油组合物总量为基准,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为800质量ppm以上,以上述润滑油组合物总量为基准,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量为100质量ppm以上400质量ppm以下,上述润滑油组合物的硫酸灰分为0.70质量%以下,上述润滑油组合物的总碱值为4.0mgKOH/g以上。
Description
技术领域
本发明涉及润滑油组合物及其制造方法。
背景技术
近年来,为了提高发动机的输出功率而装载有增压器的发动机不断增加。
装载有增压器的发动机由于施加于润滑油组合物的热负荷高,因此润滑油组合物容易劣化。劣化了的润滑油组合物清洁性不足,因此需要配混金属系清洁剂以维持清洁性、总碱值。
但是,由金属系清洁剂等产生的硫酸灰分成为润滑油组合物劣化时的沉积物的原因之一。并且,产生的沉积物成为使发动机部件磨损的主要原因。
另外,从近年来的环境规定的角度考虑,需要燃油效率高的润滑油组合物。因此,要求润滑油组合物即使是劣化后也维持减摩擦作用。
关于润滑油组合物劣化的抑制,例如提出了专利文献1和2的技术。
现有技术文献
专利文献
专利文献1 : 日本专利第5710501号公报
专利文献2 : 日本专利第5930904号公报。
发明内容
发明要解决的问题
专利文献1公开了至少含有90重量%的基础油和硫化脂肪酸等特定的抗氧化剂的润滑油组合物。
专利文献2公开了含有基础油、特定的受阻胺系化合物和有机钼化合物的润滑油组合物。
专利文献1的润滑油组合物抑制由氧化导致的润滑油组合物的劣化。另外,专利文献2的润滑油组合物抑制由NOx导致的润滑油组合物的劣化。
但是,专利文献1和2的润滑油组合物并未研究润滑油组合物劣化后的减摩擦作用的维持。
本发明是鉴于上述情况而完成的发明,其课题在于提供尽管硫酸灰分少但清洁性良好,且劣化后也具有良好的减摩擦作用的润滑油组合物及其制造方法。
解决课题的手段
即,本发明提供下述[1]~[2]。
[1]润滑油组合物,其含有基础油(A)、不含金属的硫系抗氧化剂(B)和分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C),以上述润滑油组合物总量为基准,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为800质量ppm以上,以上述润滑油组合物总量为基准,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量为100质量ppm以上400质量ppm以下,上述润滑油组合物的硫酸灰分为0.70质量%以下,上述润滑油组合物的总碱值为4.0mgKOH/g以上。
[2]润滑油组合物的制造方法,其具有制备含有基础油(A)、不含金属的硫系抗氧化剂(B)和分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C)的润滑油组合物的工序,以满足下述条件(i)~(iv)的方式进行上述制备,
(i)以上述润滑油组合物总量为基准,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为800质量ppm以上,
(ii)以上述润滑油组合物总量为基准,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量为100质量ppm以上400质量ppm以下,
(iii)上述润滑油组合物的硫酸灰分为0.70质量%以下,
(iv)上述润滑油组合物的总碱值为4.0mgKOH/g以上。
发明的效果
本发明的润滑油组合物尽管硫酸灰分少但清洁性良好,且即使劣化后也具有良好的减摩擦作用。另外,本发明的润滑油组合物的制造方法可以简便地制造具有上述效果的润滑油组合物。
具体实施方式
[润滑油组合物]
本实施方式的润滑油组合物含有基础油(A)、不含金属的硫系抗氧化剂(B)和分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C),以润滑油组合物总量为基准,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为800质量ppm以上,以润滑油组合物总量为基准,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量为100质量ppm以上400质量ppm以下,润滑油组合物的硫酸灰分为0.70质量%以下,润滑油组合物的总碱值为4.0mgKOH/g以上。
<基础油(A)>
作为基础油(A),可以为矿物油,也可以为合成油,还可以使用矿物油与合成油的混合油。
作为矿物油,可列举将石蜡系矿物油、中间基系矿物油、环烷系矿物油等原油进行常压蒸馏得到的常压渣油;将这些常压渣油进行减压蒸馏得到的馏出油;对该馏出油施以溶剂脱沥青、溶剂萃取、氢解、溶剂脱蜡、催化脱蜡、加氢精制等一种以上精制处理而得到的矿物油;将通过费托法等制造的WAX(GTL蜡(Gas To Liquids WAX,气化液蜡))异构化而得到的矿物油等。矿物油在美国石油协会的基础油分类中被分类为第3类(Group 3)。
作为合成油,可列举烃系合成油、醚系合成油等。作为烃系合成油,可列举聚丁烯、聚异丁烯、1-辛烯低聚物、1-癸烯低聚物、乙烯-丙烯共聚物等α-烯烃低聚物或其氢化物、烷基苯、烷基萘等。作为醚系合成油,可列举聚氧亚烷基二醇、聚苯基醚等。
基础油可以是采用上述矿物油和合成油中的一种的单一体系,也可以是二种以上矿物油的混合物、二种以上合成油的混合物、矿物油和合成油各自的一种或二种以上的混合物这样的混合体系。
基础油(A)在100℃的运动粘度优选为2.0~20.0mm2/s,更优选为2.0~15.0mm2/s,进一步优选为2.0~7.0mm2/s,更进一步优选为2.0~5.0mm2/s。
如果基础油(A)在100℃的运动粘度为2.0mm2/s以上,则蒸发损失少,因而优选。另一方面,如果基础油(A)在100℃的运动粘度为20.0mm2/s以下,则可抑制由粘性阻力导致的动力损失,得到燃油效率改善効果,因而优选。
作为基础油(A)的粘度指数,从抑制由温度变化导致的粘度变化的同时提高燃油效率的角度考虑,优选为80以上,更优选为100以上,进一步优选为120以上。
基础油(A)为选自矿物油和合成油中的2种以上的混合油时,该混合油的运动粘度和粘度指数优选为上述范围。
要说明的是,本说明书中,“在100℃的运动粘度”和“粘度指数”是指按照JISK2283:2000测定、计算得到的值。
以润滑油组合物的总量(100质量%)为基准,基础油(A)的含量优选小于90质量%。通过使基础油(A)的含量小于90质量%,可确保后述的不含金属的硫系抗氧化剂(B)、分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C)等的使用量,可使得到本发明的效果变得容易。
以润滑油组合物的总量为基准,基础油(A)的含量更优选为60质量%以上且小于90质量%,更优选为70质量%以上85质量%以下,更进一步优选为75质量%以上85质量%以下。
<不含金属的硫系抗氧化剂(B)>
不含金属的硫系抗氧化剂(B)是含有至少一个硫原子、且不含金属原子的化合物。本实施方式的润滑油组合物中,以润滑油组合物总量为基准,该不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为800质量ppm以上。
润滑油组合物不含有不含金属的硫系抗氧化剂(B)时,或者润滑油组合物即使含有不含金属的硫系抗氧化剂(B),但是以硫原子换算计的含量以润滑油组合物总量为基准小于800质量ppm时,不能维持润滑油组合物劣化后的减摩擦効果。
要说明的是,本说明书中,硫原子的含量是按照ASTM D-1552测定的值。
要说明的是,通过使不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量不过量,可容易地抑制润滑油组合物热劣化时的粘度的增加。因此,从维持润滑油组合物劣化后的减摩擦效果和抑制粘度增加的角度考虑,以润滑油组合物总量为基准,不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量优选为800ppm以上6500质量ppm以下,更优选为1000ppm以上6500质量ppm以下,进一步优选为1500ppm以上6200质量ppm以下。
作为不含金属的硫系抗氧化剂(B),可列举选自硫代氨基甲酸酯系化合物、噻二唑系化合物、多硫化物系化合物和硫化油脂中的1种以上。这些中,从抑制润滑油组合物劣化后的粘度增加的角度考虑,优选选自硫代氨基甲酸酯系化合物、噻二唑系化合物和多硫化物系化合物中的1种以上。
作为硫代氨基甲酸酯系化合物,可列举例如下述通式(1A)和(1B)所示的化合物。
[化1]
[式(1A)中,R1~R4表示碳数为1~30的烷基或苯基,R1~R4可以相同,也可以不同。R5表示碳数1~10的亚烷基]。
[化2]
[式(1B)中,R6~R7表示碳数1~30的烷基或苯基,R6~R7可以相同,也可以不同。R8表示氢原子或碳数1~10的烷基]。
式(1A)中,R1~R4优选为碳数2~12的烷基或苯基,更优选为碳数2~8的烷基或苯基,进一步优选为碳数3~5的烷基。另外,R1~R4优选相互相同。
另外,式(1A)中,R5优选为碳数1~2的亚烷基,更优选碳数为2的亚烷基(亚乙基)。
式(1B)中,R6~R7优选为碳数2~12的烷基或苯基,更优选为碳数2~8的烷基或苯基,进一步优选为碳数3~5的烷基。另外,R6~R7优选相互相同。
另外,式(1B)中,R8优选为碳数1~2的亚烷基,更优选碳数为2的亚烷基(亚乙基)。
作为上式(1A)的硫代氨基甲酸酯系化合物的具体例子,可列举亚甲基双(二乙基硫代氨基甲酸酯)、亚乙基双(二乙基二硫代氨基甲酸酯)、亚甲基双(二丙基硫代氨基甲酸酯)、亚乙基双(二丙基二硫代氨基甲酸酯)、亚甲基双(二丁基二硫代氨基甲酸酯)、亚乙基双(二丁基二硫代氨基甲酸酯)、亚甲基双(二戊基二硫代氨基甲酸酯)、亚乙基双(二戊基二硫代氨基甲酸酯)、亚甲基双(二己基二硫代氨基甲酸酯)、亚乙基双(二己基二硫代氨基甲酸酯)等。
作为上式(1B)的硫代氨基甲酸酯系化合物的具体例,可列举二乙基硫代氨基甲酸(diethylthiocarbamic acid)、二乙基硫代氨基甲酸亚甲酯(methylenediethylthiocarbamate)、二乙基二硫代氨基甲酸亚乙酯(ethylenediethyldithiocarbamate)、二丙基硫代氨基甲酸(dipropylthiocarbamic acid)、二丙基硫代氨基甲酸亚甲酯(methylene dipropylthiocarbamate)、二丙基二硫代氨基甲酸亚乙酯(ethylene dipropyldithiocarbamate)、二丁基二硫代氨基甲酸(dibutyldithiocarbamic acid)、二丁基二硫代氨基甲酸亚甲酯(methylenedibutyldithiocarbamate)、二丁基二硫代氨基甲酸亚乙酯(ethylenedibutyldithiocarbamate)、二戊基二硫代氨基甲酸(dipentyldithiocarbamic acid)、二戊基二硫代氨基甲酸亚甲酯(methylene dipentyldithiocarbamate)、二戊基二硫代氨基甲酸亚乙酯(ethylene dipentyldithiocarbamate)、二己基二硫代氨基甲酸亚甲酯(methylene dihexyldithiocarbamate)、二己基二硫代氨基甲酸亚乙酯(ethylenedihexyldithiocarbamate)等。
作为噻二唑系化合物,可列举分子中具有1,3,4-噻二唑、1,2,4-噻二唑作为骨架的化合物。
作为噻二唑系化合物的具体例,可列举2,5-双(正己基二硫基)-1,3,4-噻二唑、2,5-双(正辛基二硫基)-1,3,4-噻二唑、2,5-双(正壬基二硫基)-1,3,4-噻二唑、2,5-双(1,1,3,3-四甲基丁基二硫基)-1,3,4-噻二唑、2,5-双(叔壬基)-1,3,4-噻二唑、2,5-双(叔壬基氨基)-1,3,4-噻二唑、2,5-双(叔壬基硫基)-1,3,4-噻二唑、2,5-双(叔壬基二硫基)-1,3,4-噻二唑、2,5-双(二甲基己基)-1,3,4-噻二唑、2,5-双(二甲基己基硫基)-1,3,4-噻二唑、2,5-双(二甲基己基氨基)-1,3,4-噻二唑、2,5-双(二甲基己基二硫基)-1,3,4-噻二唑、2,5-双(十八烯基)-1,3,4-噻二唑、2,5-双(十八烯基硫基)-1,3,4-噻二唑、2,5-双(十八烯基氨基)-1,3,4-噻二唑、2,5-双(十八烯基二硫基)-1,3,4-噻二唑、2,5-双(甲基十六烯基)-1,3,4-噻二唑、2,5-双(甲基十六烯基硫基)-1,3,4-噻二唑、2,5-双(甲基十六烯基氨基)-1,3,4-噻二唑、2,5-双(甲基十六烯基二硫基)-1,3,4-噻二唑、2,5-双(2-羟基十八烷基)-1,3,4-噻二唑、2,5-双(2-羟基十八烷基硫基)-1,3,4-噻二唑、2,5-双(2-羟基十八烷基氨基)-1,3,4-噻二唑、2,5-双(2-羟基十八烷基二硫基)-1,3,4-噻二唑、2,5-双(正辛氧基羰基甲基)-1,3,4-噻二唑、2,5-双(正辛氧基羰基甲基硫基)-1,3,4-噻二唑、2,5-双(正辛氧基羰基甲基氨基)-1,3,4-噻二唑、2,5-双(正辛氧基羰基甲基二硫基)-1,3,4-噻二唑、2-巯基-5-(2-乙基己基硫基)-1,3,4-噻二唑、2-巯基-5-(2-乙基己基二硫基)-1,3,4-噻二唑、2-巯基-5-(叔壬基硫基)-1,3,4-噻二唑、2-巯基-5-(叔壬基二硫基)-1,3,4-噻二唑、2-氨基-5-(2-乙基己基氨基)-1,3,4-噻二唑、2-氨基-5-(叔壬基氨基)-1,3,4-噻二唑、2-(2-乙基己基)-1,3,4-噻二唑、2-(叔壬基)-1,3,4-噻二唑、3,5-双(正己基二硫基)-1,2,4-噻二唑、3,5-双(正辛基二硫基)-1,2,4-噻二唑、3,5-双(正壬基二硫基)-1,2,4-噻二唑、3,5-双(1,1,3,3-四甲基丁基二硫基)-1,2,4-噻二唑等。
作为多硫化物系化合物,可列举下述通式(2)表示的化合物(二烃基多硫化物)。
R21-S x-R22 (2)
式(2)中,R21和R22分别独立地为选自碳数3~20的烷基、碳数6~20的芳基、碳数7~20的烷基芳基、碳数7~20的芳基烷基或碳数3~20的烯基中的烃基,它们可以相同或不同,x表示2~10的整数。另外,R21和R22中的烷基和烯基可以为直链状或支链状的任一种。
式(2)中,R21和R22分别优选碳数为6~18,x优选为2~8,更优选为3~7。
作为二烃基多硫化物的具体例子,可列举二烷基多硫化物、烯烃多硫化物、二苄基多硫化物等。
要说明的是,烯烃多硫化物可列举碳数3~20的烯烃或其2~4聚体与硫、卤化硫等硫化剂反应得到的烯烃多硫化物。作为烯烃,优选例如丙烯、异丁烯、二异丁烯等。作为烯烃多硫化物,可列举通式(2)中R21和R22的一者为烯基、另一者为烯基或烷基的烯烃多硫化物。
硫化油脂是指动植物油的硫化物,可列举例如硫化猪油、硫化菜籽油、硫化蓖麻油、硫化大豆油等。另外,硫化油脂也包括硫化油酸等二硫化脂肪酸、硫化油酸甲酯等硫化酯。
不含金属的硫系抗氧化剂(B)的含量只要是不妨碍本发明效果的范围则没有特别限定,通常以润滑油组合物的总量为基准,优选为0.1质量%以上3.0质量%以下,更优选为0.3质量%以上2.0质量%以下,进一步优选为0.3质量%以上1.5质量%。
<分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C)>
本实施方式的润滑油组合物包括分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C)。
作为哌啶衍生骨架,可列举2,2,6,6-四甲基哌啶骨架、2,2,6,6-四甲基哌啶-N-氧自由基骨架、2,2,6,6-四甲基哌啶-N-烷基骨架和2,2,6,6-四甲基哌啶-N-酰基骨架等。
以下,有时将“分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂”称为“单受阻胺系抗氧化剂”。
本实施方式的润滑油组合物中,以润滑油组合物总量为基准,单受阻胺系抗氧化剂(C)的以氮原子换算计的含量为100质量ppm以上400质量ppm以下。
以润滑油组合物总量为基准,单受阻胺系抗氧化剂(C)的以氮原子换算计的含量小于100质量ppm时,提高总碱值所需要的金属系清洁剂的量增多,因此由于润滑油的劣化,以硫酸灰分为起因的沉积物的量增加,不能抑制发动机部件的磨损。另外,以润滑油组合物总量为基准,单受阻胺系抗氧化剂(C)的以氮原子换算计的含量超过400质量ppm时,不能维持润滑油组合物劣化后的减摩擦作用。特别是,润滑油组合物含有后述的钼系摩擦调节剂(E)时,过量的单受阻胺系抗氧化剂(C)使基于钼系摩擦调节剂(E)的减摩擦作用大大受损。
要说明的是,以润滑油组合物总量为基准,含有分子内具有2个哌啶衍生骨架的受阻胺系抗氧化剂(以下有时称为“双受阻胺系抗氧化剂”)、和/或、分子内具有3个以上哌啶衍生骨架的受阻胺系抗氧化剂100质量ppm以上400质量ppm以下时,可以减少提高总碱值所需要的金属系清洁剂的量,但是不能维持润滑油组合物劣化后的减摩擦作用。
即,为了在抑制以硫酸灰分为起因的沉积物所导致的发动机部件的磨损的同时,维持润滑油组合物劣化后的减摩擦作用,必须使用单受阻胺系抗氧化剂(C)作为受阻胺系抗氧化剂,且以润滑油组合物总量为基准,使单受阻胺系抗氧化剂的含量为100质量ppm以上400质量ppm以下。
以润滑油组合物总量为基准,单受阻胺系抗氧化剂(C)的以氮原子换算计的含量优选为200质量ppm以上400质量ppm以下,更优选为200质量ppm以上300质量ppm以下,进一步优选为200质量ppm以上250质量ppm以下。
要说明的是,本说明书中,氮原子的含量是按照JIS K2609:1998测定的值。
作为单受阻胺系抗氧化剂(C)的具体例子,可列举2,2,6,6-四甲基-4-羟基哌啶-1-氧自由基、2,2,6,6-四甲基哌啶基甲基丙烯酸酯、1,2,2,6,6-五甲基-4-哌啶基甲基丙烯酸酯、十二烷酸2,2,6,6-四甲基哌啶-4-基酯等。
单受阻胺系抗氧化剂(C)的含量只要是不损害本发明的效果的范围则没有特别限定,通常,以润滑油组合物的总量为基准,优选为0.1质量%以上1.0质量%以下,更优选为0.2质量%以上0.9质量%以下,进一步优选为0.4质量%以上0.7质量%。
本实施方式的润滑油组合物从提高初期的总碱值的角度以及维持润滑油组合物劣化后的减摩擦作用的角度考虑,优选实质上不含有单受阻胺系抗氧化剂以外的胺系抗氧化剂。特别是,优选实质上不含有单受阻胺系抗氧化剂以外的受阻胺系抗氧化剂、和/或、二芳基胺系抗氧化剂。
实质上不含有是指以润滑油组合物总量为基准单受阻胺系抗氧化剂以外的胺系抗氧化剂的含量小于0.1质量%,优选小于0.01质量%。
<金属系清洁剂(D)>
本实施方式的润滑油组合物优选还含有金属系清洁剂(D)。通过润滑油组合物含有金属系清洁剂(D),可抑制发动机内部的沉积物的生成,抑制发动机部件的磨损。
金属系清洁剂(D)可使用例如选自钙系清洁剂和镁系清洁剂中的1种以上,从燃油效率的角度考虑,优选使用选自钙系清洁剂中的1种以上。
作为钙系清洁剂,可列举磺酸钙、苯酚钙和水杨酸钙。这些中,优选容易抑制沉积物的生成的水杨酸钙。
作为镁系清洁剂,可列举磺酸镁、苯酚镁和水杨酸镁。这些中,优选容易抑制沉积物的生成的水杨酸镁。
从清洁性的角度考虑,金属系清洁剂优选总碱值为150mgKOH/g以上,更优选为150~500mgKOH/g,进一步优选为150~450mgKOH/g,更进一步优选为180~400mgKOH/g。
从提高总碱值的角度、和抑制起因于金属系清洁剂(D)的硫酸灰分的角度考虑,以润滑油组合物总量为基准,金属系清洁剂(D)的以金属原子换算计的含量优选为700质量ppm以上1400质量ppm以下,更优选为850质量ppm以上1350质量ppm以下,进一步优选为1000质量ppm以上1250质量ppm以下。
要说明的是,本说明书中,金属原子的含量(例如基于金属系清洁剂(D)的金属原子的含量、基于钼系摩擦调节剂(E)的钼原子的含量)是按照ASTM D4951测定的值。
金属系清洁剂(D)的含量只要是不阻碍本发明的效果的范围则没有特别限定,通常,以润滑油组合物的总量为基准,优选为0.1质量%以上10.0质量%以下,更优选为0.2质量%以上5.0质量%以下,进一步优选为0.5质量%以上3.0质量%。
<钼系摩擦调节剂(E)>
本实施方式的润滑油组合物优选还含有钼系摩擦调节剂(E)。通过润滑油组合物含有钼系摩擦调节剂(E),可容易地改善润滑油组合物的减摩擦作用。
作为钼系摩擦调节剂(E),只要是具有钼原子的有机化合物则可以使用,从减摩擦的角度考虑,优选二硫代磷酸钼(MoDTP)和二硫代氨基甲酸钼(MoDTC),更优选二硫代氨基甲酸钼(MoDTC)。
作为二硫代氨基甲酸钼(MoDTC),可列举下述通式(3)表示的化合物。
[化3]
式(3)中,R31~R34各自独立地表示碳数5~18的烃基,可以相同,也可以不同。优选烃基的碳数为5~16,更优选为8~14,进一步优选为12。
X31~X34各自独立地表示氧原子或硫原子,可以相互相同,也可以不同。另外,从提高相对于基础油(A)的溶解性的角度考虑,优选X31~X34中的硫原子和氧原子的摩尔比[硫原子/氧原子]为1/3~3/1,更优选为1.5/2.5~3/1。
作为R31~R34的烃基,可列举例如戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基等碳数5~18的烷基;辛烯基、壬烯基、癸烯基、十一烯基、十二烯基、十三烯基、十四烯基、十五烯基等碳数5~18的烯基;环己基、二甲基环己基、乙基环己基、甲基环己基甲基、环己基乙基、丙基环己基、丁基环己基、庚基环己基等碳数5~18的环烷基;苯基、萘基、蒽基、联苯基、三联苯基等碳数6~18的芳基;甲苯基、二甲基苯基、丁基苯基、壬基苯基、甲基苄基、二甲基萘基等烷基芳基;苯基甲基、苯基乙基、二苯基甲基等碳数7~18的芳基烷基等。
以润滑油组合物总量为基准,钼系摩擦调节剂(E)的以钼原子换算计的含量优选为300质量ppm以上1300质量ppm以下,更优选为350质量ppm以上1000质量ppm以下,进一步优选为400质量ppm以上800质量ppm以下。通过使该含量为300质量ppm以上,可以改善润滑油组合物的减摩擦作用,通过使该含量为1300质量ppm以下,可以减少硫酸灰分。
钼系摩擦调节剂(E)的含量只要是不妨碍本发明的效果的范围则没有特别限定,通常,以润滑油组合物的总量为基准,优选为0.2质量%以上2.0质量%以下,更优选为0.3质量%以上1.5质量%以下,进一步优选为0.5质量%以上1.0质量%。
<添加剂>
本实施方式的润滑油组合物在不损害本发明的效果的范围,可以含有不属于上述成分的无灰清洁剂、无灰系摩擦调节剂、耐磨剂、极压剂、粘度指数改进剂、金属钝化剂、倾点降低剂、防锈剂和消泡剂等添加剂。这些添加剂可以单独使用或将2种以上并用。
这些添加剂的各含量可在不损害本发明的效果的范围内适当调节,以润滑油组合物的总量为基准,通常为0.001~15质量%,优选为0.005~10质量%,更优选为0.01~8质量%。
要说明的是,以润滑油组合物的总量为基准,这些润滑油用添加剂的合计含量优选为25质量%以下,更优选为20质量%以下,进一步优选为15质量%以下。
作为无灰清洁剂,可列举烯基琥珀酰单亚胺、烯基琥珀酰双亚胺等烯基琥珀酰亚胺、硼改性烯基琥珀酰亚胺等。
作为无灰系摩擦调节剂,可列举例如分子中具有至少1个碳数6~30的烷基或烯基的脂肪族胺、脂肪酸酯、脂肪酸酰胺、脂肪酸、脂肪族醇、脂肪族醚等。
作为耐磨剂或极压剂,可列举例如二硫代磷酸锌等含硫化合物;亚磷酸酯类、磷酸酯类、膦酸酯类以及这些的胺盐或金属盐等含磷化合物;硫代亚磷酸酯类、硫代磷酸酯类、硫代膦酸酯类、和这些的胺盐或金属盐等含硫和磷的耐磨剂。
作为粘度指数改进剂,可列举例如聚甲基丙烯酸酯、分散型聚甲基丙烯酸酯、烯烃系共聚物(例如乙烯-丙烯共聚物等)、分散型烯烃系共聚物、苯乙烯系共聚物(例如苯乙烯-二烯共聚物、苯乙烯-异戊二烯共聚物等)等。
作为防腐蚀剂,可列举例如苯并三唑系化合物、甲苯基三唑系化合物、咪唑系化合物、嘧啶系化合物等。
作为倾点降低剂,可列举例如乙烯-乙酸乙烯酯共聚物、氯化石蜡和萘的缩合物、氯化石蜡和苯酚的缩合物、聚甲基丙烯酸酯、聚烷基苯乙烯等。
作为防锈剂,可列举例如石油磺酸盐、烷基苯磺酸酯、二壬基萘磺酸酯、烯基琥珀酸酯、多元醇酯等。
作为消泡剂,可列举例如硅油、氟硅油、氟烷基醚等。
<润滑油组合物中的各成分的比率>
本实施方式的润滑油组合物中,单受阻胺系抗氧化剂(C)的以氮原子换算计的含量与金属系清洁剂(D)的以金属原子换算计的含量之比[受阻胺系抗氧化剂(C)的以氮原子换算计的含量/金属系清洁剂(D)的以金属原子换算计的含量]优选为0.14~0.58,更优选为0.15~0.30。
通过使该比为0.14以上,由于可抑制金属系清洁剂(D)的含量,提高总碱值,因此可抑制沉积物的生成,从而抑制发动机部件的磨损。另外,通过使该比为0.58以下,可抑制单受阻胺系抗氧化剂(C)的含量,可容易地维持润滑油组合物劣化后的减摩擦作用,同时可抑制单受阻胺系抗氧化剂(C)的沉积物化。
本实施方式的润滑油组合物中,不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量与钼系摩擦调节剂(E)的以钼原子换算计的含量之比[不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量/钼系摩擦调节剂(E)的以钼原子换算计的含量]优选为0.92~13.35,更优选为1.00~9.00,进一步优选为2.00~9.00。
通过使该比为0.92以上,可抑制润滑油组合物热劣化时的粘度增加。另外,通过使该比为13.35以下,可容易地维持润滑油组合物劣化后的减摩擦作用。
本实施方式的润滑油组合物中,单受阻胺系抗氧化剂(C)的以氮原子换算计的含量与钼系摩擦调节剂(E)的以钼原子换算计的含量之比[单受阻胺系抗氧化剂(C)的以氮原子换算计的含量/钼系摩擦调节剂(E)的以钼原子换算计的含量]优选为0.15~1.35,更优选为0.20~0.60,进一步优选为0.25~0.60。
通过使该比为0.15以上,润滑油组合物劣化后,可容易地维持基于钼摩擦调节剂(E)的减摩擦效果。另外,通过使该比为1.35以下,可在发动机部件表面容易地形成钼系摩擦调节剂(E)的被膜。
<润滑油组合物的硫酸灰分>
本实施方式的润滑油组合物的硫酸灰分为0.70质量%以下。
润滑油组合物的硫酸灰分超过0.70质量%时,润滑油组合物劣化时的沉积物的量增多,不能抑制发动机部件的磨损。
润滑油组合物的硫酸灰分优选为0.68质量%以下,更优选为0.67质量%以下,进一步优选为0.66质量%以下。
对润滑油组合物的硫酸灰分的下限值没有特别限定,从提高总碱值的角度考虑,优选为0.40质量%以上,更优选为0.45质量%以上,进一步优选为0.50质量%以上。
要说明的是,本实施方式中,硫酸灰分是按照JIS K2272:1998测定的值。
<润滑油组合物的总碱值>
本实施方式的润滑油组合物的总碱值为4.0mgKOH/g以上。
润滑油组合物的总碱值小于4.0mgKOH/g时,润滑油组合物的清洁性不充分,容易生成沉积物,不能抑制发动机部件的磨损。
另一方面,润滑油组合物的总碱值过大时,有可能产生单受阻胺系抗氧化剂(C)的含量过多时的弊端、金属系清洁剂(D)的含量过多时的弊端。
从这些观点考虑,润滑油组合物的总碱值优选为4.0~7.0mgKOH/g,更优选为4.2~7.0mgKOH/g,进一步优选为4.5~7.0mgKOH/g。
要说明的是,本实施方式中,总碱值是按照JIS K2501:2003的盐酸法测定的值。
<润滑油组合物的其它性状>
以润滑油组合物总量为基准,本实施方式的润滑油组合物的硫原子的含量优选为1000~13000质量ppm,更优选为2000~11000质量ppm,进一步优选为2000~9000质量ppm。
通过使硫原子的含量为1000质量ppm以上,可维持润滑油组合物劣化后的减摩擦效果,通过使其为13000质量ppm以下,可抑制润滑油组合物热劣化时的粘度增加。
以润滑油组合物总量为基准,本实施方式的润滑油组合物的氮原子的含量优选为500~4000质量ppm,更优选为700~3500质量ppm,进一步优选为900~3000质量ppm。
通过使氮原子的含量为500质量ppm以上,可改善清洁分散性,通过使其为4000质量ppm以下,可改善在橡胶等树脂材料中的适合性。
本实施方式的润滑油组合物在100℃的运动粘度优选为3~20mm2/s,更优选为3~10mm2/s,进一步优选为5~8mm2/s。
本实施方式的润滑油组合物的粘度指数优选为100以上,更优选为120以上,进一步优选为130以上。
<润滑油组合物的用途>
本实施方式的润滑油组合物可优选用作双轮车、四轮车等汽车、发电机、船舶等的汽油发动机、柴油发动机、燃气发动机等的内燃机用润滑油组合物。特别可优选用作装载了热负荷高、润滑油组合物容易劣化的增压器、涡轮增压器等增压器的发动机用的润滑油组合物。
[润滑油组合物的制造方法]
本实施方式的润滑油组合物的製造方法具有制备含有基础油(A)、不含金属的硫系抗氧化剂(B)和分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C)的润滑油组合物的工序,以满足下述条件(i)~(iv)的方式进行上述制备,
(i)以上述润滑油组合物总量为基准,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为800质量ppm以上,
(ii)以上述润滑油组合物总量为基准,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量为100质量ppm以上400质量ppm以下,
(iii)上述润滑油组合物的硫酸灰分为0.70质量%以下,
(iv)上述润滑油组合物的总碱值为4.0mgKOH/g以上。
本实施方式的润滑油组合物的制造方法中,各构成成分的优选实施方式、条件(i)~(iv)相关的数值的优选实施方式与上述本实施方式的润滑油组合物的优选实施方式相同。
实施例
下面,通过实施例更详细地说明本发明,但本发明不受这些例子的任何限定。
1.测定
构成实施例和比较例的润滑油组合物的成分以及实施例和比较例的润滑油组合物的各种物性值按照下述方法测定。
<硫酸灰分>
按照JIS K2272:1998测定。
<总碱值>
按照JIS K2501:2003的盐酸法测定。
<硫原子的含量>
按照ASTM D-1552测定。
<氮原子的含量>
按照JIS K2609:1998测定。
<金属原子的含量>
按照ASTM D4951测定。
<在100℃的运动粘度>
按照JIS K2283:2000测定。
<粘度指数>
按照JIS K 2283:2000算出。
2.润滑油组合物的制备
以表1~2的组成比制备实施例和比较例的润滑油组合物。以下示出实施例和比较例中使用的基础油和各种添加剂的详情。
<基础油(A)>
・100N的矿物油,硫分10ppm以下,100℃运动粘度:4.2mm2/s、粘度指数:126。
<不含金属的硫系抗氧化剂(B)>
・B-1:相当于通式(1A)的硫代氨基甲酸酯系化合物(バンダ―ビルド社制造、VANLUBE7723,硫含量30.5质量%,氮含量6.9质量%)
・B-2:噻二唑系化合物(アフトンケミカル社制造,HiTEC 4313,硫含量36.0质量%,氮含量5.7质量%)
・B-3:多硫化物系化合物(DIC社制造,商品名:DAILUBE GS-120,硫含量11.4质量%)
・B-4:硫化油脂(DIC社制造,商品名:DAILUBE GS-440L,硫含量39.7质量%)。
<胺系抗氧化剂>
・单受阻胺系抗氧化剂(BASF社制造,商品名:XPDL590,氮含量:4.3质量%)
・双受阻胺系抗氧化剂1(BASF社制造,商品名:Tinuvin 765,氮含量:5.3质量%,分子内的哌啶衍生骨架的数量:2)
・双受阻胺系抗氧化剂2(BASF社制造,商品名:Tinuvin 770DF、氮含量:5.6质量%,分子内的哌啶衍生骨架的数量:2)
・二芳基胺系抗氧化剂(二苯基胺,BASF社制造,商品名:Irganox L57,氮含量:4.6质量%)。
<金属系清洁剂(D)>
・水杨酸钙(总碱值225mgKOH/g,钙原子量:7.8质量%)。
<钼系摩擦调节剂(E)>
・二硫代氨基甲酸钼(ADEKA社制造,商品名:SAKURA―LUBE 515,钼原子含量:10.0质量%)。
<添加剂混合物>
含有粘度指数改进剂、倾点降低剂、聚丁烯基琥珀酰亚胺、硼改性聚丁烯基琥珀酰亚胺、二烷基二硫代磷酸锌、防锈剂、防腐蚀剂和消泡剂的添加剂混合物。
3.评价
关于实施例和比较例制备的润滑油组合物,测定劣化处理后的摩擦系数。结果示于表1~2。
<劣化处理后的摩擦系数>
向刚制备后的实施例和比较例的润滑油组合物100g添加作为劣化促进剂的4-乙基硝基苯0.5质量%。进一步地,将油温设定为160℃,通入NOX浓度为2000体积ppm的气体48小时,将润滑油组合物进行劣化处理。该劣化处理相当于汽车行驶1万km时的劣化。
对于劣化处理后的润滑油组合物,使用下述试验机,在下述条件下进行2小时适应性运行后,测定摩擦系数。
・试验机:MTM(Mini Traction Machine)试验机、PCS Instruments社制造
・试件:标准试件(3/4”Steel-Steel)
・适应性运行和摩擦系数测定时的条件:油温80℃、负荷30N、速度100mm/s、滑动率(SRR)50%、油量35ml。
[表1]
[表2]
根据表1和表2,确认实施例1~6的润滑油组合物即使劣化后也可维持良好的减摩擦作用。另外,实施例1~6的润滑油组合物尽管硫酸灰分少到0.70质量%以下,总碱值也为4.0mgKOH/g以上,因此可期待良好的清洁性。另外,实施例1~6的润滑油组合物由于硫酸灰分少到0.70质量%以下,因此可期待抑制沉积物导致的发动机部件的磨损。另外,实施例1~6的润滑油组合物的劣化后的总碱值为1.0mgKOH/g以上,可期待长期的清洁性。
另一方面,可确认比较例1~6的润滑油组合物不能维持劣化后的减摩擦作用。另外,比较例1和7的润滑油组合物的总碱值小于4.0mgKOH/g,因此润滑油组合物的清洁性不充分,容易产生沉积物,不能期待抑制发动机部件的磨损。另外,比较例2的润滑油组合物由于硫酸灰分超过0.70质量%,不能期待抑制沉积物导致的发动机部件的磨损。另外,比较例1和2的润滑油组合物的劣化后的总碱值小于1.0mgKOH/g,不能期待长期清洁性。
Claims (12)
1.润滑油组合物,其含有基础油(A)、不含金属的硫系抗氧化剂(B)和分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C),
以上述润滑油组合物总量为基准,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为800质量ppm以上,
以上述润滑油组合物总量为基准,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量为100质量ppm以上400质量ppm以下,
上述润滑油组合物的硫酸灰分为0.70质量%以下,上述润滑油组合物的总碱值为4.0mgKOH/g以上。
2.根据权利要求1所述的润滑油组合物,其中,上述不含金属的硫系抗氧化剂(B)为选自硫代氨基甲酸酯系化合物、噻二唑系化合物、聚硫化物和硫化油脂中的1种以上。
3.根据权利要求1或2所述的润滑油组合物,其中,以上述润滑油组合物总量为基准,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为1200质量ppm以上6500质量ppm以下。
4.根据权利要求1~3中任一项所述的润滑油组合物,其中,以上述润滑油组合物总量为基准,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量为200质量ppm以上400质量ppm以下。
5.根据权利要求1~4中任一项所述的润滑油组合物,其还含有金属系清净剂(D),以上述润滑油组合物总量为基准,上述金属系清净剂(D)的以金属原子换算计的含量为700质量ppm以上1400质量ppm以下。
6.根据权利要求5所述的润滑油组合物,其中,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量与上述金属系清净剂(D)的以金属原子换算计的含量之比[上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量/上述金属系清净剂(D)的以金属原子换算计的含量]为0.14~0.58。
7.根据权利要求1~6中任一项所述的润滑油组合物,其还含有钼系摩擦调节剂(E),以上述润滑油组合物总量为基准,上述钼系摩擦调节剂(E)的以钼原子换算计的含量为300质量ppm以上1300质量ppm以下。
8.根据权利要求7所述的润滑油组合物,其中,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量与上述钼系摩擦调节剂(E)的以钼原子换算计的含量之比[上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量/上述钼系摩擦调节剂(E)的以钼原子换算计的含量]为0.92~13.35。
9.根据权利要求7或8所述的润滑油组合物,其中,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量与上述钼系摩擦调节剂(E)的以钼原子换算计的含量之比[上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量/上述钼系摩擦调节剂(E)的以钼原子换算计的含量]为0.15~1.35。
10.根据权利要求1~9中任一项所述的润滑油组合物,其中,以上述润滑油组合物总量为基准,上述基础油(A)的含量小于90质量%。
11.用于装载有增压机的发动机的润滑油组合物,其包含权利要求1~10中任一项所述的润滑油组合物。
12.润滑油组合物的制造方法,其具有制备含有基础油(A)、不含金属的硫系抗氧化剂(B)和分子内具有1个哌啶衍生骨架的受阻胺系抗氧化剂(C)的润滑油组合物的工序,以满足下述条件(i)~(iv)的方式进行上述制备,
(i)以上述润滑油组合物总量为基准,上述不含金属的硫系抗氧化剂(B)的以硫原子换算计的含量为800质量ppm以上,
(ii)以上述润滑油组合物总量为基准,上述受阻胺系抗氧化剂(C)的以氮原子换算计的含量为100质量ppm以上400质量ppm以下,
(iii)上述润滑油组合物的硫酸灰分为0.70质量%以下,
(iv)上述润滑油组合物的总碱值为4.0mgKOH/g以上。
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JP2020180267A (ja) * | 2019-04-26 | 2020-11-05 | 出光興産株式会社 | 駆動系機器用潤滑油組成物、その製造方法、駆動系機器の潤滑方法及び駆動系機器 |
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