CN103717720A - 内燃机用润滑油组合物 - Google Patents
内燃机用润滑油组合物 Download PDFInfo
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- CN103717720A CN103717720A CN201280038401.5A CN201280038401A CN103717720A CN 103717720 A CN103717720 A CN 103717720A CN 201280038401 A CN201280038401 A CN 201280038401A CN 103717720 A CN103717720 A CN 103717720A
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- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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Abstract
一种内燃机用润滑油组合物,其特征在于,含有硼化酰亚胺系分散剂,或者含有硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂,组合物中的来源于硼化酰亚胺系分散剂的硼含量(B质量%)和来源于硼化酰亚胺系分散剂的氮含量(N质量%)、或者来源于硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂的氮含量(N质量%)满足下述式(I),N≥B+0.05···(I)并且磷的含量(P质量%)和来源于金属系清洁剂的金属成分的含量(M质量%),以组合物总量为基准,满足下述的A~C中的任意一个,A:P<0.03且M<0.05B:P<0.03且0.05≤M≤0.12C:0.03≤P≤0.06且M<0.05。上述内燃机用润滑油组合物具有这样的效果,在维持对于铝材的耐磨损性的同时,可以大幅降低磷成分含量多的ZnDTP、金属系清洁剂。
Description
技术领域
本发明涉及内燃机用润滑油组合物,涉及即使降低磷成分的量、来源于金属系清洁剂的金属量,对于铝材的耐磨损性也优秀的内燃机用润滑油组合物。
背景技术
近年,以减低环境负荷为目的,在汽车业界渐渐引入了对于尾气的严格限定,并进行尾气的后处理装置的开发。尾气中除了含有使全球气候变暖的物质二氧化碳(CO2)之外,还含有作为有害物质的颗粒状物质(PM)、烃(HC)、一氧化碳(CO)、氮氧化物(NOx)等,其中PM、NOx的限定值已变得非常严格。作为这些削减排出量的对策,人们在汽油车辆上安装三元催化剂,在柴油车辆上安装柴油机微粒过滤器(DPF)。通过这些方法将尾气净化,从而排出到大气中。
近年有这样的报告,发动机油中的磷成分使三元催化剂的活性点中毒,并使催化剂的功能降低,此外来源于金属成分的灰分堆积于DPF中使其寿命缩短等。目前,作为发动机油标准的ILSAC标准、JASO标准中规定了磷量、灰分的上限值,推进了将这些减量的发动机油的开发。
另一方面,从提高油耗性的观点出发,人们正在以发动机、传动部件的非铁化的方式推进轻量化。其中多采用铝合金,特别是Al-Si合金,但是由于目前抗磨剂中使用二硫代磷酸锌(ZnDTP)等以对Fe形成涂膜为主反应的添加剂,因此就有对于Al-Si合金等铝材的耐磨损性下降的担心。
因此,人们正在进行针对铝材的优秀的抗磨剂的研究(例如参考专利文献1)。但是这些抗磨剂都有这样的情况,如果不与磷含量多的ZnDTP并用的话,就不能得到充分的效果,不能消除对于尾气后处理装置的坏影响。
因而,期望出现即使进一步地减少磷成分或者不含磷成分,对于铝材也有优异的耐磨损性的内燃机用润滑油组合物。
现有技术文献
专利文献
专利文献1:日本专利特表2010-528155号公报
发明内容
发明要解决的课题
在这样的情况下,本发明的目的为提供对于铝材的耐磨损性优异的润滑油组合物,提供维持对于铝材的耐磨损性的同时,能够大幅降低磷含量多的ZnDTP、金属系清洁剂的内燃机用润滑油组合物。
解决课题的手段
本发明人为了开发前述的优选内燃机用润滑油组合物,反复专心研究,结果发现通过调整来源于酰亚胺系分散剂和硼化酰亚胺系分散剂的氮含量和硼含量,可以达到该目的。本发明是基于该发现而完成的发明。
即本发明提供:
1、一种内燃机用润滑油组合物,其特征在于,含有硼化酰亚胺系分散剂,或者含有硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂,组合物中的来源于硼化酰亚胺系分散剂的硼含量(B质量%)和来源于硼化酰亚胺系分散剂的氮含量(N质量%)、或者来源于硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂的氮含量(N质量%)满足下述式(I);
N≥B+0.05···(I)
并且磷的含量(P质量%)和来源于金属系清洁剂的金属成分的含量(M质量%),以组合物总量为基准,满足下述的A~C中的任意一个,
A:P<0.03且M<0.05
B:P<0.03且0.05≤M≤0.12
C:0.03≤P≤0.06且M<0.05
2、如上述1所述的内燃机用润滑油组合物,其特征在于,来源于硼化酰亚胺系分散剂的硼含量(B质量%)和来源于硼化酰亚胺系分散剂的氮含量(N质量%)、或者来源于硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂的氮含量(N质量%)满足下述式(II):
N≥B+0.1···(II)
3、如上述1或2所述的内燃机用润滑油组合物,其中,进一步含有硫系抗磨剂;以及
4、如上述3所述的内燃机用润滑油组合物,其中,硫系抗磨剂为下述通式(3)表示的二硫化物,
R1OOC-A1-S2-A2-COOR2···(3)
(式中,R1以及R2各自独立地表示可以含有氧原子、硫原子或者氮原子的碳原子数1~30的烃基,A1以及A2各自独立地表示碳原子数1~12的二价烃基。)
发明效果
根据本发明可以提供对于铝材的耐磨损性优异的润滑油组合物,提供维持对于铝材的耐磨损性的同时,能够大幅降低磷含量多的ZnDTP、金属系清洁剂的内燃机用润滑油组合物。
因而,可以提供在维持对于铝材的耐磨损性的同时,能减轻对于尾气后处理装置的影响的内燃机用润滑油组合物。
具体实施方式
本发明的内燃机用润滑油组合物,是含有硼化酰亚胺系分散剂,或者含有硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂,组合物中的来源于硼化酰亚胺系分散剂的硼含量(B质量%)和来源于硼化酰亚胺系分散剂的氮含量(N质量%)、或者来源于硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂的氮含量(N质量%)满足下述式(I)的内燃机用润滑油组合物,
N≥B+0.05···(I)。
满足上述式(I)的组合物可以提高耐磨损性。
此外满足下述式(II)的组合物可以进一步前述的效果,
N≥B+0.1···(II)。
如上所述,本发明中使用硼化酰亚胺系分散剂以及根据必要的非硼化酰亚胺系分散剂。
上述非硼化酰亚胺系分散剂是所谓的通常酰亚胺系分散剂。该非硼化酰亚胺系分散剂可以适宜使用聚丁烯琥珀酰亚胺。上述聚丁烯琥珀酰亚胺可列举下述通式(1)以及(2)
[化1]
[化2]
表示的化合物。这些通式中的PIB表示聚丁烯基,其数均分子量通常为800~3500,优选900~2000。上述数均分子量在800以上的话,就不用担心分散性变差,在3500以下的话,就不用担心保存稳定性变差。
此外,上述通式(1)以及(2)中的n通常如果为1~5的整数,更优选2~4的整数的话,就不用担心分散性变差。
作为上述聚丁烯琥珀酰亚胺的制造方法,没有特别的限定,可以根据公知的方法制造。例如,通过使聚丁烯和马来酸酐在100~200℃下反应,使得到的聚丁烯琥珀酸与二亚乙基三胺、三亚乙基三胺、四亚乙基五胺以及五亚乙基六胺等多胺反应得到。
另一方面,本发明中使用的硼化酰亚胺系分散剂优选使用硼化聚丁烯琥珀酰亚胺,其为使硼化合物作用于上述通式(1)以及(2)中例示的非硼化酰亚胺系分散剂而得到的。
作为上述硼化合物可列举硼酸、硼酸盐以及硼酸酯等。作为上述硼酸可列举如原硼酸、偏硼酸以及仲硼酸(Paraboric acid)等。此外,作为上述硼酸盐,适宜例子可列举铵盐等,例如偏硼酸铵、四硼酸铵、五硼酸铵以及八硼酸铵等硼酸铵等。此外,作为硼酸酯的适宜例子,可列举硼酸和烷基醇(优选碳原子数1~6)的酯,例如硼酸单甲酯、硼酸二甲酯、硼酸三甲酯、硼酸单乙酯、硼酸二乙酯、硼酸三乙酯、硼酸单丙酯、硼酸二丙酯、硼酸三丙酯、硼酸单丁酯、硼酸二丁酯以及硼酸三丁酯等。
另外,硼化聚丁烯琥珀酰亚胺中硼含量B和氮含量N的质量比B/N优选0.1~3,更优选0.2~2。
另外,本发明中使用的内燃机用润滑油组合物中,上述硼化琥珀酰亚胺系分散剂以及非硼化琥珀酰亚胺系分散剂(酰亚胺系分散剂)的含量除了满足前述式(I)之外没有特别的限定,但分别优选0.1~15质量%,更优选0.5~10质量%。如果是0.1质量%以上的话,能得到优秀的清洁性、分散性,如果是15质量%以下的话,能得到与含量相称的清洁性、分散性的效果。
进一步地本发明的内燃机用润滑油组合物,要求磷的含量(P质量%)以及来源于金属系清洁剂的金属成分的含量(M质量%)满足前述A~C中的任意一个。满足A~C的各情况如下所述。
〔满足A的情况〕
满足A的情况为
P<0.03且M<0.05
即以组合物总量为基准,磷的含量不足0.03质量%,且来源于金属系清洁剂的金属成分的含量不足0.05质量%。
如果上述组合物中磷含量不足0.03质量%的话,三元催化剂的活性点的中毒作用就被抑制,能够使催化剂寿命延长。因此组合物中的磷含量优选0.01质量%以下,更优选0.005质量%以下,特别优选0.001质量%以下。
此外,如果上述组合物中的来源于金属系清洁剂的金属成分不足0.05质量%的话,可以抑制来源于金属成分的灰分堆积于DPF中,可以延长其寿命。因此组合物中金属成分的含量优选0.01质量%以下,更优选0.005质量%以下,特别优选0.001质量%以下。
为了使组合物中磷含量不足0.03质量%,就需要限制含有磷的抗磨剂的混合量,或者不混合。因此,迄今为止作为内燃机用润滑油的极其优异的抗磨剂被广泛使用的二硫代磷酸锌(ZnDTP)的混合也被限制或者禁止了。
此外,为了使组合物中的来源于金属系清洁剂的金属成分不足0.05质量%,就需要限制或者禁止金属系清洁剂的混合。
〔满足B的情况〕
满足B的情况为
P<0.03且0.05≤M≤0.12
即,以组合物总量为基准,磷的含量不足0.03质量%,来源于金属系清洁剂的金属成分的含量为0.05质量%以上、0.12质量%以下。
如果上述组合物中的磷含量不足0.03质量%的话,三元催化剂的活性点的中毒作用就被抑制,能够使催化剂寿命延长。因此组合物中的磷含量优选0.01质量%以下,更优选0.005质量%以下,特别优选0.001质量%以下。
为了使组合物中的磷含量不足0.03质量%,就需要限制含有磷的抗磨剂的混合量或者不混合。因此,迄今为止作为内燃机用润滑油的极其优异的抗磨剂被广泛使用的二硫代磷酸锌(ZnDTP)的混合也被限制或者禁止了。
此外,如果上述组合物中的来源于金属系清洁剂的金属成分的含量是0.05质量%以上的话,可以进一步提高作为内燃机用润滑油要求的清洁性。另一方面,如果金属成分的含量是0.12质量%以下的话,就可以抑制来源于金属成分的灰分堆积于DPF,可以使其寿命延长。因此,金属成分的含量优选0.05质量%以上、0.10质量%以下,特别优选0.05以上0.08质量%以下。
作为带来前述金属成分的金属系清洁剂,可列举碱金属(Na、K等)或者碱土金属(Ca、Mg、Ba等)的磺酸盐、酚盐、水杨酸盐以及环烷酸盐等适当的物质。其中优选磺酸钙、酚钙、以及水杨酸钙。此外,这些金属系清洁剂的碱值优选用高氯酸法测定的0~500mgKOH/g,更优选150~400mgKOH/g,特别优选200~350mgKOH/g。
上述金属系清洁剂可以单独使用一种,也可以2种以上组合使用。
前述金属系清洁剂的含量,根据上述的来源于金属系清洁剂的金属成分的含量适当选择即可。
〔满足C的情况〕
满足C的情况为
0.03≤P≤0.06且M<0.05
即,以组合物总量为基准,磷的含量为0.03质量%以上、0.06质量%以下,且来源于金属系清洁剂的金属成分的含量不足0.05质量%。
如果组合物中的磷含量是0.03质量%以上的话,可以进一步提高耐磨损性。另一方面,如果磷的含量是0.06质量%以下的话,可以抑制三元催化剂的活性点的中毒作用,可以使催化剂寿命延长。从这些可知,磷的含量更优选0.03质量%以上、0.05质量%以下。
前述磷的含量通过磷系抗磨剂的混合量调整即可。作为代表的磷系抗磨剂可列举二硫代磷酸锌(ZnDTP)和二硫代磷酸钼(MoDTP)等二硫代磷酸金属类、磷酸或者亚磷酸酯类(有机磷酸酯、有机亚磷酸酯、烷基或者芳香基酸性磷酸酯、烷基或者芳香基氢亚磷酸酯以及它们的胺盐等)、硫代磷酸酯类、硫代亚磷酸酯类。其中,优选二硫代磷酸锌,即二烃基二硫代磷酸锌(烃基优选碳原子数1~18,更优选2~12烷基、烯基、芳基烷基、烷芳基),特别优选具有碳原子数3~8的仲烷基的二烷基二硫代磷酸锌。
另一方面,如果上述组合物中的来源于金属系清洁剂的金属成分的含量不足0.05质量%的话,可以抑制来源于金属成分的灰分堆积于DPF,能使其寿命延长。因此组合物中的金属成分的含量优选0.01质量%以下,更优选0.005质量%以下,特别优选0.001质量%以下。
优选本发明的内燃机用润滑油组合物中进一步含有硫系抗磨剂。作为硫系抗磨剂优选硫化油脂、硫化脂肪酸、硫化酯、硫化烯烃、二烃基多硫化物等不含磷的硫系抗磨剂。其中,优选下述通式(3)表示的二硫化物。
R1OOC-A1-S2-A2-COOR2···(3)
(式中、R1以及R2各自独立地表示可以含有氧原子、硫原子或者氮原子的碳原子数1~30的烃基,A1以及A2各自独立地表示碳原子数1~12的二价烃基。)
上述通式(3)表示的含硫化合物的具体例可列举二(甲氧羰基甲基)二硫醚、二(乙氧羰基甲基)二硫醚、二(正丙氧羰基甲基)二硫醚、二异丙氧基羰基甲基)二硫醚、二(正丁氧羰基甲基)二硫醚、二(正辛氧羰基甲基)二硫醚、二(正十二烷氧羰基甲基)二硫醚、二(环丙氧羰基甲基)二硫醚、1,1-二(1-甲氧羰基乙基)二硫醚、1,1-(1-甲氧羰基正丙基)二硫醚、1,1-二(1-甲氧羰基正丁基)二硫醚、1,1-(1-甲氧羰基正己基)二硫醚、1,1-二(1-甲氧羰基正辛基)二硫醚、1,1-二(1-甲氧羰基正十二烷基)二硫醚、2,2-二(2-甲氧羰基正丙基)二硫醚、α,α-二(α-甲氧羰基苄基)二硫醚、1,1-二(2-甲氧羰基乙基)二硫醚、1,1-二(2-乙氧羰基乙基)二硫醚、1,1-二(2-正丙氧羰基乙基)二硫醚、1,1-二(2-异丙氧羰基乙基)二硫醚、1,1-二(2-环丙氧羰基乙基)二硫醚、1,1-二(2-甲氧羰基正丙基)二硫醚、1,1-二(2-甲氧羰基正丁基)二硫醚、1,1-二(2-甲氧羰基正己基)二硫醚、1,1-二(3-甲氧羰基正丙基)二硫醚、2,2-二(3-甲氧羰基正戊基)二硫醚、1,1-二(2-甲氧羰基-1-苯乙基)二硫醚等。
上述硫系抗磨剂的含量,以组合物总量为基准,优选0.05~5质量%,更优选0.1~3质量%。如果混合量是0.05质量%以上的话,就能得到充分的耐磨损性,如果是5质量%以下的话,就没有产生腐蚀的担心。
本发明的润滑油组合物,在不损害上述的磷成分、金属成分等本发明的必要条件的范围内,还可以混合以往公知的内燃机用润滑油等润滑油组合物中使用的添加剂。可列举例如,其它的摩擦降低剂、粘度指数提高剂、倾点降低剂、抗氧化剂、防锈剂等。
作为上述其它的摩擦降低剂,可列举脂肪酸酯系、脂肪族胺系、高级醇系等无灰摩擦降低剂。
作为上述粘度指数提高剂可例举各种甲基丙烯酸酯或者它们的任意组合的共聚物、其氢化物等所谓的非分散型粘度指数提高剂、以及进一步使含有氮化合物的各种甲基丙烯酸酯共聚得到的所谓的分散型粘度指数提高剂等。
此外,非分散型或者分散型乙烯-α-烯烃共聚物(作为α-烯烃,可例举例如丙烯、1-丁烯、1-戊烯等)以及其氢化物、聚异丁烯以及其氢化物、苯乙烯-二烯烃氢化共聚物、苯乙烯-马来酸酐酯共聚物以及聚烷基苯乙烯等。这些粘度指数提高剂的分子量(数均分子量)例如分散型以及非分散型聚甲基丙烯酸酯为5000~1000000,优选100000~800000,聚异丁烯或者其氢化物为800~5000,乙烯-α-烯烃共聚物以及其氢化物为800~300000,优选10000~200000。
作为上述抗氧化剂,可列举酚系抗氧化剂和胺系抗氧化剂。作为酚系抗氧化剂,可列举例如4,4’-亚甲基二(2,6-二叔丁基苯酚)、4,4’-二(2,6-二叔丁基苯酚)、4,4’-二(2-甲基-6-叔丁基苯酚)、2,2’-亚甲基二(4-乙基-6-叔丁基苯酚)、2,2’-亚甲基二(4-甲基-6-叔丁基苯酚)、4,4’-亚丁基二(3-甲基-6-叔丁基苯酚)、4,4’-异亚丙基二(2,6-二叔丁基苯酚)、2,2’-亚甲基二(4-甲基-6-壬基苯酚)、2,2’-异亚丁基二(4,6-二甲基苯酚)、2,2′-亚甲基二(4-甲基-6-环己基苯酚)、2,6-二叔丁基-4-甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,4-二甲基-6-叔丁基苯酚、2,6-二叔戊基对甲酚、2,6-二叔丁基-4-(N,N′-二甲氨基甲基苯酚)、4,4’-硫代二(2-甲基-6-叔丁基苯酚)、4,4’-硫代二(3-甲基-6-叔丁基苯酚)、2,2’-硫代二(4-甲基-6-叔丁基苯酚)、二(3-甲基-4-羟基-5-叔丁基苄基)硫醚、二(3,5-二叔丁基-4-羟基苄基)硫醚、正十八烷基-3-(4-羟基-3,5-二叔丁基苯基)丙酸酯、2,2’-硫代[二乙基二-3-(3,5-二叔丁基-4-羟苯基)丙酸酯]等。其中,特别适宜的是双酚系以及含有酯基的酚系的苯酚系抗氧化剂。
此外,作为胺系抗氧化剂可列举例如单辛基二苯基胺、单壬基二苯基胺等单烷基二苯基胺系;4,4’-二丁基二苯基胺、4,4’-二戊基二苯基胺、4,4’-二己基二苯基胺、4,4’-二庚基二苯基胺、4,4’-二辛基二苯基胺、4,4’-二壬基二苯基胺等二烷基二苯基胺系;四丁基二苯基胺;四己基二苯基胺;四辛基二苯基胺、四壬基二苯基胺等多烷基二苯基胺系以及萘基胺系的抗氧化剂,具体的可列举α-萘胺、苯基-α-萘胺;还有丁基苯基-α-萘胺、戊基苯基-α-萘胺、己基苯基-α-萘胺、庚基苯基-α-萘胺、辛基苯基-α-萘胺;壬基苯基-α-萘胺等烷基取代苯基-α-萘胺等。其中二烷基二苯基胺系以及萘胺系抗氧化剂较为理想。
上述抗氧化剂可以选择使用一种,也可以2种以上组合使用。尤其优选组合使用酚系抗氧化剂的1种或者2种以上和胺系抗氧化剂的1种或者2种以上。
作为上述的防锈剂可列举烷基苯磺酸盐、二壬基萘磺酸盐、烯基琥珀酸酯、多元醇酯等。
上述其它添加剂的混合比例在通常使用的范围内适当选择即可。
本发明的润滑油组合物通过使润滑油基础油(简称为“基础油”。)中含有上述各种添加剂,得到具有目标性能的润滑油组合物。
本发明中使用的基础油没有特别的限定,可以从以往使用的公知的矿物系基础油(简称为“矿物油”)以及合成系基础油(简称为“合成油”)中适当选择来使用。
此处,作为矿物油可列举例如常压蒸馏的石蜡基系原油、中间基系原油或者环烷基系原油,或者将常压蒸馏的残渣油进行减压蒸馏而得到的溜出油,或者通过将其用通常的方法纯化得到的纯化油,例如溶剂纯化油、氢化纯化油、氢化分解油、脱蜡处理油、白土处理油等。进一步地可以使用石蜡类(疏松石蜡等)异构化油。
另一方面,作为合成油可列举例如碳原子数8~14的α-烯烃寡聚物的聚α-烯烃、聚丁烯、聚醇酯、烷基苯等。
本发明中作为基础油,可以使用上述矿物油的1种,也可以2种以上组合使用。此外,可以使用上述合成油的1种,也可以2种以上组合使用。进一步地,可以组合使用矿物油1种以上和合成油1种以上。
此外,组合物中的基础油的含量优选70质量%以上,更优选80质量%以上。
作为前述的基础油,100℃的运动粘度优选1.5~50mm2/s,更优选3~30mm2/s,特别优选3~15mm2/s。100℃的运动粘度在1.5mm2/s以上的话蒸发损失少,此外在50mm2/s以下的话,由于粘性阻力引起的功率损耗被抑制,能优秀地发挥油耗改善效果。
此外,该基础油的粘度指数优选80以上,进一步优选90以上,特别优选100以上。粘度指数在80以上的话,由于基础油的温度而引起的粘度变化小,能够发挥稳定的润滑性能。
此外作为基础油优选以JIS K2541为基准测定的硫分为50质量ppm以下。如果硫分是50质量ppm以下的话,就有提高低摩擦滑动材料的耐磨损性的效果。更优选的硫分为30质量ppm以下,进一步优选20质量ppm以下。
此外,作为基础油,从稳定性的方面考虑优选使用根据芳碳率分析的%CA为3.0以下的基础油。此处,根据芳碳率分析的%CA是表示通过芳碳率分析n-d-M法算出的芳香族成分的比例(百分比)。如果%CA是3.0以下的话,就显示出优秀的氧化稳定性。更优选%CA为1.0以下,进一步优选0.5以下。
实施例
接着,通过实施例进一步详细地说明本发明,但是本发明不被这些例子所限定。
另外、内燃机用润滑油组合物(以下简称为“润滑油组合物”)的组成以及性能用以下所示的方法测定。
<润滑油组合物的组成>
1.硼、磷、以及钙的定量
以ASTM D5185为基准测定。
2.氮的定量
以JIS K2609为基准测定。
3.硫分
以JIS K2541为基准测定。
<润滑油组合物的性能>
3.耐磨损性的评価
使用SRV摩擦试验机(往返运动型摩擦试验机),在下述的试验条件下,进行圆柱和圆盘间的摩擦试验,测定圆柱产生的磨损的伤痕直径。
试验条件
·试验片:圆柱(标准材;SUJ2)、圆盘(含有Si的铝:AA(美国铝业协会(アメリカアルミニウム協会))规格“A390”)
·试验温度:130℃
·荷重:200N
·振幅:3.0mm
·振动频率:20Hz
·试验时间:1小时
实施例A1~A10以及比较例A1~A8
制备表1以及表2所示组成的润滑油组合物,进行其耐磨损性的测定。结果表示于表1以及表2。
润滑油组合物的制备使用的各成分如下所示。
(1)基础油1:氢化纯化矿物油(100N)、40℃运动粘度21.0mm2/s、100℃运动粘度4.5mm2/s、粘度指数127、硫含量不足5质量ppm
(2)硼化酰亚胺1:聚丁烯琥珀酸单酰亚胺硼化物:聚丁烯基的数均分子量950、碱值(高氯酸法)30.6mgKOH/g、氮含量1.8质量%、硼含量2.1质量%
(3)硼化酰亚胺2:聚丁烯琥珀酸二酰亚胺硼化物:聚丁烯基的数均分子量950、碱值(高氯酸法)25mgKOH/g、氮含量1.2质量%、硼含量1.3质量%
(4)非硼化酰亚胺1:聚丁烯琥珀酸单酰亚胺:聚丁烯基的数均分子量950、碱值(高氯酸法)44mgKOH/g、氮含量2.1质量%
(5)非硼化酰亚胺2:聚丁烯琥珀酸二酰亚胺:聚丁烯基的数均分子量1300、碱值(高氯酸法)11.9mgKOH/g、氮含量1.0质量%
(6)硫系抗磨剂:二(正辛氧羰基甲基)二硫醚、硫含量158质量ppm
(7)金属系清洁剂:水杨酸钙、碱值(高氯酸法)270mgKOH/g
(8)磷系抗磨剂:二硫代烷基二硫代磷酸锌:Zn含量9.0质量%、磷含量8.0质量%、硫含量17.1质量%、烷基;仲丁基和仲己基的混合物
(9)其它添加剂:抗氧化剂(酚系抗氧化剂以及胺系抗氧化剂)、金属钝化剂(烷基苯并三唑)以及消泡剂(硅酮系)的混合物。
由表1、2可知以下的内容。
(1)满足式(I)的本发明的润滑油组合物对于铝材的耐磨损性优异(实施例A1~A10)。特别是,满足式(II)的实施例A4~A8的润滑油组合物对于铝材的耐磨损性更加优异。
与此相对的,不满足式(I)的润滑油组合物与上述实施例A1~A10的本发明相比,对于铝材的耐磨损性差(比较例A1~A8)。
(2)本发明的润滑油组合物(实施例A1~A10)即使不含P成分,其耐磨损性也优秀,此外,由于P成分含量以及来源于金属系清洁剂的金属成分的含量都极其少,因此,防止三元催化剂中毒的效果以及抑制DPF的寿命的降低的效果极其优异。
实施例B1~B9以及比较例B1~B7
制备表3以及表4所示组成的润滑油组合物,进行其耐磨损性的测定。结果表示于表3以及表4。
润滑油组合物的制备中使用的各成分以及组成以及性能的测定方法,与前述实施例A1~A10以及比较例A1~A8的情况相同。
从表3、4可知以下的内容。
(1)满足式(I)的本发明的润滑油组合物对于铝材的耐磨损性优异(实施例B1~B9)。特别是满足式(II)的实施例B5~B8的润滑油组合物,对于铝材的耐磨损性更加优异。
与此相对,不满足式(I)的润滑油组合物,对于铝材的耐磨损性都差(比较例B1~B7)。
(2)本发明的润滑油组合物(实施例B1~B9),即使几乎不含P成分,耐磨损性也优秀,此外由于P成分含量极其少,因此三元催化剂的防止中毒效果极其优异。此外,来源于金属系清洁剂的金属成分的含量为0.05质量%以上,由于含有金属清洁剂,因此清洁性极其优秀,另一方面,由于来源于金属系清洁剂的金属成分的含量为0.12质量%以下,因此抑制DPF的寿命降低的效果也优秀。
实施例C1~C10以及比较例C1~C8
制备表5以及表6所示组成的内燃机用润滑油组合物,进行其耐磨损性的测定。结果表示于表5以及表6。
润滑油组合物的制备使用的各成分以及组成以及性能的测定方法与前述实施例A1~A10以及比较例A1~A8的情况相同。
从表5、6可知以下的内容。
(1)满足式(I)的本发明的润滑油组合物对于铝材的耐磨损性优异(实施例C1~C10)。特别是,满足式(II)的实施例C5~C8的润滑油组合物,对于铝材的耐磨损性更加优异。
与此相对,不满足式(I)的润滑油组合物对于铝材的耐磨损性都差(比较例C1~C8)。
(2)本发明的润滑油组合物(实施例C1~C10)的P成分含量为0.03质量%以上,因此耐磨损性更加优异。此外,由于P成分含量为0.06质量%以下,因此三元催化剂的防止中毒效果也优秀。此外,由于金属分含量不足0.05质量%,因此,抑制DPF的寿命降低的效果也极其优异。
产业上的可利用性
本发明的提供一种内燃机用润滑油组合物,是对于铝材的耐磨损性优异,在维持对铝材的耐磨损性的同时,可以大幅降低磷成分含量多的ZnDTP、金属系清洁剂的内燃机用润滑油组合物。
因此,可以作为能够减轻对于使用铝材的内燃机的尾气后处理装置的影响的内燃机用润滑油组合物使用。
Claims (4)
1.一种内燃机用润滑油组合物,其特征在于,含有硼化酰亚胺系分散剂,或者含有硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂,组合物中的来源于硼化酰亚胺系分散剂的硼含量(B质量%)和来源于硼化酰亚胺系分散剂的氮含量(N质量%)、或者来源于硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂的氮含量(N质量%)满足下述式(I),
N≥B+0.05···(I)
并且磷的含量(P质量%)和来源于金属系清洁剂的金属成分的含量(M质量%),以组合物总量为基准,满足下述的A~C中的任意一个,
A:P<0.03且M<0.05
B:P<0.03且0.05≤M≤0.12
C:0.03≤P≤0.06且M<0.05。
2.如权利要求1所述的内燃机用润滑油组合物,其特征在于,来源于硼化酰亚胺系分散剂的硼含量(B质量%)和来源于硼化酰亚胺系分散剂的氮含量(N质量%)、或者来源于硼化酰亚胺系分散剂以及非硼化酰亚胺系分散剂的氮含量(N质量%)满足下述式(II),
N≥B+0.1···(II)。
3.如权利要求1或2所述的内燃机用润滑油组合物,其中,进一步含有硫系抗磨剂。
4.如权利要求3所述的内燃机用润滑油组合物,其中,硫系抗磨剂为下述通式(3)表示的二硫化物,
R1OOC-A1-S2-A2-COOR2···(3)
式中,R1以及R2各自独立地表示可以含有氧原子、硫原子或者氮原子的碳原子数1~30的烃基,A1以及A2各自独立地表示碳原子数1~12的二价烃基。
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