CN104837971A - 旋转式压缩机用润滑油组合物 - Google Patents
旋转式压缩机用润滑油组合物 Download PDFInfo
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- CN104837971A CN104837971A CN201380066133.2A CN201380066133A CN104837971A CN 104837971 A CN104837971 A CN 104837971A CN 201380066133 A CN201380066133 A CN 201380066133A CN 104837971 A CN104837971 A CN 104837971A
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- Prior art keywords
- lubricating oil
- mass
- rotary compressor
- oil composition
- extreme pressure
- Prior art date
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000002199 base oil Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- -1 phosphorodithioate compound Chemical class 0.000 claims description 44
- 239000002480 mineral oil Substances 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 235000010446 mineral oil Nutrition 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 5
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 5
- 150000001448 anilines Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 150000005002 naphthylamines Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 29
- 238000007254 oxidation reaction Methods 0.000 abstract description 29
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- 239000005069 Extreme pressure additive Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
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- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000010725 compressor oil Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
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- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical group C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- RUKRYLBUAIGWQI-UHFFFAOYSA-N butyl 2-[(2-butoxy-2-oxoethyl)disulfanyl]acetate Chemical compound CCCCOC(=O)CSSCC(=O)OCCCC RUKRYLBUAIGWQI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
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- 239000013530 defoamer Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
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- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000010720 hydraulic oil Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- ZLNMGXQGGUZIJL-UHFFFAOYSA-N n-octyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCCCC)C1=CC=CC=C1 ZLNMGXQGGUZIJL-UHFFFAOYSA-N 0.000 description 2
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- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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Abstract
通过在(a)基础油中含有(b)抗氧化剂和(c)相对于全部组合物为0.05质量%以上且不足2.0质量%的式(I)所示的二硫代磷酸酯化合物,提供能够维持高的氧化稳定性的同时赋予优异的极压性的旋转式压缩机用润滑油组合物。
Description
技术领域
本发明涉及旋转式压缩机用润滑油组合物。特别是本发明涉及可以维持高的氧化稳定性的同时赋予优异的极压性的旋转式压缩机用润滑油组合物。
背景技术
以往,对于压缩机油、透平油、油压工作油等设备油领域,特别是齿轮驱动方式等的压缩机油而言,要求优异的氧化稳定性和极压性,但是难以兼具这两者。即已知,通常作为氧化稳定性优异、以往使用的酸式磷酸酯胺盐、硫-磷系(SP系)极压添加剂,通常极压性不充分,另一方面,极压性优异的二烷基二硫代磷酸锌(ZnDTP)显著阻碍油的氧化稳定性。
关于提高极压性的化合物,例如专利文献1中为了改善发动机油的耐磨损性,公开了使用2.0质量%以上且8.0质量%以下的特定的二硫代磷酸酯。另外,专利文献2中为了抑制油压工作油的不优选的水解产物的生成,公开了将特定的单硫代磷酸酯和特定的二硫代磷酸酯组合来使用。
现有技术文献
专利文献
专利文献1:国际公开WO02/102945小册子
专利文献2:日本特许公开第2005-139451号公报。
发明内容
发明要解决的问题
但是,前述专利文献1所公开的技术是对于关于发动机油的课题而提出的,与压缩机油用润滑油、特别是旋转式压缩机用润滑油的氧化稳定性和极压性的兼顾无关。另外,专利文献2所公开的技术是对于关于油压工作油的课题而提出的,与压缩机油、特别是旋转式压缩机用润滑油的氧化稳定性和极压性的兼顾无关。
即,本发明的课题在于,提供旋转式压缩机用润滑油中、能够维持高的氧化稳定性的同时赋予优异的极压性的润滑油组合物。
另外,本发明的课题在于,提供上述旋转式压缩机用润滑油组合物中、除了兼具优异的氧化稳定性和极压性之外,还能够抑制淤渣的产生的旋转式压缩机用润滑油组合物。
用于解决问题的方案
即,本发明涉及:
[1]旋转式压缩机用润滑油组合物,其含有(a)基础油、(b)抗氧化剂和(c)相对于全部组合物为0.05质量%以上且不足2.0质量%的下式(I)所示的二硫代磷酸酯化合物,
[化学式1]
(式中,R1表示碳数为1~8的直链或支链的亚烷基,R2和R3分别表示碳数为3~20的烃基。)
[2]根据上述[1]所述的旋转式压缩机用润滑油组合物,其含有超过0.1质量%且不足2质量%的前述(c)式(I)所示的二硫代磷酸酯化合物。
[3]根据上述[1]或[2]所述的旋转式压缩机用润滑油组合物,其中,前述R1是碳数为1~8的直链或支链的亚烷基,R2和R3分别是碳数为3~20的直链或支链的亚烷基。
[4]根据上述[1]~[3]中任一项所述的旋转式压缩机用润滑油组合物,其中,前述抗氧化剂为选自酚系、苯胺系和萘胺系的各化合物中的至少1种。
[5]根据上述[1]~[4]中任一项所述的旋转式压缩机用润滑油组合物,其相对于全部组合物含有0.01质量%以上且10质量%以下的前述抗氧化剂。
[6]根据上述[1]~[5]中任一项所述的润滑油组合物,其中,前述基础油为矿物油。
[7]根据上述[1]~[6]中任一项所述的旋转式压缩机用润滑油组合物,其中,前述旋转式压缩机是齿轮驱动方式的旋转式压缩机。以及
[8]根据上述[1]~[7]中任一项所述的旋转式压缩机用润滑油组合物,其中,前述旋转式压缩机为螺杆式、可动叶片式、涡旋式或齿式。
发明的效果
根据本发明,可以提供旋转式压缩机用润滑油中、能够维持高的氧化稳定性的同时赋予优异的极压性的润滑油组合物。
另外,根据本发明,可以提供上述旋转式压缩机用润滑油组合物中、除了兼具优异的氧化稳定性和极压性之外,还能够抑制淤渣的产生的旋转式压缩机用润滑油组合物。
具体实施方式
以下对本发明进行更详细的说明。
通常压缩机用润滑油,从其使用形态以及使用周期的观点考虑,要求高的氧化稳定性,由此含有抗氧化剂。另一方面,压缩机用润滑油特别是齿轮驱动方式等的旋转式压缩机用润滑油要求充分的极压性,但是以往用于润滑油的SP系极压添加剂,由于润滑油的长期使用而显著损害其氧化稳定性。
这种状况下,本发明人等发现,通过将具有COOH基的特定结构的二硫代磷酸酯化合物以特定量用于旋转式压缩机用润滑油,长期不会损害其氧化稳定性,可以赋予优异的极压性,并且淤渣的产生也被抑制于实用上没有问题的水平。这种具有COOH基的二硫代磷酸酯化合物通常被认为阻碍氧化稳定性,上述发现是令人惊讶的。本发明基于上述发现而完成。
需要说明的是,前述专利文献1所公开的技术,是对于关于与压缩机油相比、将短期更换作为前提而使用的发动机油的课题提出的,因此对于淤渣抑制的要求性能低,另外没有着眼于压缩机油用润滑油的长期氧化稳定性,当然与氧化稳定性和极压性的兼顾无关。另外,前述专利文献2所公开的技术是对于关于与压缩机油相比、将短期更换作为前提而使用的油压工作油的课题提出的,对于淤渣抑制的要求性能低,另外,没有着眼于通过本发明中的二硫代磷酸酯化合物的使用实现压缩机油、特别是旋转式压缩机用润滑油的长期氧化稳定性和极压性的兼顾,该课题、技术特征没有公开本发明。
本发明的旋转式压缩机用润滑油组合物(以下有时仅称为“润滑油组合物”)含有(a)基础油、(b)抗氧化剂和(c)相对于全部组合物为0.05质量%以上且不足2.0质量%的前述式(I)所示的二硫代磷酸酯化合物。
((a)基础油)
作为本发明的旋转式压缩机用润滑油组合物的基础油,可以使用矿物油和合成油中的任意一种。对于该矿物油、合成油的种类、其它没有特别限制,作为矿物油,可列举出例如通过溶剂精制、氢化精制等通常的精制法得到的石蜡基系矿物油、中间基系矿物油或环烷基系矿物油等任意一种。
另外,作为合成油,可列举出例如聚丁烯、聚烯烃[α-烯烃(共聚物)聚合物]、各种酯(例如多元醇酯、二元酸酯、磷酸酯等)、各种醚(例如聚苯醚等)、进而疏松石蜡、GTL WAX的异构化物等。
这些矿物油、合成油可以单独使用,另外也可以将选自它们之中的两种以上基础油以任意比率混合来使用。
本发明的润滑油组合物中使用的基础油的粘度任意,但是若考虑到润滑性、冷却性以及搅拌时的摩擦损失,则优选使用40℃时的运动粘度为1mm2/s以上且10000mm2/s以下、优选5mm2/s以上且500mm2/s以下、进一步优选10mm2/s以上且100mm2/s以下的基础油。另外,使用两种以上基础油的情况下,该混合基础油的运动粘度处于上述范围内即可。
本发明中,作为基础油,从成本以及供给稳定性的观点考虑,优选使用矿物油。
((b)抗氧化剂)
作为(b)成分的抗氧化剂,若为胺系化合物、磷化合物、硫化合物和含磷?硫的化合物、酚系化合物等润滑油中通常使用的抗氧化剂则均可以使用。
例如作为胺系化合物,可列举出单辛基二苯基胺、单壬基二苯基胺等单烷基二苯基胺系化合物;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化合物;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化合物等的苯基系胺系化合物;α-萘胺、苯基-α-萘胺、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、癸基苯基-α-萘胺、十二烷基苯基-α-萘胺等萘胺系化合物。
作为磷化合物、硫化合物和含磷?硫的化合物,可列举出例如二乙基[[3,5-双(1,1-二甲基乙基)-4-羟基苯基]甲基]膦酸酯、3,5-二叔丁基-4-羟基苄基膦酸二乙酯这样的磷化合物,二-2-乙基己基二硫代磷酸锌这样的二烷基二硫代磷酸锌类,2,6-二-叔丁基-4-(4,6-双(辛硫基)-1,3,5-三嗪-2-基氨基)苯酚、五硫化磷与蒎烯的反应物等的硫代萜(thioterpene)系化合物,二月桂基硫代二丙酸酯、二硬脂基硫代二丙酸酯等二烷基硫代二丙酸酯等。
作为酚系化合物,可列举出例如2,6-二-叔丁基-4-甲基苯酚、2,6-二-叔丁基-4-乙基苯酚、2,4,6-三-叔丁基苯酚、2,6-二-叔丁基-4-羟基甲基苯酚、2,6-二-叔丁基苯酚、2,4-二甲基-6-叔丁基苯酚、2,6-二-叔丁基-4-(N,N-二甲基氨基甲基)苯酚、2,6-二-叔戊基-4-甲基苯酚、正十八烷基3-(4-羟基-3,5-二-叔丁基苯基)丙酸酯等单环酚类;4,4’-亚甲基双(2,6-二-叔丁基苯酚)、4,4’-异亚丙基双(2,6-二-叔丁基苯酚)、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、4,4’-双(2,6-二-叔丁基苯酚)、4,4’-双(2-甲基-6-叔丁基苯酚)、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、4,4’-亚丁基双(3-甲基-6-叔丁基苯酚)、2,2’-硫代双(4-甲基-6-叔丁基苯酚)、4,4’-硫代双(3-甲基-6-叔丁基苯酚)等多环酚类;等。
这些抗氧化剂之中,从抗氧化性能的观点考虑,优选磷化合物、酚系化合物、胺系化合物,更优选磷化合物、苯胺系化合物和萘胺系化合物,具体而言,优选4,4’-二辛基二苯基胺、辛基苯基-α-萘胺、3,5-二叔丁基-4-羟基苄基膦酸二乙酯等。
抗氧化剂的含量,相对于全部润滑油组合物通常为0.01质量%以上且10质量%以下的程度,下限值从抗氧化效果、上限值从对于基础油的溶解性的观点考虑,优选为0.03质量%以上且5质量%以下,更优选为0.1质量%以上且4质量%以下,进一步优选为0.5质量%以上且3质量%以下。
((c)式(I)所示的二硫代磷酸酯化合物)
本发明中,使用下述式(I)所示的二硫代磷酸酯化合物,式(I)中,R1表示碳数为1~8的直链或支链的亚烷基,R2和R3分别表示碳数为3~20的烃基。
[化学式2]
式(I)中,R1的碳数大于8时,对于基础油容易产生溶解不良。作为R1,从上述观点考虑,需要是碳数为1~8的直链或支链的亚烷基,优选碳数为2~4的直链或支链的亚烷基,更优选支链亚烷基。具体而言优选列举出-CH2CH2-、-CH2CH(CH3)-、-CH2CH(CH2CH3)-和-CH2CH(CH2CH2CH3)-等,更优选列举出-CH2CH(CH3)-、-CH2CH(CH3)CH2-。
另外,R2和R3的各自碳数小于3时,形成低分子量,因此容易产生对金属表面的吸附不良,大于20时对于基础油容易产生溶解不良。R2和R3的各自碳数,从上述观点考虑,优选为3~8的直链或支链的烷基,更优选碳数为4~6的直链或支链的烷基。具体而言,优选以选自丙基、异丙基、丁基、异丁基、叔丁基、戊基、异戊基、己基、2-乙基丁基、1-甲基戊基、1,3-二甲基丁基和2-乙基己基的各基团中的方式进行选择,它们之中,进一步优选异丁基、叔丁基。
上述式(I)所示的二硫代磷酸酯化合物,相对于全部润滑油组合物,含有0.05质量%以上且不足2.0质量%。若上述二硫代磷酸酯化合物的含量相对于全部润滑油组合物不足0.05质量%,则极压性和氧化稳定性差,若为2.0质量%以上则氧化稳定性不充分而不优选。从上述观点考虑,上述二硫代磷酸酯化合物相对于全部润滑油组合物,含有优选0.07质量%以上且不足2.0质量%、更优选超过0.1质量%且不足2.0质量%、进一步优选0.2质量%以上且1.0质量%以下、特别优选0.2质量%以上且0.5质量%以下。
(其它的润滑油添加剂)
本发明的旋转式压缩机用润滑油组合物含有前述(a)基础油、(b)抗氧化剂和(c)相对于全部组合物为0.05质量%以上且不足2.0质量%的式(I)所示的二硫代磷酸酯化合物,但是,进而另外根据需要,作为润滑油添加剂,可以配混选自润滑油中通常使用的其它极压添加剂、消泡剂、防锈剂、油性剂、清洁分散剂、金属减活剂、抗乳化剂等中的至少一种。
作为其它极压添加剂,可以使用式(I)所示的二硫代磷酸酯化合物以外的硫系极压添加剂、磷系极压添加剂、不具有COOH基的二硫代磷酸酯化合物、单硫代磷酸酯化合物等SP系极压添加剂。
作为硫系极压添加剂,可列举出例如二烷基硫醚、二苄基硫醚、多硫化二烷基()、二苄基硫醚、烷基硫醇、二苯并噻吩、二硫代乙醇酸二丁酯和2,2’-二硫代双(苯并噻唑)等,作为磷系极压添加剂,优选为磷酸酯类、亚磷酸酯类、酸式磷酸酯类、酸式亚磷酸酯类或它们的胺盐,可列举出例如磷酸三烷基酯、磷酸三芳基酯、膦酸三烷基酯、亚磷酸三烷基酯、亚磷酸三芳基酯、亚磷酸氢二烷基酯等。
另外,作为不具有COOH基的二硫代磷酸酯化合物,可列举出本发明中的式(I)所示的二硫代磷酸酯化合物中、COOH基的H被碳数为1~4的烷基等取代而成的化合物等,作为单硫代磷酸酯化合物,可列举出例如三硫代磷酸三烷基酯、三硫代磷酸三芳基酯、三硫代磷酸三芳烷基酯等。
这些极压添加剂可以单独或者组合在不阻碍本发明效果的范围使用,具体而言,可以分别相对于润滑油组合物100质量份以0.2质量份以下的量使用。
作为消泡剂,使用硅氧烷系消泡剂,优选高分子硅氧烷系消泡剂,可列举出例如有机聚硅氧烷,特别是三氟丙基甲基硅油等含氟有机聚硅氧烷是适宜的。硅氧烷系消泡剂,从消泡效果与经济性平衡的观点考虑,优选相对于全部润滑油组合物,含有0.0005质量%以上且0.5质量%以下程度。
作为防锈剂,可列举出例如金属磺酸盐、脂肪族胺类、有机亚磷酸酯、有机磷酸酯、有机磺酸金属盐、有机磷酸金属盐、烯基琥珀酸酯、多元醇酯等。这些防锈剂的含量,从配混效果的观点考虑,相对于全部润滑油组合物,通常为0.01质量%以上且10质量%以下程度,优选为0.05质量%以上且5质量%以下。
作为油性剂,可列举出脂肪族醇,脂肪酸、脂肪酸金属盐等脂肪酸系化合物、多元醇酯、脱水山梨糖醇酯、甘油酯等酯化合物,脂肪族胺等胺化合物等。油性剂的含量,从配混效果的观点考虑,相对于全部润滑油组合物,通常为0.1质量%以上且30质量%以下程度,优选为0.5质量%以上且10质量%以下。
作为清洁分散剂,可列举出例如金属磺酸盐、金属水杨酸盐、金属酚盐、脂肪族胺类、有机亚磷酸酯、有机磷酸酯、有机磺酸金属盐、有机磷酸金属盐、烯基琥珀酸酯、多元醇酯等。清洁分散剂的含量,从配混效果的观点考虑,相对于全部润滑油组合物,通常为0.01质量%以上且30质量%以下程度,优选为0.05质量%以上且10质量%以下。
作为金属减活剂,可列举出苯并三唑类、噻二唑类等。这些金属减活剂的含量,从配混效果的观点考虑,相对于全部润滑油组合物,通常为0.01质量%以上且10质量%以下程度,优选为0.01质量%以上且1质量%以下。
作为倾点下降剂,可以使用重均分子量为5万以上且15万以下程度的聚甲基丙烯酸酯等。从配混效果以及其它物性等观点考虑,倾点下降剂的含量,相对于全部润滑油组合物,通常为0.01质量%以上且5质量%以下,优选为0.02质量%以上且2质量%以下。
作为抗乳化剂,可列举出以往公知的抗乳化剂例如蓖麻油的硫酸酯盐、石油磺酸盐等阴离子性表面活性剂,季铵盐、咪唑啉型等的阳离子性表面活性剂,进而分子量1500以上且10000以下程度的氧化乙烯、氧化丙烯的缩合产物、具体而言聚氧亚烷基聚二醇及其二羧酸的酯、烷基苯酚-甲醛缩聚物的氧化烯加成物等。抗乳化剂的含量,相对于全部润滑油组合物,通常为0.01质量%以上且5质量%以下,优选为0.02质量%以上且2质量%以下。
本发明的润滑油组合物在100℃时的运动粘度(根据JIS K 2283),从通过摩擦降低实现节能性提高的观点考虑,优选为7.5mm2/s以下,更优选为4.5mm2/s以上且7.0mm2/s以下。
另外,本发明的润滑油组合物在40℃时的运动粘度,从通过摩擦降低实现节能性提高的观点考虑,优选为55mm2/s以下,更优选为30mm2/s以上且50mm2/s以下。
进而,本发明的润滑油组合物,从长期储藏稳定性的观点考虑,酸值(根据JIS K2501)优选为0mgKOH/g以上且1.0mgKOH/g以下,更优选为0mgKOH/g以上且0.5mgKOH/g以下。
另外,本发明提供使用上述润滑油组合物润滑旋转式压缩机的方法。
即,通过将本发明的润滑油组合物作为润滑油填充于旋转式压缩机,能够维持高的氧化稳定性的同时赋予优异的极压性。另外,除了兼具优异的氧化稳定性和极压性之外,进而能够抑制淤渣的产生。
作为可以适用本发明的润滑油组合物的旋转式压缩机,可列举出螺杆式、可动叶片式、涡旋式和齿式中的任意一种,特别是本发明中,优选适用于要求极压性的齿轮驱动方式的旋转式压缩机。
实施例
接着通过实施例对本发明进行具体说明,但是本发明不受这些例子任何限制。
[润滑油组合物的性状]
润滑油的各性状通过以下方法测定。
(1)运动粘度(40℃):根据JIS K 2283
(2)酸值(指示剂法):根据JIS K 2501
(3)铜板腐蚀(100℃、3小时):根据JIS K 2513
(4)硫分(ppm):根据JIS K 2541
(5)氮分(ppm):根据JIS K 2609
(6)磷含量(ppm):ICP分析
(7)锌含量(ppm):ICP分析。
[评价项目?评价方法]
(1)耐负荷性试验(shell EP试验):
根据ASTM D2783,通过四球试验机在转速1800rpm、油温(18.3~35.0℃)的条件下进行。由最大无卡咬负荷(LNL)和熔接负荷(WL)求出负荷磨损指数(LWI)。该值越大则耐负荷性越良好。
(2)耐磨损性试验(shell磨损试验):
根据ASTM D2783,通过四球试验机在负荷392N、转速1200rpm、油温75℃、试验时间60分钟的条件下进行。将3个1/2英寸球的磨损痕直径平均而算出平均磨损痕直径。
(3)旋转氧弹式氧化稳定度试验(RPVOT)
根据JIS K2514,将在试样油5g和蒸馏水5ml中装入有作为催化剂的Cu卷材的容器装入到旋转氧弹,向氧弹压入氧直至620kPa为止之后,在150℃的恒温槽中,使得氧弹保持于30度的角度的同时以每分钟100转旋转,测定由氧压力最高时降低至175kPa为止的时间(分钟)。
(4)氧化稳定度试验(修正IOT:Modified Indiana Oxidation Stability Test)
向玻璃管装入试样油300ml,向其中以Cu-Fe卷材浸渍于油的方式插入前端设置ディフューザーストーン、卷缠有作为催化剂的Cu-Fe卷材的外径7.0mm的吹入管,使得油温为130℃,由该吹入管以3L/hr吹入氧240~960小时,对于期间适时取样得到的试样油检测氧化稳定度。
(5)FZG齿轮试验
根据DIN 51354,对一对正齿轮施加扭转负荷,直至齿面发现损伤为止增加负荷的同时评价试样油的极压性。测定一对齿轮的各负荷阶段的磨损量,由磨损曲线的平均斜率磨损10mg以上的阶段作为临界负荷。试验条件如下所述。
?小齿轮转速:2250rpm
?油温:运转开始时90℃(以后90℃以上)
?油量:齿轮箱1.25l
?试验齿轮的间距圆周速度():8.30m/s
?负荷:负荷阶段1~12
?表面压力:15.7~198.9kg/mm2
?试验时间:各负荷阶段下15min
?给油法:油浴给油。
(6)微孔滤器试验
根据SAE-ARP-785-63,过滤采集前述氧化稳定度试验(修正IOT)期间取样的试样油中产生的析出物,测定其重量。
<实施例1~5及比较例1~6>
准备表1和表2所示的基础油,向其中如该表所示配混各种添加剂,制造润滑油组合物A~K后(表中的数字表示质量%),对于所得到的润滑油组合物分别评价前述润滑性能。其结果如表3和表4所示。需要说明的是,作为比较例5的润滑油组合物J,使用配混有作为极压添加剂的ZnDTP 0.54质量%的市售品(Roto Inject Fluid)
[表1]
[表2]
[表3]
[表4]
需要说明的是,所使用的基础油和各添加剂如下所述。
(基础油)
?石蜡系矿物油1
运动粘度:30.6mm2/s(40℃)、5.285mm2/s(100℃)、粘度指数:104、酸值:0.01mgKOH/g、密度:0.863(15℃)、闪点:222℃、倾点:-17.5℃
?石蜡系矿物油2
运动粘度:90.5mm2/s(40℃)、10.89mm2/s(100℃)、粘度指数:107、酸值:0.01mgKOH/g、密度:0.869(15℃)、闪点:266℃、倾点:-17.5℃
(添加剂)
?抗氧化剂1:4,4’-二辛基二苯基胺
?抗氧化剂2:对叔辛基苯基-1-萘胺
?抗氧化剂3:3,5-二叔丁基-4-羟基苄基膦酸二乙酯
?极压添加剂1:下述结构所示的含末端COOH的二硫代磷酸酯(式(I)中的R1为亚丙基、R2及R3分别为异丁基的化合物)。
[化学式3]
?极压添加剂2:下述结构所示的硫代磷酸三苯基酯
[化学式4]
?极压添加剂3:下述结构所示的三(2,4-C9-C10异烷基苯基)硫代磷酸酯
[化学式5]
?极压添加剂4:下述结构所示的二硫代乙醇酸二丁酯
[化学式6]
?极压添加剂5:下述结构所示的二硫代磷酸酯
[化学式7]
?极压添加剂6:下述结构所示的烷基酸式磷酸酯胺盐
[化学式8]
(上式中,R4及R5表示氢原子或烷基。)
?倾点下降剂:聚甲基丙烯酸酯(重均分子量:69000)
?清洁分散剂:烷基水杨酸Ca
?防锈剂:磺酸Ca
?金属减活剂:二烷基氨基甲基苯并三唑
?消泡剂:硅氧烷系消泡剂。
<实施例6和比较例7、8>
对于实施例5和比较例5、6中得到的润滑油组合物E、J和K分别评价前述各组成、性状、旋转氧弹式氧化稳定度试验(RPVOT)和FZG齿轮试验得到的结果如表5所示。
[表5]
另外,对于各润滑油组合物进行氧化稳定度试验(修正IOT),对于0~960小时期间取样的试样油,测定运动粘度(40℃)、酸值、旋转氧弹式氧化稳定度试验(RPVOT)、微孔滤器值得到的结果如表6、表7所示。
[表6]
[表7]
由表6和表7可知,比较例7由于配混ZnDTP作为极压添加剂,因此表示极压性能的FZG齿轮试验的结果良好,但是酸值和微孔滤器值表现出急剧升高趋势,不适于长期使用。另外可知,比较例8由于不配混极压添加剂,表示极压性能的FZG齿轮试验的结果差,不适于作为压缩机用润滑油的使用。
另一方面,实施例6由与比较例7、8的比较可知,能够长期维持高的氧化稳定性的同时,淤渣的产生抑制于实用上良好的程度,可以赋予优异的极压性。
产业上的可利用性
本发明的旋转式压缩机用润滑油组合物由于能够维持高的氧化稳定性的同时赋予优异的极压性,可以合适地用作螺杆式、可动叶片式、涡旋式、齿式等特别是齿轮驱动方式的旋转式压缩机用的润滑油。
Claims (8)
1.旋转式压缩机用润滑油组合物,其含有(a)基础油、(b)抗氧化剂和(c)相对于全部组合物为0.05质量%以上且不足2.0质量%的下式(I)所示的二硫代磷酸酯化合物,
[化1]
式中,R1表示碳数为1~8的直链或支链的亚烷基,R2和R3分别表示碳数为3~20的烃基。
2.根据权利要求1所述的旋转式压缩机用润滑油组合物,其含有超过0.1质量%且不足2质量%的所述(c)式(I)所示的二硫代磷酸酯化合物。
3.根据权利要求1或2所述的旋转式压缩机用润滑油组合物,其中,所述R1是碳数为1~8的直链或支链的亚烷基,所述R2和R3分别是碳数为3~20的直链或支链的亚烷基。
4.根据权利要求1~3中任一项所述的旋转式压缩机用润滑油组合物,其中,所述(b)抗氧化剂为选自磷化合物、酚系、苯胺系和萘胺系的各化合物中的至少1种。
5.根据权利要求1~4中任一项所述的旋转式压缩机用润滑油组合物,其相对于全部润滑油组合物含有0.01质量%以上且10质量%以下的所述抗氧化剂。
6.根据权利要求1~5中任一项所述的旋转式压缩机用润滑油组合物,其中,所述基础油为矿物油。
7.根据权利要求1~6中任一项所述的旋转式压缩机用润滑油组合物,其中,所述旋转式压缩机是齿轮驱动方式的旋转式压缩机。
8.根据权利要求1~7中任一项所述的旋转式压缩机用润滑油组合物,其中,所述旋转式压缩机为螺杆式、可动叶片式、涡旋式和齿式中的任意一种。
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JP2012-276903 | 2012-12-19 | ||
PCT/JP2013/083956 WO2014098152A1 (ja) | 2012-12-19 | 2013-12-18 | 回転式圧縮機用潤滑油組成物 |
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CN114930023A (zh) * | 2019-12-03 | 2022-08-19 | 松下电器制冷装置新加坡 | 密闭型制冷剂压缩机和使用其的冰箱-冷冻机 |
TWI838469B (zh) * | 2019-02-22 | 2024-04-11 | 日商Jxtg能源股份有限公司 | 冷凍機油及冷凍機用作動流體組合物 |
US12247177B2 (en) | 2019-02-22 | 2025-03-11 | Eneos Corporation | Refrigerator oil and refrigerator working fluid composition |
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EP3077488B1 (en) * | 2013-12-06 | 2023-11-01 | Basf Se | Composition and method of forming the same |
JP6513698B2 (ja) * | 2014-11-04 | 2019-05-15 | Jxtgエネルギー株式会社 | 冷凍機油 |
JP2016193994A (ja) * | 2015-03-31 | 2016-11-17 | 出光興産株式会社 | 潤滑油組成物、及び潤滑油組成物の製造方法 |
KR102490659B1 (ko) * | 2016-09-15 | 2023-01-25 | 에네오스 가부시키가이샤 | 냉동기유 및 냉동기용 작동 유체 조성물 |
JP2018048381A (ja) * | 2016-09-23 | 2018-03-29 | 住友電気工業株式会社 | 焼結部品の製造方法 |
JP2023151621A (ja) * | 2022-03-31 | 2023-10-16 | 出光興産株式会社 | 潤滑油組成物 |
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EP2937410A1 (en) | 2015-10-28 |
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US20150337231A1 (en) | 2015-11-26 |
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