CN115768858A - 冷冻机油和冷冻机用工作流体组合物 - Google Patents
冷冻机油和冷冻机用工作流体组合物 Download PDFInfo
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- CN115768858A CN115768858A CN202180046612.2A CN202180046612A CN115768858A CN 115768858 A CN115768858 A CN 115768858A CN 202180046612 A CN202180046612 A CN 202180046612A CN 115768858 A CN115768858 A CN 115768858A
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- acid
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- refrigerator
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Abstract
本发明的一个方面为一种冷冻机油,其含有基础油、以及羧酸与多元醇的偏酯,羧酸包含不饱和羧酸。
Description
技术领域
本发明涉及冷冻机油和冷冻机用工作流体组合物。
背景技术
以往,在室内空调、成套空调设备等空调机器、家庭用冷冻冷藏柜、产业用冷冻机以及车载空调等的冷冻机中会使用冷冻机油。这种冷冻机具备制冷剂循环系统,该制冷剂循环系统具有压缩机、冷凝器、膨胀机构(膨胀阀、毛细管)、蒸发器等,通过使制冷剂在该制冷剂循环系统内循环而进行冷却。
冷冻机用压缩机包括回转式压缩机、活塞/曲柄式压缩机等。例如,在活塞/曲柄式压缩机中,利用连杆将马达的旋转运动转换为往复运动,使与该连杆连接的活塞往复运动,从而将制冷剂压缩。冷冻机油与制冷剂一起被封入到压缩机内,对例如连杆、活塞等滑动构件进行润滑。例如专利文献1中公开了一种含有特定的酯添加剂的冷冻机油。
现有技术文献
专利文献
专利文献1:国际公开第2015/182173号
发明内容
发明要解决的问题
本发明的一个方面的目的在于,提供一种具有优异耐磨耗性的冷冻机油。
用于解决问题的方案
本发明人等发现,在基础油中添加多元醇与羧酸的酯的情况下,如果使用包含不饱和羧酸的羧酸作为羧酸且使用偏酯作为该酯,则可得到具有优异耐磨耗性的冷冻机油。即,本发明人等发现,通过使用包含不饱和羧酸的羧酸与多元醇的偏酯(以下也称为“不饱和羧酸偏酯”),与使用不包含不饱和羧酸(仅包含饱和羧酸)的羧酸与多元醇的偏酯(以下也称为“饱和羧酸偏酯”)的情况、不使用不饱和羧酸偏酯而仅使用全酯的情况相比,可得到优异的耐磨耗性。特别令人惊讶的是,即使构成酯的多元醇和羧酸的种类相同,但在冷冻机油包含不饱和羧酸偏酯的情况与不包含不饱和羧酸偏酯(仅包含全酯)的情况下,耐磨耗性也会产生差异。
本发明的一个方面为一种冷冻机油,其含有基础油、以及羧酸与多元醇的偏酯,羧酸包含不饱和羧酸。
不饱和羧酸的碳数可以为12以上。
多元醇可以包含季戊四醇。偏酯可以包含季戊四醇的单酯、季戊四醇的二酯以及季戊四醇的三酯。
羧酸可以进一步包含饱和羧酸。饱和羧酸的碳数可以为12以上。
本发明的另一方面为一种冷冻机用工作流体组合物,其含有上述冷冻机油和制冷剂。制冷剂可以包含不饱和氟化烃。
发明的效果
根据本发明的一个方面,能够提供一种具有优异耐磨耗性的冷冻机油。
具体实施方式
下面,对本发明的实施方式进行详细说明。本发明的一实施方式的冷冻机油含有:基础油、以及羧酸与多元醇的偏酯。偏酯(包括不饱和羧酸偏酯与饱和羧酸偏酯这两者。下面,仅称为“偏酯”时为相同含义)是多元醇的羟基中一部分被羧酸酯化、剩余部分未被酯化而以羟基的状态残留的酯。即,偏酯具有酯键和羟基。
基础油包含选自由矿物油和合成油(但不包括不饱和羧酸偏酯)组成的组中的至少1种。
作为矿物油,可举出:对原油进行常压蒸馏和减压蒸馏而得到润滑油馏分,对所得到的润滑油馏分通过单独的溶剂脱沥青、溶剂萃取、加氢裂化、溶剂脱蜡、催化脱蜡、加氢精制、硫酸清洗、白土处理等精制处理或适当组合2种以上进行精制而成的链烷烃系矿物油、环烷烃系矿物油等矿物油等,特别优选使用链烷烃系矿物油。需要说明的是,这些矿物油可以单独使用,也可以以任意的比例组合使用2种以上。
作为合成油,可举出除不饱和羧酸偏酯以外的其他酯、醚(聚乙烯基醚、聚亚烷基二醇等)、碳酸酯、酮、硅酮、聚硅氧烷等含氧系合成油;烷基苯、烷基萘、聚α-烯烃(PAO)、乙烯α-烯烃等烃系合成油等。含氧系合成油优选为除不饱和羧酸偏酯以外的其他的酯或醚。
作为除不饱和羧酸偏酯以外的其他的酯,可例示:一元酸与1元醇的一元酸酯、二元酸与1元醇的二元酸酯、羧酸与多元醇的多元醇酯、复合酯、碳酸酯及它们的混合物等。其他的酯优选为羧酸与多元醇的多元醇酯(不包括不饱和羧酸偏酯)。
作为这种多元醇酯,可举出:多元醇的羟基全部被饱和羧酸或不饱和羧酸酯化而成的全酯、多元醇的仅一部分羟基被饱和羧酸酯化而成的偏酯(饱和羧酸偏酯)等。
作为构成多元醇酯的多元醇,优选使用具有2~6个羟基的多元醇。多元醇的碳数优选为4以上、更优选为5以上,优选为12以下、更优选为10以下。多元醇优选为新戊二醇、三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、二(三羟甲基丙烷)、三(三羟甲基丙烷)、季戊四醇、二季戊四醇等受阻醇。从与制冷剂的相容性的观点出发,多元醇优选为季戊四醇、二季戊四醇及它们的混合物中的任一者。
构成全酯的羧酸可以为饱和羧酸或不饱和羧酸中的任意种,也可以为直链状或支链状中的任意种。羧酸的碳数优选为4以上、更优选为6以上、进一步优选为8以上,优选为18以下、更优选为12以下、进一步优选为10以下,优选为4~18、更优选为6~12、进一步优选为8~10。
作为饱和羧酸,可举出:戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、十二烷酸、十三烷酸、十四烷酸、十五烷酸、十六烷酸、十七烷酸、十八烷酸等。作为不饱和羧酸,可举出:戊烯酸、己烯酸、庚烯酸、辛烯酸、壬烯酸、癸烯酸、十一碳烯酸、十二碳烯酸、十三碳烯酸、十四碳烯酸、十五碳烯酸、十六碳烯酸、十七碳烯酸、十八碳烯酸等。这些饱和羧酸以及不饱和羧酸可以为直链状,也可以为支链状。
含氧系合成油(优选为酯或醚)的酸值例如可以为0.1mgKOH/g以下,优选为0.05mgKOH/g以下。含氧系合成油(优选为酯或醚)的羟值例如可以为10mgKOH/g以下,优选为5mgKOH/g以下。酸值和羟值为上述范围内时,能够进一步提高与不饱和氟化烃制冷剂一起使用时的冷冻机油的稳定性。本说明书中的酸值是指依据JIS K2501:2003测定的酸值。本说明书中的羟值是指依据JIS K0070“化学制品的酸值、皂化值、酯值、碘值、羟值和不皂化物的试验方法”测定的羟值。
基础油的含量以冷冻机油总量为基准,例如可以为50质量%以上、70质量%以上、或者90质量%以上,可以为99质量%以下。
基础油在40℃下的运动粘度没有特别限制,例如可以为3mm2/s以上、10mm2/s以上、或者20mm2/s以上,可以为500mm2/s以下或者300mm2/s以下。基础油在100℃下的运动粘度没有特别限制,例如可以为1mm2/s以上或者2mm2/s以上,可以为100mm2/s以下或者50mm2/s以下。本说明书中的运动粘度是指按照JIS K2283:2000测定的运动粘度。
构成不饱和羧酸偏酯的羧酸包含具有不饱和键(碳-碳双键)的不饱和羧酸。不饱和羧酸中的不饱和键的数量例如可以为1以上,可以为4以下、3以下、或者2以下,也可以为1。
不饱和羧酸的碳数优选为4以上、更优选为8以上、进一步优选为12以上、特别优选为16以上,优选为36以下、更优选为28以下、进一步优选为20以下,优选为4~36、更优选为8~28、进一步优选为12~20、特别优选为14~18或16~20。
作为这种不饱和羧酸,可举出:戊烯酸、己烯酸、庚烯酸、辛烯酸、壬烯酸、癸烯酸、十一碳烯酸、十二碳烯酸、十三碳烯酸、十四碳烯酸、十五碳烯酸、十六碳烯酸、十七碳烯酸、十八碳烯酸等。这种不饱和羧酸可以为直链状,也可以为支链状。不饱和羧酸特别优选包含油酸作为主成分,也可以包含棕榈油酸、亚油酸、亚麻酸等碳数14~18的不饱和脂肪酸。
作为上述多元醇,优选使用具有2~6个羟基的多元醇。作为多元醇的碳数,优选为4~12、更优选为5~10。具体而言,优选新戊二醇、三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、二(三羟甲基丙烷)、三(三羟甲基丙烷)、季戊四醇、二季戊四醇等受阻醇。由于耐磨耗性(润滑性)的提高效果特别大,因此优选多元醇包含季戊四醇。
不饱和羧酸偏酯中,只要多元醇的至少一部分羟基被不饱和羧酸酯化即可。即,上述偏酯包含下述(I)和(II)。
(I)多元醇的羟基的一部分被不饱和羧酸酯化、剩余部分未被酯化而以羟基的状态残留的化合物。
(II)多元醇的羟基的一部分被不饱和羧酸酯化、另一部分被饱和羧酸酯化、剩余部分未被酯化而以羟基的状态残留的化合物。
在上述(II)的情况下,换言之,构成不饱和羧酸偏酯的羧酸进一步包含饱和羧酸。饱和羧酸的碳数优选为4以上、更优选为8以上、进一步优选为12以上,优选为36以下、更优选为28以下、进一步优选为20以下,优选为4~36、更优选为8~28、进一步优选为12~20、特别优选为14~18。
作为饱和羧酸,具体而言,可举出:戊酸、己酸、庚酸、辛酸、壬酸、癸酸、十一烷酸、十二烷酸、十三烷酸、十四烷酸、十五烷酸、十六烷酸、十七烷酸、十八烷酸等饱和羧酸。这种饱和羧酸可以为直链状,也可以为支链状。
例如,在多元醇为季戊四醇的情况下,不饱和羧酸偏酯可以为选自季戊四醇的4个羟基之中1个被酯化而成的单酯、2个被酯化而成的二酯、以及3个被酯化而成的三酯中的1种以上。
不饱和羧酸偏酯优选包含单酯、二酯和三酯。在该情况下,不饱和羧酸偏酯中的单酯的比例可以为1质量%以上、5质量%以上、或者8质量%以上,可以为30质量%以下、20质量%以下、或者15质量%以下。不饱和羧酸偏酯中的二酯的比例可以为20质量%以上、30质量%以上、或者35质量%以上,可以为60质量%以下、50质量%以下、或者45质量%以下。不饱和羧酸偏酯中的三酯的比例可以为20质量%以上、30质量%以上、或者35质量%以上,可以为65质量%以下、55质量%以下、或者50质量%以下。
源自偏酯的不饱和键的碘值优选为20(gI2/100g)以上、更优选为40(gI2/100g)以上、进一步优选为50(gI2/100g)以上。该碘值优选为100(gI2/100g)以下、更优选为80(gI2/100g)以下、进一步优选为70(gI2/100g)以下。本说明书中的碘值是指,依据JIS K0070“化学制品的酸值、皂化值、酯值、碘值、羟值和不皂化物的试验方法”的指示剂滴定法而测定的碘值,使卤素与试样100g反应时,将所键合的卤素的量换算成碘的g数而得到的值(gI2/100g)。
不饱和羧酸偏酯的酸值没有特别限制,优选为5mgKOH/g以下,可以为3mgKOH/g以下或者2mgKOH/g以下,也可以为0.1mgKOH/g以下,可以为0.1mgKOH/g以上、0.4mgKOH/g以上或者1mgKOH/g以上。
不饱和羧酸偏酯的羟值没有特别限制,从具有偏酯结构的观点出发,例如可以为10mgKOH/g以上,优选可以为20mgKOH/g以上、50mgKOH/g以上、或者100mgKOH/g以上,可以为500mgKOH/g以下,优选可以为300mgKOH/g以下或者200mgKOH/g以下。
对于不饱和羧酸偏酯的含量,从更适宜地发挥耐磨耗性(润滑性)的提高效果的观点出发,以冷冻机油总量为基准,优选为0.001质量%以上、更优选为0.01质量%以上、进一步优选为0.1质量%以上或0.5质量%以上。从与制冷剂的相容性的观点出发,另外从能够进一步提高冷冻机油的稳定性的观点出发,不饱和羧酸偏酯的含量优选为10质量%以下、更优选为5质量%以下、进一步优选为1质量%以下。
不饱和羧酸偏酯在40℃下的运动粘度会根据其结构而不同,没有特别限制,从冷冻机油与后述制冷剂的相容性优异的观点出发,优选可以为5mm2/s以上或者10mm2/s以上,可以为100mm2/s以下、50mm2/s以下、或者30mm2/s以下。不饱和羧酸偏酯在100℃下的运动粘度没有特别限制,优选可以为1mm2/s以上或者2mm2/s以上,可以为50mm2/s以下、10mm2/s以下、或者8mm2/s以下。
不饱和羧酸偏酯的粘度指数没有特别限制,例如可以为80以上、120以上、或者150以上,可以为300以下、250以下、或者200以下。本说明书中的粘度指数是指按照JIS K2283:2000测定的粘度指数。
冷冻机油可以进一步含有除基础油和不饱和羧酸偏酯以外的添加剂。作为添加剂,例如可举出:抗氧化剂、酸捕捉剂、抗磨耗剂、消泡剂、金属减活剂、粘度指数改进剂、降凝剂、净化分散剂等。
作为抗氧化剂,例如可举出酚系抗氧化剂、胺系抗氧化剂等。作为酚系抗氧化剂,例如可例示:2,6-二叔丁基对甲酚(DBPC)、2,6-二叔丁基苯酚、4,4'-亚甲基双(2,6-二叔丁基苯酚)等。作为胺系抗氧化剂,例如可例示:苯基-α-萘胺类、二烷基化二苯胺类等。这些抗氧化剂可以单独使用1种或组合使用2种以上。抗氧化剂的含量以冷冻机油总量基准计例如可以为0.01质量%以上,可以为5质量%以下,优选可以为0.1质量%以上,可以为3质量%以下。
作为酸捕捉剂,例如可举出环氧化合物(环氧系酸捕捉剂)。作为环氧化合物,可举出:缩水甘油醚型环氧化合物、缩水甘油酯型环氧化合物、芳基环氧乙烷化合物、烷基环氧乙烷化合物、脂环式环氧化合物、环氧化脂肪酸单酯、环氧化植物油等。环氧化合物(环氧系酸捕捉剂)优选为选自由缩水甘油醚型环氧化合物和缩水甘油酯型环氧化合物组成的组中的至少1种,从即使为低浓度也能够使不饱和羧酸偏酯、后述的磷系抗磨耗剂有效发挥作用的观点出发,更优选为缩水甘油醚型环氧化合物。这些酸捕捉剂可以单独使用1种或者组合使用2种以上。酸捕捉剂的含量以冷冻机油总量基准计例如可以为0.01质量%以上,也可以为5质量%以下,优选可以为0.1质量%以上,也可以为3质量%以下。
作为抗磨耗剂,例如可举出磷系抗磨耗剂。磷系抗磨耗剂例如可举出磷酸酯、酸性磷酸酯、酸性磷酸酯的胺盐、氯化磷酸酯、亚磷酸酯、硫代磷酸酯等。磷酸酯优选为磷酸三苯酯(TPP)、磷酸三甲苯酯(TCP)、或者三苯基硫代磷酸酯(TPPT)。抗磨耗剂可以单独使用1种或者组合使用2种以上。抗磨耗剂的含量以冷冻机油总量基准计优选为0.01质量%以上、更优选为0.1质量%以上、进一步优选为1质量%以上,优选为5质量%以下、更优选为3质量%以下。
作为消泡剂,可以使用通常作为冷冻机油用消泡剂使用的任意的化合物,例如可举出二甲基硅酮、氟硅酮等硅酮类。消泡剂可以单独使用1种或者组合使用2种以上。消泡剂的含量以冷冻机油总量基准计优选为5质量%以下、更优选为3质量%以下,优选为0.01质量%以上、更优选为0.1质量%以上、进一步优选为1质量%以上。
作为金属减活剂,例如可举出苯并三唑、苯并三唑衍生物等。金属减活剂可以单独使用1种或者组合使用2种以上。金属减活剂的含量以冷冻机油总量基准计优选为5质量%以下、更优选为3质量%以下,优选为0.01质量%以上、更优选为0.1质量%以上、进一步优选为1质量%以上。
作为粘度指数改进剂,可举出非分散型或分散型的粘度指数改进剂。具体而言,可举出:非分散型或分散型聚甲基丙烯酸酯类、非分散型或分散型乙烯-α烯烃共聚物或其氢化物、聚异丁烯或其氢化物、苯乙烯-二烯加氢共聚物、聚甲基丙烯酸酯-烯烃共聚物、以及聚烷基苯乙烯等。它们可以单独使用1种或者组合使用2种以上。这些粘度指数改进剂的重均分子量例如可以为1万以上,也可以为100万以下。粘度指数改进剂的含量以冷冻机油总量基准计优选为5质量%以下、更优选为3质量%以下,优选为0.01质量%以上、更优选为0.1质量%以上、进一步优选为1质量%以上。
作为降凝剂,可举出与上述粘度指数改进剂不同的聚(甲基)丙烯酸烷基酯等。降凝剂的含量以冷冻机油总量基准计优选为5质量%以下、更优选为3质量%以下,优选为0.01质量%以上、更优选为0.1质量%以上、进一步优选为1质量%以上。
作为净化分散剂,可以使用常用的净化分散剂,例如可以使用琥珀酰亚胺、聚烷基胺、聚醚胺等。它们可以单独使用1种或者组合使用2种以上。净化分散剂的含量以冷冻机油总量基准计优选为5质量%以下、更优选为3质量%以下,优选为0.01质量%以上、更优选为0.1质量%以上、进一步优选为1质量%以上。
冷冻机油在40℃下的运动粘度只要根据其使用目的而适当调整即可,没有特别限制,例如可以为3mm2/s以上、10mm2/s以上、或者20mm2/s以上,可以为500mm2/s以下或者300mm2/s以下。冷冻机油在100℃下的运动粘度没有特别限制,例如可以为1mm2/s以上或者2mm2/s以上,可以为100mm2/s以下或者50mm2/s以下。
冷冻机油的粘度指数没有特别限制,例如可以为10以上、50以上、或者70以上,可以为500以下、300以下、或者250以下。
冷冻机油的酸值例如可以为0.1mgKOH/g以下,优选为0.05mgKOH/g以下。冷冻机油的羟值例如可以为10mgKOH/g以下,优选为5mgKOH/g以下。酸值和羟值为上述范围内时,能够进一步提高与不饱和氟化烃制冷剂一起使用时的冷冻机油的稳定性。
通常,在具备具有压缩机、冷凝器、膨胀机构和蒸发器的制冷剂循环系统的冷冻机中,冷冻机油以与制冷剂混合的冷冻机用工作流体组合物的状态存在,例如对滑动构件进行润滑。即,本发明的另一实施方式为一种冷冻机用工作流体组合物,其含有上述冷冻机油和制冷剂。
冷冻机用工作流体组合物中的冷冻机油的含量相对于制冷剂100质量份例如可以为1质量份以上或者2质量份以上,可以为500质量份以下或者400质量份以下。
作为制冷剂,例如可例示:饱和氟化烃、不饱和氟化烃、烃、全氟醚类等含氟醚、双(三氟甲基)硫醚、以及、氨、二氧化碳等天然系制冷剂、以及选自这些制冷剂中的2种以上的混合制冷剂。
饱和氟化烃优选为碳数1~3、更优选为碳数1~2的饱和氟化烃。作为饱和氟化烃,具体而言,可举出:二氟甲烷(R32)、三氟甲烷(R23)、五氟乙烷(R125)、1,1,2,2-四氟乙烷(R134)、1,1,1,2-四氟乙烷(R134a)、1,1,1-三氟乙烷(R143a)、1,1-二氟乙烷(R152a)、氟乙烷(R161)、1,1,1,2,3,3,3-七氟丙烷(R227ea)、1,1,1,2,3,3-六氟丙烷(R236ea)、1,1,1,3,3,3-六氟丙烷(R236fa)、1,1,1,3,3-五氟丙烷(R245fa)以及1,1,1,3,3-五氟丁烷(R365mfc)、或者它们的2种以上的混合物。
不饱和氟化烃优选为碳数2~4或2~3的不饱和氟化烃、更优选为氟丙烯、进一步优选为氟数为3~5的氟丙烯。不饱和氟化烃优选为1,2,3,3,3-五氟丙烯(HFO-1225ye)、1,3,3,3-四氟丙烯(HFO-1234ze)、2,3,3,3-四氟丙烯(HFO-1234yf)、1,2,3,3-四氟丙烯(HFO-1234ye)和3,3,3-三氟丙烯(HFO-1243zf)中的任1种或2种以上的混合物。从制冷剂物性的观点出发,不饱和氟化烃优选为选自HFO-1225ye、HFO-1234ze和HFO-1234yf中的1种或2种以上。
烃优选为碳数1~5的烃、更优选为碳数2~4的烃。作为烃,具体而言,例如可举出:甲烷、乙烯、乙烷、丙烯、丙烷(R290)、环丙烷、正丁烷、异丁烷(R600a)、环丁烷、甲基环丙烷、2-甲基丁烷、正戊烷或它们的2种以上的混合物。对于烃而言,在这些中优选25℃、1个大气压下为气体的烃,更优选为丙烷、正丁烷、异丁烷、2-甲基丁烷或它们的混合物。
冷冻机油优选与包含不饱和氟化烃的制冷剂一起使用、更优选与包含HFO-1234yf的制冷剂一起使用。即,冷冻机用工作流体组合物中的制冷剂优选包含不饱和氟化烃、更优选包含HFO-1234yf。不饱和氟化烃的含量以制冷剂总量基准计可优选为20质量%以上、更优选为60质量%以上、进一步优选为70质量%以上、特别优选为80质量%以上。
冷冻机油和冷冻机用工作流体组合物可适宜地用于具有往复移动式或旋转式密闭型压缩机的空调、冰箱、开放型或密闭型车载空调、除湿机、热水器、冷冻库、冷冻冷藏仓库、自动售货机、展示柜、化学设备等的冷冻机、具有离心式压缩机的冷冻机等。
冷冻机油和冷冻机用工作流体组合物对上述压缩机中的滑动构件进行润滑。滑动构件优选包含铝。冷冻机油可以特别适宜地对包含铁的滑动部件与包含铝的滑动部件的组合进行润滑。
实施例
下面,基于实施例更具体地说明本发明,但本发明并不限定于以下实施例。
[冷冻机油]
使用以下所示的各成分,制备具有表1所示的组成(以冷冻机油总量为基准的质量%)的冷冻机油。任一冷冻机油的酸值均为0.05mgKOH/g以下、羟值均为5mgKOH/g以下。
(A)将下述a1和a2以质量比75/25混合而成的基础油(40℃下的运动粘度:83.29mm2/s、100℃下的运动粘度:9.63mm2/s、酸值:0.05mgKOH/g以下、羟值:5mgKOH/g以下)
a1:季戊四醇与2-乙基己酸/3,5,5-三甲基己酸的混合羧酸(混合比(质量比):48/52)的全酯
a2:二季戊四醇与2-乙基己酸/3,5,5-三甲基己酸的混合羧酸(混合比(质量比):50/50)的全酯
(B)季戊四醇与以十八碳烯酸和十六烷酸为主成分的碳数14~18的混合羧酸(十八碳烯酸:87质量%、十六烷酸:5质量%、其他羧酸:8质量%)的偏酯(单酯:10质量%、二酯:37质量%、三酯:40质量%)、以及、季戊四醇与以十八碳烯酸和十六烷酸为主成分的碳数14~18的混合羧酸(十八碳烯酸:87质量%、十六烷酸:5质量%、其他羧酸:8质量%)的全酯(13质量%)的混合物(碘值:66.3(gI2/100g)、酸值:1.5mgKOH/g、羟值:130mgKOH/g、40℃运动粘度:12.5mm2/s、100℃运动粘度:3.6mm2/s、粘度指数:190)
(b1)季戊四醇与以十八碳烯酸与以十六烷酸为主成分的碳数14~18的混合羧酸(十八碳烯酸:88质量%、十六烷酸:5质量%、其他羧酸:7质量%)的全酯(碘值:88(gI2/100g)、酸值:0.4mgKOH/g、羟值:6mgKOH/g、40℃运动粘度:66mm2/s、100℃运动粘度:12.5mm2/s、粘度指数:188)
(b2)三羟甲基丙烷与癸酸的偏酯(单酯:27质量%、二酯:46质量%)、以及、三羟甲基丙烷与癸酸的全酯(27质量%)的混合物
(C)磷系抗磨耗剂
(D)环氧系酸捕捉剂
(D1)缩水甘油酯型环氧化合物
(D2)缩水甘油醚型环氧化合物
(E)酚系抗氧化剂
[耐磨耗性的评价]
使用密闭式FALEX试验机(销:3135steel(含铁的滑动构件)、V形块:4032Al(含铝的滑动构件)),将试验条件设定为试验载荷0.3MPaG、试验时间5小时、转速290rpm、试验温度25℃(室温)。试验片使用依据ASTM D2670磨耗量试验的试验片,在2,3,3,3-四氟丙烯制冷剂吹入环境下(制冷剂吹入量:10L/h)实施耐磨耗性试验,测定试验后的块磨耗幅度的平均值(mm)。将结果示于表1。表1中,磨耗幅度越小,表示耐磨耗性越良好。
[表1]
Claims (8)
1.一种冷冻机油,其含有:
基础油、以及
羧酸与多元醇的偏酯,
所述羧酸包含不饱和羧酸。
2.根据权利要求1所述的冷冻机油,其中,所述不饱和羧酸的碳数为12以上。
3.根据权利要求1或2所述的冷冻机油,其中,所述多元醇包含季戊四醇。
4.根据权利要求3所述的冷冻机油,其中,所述偏酯包含季戊四醇的单酯、季戊四醇的二酯以及季戊四醇的三酯。
5.根据权利要求1~4中任一项所述的冷冻机油,其中,所述羧酸进一步包含饱和羧酸。
6.根据权利要求5所述的冷冻机油,其中,所述饱和羧酸的碳数为12以上。
7.一种冷冻机用工作流体组合物,其含有:
权利要求1~6中任一项所述的冷冻机油、以及
制冷剂。
8.根据权利要求7所述的冷冻机用工作流体组合物,其中,所述制冷剂包含不饱和氟化烃。
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JPS5440260A (en) * | 1977-09-06 | 1979-03-29 | Ajinomoto Co Inc | Lubricating composition for plastic work upon aluminum and its alloy |
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JP4316042B2 (ja) * | 1999-03-05 | 2009-08-19 | 出光興産株式会社 | 冷凍機油組成物 |
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JP5464512B2 (ja) * | 2009-05-18 | 2014-04-09 | 日本サン石油株式会社 | カーエアコン用作動流体 |
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JP7408344B2 (ja) * | 2019-10-23 | 2024-01-05 | シェルルブリカンツジャパン株式会社 | 潤滑油組成物 |
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WO1991009097A1 (en) * | 1989-12-14 | 1991-06-27 | Idemitsu Kosan Co., Ltd. | Refrigerator oil composition for hydrofluorocarbon refrigerant |
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