CN104919029B - 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 PDF

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CN104919029B
CN104919029B CN201480004718.6A CN201480004718A CN104919029B CN 104919029 B CN104919029 B CN 104919029B CN 201480004718 A CN201480004718 A CN 201480004718A CN 104919029 B CN104919029 B CN 104919029B
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refrigerator oil
refrigerant
refrigerator
oil
acid
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CN104919029A (zh
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斋藤正典
新保纮子
阿出川邦子
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Eneos Corp
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JX Nippon Oil and Energy Corp
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/70—Soluble oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B31/00—Compressor arrangements
    • F25B31/002—Lubrication

Abstract

本发明提供冷冻机油，其含有基础油、硫醚化合物以及没食子酸酯，将冷冻机油总量作为基准，硫醚化合物的含量为0.01～2.0质量％、没食子酸酯的含量为10～500质量ppm、40℃下的运动粘度为3～500mm2/s。

Description

冷冻机油和冷冻机用工作流体组合物
技术领域
本发明涉及冷冻机中使用的冷冻机油和冷冻机用工作流体组合物。需要说明的是，在本发明中所说的“冷冻机”中包含汽车用空调、除湿器、冰箱、冷冻冷藏仓库、自动售货机、陈列橱、化工装置等中的冷却装置，住宅用空调、柜式空调、供应热水用的热泵等。
背景技术
现在，作为冰箱、车载空调、室内空调、工业用冷冻机等的制冷剂，广泛使用作为氟代烷烃(HFC)的1,1,1,2-四氟乙烷(R134a)、作为二氟甲烷(R32)与五氟乙烷(R125)的以质量比计为1/1的混合制冷剂的R410A等。但是，虽然这些HFC制冷剂的臭氧消耗潜能值(ODP)为零，但是全球变暖潜能值(GWP)高达1000以上，因此根据所谓的氟化气体条例(F-GasRegulation)被限制使用。
作为GWP高的制冷剂的代替物，由于其热力学的特性而研究了2,3,3,3-四氟丙烯(HFO-1234yf)、二氟甲烷(R32)单独作为候补的情况。对于这些制冷剂、与其它制冷剂的混合制冷剂而言，研究GWP与各种特性实现平衡的制冷剂。作为HFC制冷剂的代替物，必须为低GWP，HFO-1234yf的GWP低至4。R32的GWP虽然稍高至675，但是气体的压力高，为高效率制冷剂，因此作为有力候补被研究。
另外，已经在冰箱用途中实用化的异丁烷(R600a)、丙烷(R290)之类的烃制冷剂的GWP低至20以下、物性值是适宜的，因此虽为可燃性但也被研究，GWP为基准值1的二氧化碳(R744)也单独或作为为了不燃化而混合的制冷剂而被研究。
使用这些制冷剂的情况下润滑条件变严苛，因此对混合制冷剂与冷冻机油的工作流体要求以往以上的高耐磨耗性。
一般而言，作为使润滑油的润滑性提高的耐磨耗添加剂，已知醇、酯、长链脂肪酸等油性剂；磷酸酯、二硫代磷酸金属盐等耐磨耗剂；有机硫化合物、有机卤素化合物等极压剂。冷冻机油的情况下，若不是即使与制冷剂共存也不析出并且对稳定性没有坏影响的添加剂则不能使用，因此使用醇系、酯系的油性剂、磷酸酯之中的磷酸三苯酯、磷酸三甲苯酯。
另外，专利文献1中公开了并用添加有磷系添加剂和特定的环氧化合物的包含冷冻机用途的润滑油，专利文献2中公开了作为HFC制冷剂用途而并用添加磷酸三苯酯与三(烷基苯基)磷酸酯的压缩机用润滑油，专利文献3中公开了作为HFC制冷剂用途而添加有磷酸三甲苯酯与包含缩水甘油醚的环氧或碳二亚胺的冷冻机油。
但是，这些添加剂之中油性剂由于吸附而为润滑覆膜，因此混合润滑领域这样的负荷条件比较缓和的情况下，能够维持低摩擦系数，但负荷条件变严苛时，丧失耐磨耗的效果。另一方面，磷酸三苯酯、磷酸三甲苯酯有一定程度的耐磨耗效果，但是作为在润滑条件严苛的低GWP制冷剂共存下的耐磨耗性是不充分的。
由此，谋求具有更高耐磨耗性的冷冻机油，作为冷冻/空调系统内与制冷剂混合的工作流体，要求具有高耐磨耗性。
现有技术文献
专利文献
专利文献1：日本特开平5-171174号公报
专利文献2：日本特开平8-157847号公报
专利文献3：日本特开平9-189453号公报
发明内容
发明要解决的问题
本发明是鉴于上述课题而作出的，目的在于提供即使在制冷剂共存下的严苛润滑条件下，耐磨耗的效果也大、长期可靠性优异的冷冻机油和冷冻机用工作流体组合物。
用于解决问题的方案
本发明人等发现，向基础油混配了硫醚化合物和没食子酸酯的冷冻机油、进而包含制冷剂的冷冻机用工作流体，能够对其它特性无坏影响地大幅提高冷冻机油的耐磨耗性，从而完成本发明。
即，本发明提供下述[1]～[9]所述的冷冻机油和冷冻机用工作流体组合物。
[1]一种冷冻机油，其含有基础油、硫醚化合物、和没食子酸酯，将冷冻机油总量作为基准，前述硫醚化合物的含量为0.01～2.0质量％、前述没食子酸酯的含量为10～500质量ppm，所述冷冻机油的40℃下的运动粘度为3～500mm2/s。
[2]根据[1]所述的冷冻机油，其中，前述基础油为选自碳/氧摩尔比为2.5以上且5.8以下的酯和碳/氧摩尔比为2.5以上且5.8以下的醚中的至少一种，前述冷冻机油的40℃下的运动粘度为3～300mm2/s。
[3]根据[1]或[2]所述的冷冻机油，其中，前述基础油为选自由碳数4以上且9以下的脂肪酸与碳数4以上且12以下的多元醇合成的多元醇酯、聚亚烷基二醇、将聚亚烷基二醇的两末端的羟基进行了醚化的化合物和聚乙烯基醚中的至少一种。
[4]根据[1]～[3]中任一项所述的冷冻机油，其中，将冷冻机油总量作为基准，进一步含有0.05～3质量％正磷酸酯。
[5]根据[1]～[4]中任一项所述的冷冻机油，其中，前述硫醚化合物为硫代双酚化合物，前述没食子酸酯具有碳数1～18的烷基。
[6]根据[1]～[5]中任一项所述的冷冻机油，其中，将冷冻机油总量作为基准，进一步含有2～20质量％四(2-乙基己酸)季戊四醇酯。
[7]一种工作流体组合物，其包含全球变暖潜能值为700以下的制冷剂和[1]～[6]中任一项记载的冷冻机油。
[8]根据[7]所述的工作流体组合物，其中，前述制冷剂为含有选自氟代烷烃、氟代烯烃、二氧化碳以及碳数2～4的烃中的至少一种的制冷剂。
[9]根据[8]所述的工作流体组合物，其中，前述制冷剂为含有选自二氟甲烷和2,3,3,3-四氟丙烯中的至少一种的制冷剂。
发明的效果
本发明的冷冻机油和工作流体组合物即使在与制冷剂共存的严苛润滑条件下，耐磨耗的效果也大、发挥能够长期稳定地使用之类的特别的效果。
具体实施方式
本发明的实施方式所述的冷冻机油含有基础油，和将冷冻机油总量作为基准的0.01～2.0质量％硫醚化合物和10～500质量ppm没食子酸酯，40℃下的运动粘度为3～500mm2/s。
本实施方式中，基础油可以使用矿物油系基础油和合成油系基础油中的至少一种。将这些基础油混合两种以上使用也无妨。
作为矿物油系基础油，有石蜡系矿物油、环烷系矿物油、混合基系矿物油，均为将对原油进行常压蒸馏，进而进行减压蒸馏得到的润滑油馏分适宜地组合脱溶剂、溶剂萃取、加氢精制、加氢裂解、溶剂脱蜡、加氢脱蜡、白土处理等润滑油精制手段进行处理得到的精制润滑油馏分，可以适宜地使用。其中，控制组成的工序为溶剂萃取、加氢精制、加氢裂解，控制倾点等低温特性的工序为将蜡分去除的溶剂脱蜡、加氢脱蜡，白土处理主要是去除氮成分、提高基础油的稳定性的工序。可以单独地使用由各种原料与各种精制手段的组合而得到的性状不同的精制润滑油馏分，也可以组合使用2种以上。
另外，作为合成油系基础油，可列举出酯、醚之类的含氧化合物，聚-α-烯烃(PAO)、乙烯-α-烯烃低聚物、烷基苯、烷基萘之类的烃油。
作为基础油的含氧化合物之中，酯为各种分子结构的化合物，具有各自特有的粘度特性、低温特性，是具有与相同粘度的烃系基础油相比时闪点高的特征的基础油。对于酯，可以对醇与脂肪酸进行脱水缩合反应而得到，本实施方式中，在化学稳定性的方面，作为适宜的基础油成分可列举出二元酸与一元醇的二酯、多元醇(尤其是新戊基多元醇)与一元脂肪酸的多元醇酯、或多元醇与多元酸与一元醇(或一元脂肪酸)的复合酯。
作为该含氧化合物使用酯的情况下，从与极性大的低GWP的制冷剂(R32等)的相容性的观点出发，优选碳/氧摩尔比为2.5以上且5.8以下的酯。进而，更优选与作为低GWP的各种制冷剂的相容性更优异的、直链或支链的碳数4～9的脂肪酸与碳数4～12的多元醇合成的多元醇酯。
作为碳数4～9的直链脂肪酸，具体而言，可列举出丁酸、戊酸、己酸、庚酸、辛酸、壬酸。作为支链脂肪酸，具体而言，可列举出支链状的丁酸、支链状的戊酸、支链状的己酸、支链状的庚酸、支链状的辛酸、支链状的壬酸。进一步具体而言，优选在α位和/或β位具有支链的脂肪酸，优选2-甲基丙酸、异丁酸、2-甲基丁酸、2-甲基戊酸、2-甲基己酸、2-乙基戊酸、2-甲基庚酸、2-乙基己酸、3,5,5-三甲基己酸等，其中最优选2-甲基丙酸、2-乙基己酸和/或3,5,5-三甲基己酸。需要说明的是，也可以包含除碳数4～9的脂肪酸以外的脂肪酸。
作为多元醇，优选具有2～6个羟基的多元醇。另外，多元醇的碳数优选4～12。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)、季戊四醇、二(季戊四醇)等受阻醇。从与制冷剂的相容性和水解稳定性优异出发，最优选季戊四醇或者季戊四醇和二(季戊四醇)的混合酯。
作为基础油的含氧化合物之中，作为醚可列举出聚亚烷基二醇、对聚亚烷基二醇的一个末端或两末端进行了醚化的化合物、聚乙烯基醚等。作为聚亚烷基二醇，有聚丙二醇、聚乙二醇、环氧丙烷与环氧乙烷的共聚物等。通常为对单个末端的羟基进行醚化、将剩余末端以羟基原样残留的物质，但是对两末端进行了醚化的化合物为低吸湿性，是优选的，作为骨架，与高吸湿性的氧化乙烯相比，优选氧化丙烯类型。对末端进行醚化的情况下，从与制冷剂的相容性出发，作为烷基碳数优选1～4、碳数越少相容性越好。考虑相容性、稳定性、电绝缘性、低吸湿性等时，最优选对两末端进行了甲基醚化的聚丙二醇。
作为基础油优选的聚乙烯基醚，具有以下述通式(1)表示的结构单元。对于该聚乙烯基醚，可以是其结构单元相同的均聚物，也可以是以两种以上的结构单元构成的共聚物，但由于通过制为共聚物能够很好地调整特性平衡，因此优选。
[式(1)中，R1、R2以及R3任选相同或不同，分别表示氢原子或烃基，R4表示二价的烃基或二价的含有醚键氧的烃基，R5表示烃基，m表示0以上的整数，m的平均值优选为0～10的数，R1～R5在每个结构单元中任选相同或不同，一个结构单元中m为2以上的情况下，多个R4O任选相同或不同。]
针对这些醚，更优选为与低GWP制冷剂、尤其是含有R32的制冷剂的相容性优异的、碳/氧摩尔比为2.5以上且5.8以下的醚。
作为合成系基础油的烃油之中，广泛被使用的是PAO，其为α-烯烃的聚合物，因此根据其聚合度决定特性。冷冻机用润滑油的领域中使用烷基苯，根据烷基的结构有直链型和支链型，由于特性不同因而根据目的分开使用。
通常，对于这些矿物油系、合成油系的基础油，可以适宜组合、以适宜的比例进行混配以使其满足各种用途中被要求的各种性能。此时，矿物油系和合成油系的基础油各自使用多个也无妨。
作为本实施方式中的硫醚化合物，可以使用单硫醚化合物、二硫醚化合物、多硫醚化合物等中的任一种，优选单硫醚化合物。单硫醚化合物由于如下观点而优选：例如与二硫醚化合物相比活性低、冷冻机油的稳定性、抑制在冷冻机器内部大量使用的铜的变质。
作为硫醚化合物，可列举出二苯硫醚、二苄基硫醚、二癸硫醚、二(十二烷基)硫醚、硫代双酚化合物等，但在本发明的用途中，优选一般而言已知作为抗氧化剂、具有自由基捕捉能力、也作为稳定剂的硫代双酚化合物。作为硫代双酚化合物，优选使用以下通式(2)表示的化合物。
(式(2)中，R6和R7任选相同或不同，分别表示烃基，p、q、r以及s任选相同或不同，分别表示p+q、r+s的总计为0～5的0～5的整数。但是，q或s中的至少任一种为1以上。另外，t和u任选相同或不同，分别表示0～10的整数。)
通式(2)中，R6和R7任选相同或不同，分别表示烃基，p、q、r以及s任选相同或不同，分别表示p+q、r+s的总计为0～5的0～5的整数。但是，q或s中的至少任一种为1以上，最优选两者为1。另外，t和u任选相同或不同，分别表示0～10的整数。t和u优选0～4，更优选两者为0或1、最优选两者为0。作为烃基优选的是，碳数1～10、优选为1～6的烷基、环烷基、链烯基、苯基，具体而言，例如可列举出甲基、乙基、正丙基、异丙基、正丁基、仲丁基、叔丁基。
作为以通式(2)表示的化合物的优选例子，具体而言，可列举出4,4’-硫代双(3-甲基-6-叔丁基苯酚)、4,4’-硫代双(2,6-二叔丁基苯酚)、4,4’-硫代双(2-甲基-6-叔丁基苯酚)、2,2’-硫代双(4-甲基-6-叔丁基苯酚)、2,2’-硫代双(4,6-二叔丁基苯酚)、双(3,5-二叔丁基-4-羟基苄基)硫醚等。
将冷冻机油总量作为基准，硫醚化合物的含有比例为0.01～2质量％、优选为0.05～1质量％、更优选为0.1～0.5质量％。上述范围中，耐磨耗性提高效果高、且无由气氛引起腐蚀磨耗之虞，是优选的。
关于本实施方式中的没食子酸酯，没食子酸为在芳香环上键合3个羟基的芳香族羧酸，别名为3,4,5-三羟基苯甲酸。并且，没食子酸与醇反应得到的酯为没食子酸酯。作为没食子酸酯，有：没食子酸甲酯、没食子酸乙酯、没食子酸丙酯、没食子酸异戊酯、没食子酸辛酯、没食子酸十二酯等，还有作为食品用添加剂所使用的物质。作为本实施方式中的没食子酸酯，优选烷基的碳数为1～18的化合物，烷基的碳数超过18时，其耐磨耗的效果降低。更优选与碳数1～8的醇得到的酯，最优选没食子酸乙酯、没食子酸丙酯。
将冷冻机油总量作为基准，没食子酸酯的含有比例为10～500质量ppm、优选为10～100质量ppm。通过设为上述范围，稳定性高，并且在基础油中的溶解性不会降低而导致在低温下析出，可以得到充分的耐磨耗性增高效果。
本实施方式中，冷冻机油可以进一步含有正磷酸酯作为耐磨耗添加剂。
作为正磷酸酯优选的化合物，可列举出磷酸三苯酯(TPP)、磷酸三甲苯酯(TCP)、具有碳数3～4的烷基的烷基苯基磷酸酯(APP)等。TPP、TCP为单一结构的物质，APP的烷基苯基为1个(单型)、2个(二型)、3个(三型)的混合物，但其比值没有特别地限定。
将冷冻机油总量作为基准，正磷酸酯的含有比例优选为0.05～3质量％、更优选为0.1～2质量％、进一步优选为0.2～1.5质量％。通过设为上述范围，可以得到足够的耐磨耗性增高效果，且可以得到高稳定性。
本实施方式中，通过向冷冻机油中进一步混配四(2-乙基己酸)季戊四醇酯，工作流体的耐磨耗性大幅提高。四(2-乙基己酸)季戊四醇酯为由季戊四醇与2-乙基己酸合成的酯。期望它们为季戊四醇的全部的羟基被酯化的完全酯(也称为“全酯”)。作为这些酯的酸值优选为0.1mgKOH/g以下、作为羟基值优选为10mgKOH/g以下。将冷冻机油总量作为基准，上述酯的混配量为2～20质量％，根据基础油的类型、粘度，最适宜的混配量不同，优选为2～7质量％。其机理尚未明确，但是过多或过少时不发挥大幅地提高耐磨耗性的效果。
本实施方式中，在不损害本发明的目的的范围内，为了使性能进一步提高，在冷冻机油中可以含有以往的润滑油中所使用的抗氧化剂、摩擦调节剂、抗磨剂、极压剂、防锈剂、金属减活剂、消泡剂等添加剂。
作为抗氧化剂，可列举出二叔丁基对甲酚之类的酚系化合物、烷基二苯胺之类的胺系化合物等，作为摩擦调节剂，可列举出脂肪族胺、脂肪族酰胺、脂肪族酰亚胺、醇、酯等，作为抗磨剂，可列举出酸式磷酸酯胺盐、亚磷酸酯胺盐、二烷基二硫代磷酸锌等，作为极压剂，可列举出硫化烯烃、硫化油脂等，作为防锈剂，可列举出链烯基琥珀酸酯或部分酯等，作为金属减活剂，可列举出苯并三唑、噻二唑等，作为消泡剂，可列举出有机硅化合物、聚酯化合物等。
冷冻机油的40℃下的运动粘度为3～500mm2/s、优选为3～300mm2/s、更优选为5～150mm2/s。通过设为上述范围，能够提高充分的耐磨耗性、与制冷剂的相容性。
除冷冻机油的40℃下的运动粘度以外的性状没有特别地限定，粘度指数优选10以上。另外，倾点优选为-10℃以下、更优选为-20℃以下。另外，闪点优选为120℃以上、更优选为200℃以上。
另外，关于冷冻机油的酸值也没有特别地限定，但为了防止对冷冻机或配管中所使用的金属的腐蚀、抑制冷冻机油自身的劣化，可以优选设为0.1mgKOH/g以下、更优选设为0.05mgKOH/g以下。需要说明的是，本发明中的酸值是指根据JISK2501“石油制品和润滑油-中和试验方法”测定的酸值。
冷冻机油的水分含量没有特别限定，优选为200ppm以下、更优选为100ppm以下、最优选为50ppm以下。尤其是在密闭型的冷冻机中使用的情况下，从对冷冻机油的稳定性、电绝缘性的观点出发，需求水分含量少。
冷冻机器的情况下，从如前所述地防止全球变暖的观点出发，有意从全球变暖潜能值(GWP)高的现行的HFC制冷剂向低GWP的制冷剂过渡，需要在其中应用的冷冻机油。
如今，1,1,1,2-四氟乙烷(R134a)广泛用作冰箱和车载空调用途，作为二氟甲烷(R32)与五氟乙烷(R125)的质量比1/1的混合制冷剂的R410A广泛用作室内空调用途。作为这些制冷剂用冷冻机油的基础油，有适度相互溶解性(相容性)的酯、聚醚、尤其是多元醇酯、聚亚烷基二醇、聚乙烯基醚是适宜的。
在冷冻/空调设备的制冷剂循环周期中，润滑压缩机的冷冻机油与制冷剂一起在循环内进行循环，因此要求冷冻机油与制冷剂的相容性。冷冻机油与制冷剂不相容时，从压缩机排出的冷冻机油容易滞留在循环内，其结果，产生压缩机内的油量降低、润滑不良导致磨耗、闭塞毛细管等膨胀机构的问题。
但是，上述制冷剂的GWP均高达1000以上，因此估计其使用会因所谓的氟化气体条例而被限制。作为其代替物，研究了作为低GWP的不饱和烃的氟代烯烃(HFO)、二氟甲烷(R32)或异丁烷(R600a)、丙烷(R290)之类的烃制冷剂、二氧化碳(R744)、进而包含它们的混合制冷剂，其成为有力候补。
作为不饱和烃，有2,3,3,3-四氟丙烯(HFO-1234yf)、1,3,3,3-四氟丙烯(HFO-1234ze)、1,2,3,3,3-五氟丙烯(HFO-1225ye)等。这些HFO制冷剂在分子内具有易被分解的烯烃结构，因此存在GWP低、但稳定性低的特征。尤其是，由于在高负载的条件下基于金属/金属接触的滑动部的局部放热，从而磨耗并且促进制冷剂的分解而生成氢氟酸，因此有导致制冷剂与冷冻机油相容的工作流体的劣化之虞，并且关于润滑性应是腐蚀磨耗的原因，因此冷冻机油的润滑性是极其重要的特性。
另外，作为沸点低、高压的氟代烷烃(HFC)的R32或包含大量R32的混合制冷剂的情况下，压缩机的排出温度变高，因此冷冻机油的油膜变薄，成为严苛的润滑条件。另外，烃制冷剂的情况下，烃分子内没有有助于润滑性提高的氟、并且对冷冻机油的溶解度高，因此降低冷冻机油的粘度，成为严苛润滑条件。如此，低GWP的制冷剂候补从润滑性的观点出发均成为严苛条件，因此所使用的冷冻机油中需求高润滑性。
本实施方式中的制冷剂没有特别地限定，优选相容的制冷剂，即常温下不分为两层而相容的制冷剂。另外，从环境保护的方面出发，优选全球变暖潜能值(GWP)为700以下的物质，特别是，更优选含有选自氟代烷烃(HFC)、氟代烯烃(HFO)、二氧化碳(R744)、碳数2～4的烃中的1种以上物质，最优选含有二氟甲烷(R32)和/或2,3,3,3-四氟丙烯(HFO-1234yf)的制冷剂。
本实施方式所述的冷冻机用工作流体组合物中，冷冻机油/制冷剂的混配比例没有特别地限制，通常，相对于制冷剂100质量份为1～1000质量份、优选为2～800质量份.
实施例
以下，基于实施例和比较例对本发明进行更具体地说明，但本发明不限定于以下实施例。
[实施例1～12、比较例1～10]
实施例1～12和比较例1～10中，使用以下示出的基础油、添加剂，制备具有表1～3所示组成的冷冻机油。需要说明的是，表1～3所示的基础油和添加剂的含有比例均为将冷冻机油总量作为基准的含有比例。
[基础油]
(A-1)多元醇酯(POE-1)：季戊四醇与混合酸的酯(运动粘度68.1mm2/s@40℃、粘度指数84、倾点-40℃、闪点240℃)，所述混合酸中，2-甲基丙酸与3,5,5-三甲基己酸以质量比计为35:65
(A-2)多元醇酯(POE-2)：季戊四醇与混合酸的酯(运动粘度66.7mm2/s@40℃、粘度指数92、倾点-40℃、闪点248℃)，所述混合酸中2-乙基己酸与3,5,5-三甲基己酸以质量比计为50:50
(A-3)聚亚烷基二醇(PAG)：两末端以甲基封端的聚氧化丙烯(平均分子量1000、运动粘度46.0mm2/s@40℃、粘度指数190、倾点-45℃、闪点218℃)
(A-4)聚乙烯基醚(PVE)：乙基乙烯基醚与异丁基乙烯基醚的共聚物(乙基乙烯基醚:异丁基乙烯基醚以重量比计为7:1)、(平均分子量910、运动粘度66.4mm2/s@40℃、粘度指数85、倾点-35℃、闪点210℃)
(A-5)矿物油(MO)：石蜡系精制矿物油(运动粘度22.3mm2/s@40℃、粘度指数95、倾点-15℃、闪点200℃)
需要说明的是，运动粘度和粘度指数以JIS K2283、倾点以JIS K2269、闪点以JISK2265为基准进行测定。
[硫醚化合物]
(S-1)二苄基硫醚
(S-2)二(十二烷基)硫醚
(S-3)4,4’-硫代双(3-甲基-6-叔丁基苯酚)
[没食子酸酯]
(G-1)没食子酸丙酯(没食子酸正丙酯)
(G-2)没食子酸辛酯(没食子酸正辛酯)
[正磷酸酯]
(P-1)磷酸三甲苯酯(TCP)
[其它混配基材]
(D-1)四(2-乙基己酸)季戊四醇酯(季戊四醇与2-乙基己酸的酯、酸值0.01mgKOH/g、羟基值1.2mgKOH/g)
接着，将实施例1～12和比较例1～10的冷冻机油与表1～3所示的各种制冷剂组合，进行以下的润滑性试验和稳定性试验。需要说明的是，表1～3中的“1234yf”是指HFO-1234yf。
(润滑性试验)
润滑性试验以ASTM D3233-73为基准，使用法列克司(针/V型物)试验机，在一定负载下进行磨耗试验。
关于法列克司磨耗试验，在控制制冷剂吹入的气氛下(70ml/min)、初期温度50℃、转速290rpm、负载50Lbf下进行5分钟试运行，之后，以相同的转速在负载100Lbf下进行1小时主试验，测定试验后的针与V型物的磨耗量的总计值(mg)。
需要说明的是，作为吹入制冷剂使用R32、HFO-1234yf、R600a(异丁烷)。
(稳定性试验)
稳定性试验以JIS K2211-09(高压釜测试)为基准，称取90g将含水量调整至100ppm的试样油到高压釜中，将催化剂(铁、铜、铝的线均为外径1.6mm×长度50mm)与10g各个制冷剂(R32、HFO-1234yf、R600a)封入后，加热至175℃，测定100小时后的试样油的外观和酸值(JIS C2101)。
需要说明的是，稳定性试验前的试样油(新油)的酸值均为0.01mgKOH/g。
[表1]
[表2]
[表3]
关于稳定性，由表1～3可知，与HFO-1234yf组合时酸值存在一定的上升，但对实施例1～12为没有问题的水准；比较例中，混配较多没食子酸丙酯(G-1)的比较例6中发现了析出和酸值的上升。
关于润滑性，可知实施例1～12磨耗量均较小，耐磨耗性良好。尤其可知进一步混配了正磷酸酯(P-1)的实施例3、8、混配了混配基材(D-1)的实施例4的磨耗量小。
与此相对，比较例1、2的磨耗量颇大，另外，可知比较例3～10中，虽与比较例1、2相比其磨耗量减小，但是即使是添加剂混配量比实施例多的情况下，其耐磨耗的效果也远不及实施例。例如，实施例1、2与较例3、4相比时，可知由于硫醚化合物与少量的没食子酸酯的混配大幅地提高耐磨耗性。另外，比较例5的仅添加没食子酸酯时，没有那种程度的耐磨耗效果。比较例6中耐磨耗性虽然提高了一些，但是稳定性降低，存在出现腐蚀磨耗的可能性。
产业上的可利用性
本发明的冷冻/空调用的工作流体组合物是即使在严苛润滑条件下也能够维持耐磨耗效果的长期可靠性优异的工作流体，因此可以在具有压缩机、冷凝器、节流装置、蒸发器等且在它们之间使制冷剂循环的冷却效率高的冷冻/空调系统中，尤其是在具有旋转式、摆动式、滚动式等压缩机的系统中适宜地使用，可以在室内空调、柜式空调、冰箱、车载空调、工业用冷冻机等领域使用。

Claims (11)

1.一种冷冻机油，其含有基础油、硫醚化合物以及没食子酸酯，
将冷冻机油总量作为基准，所述硫醚化合物的含量为0.1～0.5质量％、所述没食子酸酯的含量为10～100质量ppm，
所述冷冻机油的40℃下的运动粘度为3～500mm2/s，
所述冷冻机油与仅由选自氢氟烃、二氧化碳以及碳数2～4的烃中的至少一种组成的制冷剂一同使用，
所述基础油为由碳数4以上且9以下的脂肪酸与碳数4以上且12以下的多元醇合成的多元醇酯，
所述硫醚化合物选自二苄基硫醚、二(十二烷基)硫醚和硫代双酚化合物中的至少一种，
所述没食子酸酯具有碳数1～18的烷基。
2.根据权利要求1所述的冷冻机油，其中，所述基础油的碳/氧摩尔比为2.5以上且5.8以下，所述冷冻机油的40℃下的运动粘度为3～300mm2/s。
3.根据权利要求1或2所述的冷冻机油，其中，将冷冻机油总量作为基准，进一步含有0.05～3质量％正磷酸酯。
4.根据权利要求1或2所述的冷冻机油，其中，所述硫醚化合物为硫代双酚化合物。
5.根据权利要求3所述的冷冻机油，其中，所述硫醚化合物为硫代双酚化合物。
6.根据权利要求1或2所述的冷冻机油，其中，将冷冻机油总量作为基准，进一步含有2～20质量％四(2-乙基己酸)季戊四醇酯。
7.根据权利要求3所述的冷冻机油，其中，将冷冻机油总量作为基准，进一步含有2～20质量％四(2-乙基己酸)季戊四醇酯。
8.根据权利要求4所述的冷冻机油，其中，将冷冻机油总量作为基准，进一步含有2～20质量％四(2-乙基己酸)季戊四醇酯。
9.根据权利要求5所述的冷冻机油，其中，将冷冻机油总量作为基准，进一步含有2～20质量％四(2-乙基己酸)季戊四醇酯。
10.一种冷冻机用工作流体组合物，其包含全球变暖潜能值为700以下的制冷剂和权利要求1～9中任一项所述的冷冻机油,所述制冷剂仅由选自氢氟烃、二氧化碳以及碳数2～4的烃中的至少一种组成。
11.根据权利要求10所述的冷冻机用工作流体组合物，其中，所述制冷剂为含有二氟甲烷的制冷剂。
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