CN101341235B - 冷冻机油组合物、使用其的冷冻机用压缩机和冷冻装置 - Google Patents

冷冻机油组合物、使用其的冷冻机用压缩机和冷冻装置 Download PDF

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CN101341235B
CN101341235B CN2006800482597A CN200680048259A CN101341235B CN 101341235 B CN101341235 B CN 101341235B CN 2006800482597 A CN2006800482597 A CN 2006800482597A CN 200680048259 A CN200680048259 A CN 200680048259A CN 101341235 B CN101341235 B CN 101341235B
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machine oil
oil
compressor
refrigerated machine
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CN101341235A (zh
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金子正人
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Abstract

本发明提供可以满足油泥分散性和防止冷冻机用压缩机的含有铝和/或铁的滑动部的磨损、烧结两方面的冷冻机用组合物，使用该冷冻机用组合物的压缩机和冷冻装置。为以在选自矿物油和合成油中的至少1种基油中，以冷冻机油组合物总量为基准，含有0.01～5质量％的分子内具有2个以上酰胺基的聚酰胺化合物的至少1种为特征的冷冻机油组合物、使用该冷冻机油组合物的压缩机和冷冻装置。

Description

冷冻机油组合物、使用其的冷冻机用压缩机和冷冻装置
技术领域
本发明涉及冷冻机油组合物、使用该冷冻机油组合物的冷冻机用压缩机和冷冻装置，更具体地说，涉及在基油中添加了特定化合物的冷冻机油组合物，使用该冷冻机油组合物的、在包含铝和/或铁的滑动部上涂布了有机涂膜或无机涂膜作为滑动材料的冷冻机用压缩机以及冷冻装置。
背景技术
冷冻机用压缩机的各滑动部的润滑性通过与制冷剂具有相容性的冷冻机油确保，但是包含铝和/或铁的滑动部的磨损、烧结的问题依然存在。进一步地，由于油泥分散性低，存在堵塞毛细管的问题。
对此，专利文献1中，提出了使用在含有特定的聚醚类的基油中含有硫代磷酸烷基酯类、硫代磷酸芳基酯类等硫代磷酸酯类的冷冻机油组合物。
此外，专利文献2中，提出了在矿物油和/或合成油中以0.05～5重量％的比率含有硫醇的滑动部件用润滑油组合物。
但是，不能满足油泥分散性和防止滑动部的磨损、烧结性能两方面。
因此，要求通过进一步改善冷冻机油，或通过改善冷冻机油和滑动材料两者，确立满足油泥分散性和防止滑动部的磨损、烧结性能两方面的冷冻机润滑系统。
专利文献1：日本特开2000-17282号公报
专利文献2：日本特开平5-117680号公报
发明内容
本发明是鉴于该状况而提出的，其目的在于，提供可以满足油泥分散性和防止冷冻机用压缩机的包含铝和/或铁的滑动部的磨损、烧结两方面的冷冻机用组合物，使用该冷冻机用组合物的压缩机和冷冻装置。
本发明人为了达成上述目的而进行了深入研究，结果发现通过使用特定组成的冷冻机油组合物，进一步通过将特定组成的冷冻机油组合物与在构成压缩机构部的部件的至少1部分滑动部上涂布的特定滑动材料组合，可以解决上述问题。本发明是基于上述发现完成的。
即，本发明提供：
1.冷冻机油组合物，其特征在于，在选自矿物油和合成油中的至少1种基油中，以冷冻机油组合物总量为基准，含有分子内具有2个以上酰胺基的聚酰胺化合物的至少1种0.01～5质量％。
2.如上述1所述的冷冻机油组合物，其中，基油为选自环烷系矿物油、石蜡系矿物油、烷基苯、烷基萘、聚-α-烯烃、聚亚烷基二醇、聚氧化烯单醚、聚氧化烯二醚、聚乙烯基醚、聚乙烯基醚-聚亚烷基二醇共聚物、多元醇酯、聚碳酸酯中的1种以上。
3.如上述1或2所述的冷冻机油组合物，其中，基油在40℃的运动粘度为2～500mm2/s。
4.如上述1～3中任一项所述的冷冻机油组合物，其中，聚酰胺化合物为选自饱和脂肪酸双酰胺、不饱和脂肪酸双酰胺和芳族双酰胺中的1种以上。
5.如上述1～4中任一项所述的冷冻机油组合物，其还含有磷酸酯类。
6.如上述1～5中任一项所述的冷冻机油组合物，其还含有选自抗氧化剂和酸捕捉剂中的至少1种。
7.冷冻机用压缩机，其为使用在选自矿物油和合成油中的至少1种基油中，以冷冻机油组合物总量为基准，含有分子内具有2个以上酰胺基的聚酰胺化合物的至少1种0.01～5质量％的冷冻机油组合物的压缩机，其特征在于，在构成压缩机构部的部件的含有铝和/或铁的滑动部上涂布以含有氮原子、氧原子和/或硫原子的树脂为粘合剂，含有选自二硫化钼、含氟树脂、石墨和炭黑中的至少1种的润滑皮膜形成用组合物。
8.如上述7所述的冷冻机用压缩机，其中，压缩机压缩选自二氧化碳、氢氟烃、烃和氨中的制冷剂。
9.如上述7或8所述的冷冻机用压缩机，其中，压缩机的压缩机构为选自涡旋、旋转、摆动和活塞式中的至少1种。以及
10.冷冻装置，其为使选自二氧化碳、氢氟烃、烃和氨中的制冷剂在含有压缩机、散热器、膨胀机构和蒸发器的冷冻回路上循环的冷冻装置，其特征在于，压缩机所使用的冷冻机油组合物使用在选自矿物油和合成油中的在40℃的运动粘度为2～500mm2/s的基油中，以组合物总量为基准，含有0.01～5质量％的分子内具有2个以上酰胺基的聚酰胺化合物的至少1种的冷冻机油组合物，并且为在含有铝和/或铁的滑动部上涂布润滑皮膜形成用组合物的压缩机，所述润皮膜形成用组合物含有作为粘合剂的含有选自聚酰胺、聚酰胺酰亚胺、聚酰亚胺、聚苯并唑、聚苯硫醚和聚缩醛中的至少1种的树脂和选自二硫化钼、含氟树脂、石墨和炭黑中的至少1种。
根据本发明的冷冻机油组合物，可以满足油泥分散性和防止冷冻机用压缩机的含有铝和/铁的滑动部的磨损、烧结两方面。
具体实施方式
本发明的冷冻机油组合物中，作为基油，使用选自矿物油和合成油中的至少1种。作为矿物油，可以举出环烷系矿物油、石蜡系矿物油。另一方面，作为合成油，可以举出烷基苯、烷基萘、聚-α-烯烃、聚亚烷基二醇、聚氧化烯单醚、聚氧化烯二醚、聚乙烯基醚、聚乙烯基醚-聚亚烷基二醇共聚物、多元醇酯、聚碳酸酯等。
这些矿物油和合成油中，优选聚乙烯基醚、聚亚烷基二醇、聚氧化烯单醚、聚氧化烯二醚、聚乙烯基醚-聚亚烷基二醇共聚物、多元醇酯和聚碳酸酯。
本发明的冷冻机油组合物中使用的基油在40℃的运动粘度优选为2～500mm2/s，进一步优选为3～300mm2/s。若为2mm2/s以上，则润滑性优异，若为500mm2/s以下，则粘性阻力小，节省能量性优异，同时油回火(油戾りも)也优异。
作为配合在本发明的冷冻机油组合物中的分子内具有2个以上酰胺基的聚酰胺化合物，优选饱和脂肪酸双酰胺、不饱和脂肪酸双酰胺和/或芳族双酰胺。
以冷冻机油组合物总量为基准，本发明的冷冻机油组合物含有这些聚酰胺化合物的1种以上0.01～5质量％，优选含有0.1～4质量％，特别优选含有0.2～2质量％。这是由于小于0.01质量％时，润滑性、油泥分散性差，若超过5质量％则稳定性差。
作为饱和脂肪酸双酰胺，优选举出：亚甲基双月桂酸酰胺、亚甲基双硬脂酸酰胺、亚甲基双羟基硬脂酸酰胺、亚乙基双辛酸酰胺、亚乙基双癸酸酰胺、亚乙基双月桂酸酰胺、亚乙基双硬脂酸酰胺、亚乙基双异硬脂酸酰胺、亚乙基双羟基硬脂酸酰胺、亚乙基双山萮酸酰胺、六亚甲基双硬脂酸酰胺、六亚甲基双山萮酸酸酰胺、六亚甲基双羟基硬脂酸酰胺、亚丁基双羟基硬脂酸酰胺、N，N’-二硬脂基己二酸酰胺、N，N’-二硬脂基癸二酸酰胺、辛酸与二亚乙基三胺(摩尔比3/1)的缩合物、月桂酸与三亚乙基四胺(摩尔比4/1)的缩合物、丙酸与十三亚乙基十四胺(摩尔比11/1)的缩合物以及异硬脂酸与四亚乙基五胺(摩尔比3/1)的缩合物。
此外，作为不饱和脂肪酸二酰胺，优选举出亚甲基双油酸酰胺、亚乙基双油酸酰胺、亚乙基双芥酸酰胺、六亚甲基双油酸酰胺、N，N’-二油基己二酸酰胺、N，N’-二油基癸二酸酰胺以及油酸与三亚乙基四胺(摩尔比3/1)的缩合物。
进一步地，作为芳族双酰胺，优选举出间亚二甲苯基双硬脂酸酰胺和N，N’-二硬脂基异酞酸酰胺。
本发明的冷冻机油组合物，根据需要可以配合公知的各种添加剂。本发明的冷冻机油组合物中，优选含有磷酸酯类作为极压剂。其中，磷酸酯类包含磷酸酯、酸式磷酸酯(酸性リン酸エステル)、亚磷酸酯、酸式亚磷酸酯(酸性亜リン酸エステル)以及它们的胺盐。
作为磷酸酯，有三芳基磷酸酯、三烷基磷酸酯、三烷基芳基磷酸酯、三芳基烷基磷酸酯、三烯基磷酸酯等，具体地说，可以举出例如三苯基磷酸酯、三甲苯基磷酸酯、苄基二苯基磷酸酯、乙基二苯基磷酸酯、三丁基磷酸酯、乙基二丁基磷酸酯、甲苯基二苯基磷酸酯、二甲苯基苯基磷酸酯、乙基苯基二苯基磷酸酯、二乙基苯基苯基磷酸酯、丙基苯基二苯基磷酸酯、二丙基苯基苯基磷酸酯、三乙基苯基磷酸酯、三丙基苯基磷酸酯、丁基苯基二苯基磷酸酯、二丁基苯基苯基磷酸酯、三丁基苯基磷酸酯、三己基磷酸酯、三(2-乙基己基)磷酸酯、三癸基磷酸酯、三月桂基磷酸酯、三肉豆蔻基磷酸酯、三棕榈基磷酸酯、三硬脂基磷酸酯、三油基磷酸酯等。
作为酸式磷酸酯，具体地说，可以举出例如2-乙基己基酸式磷酸酯、乙基酸式磷酸酯、丁基酸式磷酸酯、油基酸式磷酸酯、二十四烷基酸式磷酸酯、异癸基酸式磷酸酯、月桂基酸式磷酸酯、十三癸基酸式磷酸酯、硬脂基酸式磷酸酯、异硬脂基酸式磷酸酯等。
作为亚磷酸酯，具体地说，可以举出例如三乙基亚磷酸酯、三丁基亚磷酸酯、三苯基亚磷酸酯、三甲苯基亚磷酸酯、三(壬基苯基)亚磷酸酯、三(2-乙基己基)亚磷酸酯、三癸基亚磷酸酯、三月桂基亚磷酸酯、三异辛基亚磷酸酯、二苯基异癸基亚磷酸酯、三硬脂基亚磷酸酯、三油基亚磷酸酯等。
作为酸式亚磷酸酯，具体地说，可以举出例如二丁基氢亚磷酸酯、二月桂基氢亚磷酸酯、二油基氢亚磷酸酯、二硬脂基氢亚磷酸酯、二苯基氢亚磷酸酯等。以上的磷酸酯类中，优选油基酸式磷酸酯、硬脂基酸式磷酸酯。
上述磷酸酯、酸式磷酸酯、亚磷酸酯或酸式亚磷酸酯胺盐中使用的胺如下所示。
作为单取代胺的例子，可以举出丁基胺、戊基胺、己基胺、环己基胺、辛基胺、月桂基胺、硬脂基胺、油基胺、苄基胺等。作为二取代胺的例子，可以举出二丁基胺、二戊基胺、二己基胺、二环己基胺、二辛基胺、二月桂基胺、二硬脂基胺、二油基胺、二苄基胺、硬脂基-单乙醇胺、癸基-单乙醇胺、己基-单丙醇胺、苄基-单乙醇胺、苯基-单乙醇胺、甲苯基-单丙醇胺等。此外，作为三取代胺的例子，可以举出三丁基胺、三戊基胺、三己基胺、三环己基胺、三辛基胺、三月桂基胺、三硬脂基胺、三油基胺、三苄基胺、二油基-单乙醇胺、二月桂基-单丙醇胺、二辛基-单乙醇胺、二己基-单丙醇胺、二丁基-单丙醇胺、油基-二乙醇胺、硬脂基-二丙醇胺、月桂基-二乙醇胺、辛基-二丙醇胺、丁基-二乙醇胺、苄基-二乙醇胺、苯基-二乙醇胺、甲苯基-二丙醇胺、二甲苯基-二乙醇胺、三乙醇胺、三丙醇胺等。
此外，本发明的冷冻机油组合物优选含有抗氧化剂、酸捕捉剂。
作为抗氧化剂，可以举出酚类、胺类抗氧化剂。具体地说，优选配合2，6-二叔丁基-4-甲基苯酚(DBPC)、2，6-二叔丁基-4-乙基苯酚、2，2’-亚甲基双(4-甲基-6-叔丁基苯酚)、2，4-二甲基-6-叔丁基苯酚、2，6-二叔丁基苯酚等酚类，N，N’-二异丙基-对苯二胺、N，N’-二仲丁基-对苯二胺、苯基-α-萘基胺、N，N’-二苯基-对苯二胺等胺类抗氧化剂。从效果和经济性等方面考虑，在组合物中通常以冷冻机油组合物总量为基准配合0.01～5质量％抗氧化剂、优选配合0.05～3质量％抗氧化剂。
作为酸捕捉剂，可以举出例如，苯基缩水甘油基醚、烷基缩水甘油基醚、亚烷基二醇缩水甘油基醚、环己烯化氧、α-烯烃氧化物、环氧化大豆油等环氧化合物。其中，从相容性方面考虑，优选苯基缩水甘油基醚、烷基缩水甘油基醚、亚烷基二醇缩水甘油基醚、环己烯化氧、α-烯烃氧化物。
该烷基缩水甘油基醚的烷基和亚烷基二醇缩水甘油基醚的亚烷基可以具有支链，碳原子数通常为3～30，优选为4～24，特别优选为6～16。此外，α-烯烃氧化物使用总碳原子数一般为4～50、优选4～24、特别优选6～16的α-烯烃氧化物。本发明中，上述酸捕捉剂可以使用1种，或者也可以将2种以上组合使用。此外，其配合量，从效果和抑制污泥产生方面考虑，相对于组合物，通常以冷冻机油组合物总量为基准，为0.005～5质量％，特别优选为0.05～3质量％。
此外，在本发明的冷冻机油组合物中，可以含有以往润滑油中使用的公知的添加剂，例如可以含有上述以外的极压剂。作为该极压剂，可以举出例如单硫化物类、多硫化物类、亚砜类、砜类、硫代亚磺酸酯类、硫化油脂、硫代碳酸酯类、噻吩类、噻唑类、甲磺酸酯类等有机硫化合物类的极压剂，硫代磷酸三酯类等硫代磷酸酯类的极压剂，高级脂肪酸、羟基芳基脂肪酸类、多元醇酯类、丙烯酸酯类等酯类的极压剂，氯代烃类、氯代羧酸衍生物等有机氯类的极压剂，氟代脂肪族羧酸类、氟乙烯树脂、氟代烷基聚硅氧烷类、氟化石墨等有机氟类的极压剂，高级醇等醇类的极压剂，环烷酸盐类(环烷酸铅等)、脂肪酸盐类(脂肪酸铅等)、硫代磷酸盐类(二烷基二硫代磷酸锌等)、硫代氨基甲酸盐类、有机钼化合物、有机锡化合物、有机锗化合物、硼酸酯等金属化合物类的极压剂等。
此外，可以适当配合苯并三唑或其衍生物等铜钝化剂等。此外，可以根据需要添加耐负荷添加剂、氯捕捉剂、清洁分散剂、粘度指数提高剂、油性剂、防锈剂、防腐蚀剂、倾点下降剂、消泡剂等。这些添加剂的含量，通常以冷冻机油组合物总量为基准，为0.1～10质量％、优选为0.5～10质量％。
本发明的特征在于，在构成冷冻机用压缩机的压缩机构部的部件的至少1部分的含有铝和/或铁的滑动部上，涂布滑动材料。作为该滑动材料，优选使用有机涂膜或无机涂膜。
上述有机涂膜进一步优选含有以热变形温度为100℃以上的树脂为粘合剂、含有固体润滑剂的润滑皮膜形成用组合物。
其中，热变形温度(HDT：Heat Distortion Temperature)指的是在施加一定负荷的状态下，以一定速度升温时塑料变形的温度。本发明中，以通过热变形温度试验ASTM D648(1.8MPa)得到的温度表示。
此外，作为无机涂膜，优选使用石墨、类金刚石碳(DLC)、碳化钛(TiC)、氮化硼(BN)等无机材料膜和/或金属镀敷膜。作为金属镀敷膜，优选为选自镀镍、镀敷、镀锡、镀铬、カニフロン镀敷、卡宁吉恩镀镍、镀铁类合金、镀铝类合金和镀铜类合金中的至少1种。
作为这些无机材料膜和金属镀敷膜的制法，优选真空蒸镀法。作为真空蒸镀法，可以举出等离子体CVD方式等化学蒸镀(CVD)法、离子镀方式或溅射方式等物理蒸镀(PVD)法。此外，作为金属镀敷膜的制法，可以使用电解镀敷或无电解镀敷。
本发明中，若使用上述润滑皮膜形成用组合物作为滑动材料，则通过与上述聚酰胺化合物的相互作用，冷冻机用压缩机起动时和运转时含有铝和/或铁的滑动部的润滑性大幅提高，所以特别优选。
作为上述润滑皮膜形成用组合物中使用的粘合剂，优选热变形温度为100℃以上的树脂，更优选热变形温度为150℃以上，进一步优选为200℃以上，特别优选为250℃以上。
具体地说，优选含有氮原子、氧原子和/或硫原子的树脂，可以举出环氧树脂、酚醛树脂、含氟树脂、不饱和聚酯、聚缩醛、聚酰亚胺、聚酰胺酰亚胺、聚酰胺、聚碳酸酯、聚砜、聚苯硫醚、聚苯并唑等，但是特别是聚酰胺、聚酰亚胺、聚酰胺酰亚胺、聚苯并唑、聚苯硫醚和聚缩醛从热稳定性优异方面考虑优选。
作为聚酰胺，可以举出芳族聚酰胺、聚醚酰胺和它们的改性体等，作为聚酰亚胺，可以举出芳族聚酰亚胺、聚醚酰亚胺以及它们的改性体等，作为聚酰胺酰亚胺，可以举出芳族聚酰胺酰亚胺以及它们的改性体等。此外，作为聚苯并唑，优选为聚苯并咪唑等。这些树脂可以单独使用1种，或将2种以上混合使用。
本发明中优选上述粘合剂包含于润滑被膜形成用组合物中，涂布在构成压缩机构部的部件的至少一部分的含有铝和/或铁的滑动部上。该润滑被膜形成用组合物中的粘合剂的含量，以该组合物总量为基准优选为20～100质量％。若为20质量以上％则可以将后述固体润滑剂牢固地保持在润滑被膜中，得到充分的润滑性。要说明的是，在配合固体润滑剂时，进一步优选润滑被膜形成用组合物中的粘合剂的含量为20～80质量％。
接着，作为固体润滑剂，若为以固体状态表现出润滑性的物质则不特别限定，具体地说，可以举出石墨、炭黑、二硫化钼、硫化钨、含氟聚合物(特别是含氟树脂)、氮化硼、石墨等，其中，优选二硫化钼、含氟树脂、石墨和炭黑。这些固体润滑剂可以单独使用1种，或将2种以上混合使用。
对固体润滑剂在润滑被膜中的平均粒径不特别限定，但是1～100μm从形成致密的润滑皮膜方面考虑优选。
相对于上述粘合剂树脂100质量份，固体润滑剂的含量优选为20～80质量份。若为20质量份以上则得到充分的润滑性，若为80质量份以下则不会由于粘合剂的含量减少而导致润滑被膜中的固体润滑剂的保持性降低，不产生固体润滑剂的磨损或剥离。进一步优选固体润滑剂的含量相对于粘合剂树脂100质量份为30～70质量份。
此外，在润滑被膜形成用组合物中优选添加皮膜形成辅助剂。作为皮膜形成辅助剂，优选为具有环氧基的化合物、硅烷偶联剂等，可以提高固体润滑剂的保持性。
皮膜形成辅助剂相对于上述粘合剂树脂的含量，以粘合剂树脂和皮膜形成辅助剂的质量比计，优选为99∶1～70∶30。
在润滑被膜形成用组合物中，根据需要可以配合公知的各种添加剂。例如，可以适当配合三甲苯基磷酸酯(TCP)等磷酸酯、三(壬基苯基)亚磷酸酯等亚磷酸酯等极压剂，酚类、胺类抗氧化剂，苯基缩水甘油基醚、环己烯化氧、环氧化大豆油等稳定剂，苯并三唑或其衍生物等铜钝化剂等。此外，可以根据需要添加耐负荷添加剂、氯捕捉剂、清洁分散剂、粘度指数提高剂、油性剂、防锈剂、防腐蚀剂、流动点下降剂等。这些添加剂的含量，通常以润滑被膜形成用组合物总量为基准，为0.1～10质量％、优选为0.5～10质量％。
对于润滑被膜的膜厚，在发挥本发明效果的范围内不特别限定，但是优选为2～50μm。若为2μm以上则充分的润滑性得到确保，若为50μm以下则耐疲劳性得到维持。由以上观点，润滑被膜的膜厚进一步优选为4～25μm。
上述润滑被膜形成用组合物涂布在构成压缩机构部的至少一部分部件的含有铝和/或铁的滑动部上，对涂布方法不特别限定，可以举出例如下述方法：在有机溶剂中溶解上述粘合剂，分散固体润滑剂，制得润滑被膜形成用组合物后，将该组合物直接涂布在含有铝和/或铁的滑动部上的方法；在该组合物中浸渍含有铝和/或铁的滑动部的方法等。在含有铝和/或铁的滑动部上涂布等的组合物通过干燥等方法除去溶剂，形成润滑皮膜。
本发明的冷冻机油可以用于各种制冷剂。可以合适地用于二氧化碳制冷剂、烃类制冷剂、氨类制冷剂、氢氟烃类制冷剂等中。这些制冷剂中，特别优选用于二氧化碳制冷剂中。
接着，本发明中，冷冻机用压缩机优选为使用上述冷冻机油组合物的压缩机，在构成压缩机构部的部件的含有铝和/或铁的滑动部上，涂布以含有氮原子、氧原子和/或硫原子的树脂为粘合剂，含有选自二硫化钼、含氟树脂、石墨和炭黑中的至少1种的润滑皮膜形成用组合物。其中，构成压缩机构部的部件，例如对于往复式活塞式压缩机，指的是活塞、气缸等，在这些部件的含有铝和/或铁的滑动部上涂布上述润滑皮膜形成用组合物，使用上述冷冻机油组合物，由此确保这些含有铝和/或铁的滑动部的润滑性。
此外，本发明包含使选自二氧化碳、氢氟烃、烃和氨中的制冷剂在含有上述压缩机、散热器、膨胀机构和蒸发器的冷冻回路上循环的冷冻装置。
而且，为了抑制水解、腐蚀而更优选该冷冻装置的系统内的水分含量为300ppm以下。此外，为了抑制氧化劣化而更优选残留空气为50ppm以下。
实施例
接着通过实施例对本发明进行更具体的说明，但是本发明不被这些例子所限定。
冷冻机油组合物的评价通过下述方法进行。
(1)密闭环块磨损试验
在负荷100N、转速1000rpm、时间20分钟、温度50℃、制冷剂：二氧化碳、制冷剂压：1MPa、块/环＝A4032/モニクロ铸铁的条件下，对块磨损宽度(mm)进行评价。
(2)分散性试验
在各供试油中混合磺酸钡类防锈剂0.5质量％，保持在-5℃，比较有无析出。
实施例1～15和比较例1～3
通过表1所示的配合内容，制备18种冷冻机油组合物。根据上述方法评价，结果如表1所示。
A1：聚乙烯基醚(40℃运动粘度：68.1mm2/s)
A2：聚亚烷基二醇(40℃运动粘度：46.7mm2/s)
A3：聚乙烯基醚-聚亚烷基二醇共聚物(摩尔比1/1)(40℃运动粘度：75.2mm2/s)
A4：多元醇酯(40℃运动粘度：68.5mm2/s)
A5：聚碳酸酯(40℃运动粘度：67.9mm2/s)
A6：石蜡系矿物油(40℃运动粘度：101.0mm2/s)
B1：亚甲基双月桂酸酰胺(日本化成(株)制)
B2：亚甲基双硬脂酸酰胺(日本化成(株)制)
B3：亚甲基双辛酸酰胺(日本化成(株)制)
B4：亚乙基双月桂酸酰胺(日本化成(株)制)
B5：亚乙基双油酸酰胺(日本化成(株)制)
B6：辛酸与二亚乙基三胺(摩尔比3/1)的缩合物
B7：月桂酸与三亚乙基四胺(摩尔比4/1)的缩合物
B8：油酸与三亚乙基四胺(摩尔比3/1)的缩合物
B9：异硬脂酸与四亚乙基五胺(摩尔比3/1)的缩合物
B10：丙酸与十三亚乙基十四胺(摩尔比11/1)的缩合物
C1：三甲苯基磷酸酯(TCP)
C2：C14-α-烯烃氧化物
C3：2，6-二叔丁基-4-甲基苯酚(DBPC)
C4：硅类消泡剂
由表1可知，本发明的冷冻机油组合物，在冷冻机用压缩机的含有铝和/或铁的滑动部的磨损、烧结防止性能和油泥分散性两方面优异。
然后，在构成压缩机构部的部件的含有铝和/或铁的滑动部上，以厚度30μm涂布润滑皮膜形成用组合物，该润滑皮膜形成用组合物以聚酰胺酰亚胺为粘合剂，以聚酰胺酰亚胺/二硫化钼/聚四氟乙烯(PTFE)＝100/25/25(质量份)的比率使用二硫化钼和聚四氟乙烯(PTFE)作为固体润滑剂，涂布后进行加工以使膜厚为10～20μm、表面粗糙度Rz(10点平均粗糙度)为3.2μm以下，在如此得到的冷冻机用压缩机中分别使用实施例1～15的15种冷冻机油组合物进行运转，对冷冻机用压缩机起动时和运转时铝滑动部和铁滑动部的润滑性进行评价后可知，在所有滑动部中，实施例1～15的冷冻机油组合物优异。
产业实用性
本发明的冷冻机油组合物、使用该冷冻机油组合物的压缩机和冷冻装置用于开放型、半密闭型和密闭型冷冻机中，合适地用于车空调机、气体热泵、空调设备、冷藏装置、自动售货机、陈列柜等的冷冻系统、热水供给系统和地板供暖系统中。

Claims (9)

1.冷冻机油组合物，其特征在于，在选自矿物油和合成油中的至少1种基油中，以冷冻机油组合物总量为基准，含有分子内具有2个以上酰胺基的多酰胺化合物的至少1种0.01～5质量％，所述多酰胺化合物为选自饱和脂肪酸双酰胺、不饱和脂肪酸双酰胺和芳族双酰胺中的1种以上。
2.权利要求1所述的冷冻机油组合物，其中，基油为选自环烷系矿物油、石蜡系矿物油、烷基苯、烷基萘、聚-α-烯烃、聚亚烷基二醇、聚氧化烯单醚、聚氧化烯二醚、聚乙烯基醚、聚乙烯基醚-聚亚烷基二醇共聚物、多元醇酯、聚碳酸酯中的1种以上。
3.权利要求1或2所述的冷冻机油组合物，其中，基油在40℃的运动粘度为2～500mm2/s。
4.权利要求1或2所述的冷冻机油组合物，其还含有磷酸酯类。
5.权利要求1或2所述的冷冻机油组合物，其还含有选自抗氧化剂和酸捕捉剂中的至少1种。
6.润滑方法，其为使用在选自矿物油和合成油中的至少1种基油中，以冷冻机油组合物总量为基准，含有分子内具有2个以上酰胺基的多酰胺化合物的至少1种0.01～5质量％的冷冻机油组合物的冷冻机用压缩机中的润滑方法，所述多酰胺化合物为选自饱和脂肪酸双酰胺、不饱和脂肪酸双酰胺和芳族双酰胺中的1种以上，其特征在于，在构成压缩机构部的部件的含有铝和/或铁的滑动部上涂布以含有氮原子、氧原子和/或硫原子的树脂为粘合剂，含有选自二硫化钼、含氟树脂、石墨和炭黑中的至少1种的润滑皮膜形成用组合物。
7.权利要求6所述的润滑方法，其中，压缩机压缩选自二氧化碳、氢氟烃、烃和氨中的制冷剂。
8.权利要求6或7所述的润滑方法，其中，压缩机的压缩机构为选自涡旋、旋转、摆动和活塞式中的至少1种。
9.润滑方法，其为使选自二氧化碳、氢氟烃、烃和氨中的制冷剂在含有压缩机、散热器、膨胀机构和蒸发器的冷冻回路上循环的冷冻装置中的润滑方法，其特征在于，上述压缩机使用在选自矿物油和合成油中的在40℃的运动粘度为2～500mm2/s的基油中，以组合物总量为基准，含有0.01～5质量％的分子内具有2个以上酰胺基的多酰胺化合物的至少一种的冷冻机油组合物，所述多酰胺化合物选自饱和脂肪酸双酰胺、不饱和脂肪酸双酰胺和芳族双酰胺中的1种以上，并且为在含有铝和/或铁的滑动部上涂布润滑皮膜形成用组合物的压缩机，所述润滑皮膜形成用组合物含有作为粘合剂的含有选自聚酰胺、聚酰胺酰亚胺、聚酰亚胺、聚苯并唑、聚苯硫醚和聚缩醛中的至少1种的树脂和选自二硫化钼、含氟树脂、石墨和炭黑中的至少1种。
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KR20080079267A (ko) 2008-08-29
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US8043523B2 (en) 2011-10-25
JP4885533B2 (ja) 2012-02-29
TWI411675B (zh) 2013-10-11
TW200736381A (en) 2007-10-01
US20110252825A1 (en) 2011-10-20
CN101341235A (zh) 2009-01-07
WO2007072832A1 (ja) 2007-06-28
US20090090128A1 (en) 2009-04-09
US8465665B2 (en) 2013-06-18

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