TWI601811B - Refrigerant oil and freezer are used as dynamic fluid composition - Google Patents
Refrigerant oil and freezer are used as dynamic fluid composition Download PDFInfo
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
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- C09K5/02—Materials undergoing a change of physical state when used
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- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
- C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
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- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
- C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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Description
本發明係關於一種冷凍機用作動流體組合物。再者,本發明中所謂「冷凍機」包括:汽車用空氣調節機、除濕器、冰箱、冷凍冷藏倉庫、自動販賣機、展示櫃、化工廠等中之冷卻裝置、住宅用空氣調節機、箱型空氣調節機、供應熱水用熱泵等。
目前,作為冰箱、車載空氣調節機、室內空氣調節機、產業用冷凍機等之冷媒,廣泛使用作為氫氟碳化物(HFC)之1,1,1,2-四氟乙烷(R134a)、或二氟甲烷(R32)與五氟乙烷(R125)以質量比計為1/1之混合冷媒即R410A等。然而,該等HFC冷媒雖然臭氧破壞係數(ODP)為0,但全球暖化係數(GWP)高達1000以上,因此其等之使用受到旨在地球環境保護之所謂含氟氣體法規(F-Gas Regulation)之限制。
作為GWP較高之冷媒之代替品,單獨之2,3,3,3-四氟丙烯(HFO-1234yf)或二氟甲烷(R32)因其熱力學特性而作為候補被研究。該等冷媒或與其他冷媒之混合冷媒亦被研究是否為取得GWP與各種特性之平衡者。作為HFC冷媒之代替品,必須為低GWP,而HFO-1234yf之GWP低至4。R32之GWP稍高為675,但氣體之壓力較高,為高效冷媒,因此作為有力候補而被研究。
又,已於冰箱用途中實用化之異丁烷(R600a)或丙烷(R290)等烴冷媒由於GWP較低為20以下,物性值較佳,故而雖然具有可燃性但亦被研究,GWP為基準1之二氧化碳(R744)亦單獨被研究,或作為以不燃化
為目的進行混合之冷媒而被研究。
於使用該等冷媒之情形時,潤滑條件變嚴苛,因此對於冷媒與冷凍機油混合而成之作動流體要求先前以上之高耐磨耗性。
通常,作為提高潤滑油之潤滑性之耐磨耗添加劑,已知有:醇、酯、長鏈脂肪酸等油性劑,或磷酸酯、二硫代磷酸酯金屬鹽等耐磨耗劑,有機硫化合物、有機鹵素化合物等極壓添加劑。於冷凍機油之情形時,只要並非即便與冷媒共存亦不析出且不對穩定性造成不良影響之添加劑則無法使用,因此使用醇系、酯系之油性劑或磷酸酯中之磷酸三苯酯、磷酸三甲苯酯。
又,專利文獻1中提出一併添加磷系添加劑與特定之環氧化合物的包括冷凍機用途之潤滑油;專利文獻2中提出作為HFC冷媒用而一併添加磷酸三苯酯與磷酸三(烷基苯基)酯之壓縮機用潤滑油;專利文獻3中提出添加有作為HFC冷媒用之磷酸三甲苯酯與包含縮水甘油醚之環氧樹脂或碳二醯亞胺的冷凍機油。
然而,該等添加劑中,油性劑係藉由吸附而形成潤滑皮膜,因此於如混合潤滑區域之負荷條件相對適度之情形時,可將摩擦係數維持得較低,但若負荷條件變嚴苛,則失去耐磨耗之效果。另一方面,磷酸三苯酯或磷酸三甲苯酯雖然具有一定程度之耐磨耗效果,但於潤滑條件嚴苛之低GWP冷媒共存下的耐磨耗性不充分。
根據該等情況,業界謀求具有更高耐磨耗性之冷凍機油,對於冷凍/空氣調節機系統內要求作為與冷媒混合而成之作動流體而具有較高之耐磨耗性者。
專利文獻1:日本專利特開平5-171174號公報
專利文獻2:日本專利特開平8-157847號公報
專利文獻3:日本專利特開平9-189453號公報
本發明係鑒於上述課題而完成者,其目的在於提供一種即便於與低GWP冷媒之共存下之嚴苛潤滑條件下耐磨耗之效果亦較大,長期可靠性優異的冷凍機油及作動流體組合物。
本發明者等人發現,於基油中調配有硫醚化合物及正磷酸酯之冷凍機油、進而包含低GWP冷媒之冷凍/空氣調節機用之作動流體可在不對其他特性造成不良影響之情況下大幅度提高冷凍機油之耐磨耗性,從而完成本發明。
即,本發明提供下述[1]至[8]所記載之冷凍機用作動流體組合物。
[1]一種冷凍機油,其含有基油、硫醚化合物及正磷酸酯,以冷凍機油總量為基準,上述硫醚化合物之含量為0.01~2.0質量%,上述正磷酸酯之含量為0.1~5.0質量%,且該冷凍機油於40℃下之動黏度為3~500mm2/s。
[2]如[1]之冷凍機油,其中上述基油為選自碳/氧莫耳比為2.5以上且5.8以下之酯及碳/氧莫耳比為2.5以上且5.8以下之醚中之至少1種,且上述冷凍機油於40℃下之動黏度為3~300mm2/s。
[3]如[1]或[2]之冷凍機油,其中上述基油為選自以碳數4以上且9以下之脂肪酸與碳數4以上且12以下之多元醇合成之多元醇酯、聚伸烷基二醇、將聚伸烷基二醇之兩末端之羥基進行醚化而成之化合物及聚乙烯醚中之至少1種。
[4]如[1]至[3]中任一項之冷凍機油,其中上述硫醚化合物為硫代雙酚化合物,上述正磷酸酯為選自磷酸三苯酯、磷酸三甲苯酯及具有碳數3~4之烷基之烷基苯基磷酸酯中之至少1種。
[5]如[1]至[4]中任一項之冷凍機油,其中以冷凍機油總量為基準進而含有季戊四醇四(2-乙基己酸酯)2~20質量%。
[6]一種冷凍機用作動流體組合物,其包含全球暖化係數為700以下之冷媒、及如[1]至[5]中任一項之冷凍機油。
[7]如[6]之冷凍機用作動流體組合物,其中上述冷媒為含有選自氫氟碳化物、氫氟烯、二氧化碳及碳數2~4之烴中之至少1種的冷媒。
[8]如[6]或[7]之冷凍機用作動流體組合物,其中上述冷媒為含有選自二氟甲烷及2,3,3,3-四氟丙烯中之至少1種的冷媒。
本發明之冷凍機油及冷凍機用作動流體組合物發揮出即便於與低GWP冷媒共存之嚴苛潤滑條件下耐磨耗之效果亦較大,可長期穩定地使用的特殊效果。
本發明之實施形態之冷凍機油係含有基油、以及以冷凍機油總量為基準之硫醚化合物0.01~2.0質量%及正磷酸酯0.1~5.0質量%,且於40℃下之動黏度為3~500mm2/s者。
於本實施形態中,基油可使用選自礦物油系基油及合成油系基油中之至少1種。可將2種以上該等基油混合而使用。
作為礦物油系基油,有鏈烷系礦物油、環烷系礦物油、混合基系礦物油,但均為將溶劑脫瀝青、溶劑萃取、氫化精製、氫化分解、溶劑脫蠟、氫化脫蠟、白土處理等潤滑油精製手段適當組合而對將原油進行常壓蒸餾進而進行減壓蒸餾而獲得的潤滑油餾分進行處理所得的精製潤滑油餾分,可適宜地使用。其中,控制組成之步驟為溶劑萃取、氫化精製、氫化分解,控制流動點等低溫特性之步驟為去除蠟成分之
溶劑脫蠟、氫化脫蠟,白土處理為主要去除氮成分而提高基油之穩定性的步驟。可將藉由各種原料與各種精製手段之組合而獲得之性狀不同之精製潤滑油餾分單獨使用,亦可將2種以上組合使用。
又,作為合成油系基油,可列舉:酯、醚之類的含氧化合物或聚-α-烯烴(PAO)、乙烯-α-烯烴低聚物、烷基苯、烷基萘之類的烴油。
含氧化合物基油中,酯係如下特徵之基油:存在各種分子結構之化合物,且各自具有特有之黏度特性、低溫特性,與同一黏度之烴系基油相比引火點較高。酯可使醇與脂肪酸發生脫水縮合反應而獲得,但於本實施形態中,就化學穩定性方面而言,可列舉二元酸與一元醇之二酯、多元醇(尤其是新戊基多元醇)與一元脂肪酸之多元醇酯、或多元醇與多元酸與一元醇(或一元脂肪酸)之複合酯作為較佳之基油成分。
於使用酯作為含氧化合物基油之情形時,就與極性較大之低GWP冷媒(R32等)之相溶性方面而言,較佳為碳/氧莫耳比為2.5以上且5.8以下之酯。進而,更佳為與低GWP之各種冷媒之相溶性更優異之由直鏈或支鏈之碳數4~9之脂肪酸與碳數4~12之多元醇合成的多元醇酯。
作為碳數4~9之直鏈脂肪酸,具體而言,可列舉:丁酸、戊酸、己酸、庚酸、辛酸、壬酸。作為支鏈脂肪酸,具體而言,可列舉:支鏈狀之丁酸、支鏈狀之戊酸、支鏈狀之己酸、支鏈狀之庚酸、支鏈狀之辛酸、支鏈狀之壬酸。更具體而言,較佳為α位及/或β位具有支鏈之脂肪酸,較佳為異丁酸、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,其中最佳為2-乙基己酸及/或3,5,5-三甲基己酸。再者,亦可含有碳數4~9之脂肪酸以外之脂肪酸。
作為多元醇,較佳為具有2~6個羥基之多元醇。又,多元醇之碳數較佳為4~12。具體而言,較佳為新戊二醇、三羥甲基乙烷、三羥甲
基丙烷、三羥甲基丁烷、二(三羥甲基丙烷)、季戊四醇、二(季戊四醇)等受阻醇。季戊四醇或季戊四醇與二(季戊四醇)之混合酯由於與冷媒之相溶性及水解穩定性優異,故而最佳。
作為醚,可列舉:聚伸烷基二醇、將聚伸烷基二醇之一末端或兩末端進行醚化而成之化合物、聚乙烯醚等。作為聚伸烷基二醇,有聚丙二醇、聚乙二醇、環氧丙烷與環氧乙烷之共聚物等。關於末端結構,就吸濕性方面而言,較佳為至少一者為烷基,尤佳為甲基。又,就易製造性及成本方面而言,較佳為任一末端為烷基且另一末端為氫原子,尤佳為一末端為甲基且另一末端為氫原子。關於主骨架,就潤滑性方面而言,較佳為含有氧伸乙基(EO)與氧伸丙基(PO)之共聚物,氧伸乙基於氧伸乙基與氧伸丙基之總和中所占之比率(EO/(PO+EO))較佳為處於0.1~0.8之範圍,更佳為處於0.3~0.6之範圍。又,就吸濕性或熱/化學穩定性方面而言,EO/(PO+EO)之值較佳為處於0~0.5之範圍,更佳為處於0~0.2之範圍,最佳為0(即環氧丙烷均聚物)。
聚乙烯醚具有下述通式(1)所表示之結構單元。本實施形態中之聚乙烯醚可為該結構單元相同之均聚物,亦可為由2種以上結構單元構成之共聚物,但藉由選擇共聚物而可平衡性良好地調整特性,因此較佳。
[式中,R1、R2及R3可相同亦可不同,分別表示氫原子或烴基,R4表示二價烴基或二價含醚鍵氧烴基,R5表示烴基,m為0以上之整數,較佳為m之平均值為0~10之數,R1~R5於每一結構單元可相同亦可不
同,於一個結構單元中m為2以上之情形時,複數個R4O可相同亦可不同]
關於該等醚,更佳為與低GWP冷媒、尤其是含有R32之冷媒之相溶性優異之碳/氧莫耳比為2.5以上且5.8以下的醚。
烴油中,PAO被廣泛使用。PAO為α-烯烴之聚合物,因此可藉由其聚合度而調節特性。冷凍機用潤滑油之領域中使用烷基苯,根據烷基之結構而有直鏈型與支鏈型,由於特性不同,故而根據目的區別使用。
上述礦物油系基油及合成油可適當組合,以適當比率進行調配以滿足各用途所要求之各種性能。此時,礦物油系及合成油系之基油可分別使用複數種。
作為本實施形態之硫醚化合物,可使用單硫醚化合物、二硫醚化合物、聚硫醚化合物等中之任一者,但較佳為單硫醚化合物。單硫醚化合物與例如二硫醚化合物相比活性較低,於冷凍機油之穩定性、抑制冷凍機器內部大量使用之銅之變質等方面而言較佳。
作為硫醚化合物,可列舉:二苯基硫醚、二苄基硫醚、二癸基硫醚、二(十二烷基)硫醚、硫代雙酚化合物等,本發明之用途中,較佳為通常作為抗氧化劑而為人所知、具有自由基捕捉能力且亦為穩定劑的硫代雙酚化合物。作為硫代雙酚化合物,較佳為使用以下通式(2)所表示之化合物。
(式中,R6及R7可相同亦可不同,分別表示烴基,p、q、r及s可相同亦可不同,分別表示p+q、r+s之合計為0~5之0~5之整數。其中,q或s之至少任一者為1以上。又,t及u可相同亦可不同,分別表示0~10之整數)
通式(2)中,R6及R7可相同亦可不同,分別表示烴基,p、q、r及s可相同亦可不同,分別表示p+q、r+s之合計為0~5之0~5之整數。其中,q或s之至少一者為1以上,最佳為兩者為1。又,t及u可相同亦可不同,分別表示0~10之整數。t及u較佳為0~4,更佳為兩者為0或1,最佳為兩者為0。烴基之較佳者為碳數1~10、較佳為1~6之烷基、環烷基、烯基、苯基,具體而言,例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基。
作為通式(2)所表示之化合物之較佳例,具體而言,可列舉:4,4'-硫代雙(3-甲基-6-第三丁基苯酚)、4,4'-硫代雙(2,6-二第三丁基苯酚)、4,4'-硫代雙(2-甲基-6-第三丁基苯酚)、2,2'-硫代雙(4-甲基-6-第三丁基苯酚)、2,2'-硫代雙(4,6-二第三丁基苯酚)、雙(3,5-二第三丁基-4-羥基苄基)硫醚等。
硫醚化合物之含有比率以冷凍機油總量為基準而為0.01~2.0質量%,較佳為0.05~1.0質量%,更佳為0.1~0.5質量%。未達上述下限值時,耐磨耗性提高效果不充分,又,若超過上述上限值,則有根據氛圍反而引起腐蝕磨耗之虞。
作為本實施形態中之正磷酸酯,較佳為磷酸三苯酯(TPP)、磷酸三甲苯酯(TCP)、具有碳數3~4之烷基之烷基苯基磷酸酯(APP)。TPP、TCP為單一結構,而APP為烷基苯基為1個(單型)、2個(二型)、3個(三型)之混合物,其混合比並無特別限定。
正磷酸酯之含有比率以冷凍機油總量為基準而為0.1~5.0質量%,較佳為0.1~3.0質量%,更佳為0.2~2.0質量%。若未達上述下限值,
則耐磨耗性提高效果不充分,又,若超過上述上限值,則有穩定性降低之虞。
於本實施形態中,可藉由在冷凍機油中進而調配季戊四醇四(2-乙基己酸酯),而進一步提高作動流體之耐磨耗性。季戊四醇四(2-乙基己酸酯)係由季戊四醇與2-乙基己酸合成之酯。該等較佳為季戊四醇之所有羥基經酯化而成的完全酯(亦稱為「全酯」)。該等酯之酸值較佳為0.1mgKOH/g以下,羥值較佳為10mgKOH/g以下。上述酯之調配量以冷凍機油總量為基準而較佳為2~20質量%,最佳調配量根據基油之類型、黏度而異,更佳為2~7質量%。其機制尚不明確,但多於或少於上述範圍均不發揮大幅度提高耐磨耗性之效果。
於本實施形態中,為了進一步提高性能,可使冷凍機油於無損本發明之目的之範圍內含有先前便用於潤滑油之抗氧化劑、摩擦調整劑、磨耗防止劑、極壓添加劑、防銹劑、金屬鈍化劑、消泡劑等添加劑。
作為抗氧化劑,可列舉二第三丁基對甲酚之類的酚系化合物、烷基二苯基胺之類的胺系化合物等;作為摩擦調整劑,可列舉脂肪族胺、脂肪族醯胺、脂肪族醯亞胺、醇、酯等;作為磨耗防止劑,可列舉酸式磷酸酯胺鹽、亞磷酸酯胺鹽、二烷基二硫代磷酸鋅等;作為極壓添加劑,可列舉硫化烯烴、硫化油脂等;作為防銹劑,可列舉烯基琥珀酸酯或部分酯等;作為金屬鈍化劑,可列舉苯并三唑、噻二唑、沒食子酸酯等;作為消泡劑,可列舉聚矽氧化合物、聚酯化合物等。
冷凍機油於40℃下之動黏度為3~500mm2/s,較佳為3~300mm2/s,更佳為5~150mm2/s。藉由為上述範圍,可提高充分之耐磨耗性及與冷媒之相溶性。
冷凍機油於40℃下之動黏度以外之性狀並無特別限定,黏度指數較佳為10以上。又,流動點較佳為-10℃以下,更佳為-20℃以下。又,
引火點較佳為120℃以上,更佳為200℃以上。
又,關於冷凍機油之酸值,並無特別限定,為了防止對冷凍機或配管所使用之金屬之腐蝕、抑制冷凍機油本身之劣化,可設為較佳為0.1mgKOH/g以下,更佳為0.05mgKOH/g以下。再者,本發明中所謂酸值係指依據JIS K2501「石油製品及潤滑油-中和試驗方法」所測得之酸值。
冷凍機油之含水量並無特別限定,較佳為200ppm以下,更佳為100ppm以下,最佳為50ppm以下。尤其是用於密閉型冷凍機之情形時,就冷凍機油之穩定性或電絕緣性之觀點而言,謀求含水量較少。
於冷凍機之情形時,如前所述就防止全球暖化之觀點而言,存在自GWP較高之現有HFC冷媒向低GWP之冷媒過渡之動向,變得需要適應此情況之冷凍機油,而謀求冷媒與冷凍機油混合而成之適宜作動流體。
目前,1,1,1,2-四氟乙烷(R134a)被廣泛用於冰箱及車載空氣調節機用途,二氟甲烷(R32)與五氟乙烷(R125)之質量比1/1之混合冷媒即R410A被廣泛用於室內空氣調節機用途。作為該等冷媒用之冷凍機油之基油,適宜為具有適度相互溶解性(相溶性)之酯、聚醚、尤其是多元醇酯、聚伸烷基二醇、聚乙烯醚。
於冷凍/空氣調節機設備之冷媒循環體系中,潤滑壓縮機之冷凍機油與冷媒一起於體系內循環,因此要求冷凍機油與冷媒之相溶性。若冷凍機油與冷媒不相溶,則自壓縮機噴出之冷凍機油容易滯留於循環體系內,結果產生壓縮機內之油量降低而由潤滑不良導致磨耗、或堵塞毛細管等膨脹機構之問題。
然而,上述冷媒均為GWP高達1000以上,故而預料其等之使用受所謂含氟氣體法規限制。作為代替而研究作為低GWP之不飽和烴之氫氟烯(HFO)或二氟甲烷(R32)或異丁烷(R600a)或丙烷(R290)等烴冷
媒、二氧化碳(R744)、以及包含該等之混合冷媒,其等為有力候補。
作為不飽和烴,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。該等HFO冷媒係於分子內具有容易被分解之烯烴結構,因此特徵在於GWP較低且另一方面穩定性較低。尤其是,於高荷重之條件下由金屬/金屬接觸而引起滑動部之局部發熱,藉此促進磨耗以及冷媒之分解而生成氫氟酸,因此有引起冷媒與冷凍機油相溶而成之作動流體之劣化之虞,並且關於潤滑性,其可成為腐蝕磨耗之原因,因此冷凍機油之潤滑性為極其重要之特性。
又,於沸點較低之高壓氫氟碳化物(HFC)即R32或含有大量R32之混合冷媒之情形時,壓縮機之噴出溫度變高,因此冷凍機油之油膜變薄,造成嚴苛之潤滑條件。又,於烴冷媒之情形時,烴分子內並無有助於提高潤滑性之氟,且其於冷凍機油中之溶解度較高,因此降低冷凍機油之黏度,造成嚴苛之潤滑條件。如上所述般低GWP之冷媒候補係就潤滑性之觀點而言均造成嚴苛之條件,因此對所使用之冷凍機油要求較高之潤滑性。
關於本實施形態中之冷媒,只要GWP為700以下則此外並無特別限定,較佳為相溶之冷媒、即於常溫下不分離為二層而相溶之冷媒。尤其是,更佳為含有選自氫氟碳化物(HFC)、氫氟烯(HFO)、二氧化碳(R744)、碳數2~4之烴中之1種以上者,最佳為含有二氟甲烷(R32)及/或2,3,3,3-四氟丙烯(HFO-1234yf)之冷媒。
於本實施形態之冷凍機用作動流體組合物中,冷凍機油/冷媒之調配比率並無特別限制,通常相對於冷媒100重量份為1~1000重量份,較佳為2~800重量份。
以下,基於實施例及比較例更具體地說明本發明,但本發明不受
以下實施例之任何限定。
於實施例1~12及比較例1~12中,使用以下所示之基油、添加劑,製備具有表1~3所示之組成之冷凍機油。再者,表1~3所示之基油及添加劑之含有比率均為以冷凍機油總量為基準之含有比率。
(A-1)多元醇酯(POE-1):季戊四醇與2-甲基丙酸和3,5,5-三甲基己酸以質量比計為35:65之混合酸的酯(40℃下之動黏度68.1mm2/s、黏度指數84、流動點-40℃、引火點240℃、碳/氧莫耳比3.6)
(A-2)多元醇酯(POE-2):季戊四醇與2-乙基己酸和3,5,5-三甲基己酸以質量比計為5:5之混合酸的酯(40℃下之動黏度66.7mm2/s、黏度指數92、流動點-40℃、引火點248℃、碳/氧莫耳比4.8)
(A-3)聚伸烷基二醇(PAG):兩末端經甲基封端之聚氧丙烯(平均分子量1000、40℃下之動黏度46.0mm2/s、黏度指數190、流動點-45℃、引火點218℃、碳/氧莫耳比3.0)
(A-4)聚乙烯醚(PVE):乙基乙烯醚與異丁基乙烯醚之共聚物(乙基乙烯醚:異丁基乙烯醚以重量比計為7:1)、(平均分子量910、40℃下之動黏度66.4mm2/s、黏度指數85、流動點-35℃、引火點210℃、碳/氧莫耳比4.3)
(A-5)礦物油系基油(MO):鏈烷系精製礦物油(40℃下之動黏度22.3mm2/s、黏度指數95、流動點-15℃、引火點200℃)
再者,動黏度及黏度指數係依據JIS K2283進行測定,流動點係依據JIS K2269進行測定,引火點係依據JIS K2265進行測定。
(S-1)二苄基硫醚
(S-2)二-十二烷基硫醚
(S-3)4,4'-硫代雙(3-甲基-6-第三丁基苯酚)
(P-1)磷酸三甲苯酯(TCP)
(P-2)磷酸三苯酯(TPP)
(P-3)磷酸三癸酯(TDP)
(D-1)季戊四醇四(2-乙基己酸酯)(季戊四醇與2-乙基己酸之酯、酸值0.01mgKOH/g、羥值1.2mgKOH/g)
繼而,將實施例1~12及比較例1~12之冷凍機油與表1~3所示之各種冷媒組合,進行以下之潤滑性試驗及穩定性試驗。再者,表1~3中之「1234yf」係指HFO-1234yf。
潤滑性試驗係依據ASTM D3233-73,使用FALEX(試驗軸及V型塊,(Pin and V Block))試驗機,於一定荷重下進行磨耗試驗。
FALEX磨耗試驗係於冷媒吹送控制氛圍下(70ml/min)以初始溫度50℃、轉速290rpm、荷重50Lbf進行調試並進行5分鐘運轉,此後,以相同轉速於荷重100Lbf下進行本試驗1小時,測定試驗後之試驗軸及V型塊之磨耗量之合計值(mg)。
再者,作為吹送冷媒,使用R32、HFO-1234yf、R600a(異丁烷)。
穩定性試驗係依據JIS K2211-09(熱壓膨脹試驗),稱取含水量被調整為100ppm之試料油90g置於熱壓器中,封入觸媒(鐵、銅、鋁之線、均為外徑1.6mm×50mm)及各冷媒(R32、HFO-1234yf、R600a)10g後,加熱至175℃,測定100小時後之試料油之外觀及酸值(JIS C2101)。
再者,穩定性試驗前之試料油(新油)之酸值均為0.01mgKOH/g。
關於穩定性,由表1~3得知,利用與HFO-1234yf之組合雖然出現酸值稍許上升,但實施例1~12、比較例1~12均為無問題之級別。
關於潤滑性,得知實施例1~12均為磨耗量較少,且耐磨耗性良好。相對於此,得知於比較例1、2之情形時,磨耗量很大,又,比較例3~12於與比較例1、2相比磨耗量減少,但添加劑調配量多於實施例的情形時,其耐磨耗之效果遠不及實施例。
又,將實施例4與實施例1、比較例5、12進行比較得知,藉由(D-1)之適當調配,可獲得顯著之耐磨耗效果。
本發明之冷凍/空氣調節機用之作動流體組合物係即便於嚴苛之潤滑條件下亦可維持耐磨耗效果之長期可靠性優異的作動流體,因此於具有壓縮機、凝結器、節流裝置、蒸發器等,且使冷媒於該等之間循環之冷卻效率較高之冷凍/空氣調節機系統中,尤其是具有旋轉型、擺動型、渦捲型等之壓縮機之系統中,可適宜地使用,可用於室內空氣調節機、箱型空氣調節機、冰箱、車載空氣調節機、產業用冷凍機等領域。
Claims (7)
- 一種冷凍機油,其含有基油、硫醚化合物、正磷酸酯及季戊四醇四(2-乙基己酸酯),以冷凍機油總量為基準,上述硫醚化合物之含量為0.01~2.0質量%,上述正磷酸酯之含量為0.1~5.0質量%,上述季戊四醇四(2-乙基己酸酯)之含量為2~20質量%,上述冷凍機油於40℃下之動黏度為3~500mm2/s。
- 如請求項1之冷凍機油,其中上述基油為選自碳/氧莫耳比為2.5以上且5.8以下之酯及碳/氧莫耳比為2.5以上且5.8以下之醚中之至少1種,且上述冷凍機油於40℃下之動黏度為3~300mm2/s。
- 如請求項1或2之冷凍機油,其中上述基油為選自以碳數4以上且9以下之脂肪酸與碳數4以上且12以下之多元醇合成之多元醇酯、聚伸烷基二醇、將聚伸烷基二醇之兩末端之羥基進行醚化而成之化合物及聚乙烯醚中之至少1種。
- 如請求項1或2之冷凍機油,其中上述硫醚化合物為硫代雙酚化合物,上述正磷酸酯為選自磷酸三苯酯、磷酸三甲苯酯及具有碳數3~4之烷基之烷基苯基磷酸酯中之至少1種。
- 一種冷凍機用作動流體組合物,其包含全球暖化係數為700以下之冷媒、及如請求項1至4中任一項之冷凍機油。
- 如請求項5之冷凍機用作動流體組合物,其中上述冷媒為含有選自氫氟碳化物、氫氟烯、二氧化碳及碳數2~4之烴中之至少1種的冷媒。
- 如請求項5或6之冷凍機用作動流體組合物,其中上述冷媒為含有選自二氟甲烷及2,3,3,3-四氟丙烯中之至少1種的冷媒。
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WO2016056392A1 (ja) * | 2014-10-09 | 2016-04-14 | Jx日鉱日石エネルギー株式会社 | 冷凍機油及び冷凍機用作動流体組成物 |
CN107250332B (zh) * | 2015-03-02 | 2021-02-12 | Jxtg能源株式会社 | 冷冻机油及冷冻机用工作流体组合物 |
WO2016140187A1 (ja) * | 2015-03-02 | 2016-09-09 | Jxエネルギー株式会社 | 冷凍機油及び冷凍機用作動流体組成物 |
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