TWI598436B - The freezer is used as a motor fluid composition and as a refrigerator oil - Google Patents
The freezer is used as a motor fluid composition and as a refrigerator oil Download PDFInfo
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Description
本發明係關於一種冷凍機用作動流體組合物及冷凍機油,更詳細而言,係關於一種可將摩擦係數維持於較低、耐磨性較高並可有助於可靠性提昇及省電之冷凍機用作動流體組合物及冷凍機油。
先前,作為冰箱、車載空調、室內空調、產業用冷凍機等之冷媒,廣泛使用作為氫氟碳(HFC)之1,1,1,2-四氟乙烷(R134a)、或作為以二氟乙烷(R32)與五氟乙烷(R125)之質量比計為1/1之混合冷媒之R410A等。
然而,該等HFC冷媒由於全球暖化係數(GWP,Global Warming Potential)較高,為1000以上,故一直因所謂F-氣體限制而限制使用。作為HFC冷媒之替代品,必需為低GWP,作為其中之一,有已於冰箱用途中實用化之如異丁烷(R600a)之烴冷媒。烴冷媒由於GWP極低,為20以下,物性值較佳,故進行了廣泛之研究。
於烴冷媒共存下,在烴分子內無提高潤滑性之氯、氟,因此與HFC冷媒等不同,無法期待由冷媒所引起之潤滑性提昇,又,烴對冷凍機油之溶解度較高而降低油之黏度,因此潤滑條件變得嚴格,對冷凍機油要求有高於先前之耐磨性。進而,就省電之觀點而言,亦要求有可將摩擦係數維持於較低之性能。
於廣泛之潤滑油領域中,作為耐磨添加劑,通常已知醇、酯、長鏈脂肪酸等油性劑、或磷酸酯、二硫代磷酸金屬鹽等耐磨劑、有機
硫化合物、有機鹵素化合物等極壓添加劑。另一方面,關於冷凍機油,若非即便與冷媒共存亦不會析出且不會對穩定性造成不良影響之添加劑,則無法使用。因此,於先前之冷凍機油中,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,於專利文獻1中揭示有包含併用添加磷系添加劑及特定之環氧化合物之冷凍機用途之潤滑油,於專利文獻2中揭示有併用添加磷酸三苯酯及磷酸三(烷基苯基)酯作為HFC冷媒用途之壓縮機用潤滑油,於專利文獻3中揭示有添加磷酸三甲苯酯、及包含縮水甘油醚之環氧或碳二醯亞胺作為HFC冷媒用途之冷凍機油。
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
然而,根據本發明者之研究,使用上述添加劑之冷凍機油作為烴冷媒用冷凍機油而於以下方面尚有改善之餘地。
即,首先,上述添加劑中之油性劑係藉由吸附而形成潤滑皮膜者。因此,於如混合潤滑區域之相對負載條件適度之情形時,可將摩擦係數維持於較低,但於烴冷媒共存下,若負載條件變嚴,則會喪失耐磨之效果。
另一方面,磷酸三苯酯或磷酸三甲苯酯雖具有耐磨之效果,但在滑動部表面形成較硬之皮膜,因此摩擦係數變高,不適於改善了省電化之冷凍機,尤其是於就地球環境而言優異之烴冷媒共存下,如上所述,潤滑條件變嚴,因此需要具有較高之耐磨性並且維持較低之摩
擦係數之添加劑。
本發明係鑒於上述先前技術所具有之問題而成者,其目的在於提供一種冷凍機用作動流體組合物及冷凍機油,其即便於烴冷媒共存下之嚴格之潤滑條件下,亦可獲得優異之耐磨性,並且可維持足夠低之摩擦係數,省電化及長期可靠性優異。
本發明者等人發現,於潤滑油基油中調配特定之磷化合物,藉此於烴冷媒共存下不會對其他特性造成不良影響,可提高冷凍機用作動流體組合物及冷凍機油之耐磨性,且可將摩擦係數維持於較低,從而完成本發明。
即,本發明提供一種冷凍機用作動流體組合物,其含有冷凍機油、及碳數2~4之烴冷媒,該冷凍機油含有選自礦物油及合成油中之至少1種潤滑油基油、以及選自具有1個碳數3~5之烷基之單(烷基苯基)二苯基磷酸酯及具有2個碳數3~5之烷基之二(烷基苯基)苯基磷酸酯中之至少1種磷化合物,該磷化合物之含量以冷凍機油總量作為基準而為0.01~5質量%。
上述磷化合物較佳為選自具有1個碳數4之烷基之單(丁基苯基)二苯基磷酸酯及具有2個碳數4之烷基之二(丁基苯基)苯基磷酸酯中之至少1種。
上述潤滑油基油較佳為選自礦物油、烷基苯、聚-α-烯烴、酯及醚中之至少1種,該潤滑油基油於40℃下之動黏度為3~500mm2/s。
進而,上述潤滑油基油較佳為選自礦物油、烷基苯、聚-α-烯烴、二酯、多元醇酯、複合酯、聚伸烷基二醇、聚伸烷基二醇化合物及聚乙烯醚中之至少1種以上,該潤滑油基油於40℃下之動黏度為3~300mm2/s。
上述烴冷媒較佳為選自丙烷(R290)、丙烯(R1270)、正丁烷
(R600)及異丁烷(R600a)中之至少1種。
又,本發明提供一種冷凍機油,其含有選自礦物油及合成油中之至少1種潤滑油基油、及選自具有1個碳數3~5之烷基之單(烷基苯基)二苯基磷酸酯及具有2個碳數3~5之烷基之二(烷基苯基)苯基磷酸酯中之至少1種磷化合物,該磷化合物之含量以冷凍機油總量作為基準而為0.01~5質量%,且與碳數2~4之烴冷媒一併使用。
根據本發明,提供一種冷凍機用作動流體組合物及冷凍機油,其可發揮以下特殊效果:即便於烴冷媒共存下之嚴格之潤滑條件下,亦可具有耐磨之效果並且維持較低之摩擦係數,可實現省電化,且可長時間穩定地使用。
以下,對本發明之較佳實施形態進行詳細說明。
本發明之第1實施形態之冷凍機油含有選自礦物油及合成油中之至少1種潤滑油基油、及選自具有1個碳數3~5之烷基之單(烷基苯基)二苯基磷酸酯及具有2個碳數3~5之烷基之二(烷基苯基)苯基磷酸酯中之至少1種磷化合物,該磷化合物之含量以冷凍機油總量作為基準而為0.01~5質量%。該冷凍機油係與碳數2~4之烴冷媒一併使用。
本實施形態之冷凍機油含有選自礦物油及合成油中之至少1種作為潤滑油基油。
作為礦物油,可為石蠟系、環烷系、混合基系中之任一者。又,可較佳地使用適當組合脫溶劑、溶劑提取、氫化純化、氫化分解、溶劑脫蠟、氫化脫蠟、白土處理等潤滑油純化手段對潤滑油餾分
進行處理而獲得之純化潤滑油餾分,上述潤滑油餾分係對該等礦物油之各自或2種以上之混合物進行常壓蒸餾,進而進行減壓蒸餾而獲得。可單獨使用由各種原料與各種純化手段之組合所獲得之性狀不同之純化潤滑油餾分,亦可組合2種以上而使用。
又,作為合成油系之潤滑油基油,可列舉:如酯、醚之含氧化合物、或如聚-α-烯烴(PAO)、乙烯-α-烯烴低聚物、烷基苯、烷基萘之烴油。
關於含氧化合物基油中之酯,市售有各種分子結構之化合物,且為具有如下特徵之基油:分別具有特有之黏度特性、低溫特性,與相同黏度之烴系基油相比,引火點較高。酯可使醇與脂肪酸進行脫水縮合反應而獲得,於本發明中,就化學穩定性之方面而言,作為較佳之基油成分,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。其中,較佳為穩定性優異之多元醇酯。
作為醚,可列舉聚伸烷基二醇、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,就吸濕性之方面而言,較佳為至少一個末端為烷基,尤佳為甲基。又,就製造容易性及成本之方面而言,較佳為任一末端為烷基,另一末端為氫原子,尤佳為一末端為甲基,另一末端為氫原子。關於主骨架,就潤滑性方面而言,較佳為包含氧化乙烯基(EO)及氧化丙烯基(PO)之共聚物,氧化乙烯基於氧化乙烯基與氧化丙烯基之總和中所占之比率(EO/PO+EO)較佳為於0.1~0.8之範圍,更佳為於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)之值較佳為於0~0.5之範圍,更佳為於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
聚乙烯醚可為其結構單元相同之均聚物,亦可為包含2種以上之結構單元之共聚物,藉由形成共聚物,可以較佳之平衡性調整特性,故而較佳。
[式中,R1、R2及R3可相同亦可不同,分別表示氫原子或碳數1~8之烴基,R4表示碳數1~10之二價烴基或碳數2~20之二價之經醚鍵結之含氧烴基,R5表示碳數1~20之烴基,m表示使關於上述聚乙烯醚之m之平均值成為0~10之數,R1~R5於每個結構單元中可相同亦可不同,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]。
合成系烴油中之聚-α-烯烴(PAO)為α-烯烴之聚合物,因此可根據其聚合度而適當選定特性。
又,烷基苯根據烷基之結構而有直鏈型及支鏈型,特性不同,因此根據目的而區分使用。
於本實施形態中,可單獨使用上述礦物油及合成油中之1種,又,亦可組合2種以上而使用。
潤滑油基油於40℃下之動黏度較佳為3~500mm2/s,更佳為3~300mm2/s,進而較佳為5~150mm2/s。又,潤滑油基油之黏度指數較佳為10以上。再者,本發明中之所謂於40℃下之動黏度及黏度指數,分別係指依據JIS(Japanese Industrial Standards,日本工業標準)K2283而測得之值。
又,潤滑油基油之流動點較佳為-10℃以下,更佳為-20℃以下。再者,本發明中之所謂流動點,係指依據JIS K2269而測得之值。
又,潤滑油基油之引火點較佳為120℃以上,更佳為200℃以上。再者,本發明中之所謂引火點,係指依據JIS K2265而測得之值。
又,本實施形態之冷凍機油含有選自具有1個碳數3~5之烷基之單(烷基苯基)二苯基磷酸酯及具有2個碳數3~5之烷基之二(烷基苯基)苯基磷酸酯中之至少1種磷化合物。
本實施形態中之上述磷化合物可以下述通式(2)表示。
(R6-Ph)n-P(=O)-(Ph)3-n (2)
[式中,R6表示碳數3~5之烷基,Ph表示苯基,n表示1或2之整數]。
於n為1時,上述通式(2)所表示之磷化合物為具有1個碳數3~5之烷基之單(烷基苯基)二苯基磷酸酯。作為該單(烷基苯基)二苯基磷酸酯,具體而言,可列舉:異丙基苯基二苯基磷酸酯、第三丁基苯基二苯基磷酸酯、正丁基苯基二苯基磷酸酯等。
於n為2時,上述通式(2)所表示之磷化合物為具有2個碳數3~5之烷基之二(烷基苯基)苯基磷酸酯。作為該二(烷基苯基)二苯基磷酸酯,可列舉:二(異丙基苯基)苯基磷酸酯、二(第三丁基苯基)苯基磷酸酯、二(正丁基苯基)苯基磷酸酯等。
就冷凍機油之潤滑性方面而言,通式(2)中之R6較佳為丁基。作為丁基,可列舉作為直鏈烷基之正丁基、作為支鏈烷基之第三丁基等。再者,若R6之碳數為2以下,則摩擦係數變高,難以達成省電化。本發明者推測其原因在於形成於滑動部之磷化合物之皮膜變硬。另一方面,若R6之碳數超過5,則耐磨之效果變小。本發明者推測其原因在於磷化合物對潤滑油基油之親和力變大,滑動部中之磷化合物
之濃度極度地減少。
上述磷化合物之含量以冷凍機油總量作為基準而為0.01~5質量%,較佳為0.1~3質量%。若含量未達上述下限值,則無法發揮提高潤滑性之效果。又,若含量超過上述上限值,則對冷凍機油之穩定性或系統內之有機材料之膨潤等之影響變大。
本實施形態之冷凍機油亦可為僅包含上述潤滑油基油及磷化合物者,於無損本發明之目的之範圍內,為了進一步提高性能,可進而含有抗氧化劑、摩擦調整劑、防銹劑、金屬減活化劑、消泡劑等添加劑。
作為抗氧化劑,可列舉如二-第三丁基-對甲酚之酚系化合物、如烷基二苯胺之胺系化合物等,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、酸性磷酸酯胺鹽、亞磷酸酯胺鹽等,作為防銹劑,可列舉烯基琥珀酸酯或部份酯等,作為金屬減活化劑,可列舉苯并三唑等,作為消泡劑,可列舉聚矽氧化合物、酯系消泡劑等。
本實施形態之冷凍機油可較佳地用作使用碳數2~4之烴冷媒之冷凍機用之潤滑油。此處,於使本實施形態之冷凍機油適用於使用異丁烷作為冷媒之冰箱之情形時,亦必需具有適用於馬達內置型(密閉型)壓縮機之冷凍機油之特性,即具有較高之電性絕緣性。因此,本實施形態之冷凍機油較佳為於調配添加劑後,體積電阻率為109Ω.m以上。再者,本發明中之所謂體積電阻率,係指依據JIS C2101而測得之值。又,於使用添加劑之情形時,該體積電阻率係指調配添加劑後之冷凍機油之體積電阻率。
本發明之第2實施形態之冷凍機用作動流體組合物含有冷凍機油、及碳數2~4之烴冷媒,該冷凍機油含有選自礦物油及合成油中之
至少1種潤滑油基油、以及選自具有1個碳數3~5之烷基之單(烷基苯基)二苯基磷酸酯及具有2個碳數3~5之烷基之二(烷基苯基)苯基磷酸酯中之至少1種磷化合物,該磷化合物之含量以冷凍機油總量作為基準而為0.01~5質量%。再者,本實施形態之冷凍機用作動流體組合物所含之冷凍機油與上述第1實施形態之冷凍機油相同,故而此處省略重複之說明。
作為本實施形態中之碳數2~4之烴冷媒,具體而言,可列舉乙烷、丙烷、正丁烷、異丁烷等。其中,異丁烷(R600a)係用作冰箱用途,丙烷(R290)係作為室內空調用途而進行實用化研究,於本實施形態中,可較佳地使用該等烴冷媒。尤其是,本實施形態之冷凍機用作動流體組合物可藉由冷凍機油之低黏度化而達成省電,故而適合作為主要使用其效果較大之往復型壓縮機之冰箱用途,可謂尤其適合作為異丁烷冷媒用途。
於本實施形態之冷凍機用作動流體組合物中,冷媒及冷凍機油之含有比率並無特別限制,冷媒/冷凍機油較佳為10/90~90/10,更佳為30/70~70/30。
以下,基於實施例及比較例而更詳細地說明本發明,但本發明並不限定於以下實施例。
於實施例1~8及比較例1~6中,分別使用以下所示之潤滑油基油及添加劑而製備具有表1~4所示之組成之冷凍機油。
A1:季戊四醇、與2-乙基己酸及3,5,5-三甲基己酸之混合酸(質量比1:1)之酯(40℃下之動黏度為68.0mm2/s、黏度指數為90、流動點為-40℃、引火點為260℃)
A2:癸二酸二辛酯(40℃下之動黏度為11.6mm2/s、黏度指數為150、流動點為-50℃、引火點為220℃)
A3:兩末端為甲基且經醚封阻之聚氧丙烯(平均分子量為1000、40℃下之動黏度為46.0mm2/s、黏度指數為190、流動點為-45℃、引火點為218℃)
A4:石蠟系純化礦物油(40℃下之動黏度為22.0mm2/s、黏度指數為95、流動點為-15℃、引火點為210℃)
A5:直鏈型烷基苯(40℃下之動黏度為8.1mm2/s、黏度指數為45、流動點為-50℃、引火點為154℃)
B1:單(正丁基苯基)二苯基磷酸酯
B2:二(異丙基苯基)苯基磷酸酯
B3:單(第三丁基苯基)二苯基磷酸酯/二(第三丁基苯基)苯基磷酸酯=65/35(質量比)之混合物
C1:油性劑:甘油單油酸酯(GMO)
C2:耐磨劑:磷酸三苯酯(TPP)
C3:耐磨劑:磷酸三甲苯酯(TCP)
繼而,使用實施例1~8及比較例1~6之冷凍機油,進行以下之潤滑性試驗及熱穩定性試驗。
使用ASTM D-2714-88之Falex環塊法摩擦磨耗試驗機,試樣係塊為合金工具鋼SKS3(JIS G4404)、環為鎳鉻鉬鋼SNCM220(JIS G4103),將試驗條件設為荷重:300N、周速:0.1m/s、溫度:50℃、試驗時間:30分鐘,而進行摩擦磨耗試驗。再者,試樣油量為100ml,模擬利用烴冷媒進行稀釋之情況,添加20ml作為不會氣化
之烴之正癸烷並進行稀釋,將合計之樣本量設為120ml。
作為試驗結果,摩擦係數係測量於試驗後半部分(約25分鐘)穩定時之值而表示,磨耗係利用附帶刻度之顯微鏡測量試驗結束後之塊上之磨耗寬度(mm)而表示。將所獲得之結果示於表1~4。
於高壓釜中稱取將含有水分量調整為100ppm以下之試樣油90g,填充觸媒(鐵、銅、鋁線,均為外徑1.6mm×50mm)及異丁烷冷媒10g後,加熱至175℃,測定100小時後之試樣油之外觀及酸值(JIS C2101)。將所獲得之結果示於表1~4。再者,熱穩定性試驗前之試樣油(新油)之酸值均為0.01mgKOH/g。
如表1、2所示,實施例1~8之冷凍機油顯示與比較例1之冷凍機油相比摩擦係數較低、磨耗寬度較小之結果。
繼而,若對實施例1~8與比較例2、4進行比較,則作為磨耗指標之磨耗寬度於為比較例2、4之情形時,顯示遠大於實施例1~8之值。該結果支持如下觀點:作為吸附型之油性劑雖將摩擦係數設為一定量,但耐磨性較差。
又,若對實施例1~8與比較例3、5、6進行比較,則比較例3、5、6之摩擦係數顯示較實施例1~8高約20%之值。就冷凍機壓縮機之省電之觀點而言,其可謂較大之差。
根據該等結果可知,實施例1~8之冷凍機油係穩定性良好,就
潤滑性而言,即便於利用烴進行稀釋之情形時,耐磨性亦較高,可將摩擦係數維持於較低之冷凍機油。
本發明之冷凍機油即便於冷凍機用冷媒因現行HFC冷媒之限制而替換為全球暖化係數即GWP更低者之變化中,用於作為其替代品之一的烴冷媒,亦可藉由其較高之耐磨性及可將摩擦係數維持於較低之特性而實現省電化,並且可作為長期可靠性較高之油而較佳地用於已實現部分實用化之冰箱、室內空調、一般產業用冷凍機等中。
Claims (6)
- 一種冷凍機用作動流體組合物,其含有冷凍機油、及碳數2~4之烴冷媒,該冷凍機油含有僅由選自酯及醚中之至少1種構成之潤滑油基油、以及選自具有1個碳數3~5之烷基之單(烷基苯基)二苯基磷酸酯及具有2個碳數3~5之烷基之二(烷基苯基)苯基磷酸酯中之至少1種磷化合物,該磷化合物之含量以冷凍機油總量作為基準而為0.01~5質量%。
- 如請求項1之冷凍機用作動流體組合物,其中上述磷化合物為選自具有1個碳數4之烷基之單(丁基苯基)二苯基磷酸酯及具有2個碳數4之烷基之二(丁基苯基)苯基磷酸酯中之至少1種。
- 如請求項1或2之冷凍機用作動流體組合物,其中上述潤滑油基油僅由選自酯及醚中之至少1種構成,該潤滑油基油於40℃下之動黏度為3~500mm2/s。
- 如請求項1或2之冷凍機用作動流體組合物,其中上述潤滑油基油為選自二酯、多元醇酯、複合酯、聚伸烷基二醇、聚伸烷基二醇化合物及聚乙烯醚中之至少1種以上,該潤滑油基油於40℃下之動黏度為3~300mm2/s。
- 如請求項1或2之冷凍機用作動流體組合物,其中上述烴冷媒為選自丙烷、丙烯、正丁烷及異丁烷中之至少1種。
- 一種冷凍機油,其含有僅由選自酯及醚中之至少1種構成之潤滑油基油、及選自具有1個碳數3~5之烷基之單(烷基苯基)二苯基磷酸酯及具有2個碳數3~5之烷基之二(烷基苯基)苯基磷酸酯中之至少1種磷化合物, 該磷化合物之含量以冷凍機油總量作為基準而為0.01~5質量%,且該冷凍機油係與碳數2~4之烴冷媒一併使用。
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US11505760B2 (en) * | 2016-02-24 | 2022-11-22 | Eneos Corporation | Refrigerator oil |
EP3492563B1 (en) * | 2016-07-28 | 2023-06-14 | JXTG Nippon Oil & Energy Corporation | Refrigerating machine oil |
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CN104204163A (zh) | 2014-12-10 |
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US9562182B2 (en) | 2017-02-07 |
EP2835415B1 (en) | 2018-05-09 |
EP2835415A1 (en) | 2015-02-11 |
CN105238360A (zh) | 2016-01-13 |
EP2835415A4 (en) | 2015-06-17 |
JP2013203988A (ja) | 2013-10-07 |
KR102057019B1 (ko) | 2019-12-18 |
IN2014DN08800A (zh) | 2015-05-22 |
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KR20140142261A (ko) | 2014-12-11 |
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