TWI660041B - 冷凍機用作動流體組合物及冷凍機油 - Google Patents

冷凍機用作動流體組合物及冷凍機油 Download PDF

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TWI660041B
TWI660041B TW104102001A TW104102001A TWI660041B TW I660041 B TWI660041 B TW I660041B TW 104102001 A TW104102001 A TW 104102001A TW 104102001 A TW104102001 A TW 104102001A TW I660041 B TWI660041 B TW I660041B
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ester
acid
mixture
neopentyl glycol
polyol
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TW201538712A (zh
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高橋仁
大城戶武
新保紘子
今野聰一郎
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日商吉坤日礦日石能源股份有限公司
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Abstract

本發明提供一種含有冷凍機油與二氧化碳等冷媒之冷凍機用作動流體組合物，該冷凍機油含有混合酯作為基油，該混合酯係將(A)由新戊二醇等多元醇、碳數6~12之多元酸及碳數4~18之一元醇等所合成之複合酯，與(B)由新戊二醇等多元醇與碳數4~18之一元脂肪酸所合成之多元醇酯，以(A)複合酯/(B)多元醇酯之質量比5/95~95/5混合而成。

Description

冷凍機用作動流體組合物及冷凍機油
本發明係關於一種冷凍機用作動流體組合物及冷凍機油。再者，於本發明中所提及之「冷凍機」中，包含汽車用空調、除濕器、冰箱、冷凍冷藏倉庫、自動售貨機、展示櫃、化學設備等中之冷卻裝置、住宅用空調、櫃式空調、熱水供應用熱泵等。
於冷動‧空調之領域中，目前作為冰箱、汽車空調、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)、或作為二氟甲烷(R32)與五氟乙烷(R125)之以質量比計為1/1之混合冷媒的R410A等。
於專利文獻1中，作為R32冷媒用冷凍機油，揭示有由三羥甲基丙烷及/或新戊二醇與特定之二元酸、以及一元醇或一元脂肪酸所合成之酯。又，於專利文獻2中，作為單一R32或包含50質量%以上之R32之混合冷媒用，揭示有如下酯系冷凍機油，該酯系冷凍機油包含20~60質量%之將一元脂肪酸之碳數設為5以下者，對於碳數大於8之脂肪酸使用支鏈脂肪酸，且40℃下之黏度為32~100cst。
進而，關於一般之工業用潤滑油之基油，於專利文獻3中揭示有包含如下合成酯之潤滑油基油，該合成酯係使包含90質量%以上之三羥甲基丙烷之醇成分、與包含碳數8~12之一元脂肪酸及己二酸且以總量計包含辛酸及/或癸酸90質量%以上之碳數8~12之一元脂肪酸、以及以總量計包含90質量%以上之己二酸的羧酸成分反應而獲得。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開2011-184536號公報
[專利文獻2]日本專利特開2002-129179號公報
[專利文獻3]日本專利特開2012-102235號公報
今後，冷凍機器之於滑動部之負載條件將變得更加嚴苛，因此於特定之冷媒共存而溶解於冷凍機油中之情形時，同時實現耐磨耗性與穩定性較為重要。
本發明係鑒於上述問題而完成者，其目的在於提供一種即便於因冷媒共存而溶解於冷凍機油中而產生之嚴苛之潤滑條件下，亦可維持較厚之油膜而耐磨耗之效果增大，且穩定性優異之冷凍機用作動流體組合物及冷凍機油。
本發明者等人發現，含有如下冷凍機油與特定之冷媒之作動流體可同時實現耐磨耗性與穩定性，從而完成了本發明，上述冷凍機油係以將由特定之多元醇及多元酸以及一元醇或一元脂肪酸所合成之複合酯、及由特定之多元醇與一元脂肪酸所合成之多元醇酯調配而成之酯作為基油。
即，本發明提供下述[1]~[6]所記載之冷凍機用作動流體組合物及下述[7]所記載之冷凍機油。
[1]一種冷凍機用作動流體組合物，其含有：冷凍機油，其含有混合酯作為基油，上述混合酯係將(A)由包含選自新戊二醇、三羥甲基丙烷及季戊四醇中之至少1種之多元醇、選自碳數6~12之多元酸中之至少1種、及選自碳數4~18之一元醇及碳數4~18之一元脂肪酸中 之至少1種所合成的複合酯，與(B)由選自新戊二醇、三羥甲基丙烷、季戊四醇及二季戊四醇中之至少1種多元醇與選自碳數4~18之一元脂肪酸中之至少1種所合成之多元醇酯，以(A)複合酯/(B)多元醇酯之質量比5/95~95/5混合而成；及冷媒，其係選自二氧化碳、1,1,1,2-四氟乙烷、二氟甲烷與五氟乙烷之混合物、二氟甲烷與五氟乙烷與1,1,1,2-四氟乙烷之混合物、及五氟乙烷與1,1,1,2-四氟乙烷與1,1,1-三氟乙烷之混合物中。
[2]如[1]之冷凍機用作動流體組合物，其中構成(A)複合酯之多元醇進而包含新戊二醇以外之碳數2~10之二元醇。
[3]如[1]或[2]之冷凍機用作動流體組合物，其中構成(A)複合酯之多元醇包含選自新戊二醇及三羥甲基丙烷中之至少1種。
[4]如[1]至[3]中任一項之冷凍機用作動流體組合物，其中構成(A)複合酯之多元酸係選自己二酸及癸二酸中之至少1種。
[5]如[1]至[4]中任一項之冷凍機用作動流體組合物，其中構成(A)複合酯之一元醇係碳數8~10之一元醇。
[6]如[1]至[5]中任一項之冷凍機用作動流體組合物，其中(B)多元醇酯係由選自新戊二醇及季戊四醇中之至少1種、與選自碳數4~9之一元脂肪酸中之至少1種所合成之酯。
[7]如[1]至[6]中任一項之冷凍機用作動流體組合物，其中(B)多元醇酯係由季戊四醇、與碳數4之支鏈脂肪酸及3,5,5-三甲基己酸之混合脂肪酸合成之酯。
[8]一種冷凍機油，其含有混合酯作為基油，上述混合酯係將(A)由包含選自新戊二醇、三羥甲基丙烷及季戊四醇中之至少1種之多元醇、選自碳數6~12之多元酸中之至少1種、及選自碳數4~18之一元醇及碳數4~18之一元脂肪酸中之至少1種所合成之複合酯，與(B)由選自新戊二醇、三羥甲基丙烷、季戊四醇及二季戊四醇中之至少1種 多元醇與選自碳數4~18之一元脂肪酸中之至少1種所合成之多元醇酯，以(A)複合酯/(B)多元醇酯之質量比5/95~95/5混合而成，且上述冷凍機油係與選自二氧化碳、1,1,1,2-四氟乙烷、二氟甲烷與五氟乙烷之混合物、二氟甲烷與五氟乙烷與1,1,1,2-四氟乙烷之混合物、及五氟乙烷與1,1,1,2-四氟乙烷與1,1,1-三氟乙烷之混合物中之冷媒一起使用。
根據本發明，可提供一種即便於因冷媒共存而溶解於冷凍機油中而產生之嚴苛之潤滑條件下，亦可維持較厚之油膜而耐磨耗之效果增大，且穩定性優異之冷凍機用作動流體組合物及冷凍機油。
以下，對本發明之較佳之實施形態進行詳細說明。
本實施形態之冷凍機油含有混合酯作為基油，該混合酯是將
(A)由包含選自新戊二醇、三羥甲基丙烷及季戊四醇中之至少1種之多元醇、選自碳數6~12之多元酸中之至少1種、及選自碳數4~18之一元醇及碳數4~18之一元脂肪酸中之至少1種所合成之複合酯，與(B)由選自新戊二醇、三羥甲基丙烷、季戊四醇及二季戊四醇中之至少1種多元醇與選自碳數4~18之一元脂肪酸中之至少1種所合成之多元醇酯，以(A)複合酯/(B)多元醇酯之質量比5/95~95/5混合而成，且上述冷凍機油係與選自二氧化碳、1,1,1,2-四氟乙烷、二氟甲烷與五氟乙烷之混合物、二氟甲烷與五氟乙烷與1,1,1,2-四氟乙烷之混合物、及五氟乙烷與1,1,1,2-四氟乙烷與1,1,1-三氟乙烷之混合物中之冷媒一起使用。
本實施形態之冷凍機用作動流體組合物含有：冷凍機油，其含有混合酯作為基油，該混合酯是將(A)由包含選自新戊二醇、三羥甲基丙烷及季戊四醇中之至少1種之多元醇、選自碳數6~12之多元酸中之至少1種、及選自碳數4~18之一元醇及碳數4~18之一元脂肪酸中之至少1種所合成之複合酯，與(B)由選自新戊二醇、三羥甲基丙烷、季戊四醇及二季戊四醇中之至少1種多元醇與選自碳數4~18之一元脂肪酸中之至少1種所合成之多元醇酯，以(A)複合酯/(B)多元醇酯之質量比5/95~95/5混合而成；及冷媒，其係選自二氧化碳、1,1,1,2-四氟乙烷、二氟甲烷與五氟乙烷之混合物、二氟甲烷與五氟乙烷與1,1,1,2-四氟乙烷之混合物、及五氟乙烷與1,1,1,2-四氟乙烷與1,1,1-三氟乙烷之混合物中。
本實施形態之冷凍機用作動流體組合物包含如下態樣：含有本實施形態之冷凍機油與選自二氧化碳、1,1,1,2-四氟乙烷、二氟甲烷與五氟乙烷之混合物、二氟甲烷與五氟乙烷與1,1,1,2-四氟乙烷之混合物、及五氟乙烷與1,1,1,2-四氟乙烷與1,1,1-三氟乙烷之混合物中之冷媒。
上述複合酯與先前之冷凍機油相比，冷媒難以溶解而與冷媒之相容性較低，但可將油膜維持為較厚。又，上述多元醇酯與冷媒之相容性良好。於本實施形態中，藉由如此般調配特性(尤其是冷媒溶解度)不同之複合酯與多元醇酯，可將冷媒共存時之油膜變厚，進而可提高作動流體之耐磨耗性。
再者，複合酯由於分子量增大，故而成為黏度較高之酯。因此，複合酯難以與冷媒相容，就向壓縮機之回油之方面而言不適合單獨用作需要與冷媒之相容性的冷凍機油之基油。本實施形態之特徵之一在於：藉由將複合酯與如上述多元醇酯般與和冷媒之相容性良好之油混合，可獲得特性之平衡。
複合酯之40℃下之動黏度較佳為20mm2/s以上，更佳為40mm2/s以上，進而較佳為50mm2/s以上，且較佳為500mm2/s以下，更佳為400mm2/s以下，進而較佳為200mm2/s以下，特佳為90mm2/s以下。複合酯之100℃下之動黏度較佳為5mm2/s以上，更佳為6mm2/s以上，進而較佳為7mm2/s以上，且較佳為30mm2/s以下，更佳為20mm2/s以下，進而較佳為15mm2/s以下。複合酯之黏度指數較佳為100以上，更佳為115以上，較佳為180以下。所謂本發明中之動黏度及黏度指數，分別意指依據JIS K2283而測定之動黏度及黏度指數。
作為複合酯之合成方法，可列舉：
(a)調整多元醇與多元酸之莫耳比，合成多元酸之羧基之一部分未經酯化而殘存之酯中間物，繼而利用一元醇將該殘存之羧基酯化之方法
(b)調整多元醇與多元酸之莫耳比，合成多元醇之羥基之一部分未經酯化而殘存之酯中間物，繼而利用一元脂肪酸將該殘存之羥基酯化之方法
等。藉由上述(b)之方法而獲得之複合酯若於用作冷凍機油時水解，則會產生相對較強之酸，故而存在與藉由上述(a)之方法而獲得之複合酯相比穩定性稍差之傾向。作為本實施形態中之複合酯，較佳為穩定性更高之藉由上述(a)之方法而獲得之複合酯。
作為構成複合酯之多元醇，使用選自新戊二醇、三羥甲基丙烷及季戊四醇中之至少1種。作為多元醇，為了確保作為基油之較佳黏度、獲得良好之低溫特性，較佳為新戊二醇、三羥甲基丙烷。作為多元醇，就可廣泛調整黏度之方面而言，更佳為新戊二醇。
就可實現潤滑性之進一步提高之方面而言，構成複合酯之多元醇較佳為除了選自新戊二醇、三羥甲基丙烷及季戊四醇中之至少1種以外，進而含有新戊二醇以外之碳數2~10之二元醇。作為新戊二醇 以外之碳數2~10之二元醇，可列舉：乙二醇、丙二醇、丁二醇、戊二醇、己二醇、2-甲基-1,3-丙二醇、3-甲基-1,5-戊二醇、及2,2-二乙基-1,3-戊二醇等。該等之中，較佳為合成後之基油之特性之平衡良好之丁二醇。作為丁二醇，可列舉：1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、及2,3-丁二醇等。該等之中，就可獲得良好之特性之方面而言，更佳為1,3-丁二醇、1,4-丁二醇。相對於選自新戊二醇、三羥甲基丙烷及季戊四醇之多元醇1莫耳，新戊二醇以外之碳數2~10之二元醇係以較佳為1.2莫耳以下、更佳為0.8莫耳以下、進而較佳為0.4莫耳以下而使用。
構成複合酯之多元酸係選自碳數6~12之多元酸中之至少1種。 作為該多元酸，可列舉：己二酸、庚二酸、辛二酸、壬二酸、癸二酸、鄰苯二甲酸、及偏苯三甲酸等。該等之中，就合成後之酯之特性之平衡優異且獲取容易之方面而言，較佳為己二酸、癸二酸，更佳為己二酸。相對於選自新戊二醇、三羥甲基丙烷及季戊四醇中之多元醇1莫耳，該多元酸係以較佳為0.4莫耳以上、更佳為0.5莫耳以上、進而較佳為0.6莫耳以上而使用，且係以較佳為4莫耳以下、更佳為3莫耳以下、進而較佳為2.5莫耳以下而使用。
於在藉由上述多元醇與多元酸之反應而產生之複合酯中間物中多元酸之羧基之一部分未經酯化而殘存之情形時，該羧基係藉由選自碳數4~18之一元醇中之至少1種而被酯化。作為碳數4~18之一元醇，可列舉：直鏈或分支之丁醇、直鏈或分支之戊醇、直鏈或分支之己醇、直鏈或分支之庚醇、直鏈或分支之辛醇、直鏈或分支之壬醇、直鏈或分支之癸醇、直鏈或分支之十二烷醇、及油醇等脂肪族醇。就特性之平衡之方面而言，該碳數4~18之一元醇較佳為碳數6~10之一元醇，更佳為碳數8~10之一元醇。該等之中，就合成後之複合酯之低溫特性變得良好之方面而言，進而較佳為2-乙基己醇及3,5,5-三甲 基己醇。
於在藉由上述多元醇與多元酸之反應而產生之複合酯中間物中多元醇之羥基之一部分未經酯化而殘存之情形時，該羥基係藉由選自碳數4~18之一元脂肪酸中之至少1種而被酯化。作為碳數4~18之一元脂肪酸，可列舉：直鏈或分支之丁酸、直鏈或分支之戊酸、直鏈或分支之己酸、直鏈或分支之庚酸、直鏈或分支之辛酸、直鏈或分支之壬酸、直鏈或分支之癸酸、直鏈或分支之十二烷酸、及油酸等。該碳數4~18之一元脂肪酸較佳為碳數8~10之一元脂肪酸，就低溫特性之方面而言，更佳為2-乙基己酸及3,5,5-三甲基己酸。
本實施形態中之多元醇酯係由選自新戊二醇、三羥甲基丙烷、季戊四醇及二季戊四醇中之至少1種多元醇及選自碳數4~18之一元脂肪酸中之至少1種所合成之多元醇酯。
作為構成多元醇酯之多元醇，就特性之平衡之方面而言，較佳為三羥甲基丙烷及季戊四醇，更佳為季戊四醇。
作為構成多元醇酯之碳數4~18之一元脂肪酸，可列舉：直鏈或分支之丁酸、直鏈或分支之戊酸、直鏈或分支之己酸、直鏈或分支之庚酸、直鏈或分支之辛酸、直鏈或分支之壬酸、直鏈或分支之癸酸、直鏈或分支之十二烷酸、及油酸等。就低溫特性之方面而言，該碳數4~18之一元脂肪酸較佳為碳數4~9之一元脂肪酸，更佳為分支之丁酸、分支之戊酸、分支之己酸、分支之庚酸、2-乙基己酸及3,5,5-三甲基己酸。
作為本實施形態之多元醇酯，就與冷媒之相容性之方面而言，較佳為季戊四醇與選自碳數4~9之支鏈脂肪酸中之2種以上之混合脂肪酸之多元醇酯，更佳為季戊四醇與碳數4之支鏈脂肪酸及碳數9之支鏈脂肪酸之混合脂肪酸之多元醇酯，進而較佳為季戊四醇與碳數4之支鏈脂肪酸及3,5,5-三甲基己酸之混合脂肪酸之多元醇酯。
多元醇酯之40℃下之動黏度較佳為5mm2/s以上，更佳為20mm2/s以上，進而較佳為30mm2/s以上，且較佳為300mm2/s以下，更佳為200mm2/s以下，進而較佳為60mm2/s。多元醇酯之100℃下之動黏度較佳為1mm2/s以上，更佳為2mm2/s以上，進而較佳為3mm2/s以上，且較佳為30mm2/s以下，更佳為15mm2/s以下，進而較佳為7mm2/s以上。多元醇酯之黏度指數較佳為70以上，更佳為80以上，進而較佳為90，且較佳為150以下。
於冷凍機用作動流體組合物中，(A)複合酯之含量與(B)多元醇酯之含量之質量比((A)之含量/(B)之含量)為5/95~95/5，為了進一步發揮各酯之特性，較佳為20/80~80/20，更佳為30/70~70/30。
冷凍機油之流動點較佳為-10℃以下，更佳為-20℃以下。所謂本發明中之流動點，意指依據JIS K2269而測定之流動點。
為了防止對用於冷凍機或配管之金屬之腐蝕、且並抑制冷凍機油本身之劣化，冷凍機油之酸值可設為較佳為0.1mgKOH/g以下，更佳為0.05mgKOH/g以下。所謂本發明中之酸值，意指依據JIS K2501「酸值試驗方法」而測定之酸值。
冷凍機油之燃點較佳為120℃以上，更佳為200℃以上。所謂本發明中之燃點，意指依據JIS K2265-4而測定之燃點。
冷凍機油之水分含量較佳為200ppm以下，更佳為100ppm以下，進而較佳為50ppm以下。尤其是於用於密閉型之冷凍機之情形時，就對冷凍機油之穩定性或電絕緣性之觀點而言，要求水分含量較少。
冷凍機油除了上述複合酯及多元醇酯以外，亦可進而含有礦物油系基油、合成系基油等其他基油。以冷凍機油總量為基準，上述複合酯之含量與上述多元醇酯之含量之合計較佳為80質量%以上，更佳為95質量%以上。
為了進而提高耐磨耗性，冷凍機油可含有各種添加劑。
作為較佳之添加劑，例如可列舉磷酸酯。磷酸酯之中，較佳為磷酸三苯酯(TPP)、磷酸三甲苯酯(TCP)。作為較佳之硫系添加劑，可列舉硫化合物。作為硫化合物，雖然有多種，但就可確保冷凍機油之穩定性且抑制於冷凍機器內部大量使用之銅之變質的方面而言，較佳為單硫醚化合物。
冷凍機油除了上述添加劑以外，亦可於不損及本發明之目的之範圍內，為了進一步提高性能而含有先前以來用於潤滑油之各種添加劑。作為該添加劑，例如可列舉抗氧化劑、摩擦調整劑、防磨耗劑、極壓劑、防銹劑、金屬減活劑、及消泡劑。
作為抗氧化劑，可列舉：二-第三丁基-對甲酚般之酚系化合物、及烷基二苯胺般之胺系化合物等。尤其是冷凍機油以冷凍機油總量為基礎，較佳為含有0.02質量%以上之酚系化合物作為抗氧化劑，又，較佳為含有0.5質量%以下。
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、磷酸酯胺鹽、及亞磷酸酯胺鹽等。作為防磨耗劑，可列舉二烷基二硫代磷酸鋅等。作為極壓劑，可列舉硫化烯烴、硫化油脂等。作為防銹劑，可列舉烯基琥珀酸之酯或部分酯等。作為金屬減活劑，可列舉苯并三唑、苯并三唑衍生物等。作為消泡劑，可列舉聚矽氧化合物、聚酯化合物等。
與本實施形態之冷凍機油一起使用之冷媒、及本實施形態之冷凍機用作動流體組合物所含有之冷媒係選自二氧化碳、1,1,1,2-四氟乙烷(R134a)、二氟甲烷(R32)與五氟乙烷(R125)之混合物、二氟甲烷(R32)與五氟乙烷(R125)與1,1,1,2-四氟乙烷(R134a)之混合物、及五氟乙烷(R125)與1,1,1,2-四氟乙烷(R134a)與1,1,1-三氟乙烷(R143a)之混合物中。該冷媒可為選自上述中之1種，亦可為2種以上。又，作為該冷 媒，除了選自上述中之冷媒以外，亦可併用其他冷媒。以冷媒總量為基準，選自上述中之冷媒之含量較佳為60~100質量%，更佳為80~100質量%。
於上述二氟甲烷(R32)與五氟乙烷(R125)之混合物中，質量比(R32/R125)例如可設為40~70/60~30。該等之中，可較佳地使用質量比(R32/R125)為60/40之混合物、質量比為50/50之混合物(R410A)、及質量比為45/55之混合物(R410B)。
於上述二氟甲烷(R32)與五氟乙烷(R125)與1,1,1,2-四氟乙烷(R134a)之混合物中，質量比(R32/R125/R134a)例如可設為15~35/5~40/40~70。該等之中，可較佳地使用質量比(R32/R125/R134a)為30/10/60之混合物、質量比為23/25/52之混合物(R407C)、及質量比為25/15/60之混合物(R407E)。
於上述五氟乙烷(R125)與1,1,1,2-四氟乙烷(R134a)與1,1,1-三氟乙烷(R143a)之混合物中，質量比(R125/R134a/R143a)例如可設為35~55/1~15/40~60。該等之中，可較佳地使用質量比(R125/R134a/R143a)為44/4/52之混合物(R404A)。
冷凍機用作動流體組合物中之冷凍機油之含量並無特別限制，相對於冷媒100質量份，較佳為1質量份以上，更佳為2質量份以上，且較佳為500質量份以下，更佳為400質量份以下。
[實施例]
以下，根據實施例及比較例對本發明更具體地進行說明，但本發明不受以下實施例之任何限定。
首先，使用以下所示之基材製備具有表1、2所示之組合之基油1~8。
[A]複合酯
(A1)使由己二酸(2.4莫耳)與新戊二醇(1莫耳)及1,4-丁二醇(0.3莫 耳)反應而產生之酯中間物進而與3,5,5-三甲基己醇(2.5莫耳)反應，並藉由蒸餾將殘存之未反應物去除而獲得之酯(40℃下之動黏度67.8mm2/s，100℃下之動黏度10.6mm2/s，黏度指數145)。
(A2)使由己二酸(1.9莫耳)與新戊二醇(1莫耳)及1,4-丁二醇(0.2莫耳)反應而產生之酯中間物進而與3,5,5-三甲基己醇(1.1莫耳)反應，並藉由蒸餾將殘存之未反應物去除而獲得之酯(40℃下之動黏度145.8mm2/s，100℃下之動黏度17.9mm2/s，黏度指數136)。
(A3)使由己二酸(2.3莫耳)與新戊二醇(1莫耳)及1,4-丁二醇(0.3莫耳)反應而產生之酯中間物進而與2-乙基己醇(2.3莫耳)反應，並藉由蒸餾將殘存之未反應物去除而獲得之酯(40℃下之動黏度67.6mm2/s，100℃下之動黏度10.6mm2/s，黏度指數145)。
(A4)使由己二酸(2.5莫耳)與新戊二醇(1莫耳)反應而產生之酯中間物進而與3,7-二甲基辛醇(2.6莫耳)反應，並藉由蒸餾將殘存之未反應物去除而獲得之酯(40℃下之動黏度68.2mm2/s，100℃下之動黏度10.4mm2/s，黏度指數139)。
(A5)使由己二酸(0.8莫耳)與新戊二醇(1莫耳)反應而產生之酯中間物進而與3,5,5-三甲基己酸(0.3莫耳)反應，並藉由蒸餾將殘存之未反應物去除而獲得之酯(40℃下之動黏度300mm2/s，100℃下之動黏度26.2mm2/s，黏度指數115)。
[B]多元醇酯
(B1)季戊四醇與2-甲基丙酸及3,5,5-三甲基己酸之混合酸(以莫耳比計為35：65)之酯(40℃下之動黏度69.4mm2/s，100℃下之動黏度8.2mm2/s，黏度指數82)。
(B2)季戊四醇與2-甲基丙酸及3,5,5-三甲基己酸之混合酸(以莫耳比計為60：40)之酯(40℃下之動黏度46.2mm2/s，100℃下之動黏度6.3mm2/s，黏度指數77)。
(B3)季戊四醇與2-乙基己酸及3,5,5-三甲基己酸之混合酸(以莫耳比計為45：55)之酯(40℃下之動黏度68.4mm2/s，100℃下之動黏度8.4mm2/s，黏度指數91)。
(B4)二季戊四醇與2-乙基己酸及3,5,5-三甲基己酸之混合酸(以莫耳比計為50：50)之酯(40℃下之動黏度222.5mm2/s，100℃下之動黏度18.8mm2/s，黏度指數94)。
(B5)新戊二醇與2-乙基己酸之酯(40℃下之動黏度7.5mm2/s，100℃下之動黏度2.0mm2/s，黏度指數31)。
(B6)季戊四醇與正戊酸及3,5,5-三甲基己酸之混合酸(以莫耳比計為65：35)之酯(40℃下之動黏度31.4mm2/s，100℃下之動黏度5.6mm2/s，黏度指數118)。
[C]烴油
(C1)聚α-烯烴(PAO)(40℃下之動黏度34.0mm2/s，100℃下之動黏度6.9mm2/s，黏度指數168)
(C2)聚α-烯烴(PAO)(40℃下之動黏度68.0mm2/s，100℃下之動黏度9.9mm2/s，黏度指數128)
該等基油之中，於[A]及[B]之酯之合成反應中不使用觸媒及溶劑而進行合成，且於最終步驟中藉由吸附處理(白土處理)將微量之雜質去除。動黏度及黏度指數係依據JIS K2283進行測定並計算。
繼而，於表3~17所示之各基油中，於任何情形時均調配0.1質量%之作為抗氧化劑之二-第三丁基-對甲酚(DBPC)而製備冷凍機油。再者，表3~17中之基油C1、C2、B6分別意指包含上述基材C1、C2、B6之基油。
針對各實施例及比較例之冷凍機油，如下述般進行耐磨耗性試驗及穩定性試驗。於耐磨耗性試驗及穩定性試驗中所使用之評價冷媒如表3~17所記載。以下示出各評價冷媒之詳細情況。
R407C：二氟甲烷/五氟乙烷/1,1,1,2-四氟乙烷之混合物(質量比 23/25/52)
CO2：二氧化碳
R404A：五氟乙烷/1,1,1,2-四氟乙烷/1,1,1-三氟乙烷之混合物(質量比44/4/52)
R134a：1,1,1,2-四氟乙烷
R410A：二氟甲烷/五氟乙烷之混合物(質量比50/50)
(耐磨耗性試驗)
使用可形成與實際壓縮機類似之冷媒環境之神鋼造機(股份)製造之高壓環境摩擦試驗機(旋轉葉輪材與固定碟片材之旋轉滑動方式)進行耐磨耗性試驗。試驗條件係根據評價冷媒之種類而設為下述耐磨耗性試驗-(1)~(5)之任一種。
耐磨耗性試驗-(1)：使用R407C作為冷媒，試驗容器內壓力為1.6MPa。
耐磨耗性試驗-(2)：冷媒使用CO2，試驗容器內壓力為1.6MPa。
耐磨耗性試驗-(3)：冷媒使用R404A，試驗容器內壓力為1.6MPa。
耐磨耗性試驗-(4)：冷媒使用R134a，試驗容器內壓力為1.6MPa。
耐磨耗性試驗-(5)：冷媒使用R410A，試驗容器內壓力為3.1MPa。
於耐磨耗性試驗-(1)~(5)之任一種中，油量600ml、試驗溫度110℃、轉速500rpm、負載荷重80kgf、試驗時間1小時之條件均為共同。使用SKH-51作為葉輪材、使用FC250作為碟片材之方面亦共同。再者，由於碟片材之磨耗量極少，因此耐磨耗性之評價係根據葉輪材之磨耗深度而進行。將所獲得之結果示於表3~17。
(穩定性試驗)
穩定性試驗係依據JIS K2211-09(熱壓試驗)，稱量將含有水分量調整為100ppm之試樣油80g至高壓釜中，封入觸媒(鐵、銅、鋁之線，均為外徑1.6mm×長度50mm)與評價冷媒20g後加熱至150℃，測定150小時後之試樣油之外觀與酸值(JIS C2101)。將所獲得之結果示於表3~17中。
[產業上之可利用性]
本發明之冷凍機用作動流體組合物及冷凍機油即便於嚴苛之潤滑條件下耐磨耗性亦優異，因此具有大幅度地提高潤滑性之顯著效果。因此，可於具有壓縮器、凝縮器、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‧空調系統中較佳地使用，尤其是可於具有旋轉型、擺動型、捲動型等之壓縮器之系統中較佳地使用，於室內空調、封裝空調、冰箱、汽車空調、產業用冷凍機等領域有用。

Claims (8)

  1. 一種冷凍機用作動流體組合物，其含有：冷凍機油，其含有混合酯作為基油，上述混合酯係將(A)由包含選自新戊二醇、三羥甲基丙烷及季戊四醇中之至少1種之多元醇、選自碳數6~12之多元酸之至少1種、及選自碳數4~18之一元醇及碳數4~18之一元脂肪酸中之至少1種所合成且40℃下之動黏度為40mm2/s以上之複合酯，與(B)由選自新戊二醇、三羥甲基丙烷、季戊四醇及二季戊四醇中之至少1種多元醇及選自碳數4~18之一元脂肪酸中之至少1種所合成之多元醇酯，以上述(A)複合酯/上述(B)多元醇酯之質量比5/95~95/5混合而成；及冷媒，其係選自二氧化碳、二氟甲烷與五氟乙烷之混合物、二氟甲烷與五氟乙烷與1,1,1,2-四氟乙烷之混合物、及五氟乙烷與1,1,1,2-四氟乙烷與1,1,1-三氟乙烷之混合物中。
  2. 如請求項1之冷凍機用作動流體組合物，其中構成上述(A)複合酯之上述多元醇進而包含新戊二醇以外之碳數2~10之二元醇。
  3. 如請求項1或2之冷凍機用作動流體組合物，其中構成上述(A)複合酯之上述多元醇包含選自新戊二醇及三羥甲基丙烷中之至少1種。
  4. 如請求項1或2之冷凍機用作動流體組合物，其中構成上述(A)複合酯之上述多元酸係選自己二酸及癸二酸中之至少1種。
  5. 如請求項1或2之冷凍機用作動流體組合物，其中構成上述(A)複合酯之上述一元醇係碳數8~10之一元醇。
  6. 如請求項1或2之冷凍機用作動流體組合物，其中上述(B)多元醇酯係由選自新戊二醇及季戊四醇中之至少1種、與選自碳數4~9之一元脂肪酸中之至少1種所合成之酯。
  7. 如請求項1或2之冷凍機用作動流體組合物，其中上述(B)多元醇酯係由季戊四醇、與碳數4之支鏈脂肪酸及3,5,5-三甲基己酸之混合脂肪酸所合成之酯。
  8. 一種冷凍機油，其含有混合酯作為基油，上述混合酯係將(A)由包含選自新戊二醇、三羥甲基丙烷及季戊四醇中之至少1種之多元醇、選自碳數6~12之多元酸中之至少1種、及選自碳數4~18之一元醇及碳數4~18之一元脂肪酸中之至少1種所合成且40℃下之動黏度為40mm2/s以上之複合酯，與(B)由選自新戊二醇、三羥甲基丙烷、季戊四醇及二季戊四醇中之至少1種多元醇及選自碳數4~18之一元脂肪酸中之至少1種所合成之多元醇酯，以上述(A)複合酯/上述(B)多元醇酯之質量比5/95~95/5混合而成，且上述冷凍機油係與之冷媒一起使用，該冷媒係選自二氧化碳、二氟甲烷與五氟乙烷之混合物、二氟甲烷與五氟乙烷與1,1,1,2-四氟乙烷之混合物、及五氟乙烷與1,1,1,2-四氟乙烷與1,1,1-三氟乙烷之混合物。
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