TW201343902A - 冷凍機油組合物及其製造方法、冷凍機用作動流體組合物 - Google Patents
冷凍機油組合物及其製造方法、冷凍機用作動流體組合物 Download PDFInfo
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- TW201343902A TW201343902A TW102106298A TW102106298A TW201343902A TW 201343902 A TW201343902 A TW 201343902A TW 102106298 A TW102106298 A TW 102106298A TW 102106298 A TW102106298 A TW 102106298A TW 201343902 A TW201343902 A TW 201343902A
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- Prior art keywords
- acid
- ester
- refrigerating machine
- oil composition
- machine oil
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- 239000000203 mixture Substances 0.000 title claims abstract description 96
- 239000012530 fluid Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 146
- 229930195729 fatty acid Natural products 0.000 claims abstract description 146
- 239000000194 fatty acid Substances 0.000 claims abstract description 146
- 150000002148 esters Chemical class 0.000 claims abstract description 130
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 111
- 239000000654 additive Substances 0.000 claims abstract description 70
- 230000000996 additive effect Effects 0.000 claims abstract description 63
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 45
- 239000002199 base oil Substances 0.000 claims abstract description 35
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 34
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 polyol ester Chemical class 0.000 claims description 94
- 239000010721 machine oil Substances 0.000 claims description 82
- 239000003507 refrigerant Substances 0.000 claims description 69
- 229920005862 polyol Polymers 0.000 claims description 49
- 239000002253 acid Substances 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 18
- 229910019142 PO4 Inorganic materials 0.000 claims description 18
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 claims description 18
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 18
- 239000010452 phosphate Substances 0.000 claims description 18
- OILUAKBAMVLXGF-UHFFFAOYSA-N 3,5,5-trimethyl-hexanoic acid Chemical compound OC(=O)CC(C)CC(C)(C)C OILUAKBAMVLXGF-UHFFFAOYSA-N 0.000 claims description 15
- 150000003568 thioethers Chemical class 0.000 claims description 15
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 10
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- DRRMRHKHTQRWMB-UHFFFAOYSA-N [3-(2-ethylhexanoyloxy)-2,2-bis(2-ethylhexanoyloxymethyl)propyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OCC(COC(=O)C(CC)CCCC)(COC(=O)C(CC)CCCC)COC(=O)C(CC)CCCC DRRMRHKHTQRWMB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
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- 125000004185 ester group Chemical group 0.000 abstract 1
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- 239000000470 constituent Substances 0.000 description 18
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- 238000005299 abrasion Methods 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
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- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 10
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- 238000002156 mixing Methods 0.000 description 9
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- 150000001875 compounds Chemical class 0.000 description 6
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
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- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 4
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- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
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- C09K5/042—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising compounds containing carbon and hydrogen only
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- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/24—Only one single fluoro component present
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- C10N2020/02—Viscosity; Viscosity index
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- Combustion & Propulsion (AREA)
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- Lubricants (AREA)
Abstract
本發明係一種冷凍機油組合物，其含有：自季戊四醇與選自碳數5~18之脂肪酸中之一種之四酯，及二季戊四醇與選自碳數5~18之脂肪酸中之一種之六酯中選出的至少一種之酯添加劑；及作為上述酯添加劑以外之酯之基礎油，上述酯添加劑之含量以上述冷凍機油組合物總量為基準為2~20質量%，且上述冷凍機油組合物之於40℃下之動黏度為3~500mm2/s。
Description
本發明係關於一種冷凍機油組合物及其製造方法以及冷凍機用作動流體組合物。
先前，作為冰箱、汽車空調、房間空調、產業用冷凍機等之冷媒，廣泛使用作為氫氟碳(HFC，Hydro Fluoro Carbon)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1/1(質量比)之混合冷媒的R410A等。
作為與上述之HFC冷媒共同使用之冷凍機油，有為提高潤滑性而調配各種添加劑者。
再者，於一般之潤滑油領域中，作為提高潤滑性之耐磨添加劑，已知有醇、酯、長鏈脂肪酸等之油性劑，或磷酸酯、金屬二硫代磷酸酯等之耐磨劑，有機硫化合物、有機鹵素化合物等之極壓添加劑。然而，於冷凍機油之情形時，就若非即便與冷媒共存但未析出且對穩定性未產生不良影響之添加劑則無法使用之方面而言，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，分別於專利文獻1中揭示有併用添加磷系添加劑與特定之環氧化合物之冷凍機用潤滑油，於專利文獻2中揭示有併用添加磷酸三苯酯與磷酸三(烷基苯基)酯之HFC冷媒用之壓縮機用潤滑油，於專利文獻3中揭示有添加包含磷酸三甲苯酯與縮水甘油醚之環氧或碳二醯亞胺作為HFC冷媒用之冷凍機油。
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，上述之HFC冷媒雖臭氧破壞係數(ODP，Ozone Depletion Potential)為零，但由於全球暖化係數(GWP，Global Warming Potential)較高為1000以上，因此根據所謂之F-氣體規制(氟-氣體規制)限制其使用。
因此，作為上述之HFC冷媒之替代冷媒，2,3,3,3-四氟丙烯(HFO-1234yf)等氫氟烯烴(HFO，Hydro Fluoro Olefin)、二氟甲烷(R32)等低GWP冷媒，與其熱力學特性一併備受關注。例如HFO-1234yf之GWP較低為4。R32之GWP稍高為675，但由於氣體之壓力較高，為高效率冷媒，因此作為有力之候補而進行研究。關於該等冷媒，考慮到GWP與各種特性之平衡，對單獨使用或以與其他冷媒之混合冷媒之形式而使用進行研究。
又，如異丁烷(R600a)或丙烷(R290)之烴系冷媒，GWP較低為20以下，且物性值較佳，因此雖具有可燃性，但已實用化於冰箱用途。
因上述之冷媒中之R32、或含有R32之混合冷媒等於使用時壓力變高，壓縮機之噴出溫度變高，故溶入冷媒之冷凍機油之油膜變薄，成為較差之潤滑條件。
又，於烴類冷媒之情形時，由於烴分子內無提高潤滑性之氟，因此與HFC冷媒等不同，無法期待由冷媒所引起之潤滑性提高。進而，由於烴類冷媒對冷凍機油之溶解度較高，因此於此情形時，冷凍
機油之黏度亦降低從而潤滑條件變差。
而且，作為與該等之GWP為700以下之冷媒(以下，視情況總稱為「低GWP冷媒」)共同使用之冷凍機油，即便直接轉用上述先前之HFC冷媒用冷凍機油，亦較難獲得充分之潤滑性。
例如，於用於上述先前之HFC冷媒用冷凍機油之添加劑之中，油性劑由於吸附而為潤滑皮膜，因此於如混合潤滑區域之相對負荷條件為適度之情形時，可維持較低之摩擦係數，但若負荷條件變差則失去耐磨之效果。
又，雖磷酸三苯酯或磷酸三甲苯酯具有一定程度之耐磨效果，但作為與潤滑條件較差之低GWP冷媒共存下之耐磨性並不充分。
本發明係鑒於先前技術所具有之課題而成者，其目的在於提供一種即便於低GWP冷媒共存下等較差之潤滑條件下耐磨之效果亦較大，長期可靠性優異且相溶之冷媒用之冷凍機油組合物及其製造方法，及冷凍機用作動流體組合物。
為解決上述課題，本發明提供一種冷凍機油組合物，其含有：自季戊四醇與選自碳數5~18之脂肪酸中之一種之四酯，及二季戊四醇與選自碳數5~18之脂肪酸中之一種之六酯中選出的至少一種酯添加劑；及作為上述酯添加劑以外之脂基礎油，上述酯添加劑之含量以上述冷凍機油組合物總量為基準為2~20質量%，上述冷凍機油組合物之於40℃下之動黏度為3~500 mm2/s。
如此，藉由將上述特定之酯添加劑之特定量調配於作為該酯添加劑以外之酯之基礎油中，進而將冷凍機油組合物之於40℃下之動黏度調整至上述之範圍內，於低GWP冷媒共存下未對其他特性產生不良影響，可大幅度提高冷凍機油之耐磨性。
此處，酯添加劑之構成脂肪酸如上所述，為選自碳數5~18之脂
肪酸中之一種。即，酯添加劑之構成脂肪酸必需為單一組成。
另一方面，於作為酯添加劑以外之酯之基礎油中，包含上述酯添加劑以外之全部之酯。例如，酯之構成醇為季戊四醇及/或二季戊四醇，即便構成脂肪酸中含有碳數5~18之脂肪酸，於構成脂肪酸為選自碳數5~18之脂肪酸中之2種以上之混合脂肪酸之情形時，或於構成脂肪酸為選自碳數5~18之脂肪酸中之1種或2種以上與其他脂肪酸之1種或2種以上之混合脂肪酸之情形時，亦可使用該等之酯作為基礎油。
再者，作為基礎油之酯之構成醇為季戊四醇及/或二季戊四醇，於構成脂肪酸為含有碳數5~18之脂肪酸之混合脂肪酸之情形時，於該基礎油合成時可產生季戊四醇與選自碳數5~18之脂肪酸中之一種之四酯及/或二季戊四醇與選自碳數5~18之脂肪酸中之一種之六酯。然而，根據本發明者之研究，即便使用此種酯作為基礎油，亦無法認定如將上述酯添加劑調配於基礎油中時之耐磨性提高效果。換言之，本發明之耐磨性效果係藉由將上述酯添加劑調配於作為該酯添加劑以外之酯之基礎油中而實現者，可認為係預計外之顯著效果。
於本發明中，較佳為上述酯添加劑為選自季戊四醇四(2-乙基己酸酯)及二季戊四醇六(己酸酯)中之至少一種。
又，較佳為冷凍機油組合物之於40℃下之動黏度為3~300 mm2/s。
進而，較佳為上述基礎油為多元醇酯。
又進而，較佳為上述基礎油為由季戊四醇與碳數4~7之羧酸及3,5,5-三甲基己酸之混合酸所獲得之多元醇酯。
又，較佳為上述基礎油為由季戊四醇與支鏈之丁酸及3,5,5-三甲基己酸所獲得之於40℃下之動黏度為30~110 mm2/s之多元醇酯。
又，較佳為上述酯添加劑之調配量以冷凍機油組合物總量為基
準為2~7質量%。
又，較佳為本發明之冷凍機油組合物以冷凍機油組合物總量為基準進而含有0.1~5質量%之磷酸酯及/或0.01~2質量%之硫醚化合物。
較佳為上述磷酸酯為選自磷酸三苯酯、磷酸三甲苯酯及含有碳數3~4之烷基之磷酸烷基苯酯中之至少一種。
又，較佳為上述硫醚化合物為硫代雙酚化合物。
又，本發明提供一種冷凍機油組合物之製造方法，其包括將酯添加劑調配於選自礦物油及合成油中之至少一種之基礎油中，進而獲得冷凍機油組合物之步驟，該酯添加劑為自季戊四醇與選自碳數5~18之脂肪酸中之一種之四酯，及二季戊四醇與選自碳數5~18之脂肪酸中之一種之六酯中選出的至少一種，且上述酯添加劑之調配量以上述冷凍機油組合物總量為基準為2~20質量%，且上述冷凍機油組合物之於40℃下之動黏度為3~500 mm2/s。
又，本發明提供一種冷凍機用作動流體組合物，其含有：上述本發明之冷凍機油組合物；冷媒，其含有選自氫氟碳、氫氟烯烴及烴類中之至少一種，且全球暖化係數(GWP)為700以下。
較佳為上述冷媒含有二氟甲烷(R32)。
如上所述，本發明之冷凍機油組合物即便於低GWP冷媒共存下之較差之潤滑負荷條件下，亦可發揮可維持耐磨之效果並且較低之摩擦係數，可長期穩定使用之特別效果。
以下，對本發明之較佳實施形態進行詳細說明。
[第1實施形態：冷凍機油組合物及其製造方法]
本發明之第1實施形態之冷凍機油組合物係含有選自季戊四醇與選自碳數5~18之脂肪酸中之一種之四酯，及二季戊四醇與選自碳數5~18之脂肪酸中之一種之六酯中的至少一種之酯添加劑，及作為上述酯添加劑以外之酯之基礎油而成。於本發明之冷凍機油組合物中，酯添加劑之含量以冷凍機油組合物總量為基準為2~20質量%，且冷凍機油組合物之於40℃下之動黏度為3~500 mm2/s。
酯添加劑之構成醇為季戊四醇及/或二季戊四醇，且於使用任一醇之情形時酯添加劑均為完全酯。再者，該構成醇亦可含有於通常之製造步驟中不可避免含有之雜質。
又，酯添加劑之構成脂肪酸為選自碳數5~18之脂肪酸中之一種，且必需為單一組成。其中，只要一分子中之構成脂肪酸為單一組成即可，於併用季戊四醇之四酯及二季戊四醇之六酯之2種以上之情形時，各完全酯之構成脂肪酸互相可相同亦可不同。再者，該構成脂肪酸亦可含有於通常之製造步驟中不可避免含有之雜質。
又，碳數5~18之脂肪酸亦可為飽和脂肪酸或不飽和脂肪酸中之任一種，且亦可為直鏈脂肪酸或支鏈脂肪酸之任一種。作為本發明之脂肪酸，具體而言，可列舉：直鏈狀或支鏈狀之戊酸、直鏈狀或支鏈狀之己酸、直鏈狀或支鏈狀之庚酸、直鏈狀或支鏈狀之辛酸、直鏈狀或支鏈狀之壬酸、直鏈狀或支鏈狀之癸酸、直鏈狀或支鏈狀之十一酸、直鏈狀或支鏈狀之十二酸、直鏈狀或支鏈狀之十三酸、直鏈狀或支鏈狀之十四酸、直鏈狀或支鏈狀之十五酸、直鏈狀或支鏈狀之十六酸、直鏈狀或支鏈狀之十七酸、直鏈狀或支鏈狀之十八酸等飽和脂肪酸；直鏈狀或支鏈狀之戊烯酸、直鏈狀或支鏈狀之己烯酸、直鏈狀或支鏈狀之庚烯酸、直鏈狀或支鏈狀之辛烯酸、直鏈狀或支鏈狀之壬
烯酸、直鏈狀或支鏈狀之癸烯酸、直鏈狀或支鏈狀之十一烯酸、直鏈狀或支鏈狀之十二烯酸、直鏈狀或支鏈狀之十三烯酸、直鏈狀或支鏈狀之十四烯酸、直鏈狀或支鏈狀之十五烯酸、直鏈狀或支鏈狀之十六烯酸、直鏈狀或支鏈狀之十七烯酸、直鏈狀或支鏈狀之十八烯酸等不飽和脂肪酸等。
酯添加劑之構成脂肪酸之碳數為5~18，較佳為5~12，更佳為6~9。若構成脂肪酸之碳數未達5，則耐磨性提高效果並不充分，又，若超過18則對低溫下之基礎油之溶解性降低。
酯添加劑可將季戊四醇及/或二季戊四醇與選自碳數5~18之脂肪酸中之1種進行脫水縮合反應而獲得。再者，亦可少量含有於酯添加劑製造時所產生之部分酯作為雜質，酯添加劑之酸值較佳為0.1 mgKOH/g以下，羥值較佳為10 mgKOH/g以下。
酯添加劑之含量以冷凍機油組合物總量為基準為2~20質量%，較佳為2~15質量%，更佳為2~7質量%。無論酯添加劑之調配量未達2質量%、或超過20質量%，耐磨性提高效果均不充分。該調配量於該範圍內，可根據基礎油之種類、動黏度等適當選定。
又，第1實施形態中之基礎油為上述酯添加劑以外之酯。酯可將醇與脂肪酸進行脫水縮合反應而獲得，於本實施形態中，就化學穩定性方面而言，可列舉以下作為較佳之基礎油成分：二元酸與1元醇之二酯、多元醇(尤其新戊基多元醇)與脂肪酸之多元醇酯、或多元醇與多元酸與一元醇(或脂肪酸)之複合酯。其中較佳為穩定性優異之多元醇酯。
進而，多元醇酯之中，由季戊四醇與碳數4~7之羧酸及3,5,5-三甲基己酸合成之酯由於酯添加劑之調配而潤滑性提高效果較大，因此較佳，更佳為該碳數4~7之羧酸為支鏈之丁酸之多元醇酯。進而，較佳為季戊四醇與支鏈之丁酸及3,5,5-三甲基己酸之多元醇酯之於40℃
下之動黏度為30~110 mm2/s。
又，作為本實施形態之基礎油，為多元醇與脂肪酸之酯，可較佳使用以下之酯(以下，稱為「多元醇脂肪酸酯(A)」)：上述脂肪酸中之碳數4~6之脂肪酸與碳數7~9之支鏈脂肪酸之莫耳比為15：85~90：10，上述碳數4~6之脂肪酸含有2-甲基丙酸，且碳數4~6之脂肪酸及碳數7~9之支鏈脂肪酸佔構成上述酯之脂肪酸之總量的合計比率為20莫耳%以上。
再者，多元醇脂肪酸酯(A)中包含多元醇之全部羥基經酯化之完全酯、多元醇之羥基之一部分未經酯化而殘留之部分酯、以及完全酯與部分酯之混合物，多元醇脂肪酸酯(A)之羥值較佳為10 mgKOH/g以下，進而較佳為5 mgKOH/g以下，最佳為3 mgKOH/g以下。
於構成多元醇脂肪酸酯(A)之脂肪酸中，碳數4~6之脂肪酸與具有支鏈之碳數7~9之脂肪酸之莫耳比為15：85~90：10，較佳為15：85~85：15，更佳為20：80~80：20，進而較佳為25：75~75：25，最佳為30：70~70：30。又，碳數4~6之脂肪酸及具有支鏈之碳數7~9之脂肪酸佔構成多元醇脂肪酸酯(A)之脂肪酸之總量之合計比率為20莫耳%以上。於未滿足有關脂肪酸組成之上述條件之情形時，不易以高水準兼具與冷媒(尤其是二氟甲烷冷媒)之充分之相溶性，及作為冷凍機油所必需之黏度。再者，此處所謂之脂肪酸之比率係以構成冷凍機油所含之多元醇脂肪酸酯(A)之脂肪酸總量為基準之值。
作為碳數4~6之脂肪酸，具體而言例如可列舉：丁酸、2-甲基丙酸、戊酸、2-甲基丁酸、3-甲基丁酸、2,2-二甲基丙酸、2-甲基戊酸、3-甲基戊酸、4-甲基戊酸、2,2-二甲基丁酸、2,3-二甲基丁酸、3,3-二甲基丁酸、己酸等。於該等之中，較佳為如2-甲基丙酸之於烷基骨架中具有支鏈者。
作為具有支鏈之碳數7~9之脂肪酸，具體而言例如可列舉：2-甲
基己酸、3-甲基己酸、4-甲基己酸、5-甲基己酸、2,2-二甲基戊酸、2,3-二甲基戊酸、2,4-二甲基戊酸、3,3-二甲基戊酸、3,4-二甲基戊酸、4,4-二甲基戊酸、2-乙基戊酸、3-乙基戊酸、1,1,2-三甲基丁酸、1,2,2-三甲基丁酸、1-乙基-1-甲基丁酸、1-乙基-2-甲基丁酸、辛酸、2-乙基己酸、3-乙基己酸、3,5-二甲基己酸、2,4-二甲基己酸、3,4-二甲基己酸、4,5-二甲基己酸、2,2-二甲基己酸、2-甲基庚酸、3-甲基庚酸、4-甲基庚酸、5-甲基庚酸、6-甲基庚酸、2-丙基戊酸、壬酸、2,2-二甲基庚酸、2-甲基辛酸、2-乙基庚酸、3-甲基辛酸、3,5,5-三甲基己酸、2-乙基-2,3,3-三甲基丁酸、2,2,4,4-四甲基戊酸、2,2,3,3-四甲基戊酸、2,2,3,4-四甲基戊酸、2,2-二異丙基丙酸等。
多元醇脂肪酸酯(A)中，碳數4~6之脂肪酸與具有支鏈之碳數7~9之脂肪酸之莫耳比為15：85~90：10，且，碳數4~6之脂肪酸只要含有2-甲基丙酸，則亦可含有碳數4~6之脂肪酸及具有支鏈之碳數7~9之脂肪酸以外之脂肪酸作為構成酸成分。
作為碳數4~6之脂肪酸及具有支鏈之碳數7~9之脂肪酸以外之脂肪酸，具體而言可列舉：乙酸、丙酸等碳數2~3之脂肪酸；庚酸、辛酸、壬酸等碳數7~9之直鏈脂肪酸；癸酸、十一酸、十二酸、十三酸、十四酸、十五酸、十六酸、十七酸、十八酸、十九酸、二十酸、油酸等碳數10~20之脂肪酸等。
於組合使用碳數4~6之脂肪酸及具有支鏈之碳數7~9之脂肪酸與該等之脂肪酸以外之脂肪酸之情形時，碳數4~6之脂肪酸及碳數7~9之支鏈脂肪酸佔構成多元醇脂肪酸酯(A)之脂肪酸之總量之合計比率必需為20莫耳%以上，較佳為25莫耳%以上，更佳為30莫耳%以上，進而更佳為80莫耳%以上。藉由該比率為20莫耳%以上，而與冷媒(尤其是二氟甲烷冷媒)之相溶性充分。
於多元醇脂肪酸酯(A)之中，酸構成成分係僅由2-甲基丙酸與
3,5,5-三甲基己酸構成者，於兼具確保必需黏度及與冷媒(尤其是二氟甲烷冷媒)之相溶性方面而言特佳。
本實施形態之多元醇脂肪酸酯(A)亦可為分子結構不同之酯之2種以上之混合物，於該情形時各個分子無需一定滿足上述之條件，只要作為構成冷凍機油中含有之季戊四醇脂肪酸酯之脂肪酸整體滿足上述條件即可。
如上所述，多元醇脂肪酸酯(A)係以碳數4~6之脂肪酸及具有支鏈之碳數7~9之脂肪酸為必需成分作為構成酯之酸成分，視需要含有其他之脂肪酸作為構成成分者。即，多元醇脂肪酸酯(A)可為僅以2種之脂肪酸作為酸結構成分者，亦可為以3種以上之結構不同之脂肪酸作為酸結構成分者，較佳為該多元醇脂肪酸酯僅含有與羰基碳鄰接之碳原子(α位碳原子)並非四級碳之脂肪酸作為酸構成成分。於構成多元醇脂肪酸酯之脂肪酸中含有α位碳原子為四級碳之脂肪酸之情形時，有二氟甲烷冷媒存在下之潤滑性並不充分之傾向。
又，作為構成多元醇脂肪酸酯(A)之多元醇，較佳為使用含有2~6個羥基之多元醇。
作為2元醇(二醇)，具體而言例如可列舉：乙二醇、1,3-丙二醇、丙二醇、1,4-丁二醇、1,2-丁二醇、2-甲基-1,3-丙二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、2-乙基-2-甲基-1,3-丙二醇、1,7-庚二醇、2-甲基-2-丙基-1,3-丙二醇、2,2-二乙基-1,3-丙二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,11-十一醇、1,12-十二醇等。又，作為三元以上之醇，具體而言例如可列舉：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)、三-(三羥甲基丙烷)、季戊四醇、二-(季戊四醇)、三-(季戊四醇)、甘油、聚甘油(甘油之2~3聚物)、1,3,5-戊三醇、山梨醇、山梨醇酐、山梨醇甘油縮合物、福壽草醇、阿糖醇、木糖醇、甘露糖醇等多元醇，木糖、阿拉伯糖、核酸糖、鼠李
糖、葡萄糖、果糖、半乳糖、甘露糖、山梨糖、纖維雙糖等糖類，及該等之部分醚化物等。於該等之中，就水解穩定性更優異之方面而言，更佳為新戊二醇、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)、三-(三羥甲基丙烷)、季戊四醇、二-(季戊四醇)、三-(季戊四醇)等受阻醇之酯，進而更佳為新戊二醇、三羥甲基乙烷、三羥甲基丙烷、三羥甲基丁烷及季戊四醇、二-(季戊四醇)之酯，進而較佳為新戊二醇、三羥甲基丙烷、季戊四醇、二-(季戊四醇)，就與冷媒之相溶性及水解穩定性特別優異之方面而言，最佳為季戊四醇、二-(季戊四醇)或季戊四醇與二-(季戊四醇)之混合酯。
作為多元醇脂肪酸酯(A)之構成脂肪酸之較佳例，可列舉以下者：(i)選自丁酸、2-甲基丙酸、戊酸、2-甲基丁酸、3-甲基丁酸、2,2-二甲基丙酸、2-甲基戊酸、3-甲基戊酸、4-甲基戊酸、2,2-二甲基丁酸、2,3-二甲基丁酸、3,3-二甲基丁酸及己酸中之1~13種，與選自2-甲基己酸、3-甲基己酸、4-甲基己酸、5-甲基己酸、2,2-二甲基戊酸、2,3-二甲基戊酸、2,4-二甲基戊酸、3,3-二甲基戊酸、3,4-二甲基戊酸、4,4-二甲基戊酸、2-乙基戊酸、3-乙基戊酸及2-乙基-3-甲基丁酸中之1~13種之組合；(ii)選自丁酸、2-甲基丙酸、戊酸、2-甲基丁酸、3-甲基丁酸、2,2-二甲基丙酸、2-甲基戊酸、3-甲基戊酸、4-甲基戊酸、2,2-二甲基丁酸、2,3-二甲基丁酸、3,3-二甲基丁酸及己酸中之1~13種，與2-甲基庚酸、3-甲基庚酸、4-甲基庚酸、5-甲基庚酸、6-甲基庚酸、2,2-二甲基己酸、3,3-二甲基己酸、4,4-二甲基己酸、5,5-二甲基己酸、2,3-二甲基己酸、2,4-二甲基己酸、2,5-二甲基己酸、3,4-二甲基己酸、3,5-二甲基己酸、4,5-二甲基己酸、2,2,3-三甲基戊酸、2,3,3-三甲基戊酸、2,4,4-三甲基戊酸、3,4,4-三甲基戊酸、2-乙基己酸、3-乙基己
酸、2-丙基戊酸、2-甲基-2-乙基戊酸、2-甲基-3-乙基戊酸及3-甲基-3-乙基戊酸中之1~25種之組合；(iii)選自丁酸、2-甲基丙酸、戊酸、2-甲基丁酸、3-甲基丁酸、2,2-二甲基丙酸、2-甲基戊酸、3-甲基戊酸、4-甲基戊酸、2,2-二甲基丁酸、2,3-二甲基丁酸、3,3-二甲基丁酸及己酸中之1~13種，與選自2-甲基辛酸、3-甲基辛酸、4-甲基辛酸、5-甲基辛酸、6-甲基辛酸、7-甲基辛酸、8-甲基辛酸、2,2-二甲基庚酸、3,3-二甲基庚酸、4,4-二甲基庚酸、5,5-二甲基庚酸、6,6-二甲基庚酸、2,3-二甲基庚酸、2,4-二甲基庚酸、2,5-二甲基庚酸、2,6-二甲基庚酸、3,4-二甲基庚酸、3,5-二甲基庚酸、3,6-二甲基庚酸、4,5-二甲基庚酸、4,6-二甲基庚酸、2-乙基庚酸、3-乙基庚酸、4-乙基庚酸、5-乙基庚酸、2-丙基己酸、3-丙基己酸、2-丁基戊酸、2,2,3-三甲基己酸、2,2,4-三甲基己酸、2,2,5-三甲基己酸、2,3,3-三甲基己酸、2,3,4-三甲基己酸、2,3,5-三甲基己酸、3,3,4-三甲基己酸、3,3,5-三甲基己酸、3,5,5-三甲基己酸、4,4,5-三甲基己酸、4,5,5-三甲基己酸、2,2,3,3-四甲基戊酸、2,2,3,4-四甲基戊酸、2,2,4,4-四甲基戊酸、2,3,4,4-四甲基戊酸、3,3,4,4-四甲基戊酸、2,2-二乙基戊酸、2,3-二乙基戊酸、3,3-二乙基戊酸、2-乙基-2,3,3-三甲基丁酸、3-乙基-2,2,3-三甲基丁酸及2,2-二異丙基丙酸中之1~50種之組合。
作為構成多元醇脂肪酸酯(A)之酸構成成分之進而較佳例，可列舉以下者：(i)2-甲基丙酸與選自2-甲基己酸、3-甲基己酸、4-甲基己酸、5-甲基己酸、2,2-二甲基戊酸、2,3-二甲基戊酸、2,4-二甲基戊酸、3,3-二甲基戊酸、3,4-二甲基戊酸、4,4-二甲基戊酸、2-乙基戊酸、3-乙基戊酸及2-乙基-3-甲基丁酸中之1~13種之組合；(ii)2-甲基丙酸與選自2-甲基庚酸、3-甲基庚酸、4-甲基庚酸、5-
甲基庚酸、6-甲基庚酸、2,2-二甲基己酸、3,3-二甲基己酸、4,4-二甲基己酸、5,5-二甲基己酸、2,3-二甲基己酸、2,4-二甲基己酸、2,5-二甲基己酸、3,4-二甲基己酸、3,5-二甲基己酸、4,5-二甲基己酸、2,2,3-三甲基戊酸、2,3,3-三甲基戊酸、2,4,4-三甲基戊酸、3,4,4-三甲基戊酸、2-乙基己酸、3-乙基己酸、2-丙基戊酸、2-甲基-2-乙基戊酸、2-甲基-3-乙基戊酸及3-甲基-3-乙基戊酸中之1~25種之組合；(iii)2-甲基丙酸與選自2-甲基辛酸、3-甲基辛酸、4-甲基辛酸、5-甲基辛酸、6-甲基辛酸、7-甲基辛酸、8-甲基辛酸、2,2-二甲基庚酸、3,3-二甲基庚酸、4,4-二甲基庚酸、5,5-二甲基庚酸、6,6-二甲基庚酸、2,3-二甲基庚酸、2,4-二甲基庚酸、2,5-二甲基庚酸、2,6-二甲基庚酸、3,4-二甲基庚酸、3,5-二甲基庚酸、3,6-二甲基庚酸、4,5-二甲基庚酸、4,6-二甲基庚酸、2-乙基庚酸、3-乙基庚酸、4-乙基庚酸、5-乙基庚酸、2-丙基己酸、3-丙基己酸、2-丁基戊酸、2,2,3-三甲基己酸、2,2,4-三甲基己酸、2,2,5-三甲基己酸、2,3,3-三甲基己酸、2,3,4-三甲基己酸、2,3,5-三甲基己酸、3,3,4-三甲基己酸、3,3,5-三甲基己酸、3,5,5-三甲基己酸、4,4,5-三甲基己酸、4,5,5-三甲基己酸、2,2,3,3-四甲基戊酸、2,2,3,4-四甲基戊酸、2,2,4,4-四甲基戊酸、2,3,4,4-四甲基戊酸、3,3,4,4-四甲基戊酸、2,2-二乙基戊酸、2,3-二乙基戊酸、3,3-二乙基戊酸、2-乙基-2,3,3-三甲基丁酸、3-乙基-2,2,3-三甲基丁酸及2,2-二異丙基丙酸中之1~50種之組合。
多元醇脂肪酸酯(A)之含量以冷凍機油總量為基準為50質量%以上，較佳為60質量%以上，更佳為70質量%以上，進而較佳為75質量%以上。再者，本實施形態之冷凍機油組合物，可含有多元醇脂肪酸酯(A)與其他酯，又，亦可進而含有後述之酯添加劑以外之添加劑作為基礎油，若多元醇脂肪酸酯(A)未達50質量%，則無法以高水準兼具必需黏度與相溶性。
於本實施形態之冷凍機油組合物含有多元醇脂肪酸酯(A)作為基礎油之情形時，亦可單獨僅使用多元醇脂肪酸酯(A)(即多元醇脂肪酸酯(A)之含量以基礎油總量為基準為100質量%)，除此之外，於無損其優異性能之程度，亦可進而含有多元醇脂肪酸酯(A)以外之酯作為基礎油。作為多元醇脂肪酸酯(A)以外之基礎油，可列舉酯添加劑及多元醇脂肪酸酯(A)以外之多元醇酯、複合酯、脂環式二羧酸酯等。
作為多元醇脂肪酸酯(A)以外之多元醇酯，可列舉新戊二醇、三羥甲基乙烷、三羥甲基丙烷、三羥甲基丁烷、季戊四醇、二季戊四醇等多元醇與脂肪酸之酯，特佳為新戊二醇與脂肪酸之酯、季戊四醇與脂肪酸之酯及二季戊四醇與脂肪酸之酯。
作為新戊二醇酯，較佳為新戊二醇與碳數5~9之脂肪酸之酯。作為此種新戊二醇酯，具體而言例如可列舉：新戊二醇二3,5,5-三甲基己酸酯、新戊二醇二2-乙基己酸酯、新戊二醇二2-甲基己酸酯、新戊二醇二2-乙基戊酸酯、新戊二醇與2-甲基己酸‧2-乙基戊酸之酯、新戊二醇與3-甲基己酸‧5-甲基己酸之酯、新戊二醇與2-甲基己酸‧2-乙基己酸之酯、新戊二醇與3,5-二甲基己酸‧4,5-二甲基己酸‧3,4-二甲基己酸之酯、新戊二醇二戊酸酯、新戊二醇二2-乙基丁酸酯、新戊二醇二2-甲基戊酸酯、新戊二醇二2-甲基丁酸酯、新戊二醇二3-甲基丁酸酯等。
作為季戊四醇酯，較佳為季戊四醇與選自碳數5~9之脂肪酸中之2種以上之混合脂肪酸之酯。作為此種季戊四醇酯，具體而言，可列舉：季戊四醇與選自戊酸、2-甲基丁酸、3-甲基丁酸、己酸、2-甲基戊酸、2-乙基丁酸、2-乙基戊酸、2-甲基己酸、3,5,5-三甲基己酸及2-乙基己酸中之2種以上之脂肪酸之酯。
作為二季戊四醇酯，較佳為二季戊四醇與選自碳數5~9之脂肪酸中之2種以上之混合脂肪酸之酯。作為此種二季戊四醇酯，具體而
言，例如可列舉二季戊四醇與選自戊酸、2-甲基丁酸、3-甲基丁酸、己酸、2-甲基戊酸、2-乙基丁酸、2-乙基戊酸、2-甲基己酸、3,5,5-三甲基己酸及2-乙基己酸中之2種以上之脂肪酸之酯。
於本實施形態之冷凍機油組合物含有酯添加劑及多元醇脂肪酸酯(A)以外之酯之情形時，多元醇脂肪酸酯(A)以外之含氧合成油之含量，只要無損本實施形態之冷凍機油之優異潤滑性與相溶性，則無特別限制，酯添加劑及多元醇脂肪酸酯(A)以外之多元醇酯之調配量，以冷凍機油總量為基準較佳為未達50質量%，更佳為45質量%以下，進而較佳為40質量%以下，進而更佳為35質量%以下，更佳為30質量%以下，最佳為25質量%以下；於調配多元醇酯以外之酯作為基礎油之情形時，以冷凍機油總量為基準較佳為未達50質量%，更佳為40質量%以下，進而較佳為30質量%以下。若季戊四醇脂肪酸酯以外之多元醇酯或其他酯之調配量過多，則不易獲得由酯添加劑及多元醇脂肪酸酯(A)之使用而產生之效果。
再者，多元醇脂肪酸酯(A)以外之多元醇酯亦可為多元醇之羥基之一部分未經酯化而保留羥基之部分酯，亦可為全部之羥基經酯化之完全酯，又亦可為部分酯與完全酯之混合物，較佳為羥值較佳為10 mgKOH/g以下，進而較佳為5 mgKOH/g以下，最佳為3 mgKOH/g以下者。
又，於本實施形態之冷凍機油含有多元醇脂肪酸酯(A)以外之多元醇酯之情形時，可含有包含單一構造之多元醇酯之1種者，又，亦可含有構造不同之2種以上之多元醇酯之混合物作為該多元醇酯。
又，多元醇脂肪酸酯(A)以外之多元醇酯，只要含有酯添加劑及與多元醇脂肪酸酯不同之構造，則亦可為1種脂肪酸與1種多元醇之酯、2種以上脂肪酸與1種多元醇之酯、1種脂肪酸與2種以上多元醇之酯、2種以上脂肪酸與2種以上多元醇之酯之任一種。
又，本實施形態之冷凍機油組合物亦可進而含有後述之各種添加劑。
本實施形態之冷凍機油組合物可進而含有磷酸酯。磷酸酯其本身具有作為耐磨添加劑之功能，若將上述酯添加劑與磷酸酯併用，則可飛躍性提高冷凍機油組合物之耐磨性。
作為較佳之酯磷酸，可列舉：磷酸三苯酯(TPP，Tri Phenyl Phosphate)、磷酸三甲苯酯(TCP，Tri Cresyl Phosphate)、含有碳數3~4之烷基之磷酸烷基苯酯(APP，Alkyl Phenyl Phosphate)。進而，作為APP，可使用烷基苯基為1個(單-型)、2個(二-型)、3個(三-型)之混合物，該等之混合比並無特別限定。
磷酸酯之調配量就更具高耐磨性效果及穩定性方面而言，以冷凍機油組合物總量為基準，較佳為0.1~3質量%，更佳為0.2~2質量%。
又，本實施形態之冷凍機油組合物可進而含有硫醚化合物。硫醚化合物其本身具有作為耐磨添加劑之功能，若將上述酯添加劑與硫醚化合物併用，則可飛躍性提高冷凍機油組合物之耐磨性。
作為硫醚化合物，較佳為單硫醚化合物。其原因在於，例如二硫醚化合物之活性較高之硫化合物使冷凍機油之穩定性降低，並使較多使用於冷凍機器內部之銅變質。
作為硫醚化合物，較佳為特別具有防止氧化即捕捉自由基能力、且亦為穩定劑之硫代雙酚化合物。
硫醚化合物之調配量，以冷凍機油組合物總量為基準，較佳為0.05~2質量%，更佳為0.1~1質量%。於硫醚化合物之調配量未達0.05質量%之情形時，有不易獲得由硫醚化合物之調配所產生之更大之耐磨性提高效果之傾向，又，若超過2質量%，則有根據使用環境而引起腐蝕磨耗之虞。
進而，於本實施形態中，亦可將磷酸酯與硫醚化合物併用。
又，本實施形態之冷凍機油組合物於無損本發明之目的之範圍內，為進一步提高性能，可含有自先前以來使用於潤滑油中之抗氧化劑、摩擦調整劑、磨耗防止劑、極壓添加劑、防銹劑、金屬減活劑、消泡劑等添加劑。
可分別列舉，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抗氧化劑，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摩擦調整劑，二烷基二硫代酸鋅等作為磨耗防止劑，硫化烯、硫化油脂等作為極壓添加劑，烯基琥珀酸酯或部分酯等作為防銹劑，苯并三唑等作為金屬減活劑，矽酮化合物、聚酯化合物等作為消泡劑。
本實施形態之冷凍機油組合物之於40℃下之動黏度為3~500 mm2/s，較佳為3~300 mm2/s，進而較佳為5~150 mm2/s。又，較佳為冷凍機油組合物之黏度指數為10以上。再者，本發明中所謂之於40℃下之動黏度及黏度指數係指依據JIS K2283而測定之值。
其他之性狀並無特別限定，冷凍機油組合物之流動點較佳為-10℃以下，更佳為-20℃以下。又，冷凍機油組合物之閃火點較佳為120℃以上，更佳為200℃以上。再者，流動點可依據JIS K2269「原油及石油製品之流動點及石油製品污點試驗方法」，又，閃火點可依據JIS K2265「原油及石油製品-閃火點試驗方法」之特氏閉杯式閃火點試驗方法而測定。
又，冷凍機油組合物之酸值並無特別限定，但為防止對用於冷凍機或配管之金屬之腐蝕，抑制冷凍機油自身之劣化，可設為較佳為0.1 mgKOH/g以下，更佳為0.05 mgKOH/g以下。再者，本發明中所謂之酸值意指依據JIS K2501「石油製品及潤滑油-中和試驗方法」而測定之酸值。
又，冷凍機油組合物之水分含量並無特別限定，但較佳為200 ppm以下，更佳為100 ppm以下，最佳為50 ppm以下。特別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，期望水分含量較少者。
本實施形態之冷凍機油組合物可藉由以下方法獲得：酯添加劑之調配量以上述冷凍機油組合物總量為基準成為2~20質量%，且，所獲得之冷凍機油組合物之於40℃下之動黏度成為3~500 mm2/s，以此方法，將上述酯添加劑調配於作為上述酯添加劑以外之酯之基礎油中。再者，於冷凍機油組合物含有酯添加劑及基礎油以外之成分(上述之磷酸酯、硫醚化合物等)之情形時，對該等成分之基礎油之調配可與酯添加劑同時進行，亦可於酯添加劑之調配前或調配後進行。
與本實施形態之冷凍機油組合物共同使用之冷媒並無特別限制，但較佳為與冷凍機油組合物相溶之冷媒，即於常溫下未進行二層分離而相溶之冷媒。進而，本實施形態之冷凍機油組合物，於與2,3,3,3-四氟丙烯(HFO-1234yf)等氫氟烯烴(HFO)或二氟甲烷(R32)等低GWP冷媒，或如異丁烷(R600a)或丙烷(R290)之烴系冷媒共同使用之情形時，可實現於先前之冷凍機油中難以達成之於較差之潤滑條件下之優異之耐磨性，因此非常有用。關於使用該等之冷媒之冷凍機用作動流體組合物，於下述之第2實施形態中更詳細進行說明。
[第2實施形態：冷凍機用作動流體組合物]
本發明之第2實施形態之冷凍機用作動流體組合物含有：上述第1實施形態之冷凍機油組合物，與含有選自氫氟碳、氫氟烯烴及烴類中之至少1種，且全球暖化係數(GWP)為700以下之冷媒。再者，本實施形態中之冷凍機油組合物與上述第1實施形態之情況相同，因此此處省略重複之說明。
作為GWP為700以下之氫氟碳(HFC)，可列舉沸點較低高壓之氫
氟碳(HFC)之R32或含有較多R32之混合冷媒(R410A等)。該等之HFC冷媒具有沸點高且高壓之特徵，因其使用時壓縮機之噴出溫度變高，故油膜變薄，而成為較差之潤滑條件。由此，於使用先前之冷凍機油之情形時耐磨性並不充分。與此相對，根據本實施形態，即便於使用上述之HFC冷媒之情形時，亦可實現優異之耐磨性。
又，作為GWP為700以下之氫氟烯烴(HFO)，可列舉：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。因該等之HFO冷媒具有易於分子內分解之烯烴構造，故具有GWP較低相反穩定性亦較低之特徵。尤其，利用於較差之潤滑條件下由金屬/金屬接觸所引起之滑動部位中之局部發熱，而於產生磨耗之同時促進冷媒之分解。由此，於使用先前之冷凍機油之情形時，有導致冷媒與冷凍機油相溶之作動流體劣化之虞。與此相對，根據本實施形態，即便於使用上述之HFO冷媒之情形時，不必損害冷凍機用作動流體組合物之穩定性，則可實現優異之耐磨性。
又，作為GWP為700以下之烴類冷媒，可列舉碳數3~6之飽和烴，尤其是異丁烷(R600a)或丙烷(R290)等。於該等之烴類冷媒之情形時，因無有助於烴分子內潤滑性提高之氟，及對冷凍機油之溶解度較高，故冷凍機油之黏度下降，而成為較差之潤滑條件。因此，於使用先前之冷凍機油之情形時耐磨性並不充分。與此相對，根據本實施形態，即便於使用上述之烴類冷媒之情形時，亦可實現優異之耐磨性。
以下，基於實施例及比較例對本發明進行詳細說明，但本發明並非係限定於以下之實施例者。
[實施例1~12、比較例1~12]
於實施例1~12及比較例1~12中，分別使用以下所示之基礎油
及添加劑，製備含有表1~3所示之組成之冷凍機油組合物。
(A)酯基礎油
(A-1)POE-1：季戊四醇與2-甲基丙酸及3,5,5-三甲基己酸以質量比計為7：3之混合酸之酯(於40℃下之動黏度：34.4 mm2/s、黏度指數：77)
(A-2)POE-2：季戊四醇與2-甲基丙酸及2-乙基己酸以質量比計為3：7之混合酸之酯(於40℃下之動黏度：36.7 mm2/s、黏度指數：78)
(A-3)POE-3：二季戊四醇與正丁酸及3,5,5-三甲基己酸以質量比計為7：3之混合酸之酯(於40℃下之動黏度：65.1 mm2/s、黏度指數：90)
(A-4)POE-4：季戊四醇與正戊酸、正庚酸及3,5,5-三甲基己酸以質量比計為4：4：2之混合酸之酯(於40℃下之動黏度：28.5 mm2/s、黏度指數：133)
(A-5)POE-5：三羥甲基丙烷與油酸之酯(於40℃下之動黏度：48.3 mm2/s、黏度指數：176)
(B)酯添加劑
(B-1)PE2EH：季戊四醇四(2-乙基己酸酯)(季戊四醇與2-乙基己酸之四酯、酸值：0.01 mgKOH/g、羥值：1 mgKOH/g)
(B-2)DPEH：二季戊四醇六(己酸酯)(二季戊四醇與正己酸之六酯、酸值：0.01 mgKOH/g、羥值：1 mgKOH/g)
(C)其他之添加劑
(C-1)磷酸三甲苯酯(TCP)
(C-2)磷酸三苯酯(TPP)
(C-3)磷酸十三烷基酯(TDP，Tris Decyl Phosphate)
(C-4)二苄基硫化物
(C-5)二(十二烷基)硫化物
(C-6)4,4'-硫代雙(3-甲基-6-第三丁基苯酚)
其次，將實施例1~12及比較例1~12之冷凍機油組合物分別與表1~3所示之冷媒進行組合，實施以下之評價試驗。
(潤滑性試驗)
於潤滑性試驗中，使用於與真實壓縮機類似之冷媒環境中製造之神鋼造機(股)製造之高壓環境摩擦試驗機(旋轉葉輪材與固定圓盤材之旋轉滑動方式)。基本試驗之條件為油量：600 ml、試驗溫度：110℃、轉速：500 rpm、負荷荷重：100 kgf、試驗時間：1小時，使用SKH-51作為葉輪材，使用FC250作為圓盤材。
試驗根據冷媒之種類於以下4種試驗條件下進行。
潤滑性試驗-(1)：冷媒係使用R32，試驗容器內壓力設為3.1 MPa。
潤滑性試驗-(2)：冷媒係使用HFO-1234yf(表中省略為yf)，試驗容器內壓力設為1.6 MPa。
潤滑性試驗-(3)：冷媒係使用R410A(質量比R32/R125=1/1)，試驗容器內壓力設為3.1 MPa。
潤滑性試驗-(4)：以相對於冷凍機油組合物之容積比為20%調配正己烷(表中省略為正C6)而進行試驗(用作R290等之烴類冷媒之替代)。壓力為稍高於常壓之程度。
再者，因圓盤材之磨耗量極少，故耐磨性之評價根據葉輪材之磨耗量進行。所獲得之結果如表1~3所示。
(穩定性試驗)
稱取水分含量調整至100 ppm之試樣油90 g至高壓釜內，裝入10 g觸媒(鐵、銅、鋁線，任一外徑均為1.6 mm×50 mm)與各個冷媒(使用R32、HFO-1234yf、R410A、正己烷)後，加熱至175℃，測定100小時後試樣油之外觀與酸值(JIS C2101)。所獲得之酯結果如表1~3所示。
再者，穩定性試驗前之試樣油(新油)之酸值全部為0.01 mgKOH/g。
根據表1~3可知，關於穩定性，雖於與HFO-1234yf之組合中會有稍許酸值上升，但實施例、比較例均為無問題之水準。
根據表1所示之結果可知，關於潤滑性，於實施例1~4中，與比較例1~4相比，磨耗量大幅度降低，耐磨之效果較大。
又，根據表2、3所示之結果可知，於實施例5~12中，藉由添加劑(B-1)、(B-2)與(C-1)~(C-6)之併用，添加劑之耐磨性提高效果之回應大幅度提高。又，根據實施例5與比較例5、7、8之比較可知，本發明之酯添加劑之調配量過少或過多，均使其添加效果放大之回應降低。
本發明之冷凍油組合物，因係於較差之潤滑條件下亦可維持耐磨之效果且長期可靠性優異之冷凍機油，故可較佳地用於具有壓縮機、冷凝器、光圈裝置、蒸發器等，並於該等之間使冷媒循環之冷卻效率較高之冷凍‧空調系統中，特別較佳地用於具有旋轉型、擺動
型、捲動型等之壓縮機之系統中，可使用於房間空調、封裝空調、冰箱、汽車空調、產業用冷凍機等之領域。
Claims (13)
- 一種冷凍機油組合物，其含有：自季戊四醇與選自碳數5~18之脂肪酸中之一種之四酯，及二季戊四醇與選自碳數5~18之脂肪酸中之一種之六酯中選出的至少一種之酯添加劑；及作為上述酯添加劑以外之酯之基礎油，上述酯添加劑之含量以冷凍機油組合物總量為基準為2~20質量%，冷凍機油組合物之於40℃下之動黏度為3~500 mm2/s。
- 如請求項1之冷凍機油組合物，其中上述酯添加劑為選自季戊四醇四(2-乙基己酸酯)及二季戊四醇六(己酸酯)中之至少一種。
- 如請求項1或2之冷凍機油組合物，其中於40℃下之動黏度為3~300 mm2/s。
- 如請求項1至3中任一項之冷凍機油組合物，其中上述基礎油為多元醇酯。
- 如請求項1至4中任一項之冷凍機油組合物，其中上述基礎油為由季戊四醇與碳數4~7之羧酸及3,5,5-三甲基己酸之混合酸所獲得之多元醇酯。
- 如請求項1至5中任一項之冷凍機油組合物，其中上述基礎油為由季戊四醇與支鏈之丁酸及3,5,5-三甲基己酸而獲得，且於40℃下之動黏度為30~110 mm2/s之多元醇酯。
- 如請求項1至6中任一項之冷凍機油組合物，其中上述酯添加劑之調配量以上述冷凍機油組合物總量為基準為2~7質量%。
- 如請求項1至7中任一項之冷凍機油組合物，其以上述冷凍機油組合物總量為基準進而含有0.1~5質量%之磷酸酯及/或0.01~2質量%之硫醚化合物。
- 如請求項8之冷凍機油組合物，其中上述磷酸酯為選自磷酸三苯酯、磷酸三甲苯酯及含有碳數3~4之烷基之磷酸烷基苯酯中的至少一種。
- 如請求項8或9之冷凍機油組合物，其中上述硫醚化合物為硫代雙酚化合物。
- 一種冷凍機油組合物之製造方法，其包括將酯添加劑調配於作為上述酯添加劑以外之酯之基礎油中而獲得冷凍機油組合物之步驟，該酯添加劑為自季戊四醇與選自碳數5~18之脂肪酸中之一種之四酯，及二季戊四醇與選自碳數5~18之脂肪酸中選出之一種之六酯中的至少一種，上述酯添加劑之調配量以上述冷凍機油組合物總量為基準為2~20質量%，上述冷凍機油組合物之於40℃下之動黏度為3~500 mm2/s。
- 一種冷凍機用作動流體組合物，其含有：如請求項1至11中任一項之冷凍機油組合物，冷媒，其含有選自氫氟碳、氫氟烯烴及烴類中之至少一種，且全球暖化係數為700以下。
- 如請求項12之冷凍機用作動流體組合物，其中上述冷媒含有二氟甲烷(R32)。
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| JP2012036442A JP5689428B2 (ja) | 2012-02-22 | 2012-02-22 | 冷凍機油組成物及びその製造方法、冷凍機用作動流体組成物 |
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| TW102106298A TWI582226B (zh) | 2012-02-22 | 2013-02-22 | A refrigerating machine oil composition and a method for producing the same, and a refrigerating machine serving as a hydrothermal composition |
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| US (1) | US9234155B2 (zh) |
| EP (1) | EP2818537B1 (zh) |
| JP (1) | JP5689428B2 (zh) |
| KR (1) | KR101897456B1 (zh) |
| CN (1) | CN104114683B (zh) |
| IN (1) | IN2014DN06608A (zh) |
| TW (1) | TWI582226B (zh) |
| WO (1) | WO2013125528A1 (zh) |
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- 2013-02-19 WO PCT/JP2013/054013 patent/WO2013125528A1/ja not_active Ceased
- 2013-02-19 KR KR1020147021417A patent/KR101897456B1/ko active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10266788B2 (en) | 2014-05-30 | 2019-04-23 | Kh Neochem Co., Ltd. | Refrigerating-machine oil composition and working fluid composition including same for refrigerating machine |
| TWI576424B (zh) * | 2014-10-09 | 2017-04-01 | 吉坤日礦日石能源股份有限公司 | The refrigerating machine oil and the refrigerator are used as the hydrothermal composition |
| US10023823B2 (en) | 2014-10-09 | 2018-07-17 | Jxtg Nippon Oil & Energy Corporation | Refrigerator oil and working fluid composition for refrigerator |
| TWI617658B (zh) * | 2015-03-02 | 2018-03-11 | Jx Nippon Oil & Energy Corp | 冷凍機油及冷凍機用作動流體組合物 |
| US10494585B2 (en) | 2015-03-02 | 2019-12-03 | Jxtg Nippon Oil & Energy Corporation | Refrigerator oil and working fluid composition for refrigerators |
Also Published As
| Publication number | Publication date |
|---|---|
| US20150028252A1 (en) | 2015-01-29 |
| JP5689428B2 (ja) | 2015-03-25 |
| KR20140125773A (ko) | 2014-10-29 |
| IN2014DN06608A (zh) | 2015-06-26 |
| US9234155B2 (en) | 2016-01-12 |
| CN104114683B (zh) | 2016-01-06 |
| EP2818537B1 (en) | 2020-01-22 |
| KR101897456B1 (ko) | 2018-09-12 |
| JP2013170255A (ja) | 2013-09-02 |
| CN104114683A (zh) | 2014-10-22 |
| EP2818537A4 (en) | 2015-04-15 |
| WO2013125528A1 (ja) | 2013-08-29 |
| TWI582226B (zh) | 2017-05-11 |
| EP2818537A1 (en) | 2014-12-31 |
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