TWI572708B - The refrigerating machine oil and the refrigerator are used as the hydrothermal composition - Google Patents
The refrigerating machine oil and the refrigerator are used as the hydrothermal composition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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- C10M105/06—Well-defined hydrocarbons aromatic
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
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Description
本發明係關於一種冷凍機油、冷凍機用作動流體組合物、含有烷基苯作為基油之組合物之用於冷凍機油或冷凍機用作動流體組合物之用途、及烷基苯之用於製造冷凍機油或冷凍機用作動流體組合物之用途。 The present invention relates to a use of a refrigerating machine oil, a refrigerating machine as a dynamic fluid composition, a composition containing an alkylbenzene as a base oil, a refrigerating machine oil or a refrigerator for use as a dynamic fluid composition, and an alkylbenzene for use in the manufacture. The use of a refrigerating machine oil or freezer as a dynamic fluid composition.
先前，於冰箱、製冷空調裝置等冷凍機中，係使用冷凍機油作為冷媒壓縮機之潤滑油。例如，作為HFC(Hydro Fluoro Carbon，氫氟碳)系冷媒用冷凍機油，已知有含有烷基苯作為基油之冷凍機油(例如參照專利文獻1)。 Conventionally, in a refrigerator such as a refrigerator or a refrigerating and air-conditioning apparatus, refrigerating machine oil is used as a lubricating oil for a refrigerant compressor. For example, as a refrigerator oil for HFC (Hydro Fluoro Carbon) refrigerant, a refrigerating machine oil containing an alkylbenzene as a base oil is known (for example, see Patent Document 1).
如專利文獻1所記載般，烷基苯對HFC冷媒顯示弱相容性，尤其於設置於冷媒循環系統之低壓側之儲液器中，冷凍機油對液冷媒之溶解性降低。因此，於使用含有烷基苯作為基油之冷凍機油之情形時，就壓縮機之可靠性之觀點而言，自儲液器之回油性係重要之課題。根據該情況，於先前之冷凍機油中，一般使用黏性較低、流動性優異之烷基苯。 As described in Patent Document 1, the alkylbenzene exhibits weak compatibility with the HFC refrigerant, and particularly in the accumulator provided on the low pressure side of the refrigerant circulation system, the solubility of the refrigerating machine oil to the liquid refrigerant is lowered. Therefore, in the case of using a refrigerating machine oil containing an alkylbenzene as a base oil, the oil return property from the accumulator is an important issue from the viewpoint of the reliability of the compressor. In view of this, in the conventional refrigerating machine oil, an alkylbenzene having a low viscosity and excellent fluidity is generally used.
專利文獻1：日本專利特開平10-246521號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 10-246521
然而，近期所使用之HFC冷媒中有具有微燃性者。根據本發明者之研究，判明：若於使用微燃性HFC冷媒之冷凍機應用含有烷基苯作為基油之先前之冷凍機油，則難以兼具回油性及阻燃性。 However, among the HFC refrigerants recently used, there is a slightly flammable one. According to the study by the present inventors, it has been found that if a refrigerating machine oil containing a base benzene as a base oil is used in a refrigerator using a slightly flammable HFC refrigerant, it is difficult to have both oil repellency and flame retardancy.
因此，本發明之目的在於提供一種可兼具回油性及阻燃性之冷凍機油及含有該冷凍機油之冷凍機用作動流體組合物。 Accordingly, an object of the present invention is to provide a refrigerating machine oil which can have both oil repellency and flame retardancy, and a refrigerating machine including the refrigerating machine oil as a dynamic fluid composition.
本發明提供一種冷凍機油，其含有具有250℃以上之5%餾出溫度及460℃以下之95%餾出溫度之烷基苯作為基油，且與微燃性氫氟碳冷媒一同使用。 The present invention provides a refrigerating machine oil comprising an alkylbenzene having a 5% distillation temperature of 250 ° C or more and a 95% distillation temperature of 460 ° C or less as a base oil, and is used together with a slightly flammable hydrofluorocarbon refrigerant.
本發明中之5%餾出溫度及95%餾出溫度分別意指依據ASTM D7213-05所規定之利用氣相層析法之蒸餾試驗方法所測定之5%餾出溫度及95%餾出溫度。 The 5% distillation temperature and the 95% distillation temperature in the present invention mean a 5% distillation temperature and a 95% distillation temperature, respectively, determined by a distillation test method by gas chromatography according to ASTM D7213-05. .
本發明又提供一種含有上述冷凍機油及微燃性氫氟碳冷媒之冷凍機用作動流體組合物。 The present invention further provides a refrigerating machine comprising the above-described refrigerating machine oil and a slightly flammable hydrofluorocarbon refrigerant as a dynamic fluid composition.
本發明又提供一種含有烷基苯作為基油之組合物之用途，其係用於冷凍機油或冷凍機用作動流體組合物，烷基苯具有250℃以上之5%餾出溫度及460℃以下之95%餾出溫度，冷凍機油係與微燃性氫氟碳冷媒一同使用，且冷凍機用作動流體組合物含有冷凍機油及微燃性氫氟碳冷媒。 The invention further provides a use of a composition comprising an alkylbenzene as a base oil, which is used in a refrigerating machine oil or a refrigerator as a dynamic fluid composition, the alkylbenzene having a 5% distillation temperature above 250 ° C and below 460 ° C The 95% distillation temperature, the refrigerating machine oil is used together with the slightly flammable hydrofluorocarbon refrigerant, and the refrigerating machine is used as a dynamic fluid composition containing refrigerating machine oil and a slightly flammable hydrofluorocarbon refrigerant.
本發明又提供一種烷基苯之用途，其係用於製造冷凍機油或冷凍機用作動流體組合物，烷基苯具有250℃以上之5%餾出溫度及460℃以下之95%餾出溫度，冷凍機油係與微燃性氫氟碳冷媒一同使用，且冷凍機用作動流體組合物含有冷凍機油及微燃性氫氟碳冷媒。 The invention further provides a use of an alkylbenzene for use in the manufacture of a refrigerating machine oil or a refrigerator as a dynamic fluid composition, the alkylbenzene having a 5% distillation temperature above 250 ° C and a 95% distillation temperature below 460 ° C. The refrigerating machine oil is used together with the slightly flammable hydrofluorocarbon refrigerant, and the refrigerating machine is used as a dynamic fluid composition containing refrigerating machine oil and a slightly flammable hydrofluorocarbon refrigerant.
根據本發明，可提供一種可兼具回油性及阻燃性之冷凍機油及含有該冷凍機油之冷凍機用作動流體組合物。 According to the present invention, it is possible to provide a refrigerating machine oil which can have both oil repellency and flame retardancy, and a refrigerating machine containing the refrigerating machine oil as a dynamic fluid composition.
1‧‧‧冷媒罐 1‧‧‧ refrigerant tank
2‧‧‧銅配管 2‧‧‧Bronze piping
2a‧‧‧銅配管中之浸漬於恆溫槽之部分 2a‧‧‧ Part of the copper piping impregnated in the thermostat
3‧‧‧流量計 3‧‧‧ Flowmeter
4‧‧‧壓力計 4‧‧‧ pressure gauge
5‧‧‧恆溫槽 5‧‧‧ thermostat
6‧‧‧壓力計 6‧‧‧ pressure gauge
7‧‧‧集油器 7‧‧‧ oil collector
圖1係表示本實施形態之烷基苯之餾出量與餾出溫度之關係之一例的曲線圖。 Fig. 1 is a graph showing an example of the relationship between the amount of alkylbenzene distilled off and the distillation temperature in the present embodiment.
圖2係表示本實施形態之烷基苯之餾出量與餾出溫度之關係之一例的表。 Fig. 2 is a table showing an example of the relationship between the amount of alkylbenzene distilled and the distillation temperature in the present embodiment.
圖3係用於實施例之回油性試驗之裝置之模式圖。 Figure 3 is a schematic view of the apparatus used in the oil return test of the examples.
以下，對本發明之較佳之實施形態詳細地進行說明。 Hereinafter, preferred embodiments of the present invention will be described in detail.
本實施形態之冷凍機油含有具有250℃以上之5%餾出溫度及460℃以下之95%餾出溫度之烷基苯作為基油，且與微燃性氫氟碳冷媒一同使用。本實施形態之冷凍機用作動流體組合物含有上述冷凍機油及微燃性氫氟碳冷媒。 The refrigerator oil of the present embodiment contains an alkylbenzene having a 5% distillation temperature of 250 ° C or higher and a 95% distillation temperature of 460 ° C or lower as a base oil, and is used together with a slightly flammable hydrofluorocarbon refrigerant. The refrigerator of the present embodiment is used as a dynamic fluid composition containing the above-described refrigerator oil and a slightly flammable hydrofluorocarbon refrigerant.
冷凍機油含有烷基苯作為基油。就提高阻燃性之觀點而言，烷基苯之5%餾出溫度較佳為250℃以上，更佳為255℃以上，進而較佳為260℃以上。就提高回油性之觀點而言，烷基苯之95%餾出溫度較佳為460℃以下，更佳為455℃以下，進而較佳為450℃以下。此外，藉由將烷基苯之95%餾出溫度設為上述範圍，有提高耐磨耗性之傾向。就同時實現阻燃性之提高及回油性之提高，進而亦提高耐磨耗性之觀點而言，烷基苯較佳為具有250℃以上之5%餾出溫度及460℃以下之95%餾出溫度、250℃以上之5%餾出溫度及455℃以下之95%餾出溫度、250℃以上之5%餾出溫度及450℃以下之95%餾出溫度、255℃以上之5%餾出溫度及460℃以下之95%餾出溫度、255℃以上之5%餾出溫度及455℃以下之95%餾出溫度、255℃以上之5%餾出溫度及450℃以下之95%餾出溫度、260℃以上之5%餾出溫度及460℃以下之95%餾出溫度、260℃以上之5%餾出溫度及455℃以下之95%餾出溫度、或260℃以上之5%餾出溫度及450℃以下之95%餾出溫度。具體而言，本 實施形態之烷基苯具有例如圖1及2所示般之蒸餾性狀(餾出量與餾出溫度之關係)。 The refrigerator oil contains alkylbenzene as a base oil. The 5% distillation temperature of the alkylbenzene is preferably 250 ° C or higher, more preferably 255 ° C or higher, and still more preferably 260 ° C or higher from the viewpoint of improving flame retardancy. From the viewpoint of improving the oil repellency, the 95% distillation temperature of the alkylbenzene is preferably 460 ° C or lower, more preferably 455 ° C or lower, and still more preferably 450 ° C or lower. Further, by setting the 95% distillation temperature of the alkylbenzene to the above range, the wear resistance tends to be improved. The alkylbenzene preferably has a 5% distillation temperature of 250 ° C or more and a 95 % distillation of 460 ° C or less from the viewpoint of simultaneously improving the flame retardancy and improving the oil repellency and further improving the abrasion resistance. Exhaust temperature, 5% distillation temperature above 250 ° C and 95% distillation temperature below 455 ° C, 5% distillation temperature above 250 ° C and 95% distillation temperature below 450 ° C, 5% distillation above 255 ° C 95% distillation temperature below 460 °C, 5% distillation temperature above 255 °C, 95% distillation temperature below 455 °C, 5% distillation temperature above 255 °C and 95% distillation below 450 °C Temperature, 5% distillation temperature above 260 ° C and 95% distillation temperature below 460 ° C, 5% distillation temperature above 260 ° C and 95% distillation temperature below 455 ° C, or 5% above 260 ° C Distillation temperature and 95% distillation temperature below 450 °C. Specifically, this The alkylbenzene of the embodiment has a distillation property (the relationship between the amount of distillation and the distillation temperature) as shown in Figs. 1 and 2, for example.
本發明中之5%餾出溫度及95%餾出溫度分別意指依據ASTM D7213-05所規定之利用氣相層析法之蒸餾試驗方法而測定之5%餾出溫度及95%餾出溫度。 The 5% distillation temperature and the 95% distillation temperature in the present invention mean a 5% distillation temperature and a 95% distillation temperature, respectively, determined by a distillation test method by gas chromatography according to ASTM D7213-05. .
作為具有如上所述之特性之烷基苯，可使用下述烷基苯(A)及/或烷基苯(B)。 As the alkylbenzene having the above characteristics, the following alkylbenzene (A) and/or alkylbenzene (B) can be used.
烷基苯(A)：具有1~4個碳數1~19之烷基，且其烷基之合計碳數為9~19之烷基苯(較佳為具有1~4個碳數1~15之烷基，且烷基之合計碳數為9~15之烷基苯) Alkylbenzene (A): an alkylbenzene having 1 to 4 alkyl groups having 1 to 19 carbon atoms and having a total alkyl group of 9 to 19 carbon atoms (preferably having 1 to 4 carbon atoms 1~) An alkyl group of 15 and an alkyl group having a total carbon number of 9 to 15)
烷基苯(B)：具有1~4個碳數1~40之烷基，且其烷基之合計碳數為20~40之烷基苯(較佳為具有1~4個碳數1~30之烷基，且烷基之合計碳數為20~30之烷基苯) Alkylbenzene (B): an alkylbenzene having 1 to 4 alkyl groups having 1 to 40 carbon atoms and an alkyl group having a total carbon number of 20 to 40 (preferably having 1 to 4 carbon atoms 1~) An alkyl group of 30, and an alkyl group having an alkyl group having a total carbon number of 20 to 30)
作為烷基苯(A)所具有之碳數1~19之烷基，具體而言，例如可列舉：甲基、乙基、丙基(包括全部之異構物，以下相同)、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基。該等烷基可為直鏈狀，亦可為支鏈狀，就穩定性、黏度特性等方面而言，較佳為支鏈狀。尤其就可獲得性之方面而言，更佳為自丙烯、丁烯、異丁烯等烯烴之低聚物所衍生之支鏈狀烷基。 Specific examples of the alkyl group having 1 to 19 carbon atoms of the alkylbenzene (A) include a methyl group, an ethyl group, a propyl group (including all the isomers, the same applies hereinafter), and a butyl group. Pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecane Base, octadecyl, nonadecyl, eicosyl. These alkyl groups may be linear or branched, and are preferably branched in terms of stability, viscosity characteristics and the like. Particularly, in terms of availability, a branched alkyl group derived from an oligomer of an olefin such as propylene, butylene or isobutylene is more preferable.
烷基苯(A)中之烷基之個數為1~4個，就穩定性、可獲得性之方面而言，較佳為1個或2個(即單烷基苯、二烷基苯、或該等之混合物)。 The number of alkyl groups in the alkylbenzene (A) is from 1 to 4, preferably from 1 or 2 in terms of stability and availability (ie, monoalkylbenzene or dialkylbenzene). Or a mixture of such).
烷基苯(A)可僅含有單一結構之烷基苯，若為滿足具有1~4個碳數1~19之烷基，且烷基之合計碳數為9~19之條件之烷基苯，則亦可含有具有不同結構之烷基苯之混合物。 The alkylbenzene (A) may contain only a single structure of alkylbenzene, and is an alkylbenzene satisfying the condition of having 1 to 4 alkyl groups having 1 to 19 carbon atoms and having an alkyl group having a total carbon number of 9 to 19. It may also contain a mixture of alkylbenzenes having different structures.
作為烷基苯(B)所具有之碳數1~40之烷基，具體而言，例如可列舉：甲基、乙基、丙基(包括全部之異構物，以下相同)、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷基、二十四烷基、二十五烷基、二十六烷基、二十七烷基、二十八烷基、二十九烷基、三十烷基、三十一烷基、三十二烷基、三十三烷基、三十四烷基、三十五烷基、三十六烷基、三十七烷基、三十八烷基、三十九烷基、四十烷基。該等烷基可為直鏈狀，亦可為支鏈狀，就穩定性、黏度特性等方面而言，較佳為支鏈狀。尤其就可獲得性之方面而言，更佳為自丙烯、丁烯、異丁烯等烯烴之低聚物所衍生之支鏈狀烷基。 Specific examples of the alkyl group having 1 to 40 carbon atoms of the alkylbenzene (B) include a methyl group, an ethyl group, a propyl group (including all the isomers, the same applies hereinafter), and a butyl group. Pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecane , octadecyl, nonadecyl, eicosyl, icosyl, behenyl, docosyl, tetracosyl, dipentadecyl, twenty-six Alkyl, hexadecyl, octadecyl, octadecyl, tridecyl, tridecyl, tridodecyl, tricosyl, tritetradecyl, Tridecyl, trihexyl, tridecyl, octadecyl, octadecyl, tetradecyl. These alkyl groups may be linear or branched, and are preferably branched in terms of stability, viscosity characteristics and the like. Particularly, in terms of availability, a branched alkyl group derived from an oligomer of an olefin such as propylene, butylene or isobutylene is more preferable.
烷基苯(B)中之烷基之個數為1~4個，就穩定性、可獲得性之方面而言，較佳為1個或2個(即單烷基苯、二烷基苯、或該等之混合物)。 The number of alkyl groups in the alkylbenzene (B) is from 1 to 4, preferably from 1 or 2 in terms of stability and availability (ie, monoalkylbenzene or dialkylbenzene). Or a mixture of such).
烷基苯(B)可僅含有單一結構之烷基苯，若為滿足具有1~4個碳數1~40之烷基、且烷基之合計碳數為20~40之條件之烷基苯，則亦可含有具有不同結構之烷基苯之混合物。 The alkylbenzene (B) may contain only a single structure of alkylbenzene, and is an alkylbenzene satisfying the condition of having 1 to 4 alkyl groups having 1 to 40 carbon atoms and having an alkyl group having a total carbon number of 20 to 40. It may also contain a mixture of alkylbenzenes having different structures.
就提高潤滑性之觀點而言，烷基苯之40℃下之動黏度較佳為3mm2/s以上，更佳為4mm2/s以上，進而較佳為5mm2/s以上。就提高回油性之觀點而言，烷基苯之40℃下之動黏度較佳為100mm2/s以下，更佳為80mm2/s以下，進而較佳為70mm2/s以下。就同時實現潤滑性之提高與回油性之提高之觀點而言，烷基苯之40℃下之動黏度較佳為3~100mm2/s，更佳為4~80mm2/s，進而較佳為5~70mm2/s。本發明中之動黏度意指依據JIS K2283：2000所測定之動黏度。 The dynamic viscosity at 40 ° C of the alkylbenzene is preferably 3 mm 2 /s or more, more preferably 4 mm 2 /s or more, and still more preferably 5 mm 2 /s or more from the viewpoint of improving lubricity. From the viewpoint of improving the oil repellency, the dynamic viscosity at 40 ° C of the alkylbenzene is preferably 100 mm 2 /s or less, more preferably 80 mm 2 /s or less, still more preferably 70 mm 2 /s or less. The dynamic viscosity at 40 ° C of the alkylbenzene is preferably from 3 to 100 mm 2 /s, more preferably from 4 to 80 mm 2 /s, from the viewpoint of improving the lubricity and the improvement of the oil repellency. It is 5~70mm 2 /s. The dynamic viscosity in the present invention means the dynamic viscosity measured in accordance with JIS K2283:2000.
就提高阻燃性之觀點而言，烷基苯之引火點較佳為150℃以上，更佳為155℃以上，進而較佳為160℃以上。本發明中之引火點意指依 據JIS K2265-4所測定之引火點。 From the viewpoint of improving the flame retardancy, the ignition point of the alkylbenzene is preferably 150 ° C or higher, more preferably 155 ° C or higher, and still more preferably 160 ° C or higher. The ignition point in the present invention means The ignition point measured according to JIS K2265-4.
就提高阻燃性之觀點而言，烷基苯之自然發火點較佳為340℃以上，更佳為345℃以上，進而較佳為350℃以上。本發明中之自然發火點意指利用依據ASTM E 659-1978之方法所測定之自然發火點。 The natural ignition point of the alkylbenzene is preferably 340 ° C or higher, more preferably 345 ° C or higher, and still more preferably 350 ° C or higher from the viewpoint of improving flame retardancy. The natural ignition point in the present invention means a natural ignition point determined by the method according to ASTM E 659-1978.
作為烷基苯之製造方法，並無限定，可例示以下之製造方法。 The method for producing the alkylbenzene is not limited, and the following production methods can be exemplified.
例如將烷化觸媒填充至圓筒形之固定床連續流通形式之反應器，將芳香族化合物及烷化劑自原料供給管線連續地供給至反應器，使芳香族化合物與烷化劑反應。於反應器中，例如，將反應溫度設為180~240℃，將反應壓力設為0.6~1.1MPa，將反應器入口之烷化劑/芳香族化合物(莫耳比)設為1.0，將液體流速設為LHSV(Liquid Hourly Space Velocity，每時之液體空間速度)=1.4~1.8。繼而，將所獲得之反應混合物自移送管線連續地送至蒸餾塔。於蒸餾塔中，例如，將理論板數設為70~90板，將壓力設為140~160mmHg，將塔頂溫度設為180~200℃，將塔底溫度設為230~270℃。藉由如此設定蒸餾塔之各條件，製造本實施形態之烷基苯。 For example, an alkylating catalyst is filled in a cylindrical fixed-bed continuous flow reactor, and an aromatic compound and an alkylating agent are continuously supplied from a raw material supply line to a reactor to react an aromatic compound with an alkylating agent. In the reactor, for example, the reaction temperature is set to 180 to 240 ° C, the reaction pressure is set to 0.6 to 1.1 MPa, and the alkylating agent/aromatic compound (mole ratio) at the inlet of the reactor is set to 1.0. The flow rate is set to LHSV (Liquid Hourly Space Velocity) = 1.4 to 1.8. Then, the obtained reaction mixture was continuously sent from the transfer line to the distillation column. In the distillation column, for example, the theoretical number of plates is set to 70 to 90 plates, the pressure is set to 140 to 160 mmHg, the temperature at the top of the column is set to 180 to 200 ° C, and the temperature at the bottom of the column is set to 230 to 270 ° C. The alkylbenzene of this embodiment was produced by setting the conditions of the distillation column in this manner.
作為上述芳香族化合物，例如可使用：苯、甲苯、二甲苯、乙基苯、甲基乙基苯、二乙基苯、及該等之混合物等。作為上述烷化劑，例如可使用：乙烯、丙烯、丁烯、異丁烯等低級單烯烴，較佳為藉由丙烯之聚合而獲得之碳數6~40之直鏈狀或支鏈狀之烯烴；藉由蠟、重質油、石油餾分、聚乙烯、聚丙烯等之熱分解而獲得之碳數6~40之直鏈狀或支鏈狀之烯烴；藉由自煤油、輕油等石油餾分分離正鏈烷烴並利用觸媒將其烯烴化而獲得之碳數6~40之直鏈狀烯烴；及該等之混合物等。作為上述烷化觸媒，可使用：氯化鋁、氯化鋅等夫里德耳-夸夫特型觸媒；硫酸、磷酸、矽鎢酸、氫氟酸、活性白土等酸性觸媒等公知之觸媒。 As the aromatic compound, for example, benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene, and the like can be used. As the alkylating agent, for example, a lower monoolefin such as ethylene, propylene, butylene or isobutylene can be used, and a linear or branched olefin having 6 to 40 carbon atoms obtained by polymerization of propylene is preferred; a linear or branched olefin having 6 to 40 carbon atoms obtained by thermal decomposition of wax, heavy oil, petroleum fraction, polyethylene, polypropylene, etc.; separated from petroleum fractions such as kerosene and light oil a linear olefin having 6 to 40 carbon atoms obtained by olefination of a normal paraffin and a olefin thereof; and a mixture thereof. As the above-mentioned alkylating catalyst, a Freud-Quartet type catalyst such as aluminum chloride or zinc chloride; an acidic catalyst such as sulfuric acid, phosphoric acid, tungstic acid, hydrofluoric acid or activated clay can be used. Catalyst.
以冷凍機油總量為基準計，烷基苯之含量可設為50質量%以上， 可設為70質量%以上，可設為80質量%以上，可設為90質量%以上。 The content of the alkylbenzene can be set to 50% by mass or more based on the total amount of the refrigerating machine oil. It can be 70% by mass or more, 80% by mass or more, and 90% by mass or more.
冷凍機油可含有包含烷基苯之基油，亦可除烷基苯以外進而含有其他基油。作為其他基油，可例示：礦物油、烯烴聚合物等烴油、酯(單酯、包含直鏈脂肪酸及/或支鏈脂肪酸作為結構脂肪酸之多元醇酯等)、聚二醇、聚乙烯醚、酮、聚苯醚、聚矽氧、聚矽氧烷、全氟醚等含氧油。 The refrigerating machine oil may contain a base oil containing an alkylbenzene, and may further contain other base oils in addition to the alkylbenzene. Examples of the other base oils include hydrocarbon oils such as mineral oils and olefin polymers, esters (monoesters, polyol esters containing linear fatty acids and/or branched fatty acids as structural fatty acids, etc.), polyglycols, and polyvinyl ethers. Oxygenated oils such as ketones, polyphenylene ethers, polyfluorene oxides, polyoxyalkylene oxides, perfluoroethers, and the like.
冷凍機油除基油之外可進而含有添加劑。 The refrigerating machine oil may further contain an additive in addition to the base oil.
作為添加劑，例如可列舉環氧化合物。作為環氧化合物，例如可列舉：縮水甘油醚型環氧化合物、縮水甘油酯型環氧化合物、環氧乙烷化合物、烷基環氧乙烷化合物、脂環式環氧化合物、環氧化脂肪酸單酯、環氧化植物油。該等環氧化合物可單獨使用1種，或將2種以上組合而使用。 As an additive, an epoxy compound is mentioned, for example. Examples of the epoxy compound include a glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an oxirane compound, an alkyl oxirane compound, an alicyclic epoxy compound, and an epoxidized fatty acid single. Ester, epoxidized vegetable oil. These epoxy compounds may be used alone or in combination of two or more.
作為縮水甘油醚型環氧化合物，可使用例如下述通式(1)所表示之芳基縮水甘油醚型環氧化合物或烷基縮水甘油醚型環氧化合物。 As the glycidyl ether type epoxy compound, for example, an aryl glycidyl ether type epoxy compound or an alkyl glycidyl ether type epoxy compound represented by the following formula (1) can be used.
[式(1)中，R1表示芳基或碳數5~18之烷基] [In the formula (1), R 1 represents an aryl group or an alkyl group having 5 to 18 carbon atoms]
作為式(1)所表示之縮水甘油醚型環氧化合物，較佳為正丁基苯基縮水甘油醚、異丁基苯基縮水甘油醚、第二丁基苯基縮水甘油醚、第三丁基苯基縮水甘油醚、戊基苯基縮水甘油醚、己基苯基縮水甘油醚、庚基苯基縮水甘油醚、辛基苯基縮水甘油醚、壬基苯基縮水甘油醚、癸基苯基縮水甘油醚、癸基縮水甘油醚、十一烷基縮水甘油醚、十二烷基縮水甘油醚、十三烷基縮水甘油醚、十四烷基縮水甘油醚、 2-乙基己基縮水甘油醚。 The glycidyl ether type epoxy compound represented by the formula (1) is preferably n-butylphenyl glycidyl ether, isobutylphenyl glycidyl ether, second butylphenyl glycidyl ether, and third butyl. Phenyl phenyl glycidyl ether, amyl phenyl glycidyl ether, hexyl phenyl glycidyl ether, heptyl phenyl glycidyl ether, octyl phenyl glycidyl ether, nonylphenyl glycidyl ether, nonylphenyl Glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, lauryl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether.
若R1所表示之烷基之碳數為5以上，則可確保環氧化合物之穩定性，可抑制其於與水分、脂肪酸、氧化劣化物反應前分解、或產生環氧化合物彼此聚合之自聚合，容易獲得目標功能。另一方面，若R1所表示之烷基之碳數為18以下，則可良好地保持與冷媒之溶解性，難以於冷凍裝置內析出而產生冷卻不良等不良狀況。 When the number of carbon atoms of the alkyl group represented by R 1 is 5 or more, the stability of the epoxy compound can be ensured, and decomposition can be suppressed before the reaction with water, a fatty acid, or an oxidized degradation product, or the epoxy compound can be polymerized from each other. Aggregation, easy to get the target function. On the other hand, when the number of carbon atoms of the alkyl group represented by R 1 is 18 or less, the solubility with the refrigerant can be favorably maintained, and it is difficult to precipitate in the refrigeration system to cause a problem such as poor cooling.
作為縮水甘油醚型環氧化合物，除了式(1)所表示之環氧化合物之外，亦可使用新戊二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、季戊四醇四縮水甘油醚、1,6-己二醇二縮水甘油醚、山梨醇聚縮水甘油醚、聚伸烷基二醇單縮水甘油醚、聚伸烷基二醇二縮水甘油醚等。 As the glycidyl ether type epoxy compound, in addition to the epoxy compound represented by the formula (1), neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether can also be used. 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether, and the like.
作為縮水甘油酯型環氧化合物，可使用例如下述通式(2)所表示者。 As the glycidyl ester type epoxy compound, for example, those represented by the following formula (2) can be used.
[式(2)中，R2表示芳基、碳數5~18之烷基、或烯基] [In the formula (2), R 2 represents an aryl group, an alkyl group having 5 to 18 carbon atoms, or an alkenyl group]
作為式(2)所表示之縮水甘油酯型環氧化合物，較佳為苯甲酸縮水甘油酯、新癸酸縮水甘油酯、2,2-二甲基辛酸縮水甘油酯、丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯。 The glycidyl ester type epoxy compound represented by the formula (2) is preferably glycidyl benzoate, glycidyl neodecanoate, glycidyl 2,2-dimethyloctanoate, glycidyl acrylate, or Glycidyl acrylate.
若R2所表示之烷基之碳數為5以上，則可確保環氧化合物之穩定性，可抑制其於與水分、脂肪酸、氧化劣化物反應前分解、或產生環氧化合物彼此聚合之自聚合，容易獲得目標功能。另一方面，若R2所表示之烷基或烯基之碳數為18以下，則可良好地保持與冷媒之溶解 性，難以於冷凍機內析出而產生冷卻不良等不良狀況。 When the number of carbon atoms of the alkyl group represented by R 2 is 5 or more, the stability of the epoxy compound can be ensured, and decomposition can be suppressed before the reaction with water, a fatty acid, or an oxidized degradation product, or the epoxy compound can be polymerized from each other. Aggregation, easy to get the target function. On the other hand, when the number of carbon atoms of the alkyl group or the alkenyl group represented by R 2 is 18 or less, the solubility in the refrigerant can be favorably maintained, and it is difficult to precipitate in the refrigerator to cause a problem such as poor cooling.
所謂脂環式環氧化合物係具有下述通式(3)所表示之構成環氧基之碳原子直接構成脂環式環之部分結構的化合物。 The alicyclic epoxy compound is a compound having a partial structure in which a carbon atom constituting an epoxy group represented by the following formula (3) directly constitutes an alicyclic ring.
作為脂環式環氧化合物，例如較佳為1,2-環氧環己烷、1,2-環氧環戊烷、3,4-環氧環己烷羧酸3',4'-環氧環己基甲酯、己二酸雙(3,4-環氧環己基甲基)酯、外-2,3-環氧降烷、己二酸雙(3,4-環氧基-6-甲基環己基甲基)酯、2-(7-氧雜雙環[4.1.0]庚-3-基)-螺(1,3-二烷-5,3'-[7]氧雜雙環[4.1.0]庚烷、4-(1'-甲基環氧基乙基)-1,2-環氧基-2-甲基環己烷、4-環氧基乙基-1,2-環氧環己烷。 As the alicyclic epoxy compound, for example, 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexanecarboxylic acid 3',4'-ring is preferred. Oxycyclohexyl methyl ester, bis(3,4-epoxycyclohexylmethyl) adipate, external-2,3-epoxy drop Alkane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2-(7-oxabicyclo[4.1.0]heptan-3-yl)-spiro (1, 3-two Alkane-5,3'-[7]oxabicyclo[4.1.0]heptane, 4-(1'-methylepoxyethyl)-1,2-epoxy-2-methylcyclohexane Alkane, 4-epoxyethyl-1,2-epoxycyclohexane.
作為烯丙基環氧乙烷化合物，可例示：1,2-環氧苯乙烯、烷基-1,2-環氧苯乙烯等。 The allyl oxirane compound may, for example, be 1,2-epoxystyrene or alkyl-1,2-epoxystyrene.
作為烷基環氧乙烷化合物，可例示：1,2-環氧丁烷、1,2-環氧戊烷、1,2-環氧己烷、1,2-環氧庚烷、1,2-環氧辛烷、1,2-環氧壬烷、1,2-環氧癸烷、1,2-環氧十一烷、1,2-環氧十二烷、1,2-環氧十三烷、1,2-環氧十四烷、1,2-環氧十五烷、1,2-環氧十六烷、1,2-環氧十七烷、1,1,2-環氧十八烷、2-環氧十九烷、1,2-環氧二十烷等。 As the alkyl oxirane compound, 1,2-butylene oxide, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1, 2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-ring Oxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2 - Epoxy octadecane, 2-epoxynonadecane, 1,2-epoxyecosane, and the like.
作為環氧化脂肪酸單酯，可例示經環氧化之碳數12~20之脂肪酸與碳數1~8之醇或酚或烷基酚之酯等。作為環氧化脂肪酸單酯，可較佳地使用環氧硬脂酸丁酯、環氧硬脂酸己酯、環氧硬脂酸苄酯、環氧硬脂酸環己酯、環氧硬脂酸甲氧基乙酯、環氧硬脂酸辛酯、環氧硬 脂酸苯酯及環氧硬脂酸丁基苯酯。 Examples of the epoxidized fatty acid monoester include an epoxidized fatty acid having 12 to 20 carbon atoms and an alcohol having 1 to 8 carbon atoms or an ester of a phenol or an alkylphenol. As the epoxidized fatty acid monoester, butyl stearyl stearate, hexyl epoxy stearate, benzyl epoxy stearate, cyclohexyl epoxy stearate, and epoxy stearic acid can be preferably used. Methoxyethyl ester, octyl epoxy stearate, epoxy hard Phenyl oleate and butyl phenyl stearate.
作為環氧化植物油，可例示：大豆油、亞麻仁油、棉籽油等植物油之環氧化合物等。 The epoxidized vegetable oil may, for example, be an epoxy compound of vegetable oil such as soybean oil, linseed oil or cottonseed oil.
就提高冷凍機油之穩定性之觀點而言，以冷凍機油總量為基準計，環氧化合物之含量較佳為0.1質量%以上，更佳為0.15質量%以上，進而較佳為0.2質量%以上。就提高潤滑性之觀點而言，以冷凍機油總量為基準計，環氧化合物之含量較佳為1.0質量%以下，更佳為0.8質量%以下，進而較佳為0.5質量%以下。 From the viewpoint of improving the stability of the refrigerating machine oil, the content of the epoxy compound is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more based on the total amount of the refrigerating machine oil. . The content of the epoxy compound is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.5% by mass or less based on the total amount of the refrigerating machine oil.
作為磷化合物(亦稱為「磷系添加劑」或「磷系抗磨耗劑」)，並無特別限定，可列舉：磷酸酯、酸式磷酸酯、硫代磷酸酯、酸式磷酸酯之胺鹽、氯化磷酸酯、亞磷酸酯等。該等磷化合物可單獨使用1種，或將2種以上組合而使用。 The phosphorus compound (also referred to as "phosphorus-based additive" or "phosphorus-based anti-wear agent") is not particularly limited, and examples thereof include a phosphate ester, an acid phosphate, a phosphorothioate, and an amine salt of an acid phosphate. , chlorinated phosphate, phosphite, and the like. These phosphorus compounds may be used alone or in combination of two or more.
作為磷酸酯，可列舉：磷酸三丁酯、磷酸三戊酯、磷酸三己酯、磷酸三庚酯、磷酸三辛酯、磷酸三壬酯、磷酸三癸酯、磷酸三(十一烷基)酯、磷酸三(十二烷基)酯、磷酸三(十三烷基)酯、磷酸三(十四烷基)酯、磷酸三(十五烷基)酯、磷酸三(十六烷基)酯、磷酸三(十七烷基)酯、磷酸三(十八烷基)酯、磷酸三油脂、磷酸三苯酯、磷酸三甲酚酯、磷酸三(二甲酚)酯、磷酸甲酚酯二苯酯、磷酸二甲酚酯二苯酯等。 Examples of the phosphate ester include tributyl phosphate, triamyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, tridecyl phosphate, tridecyl phosphate, and tris(undecyl) phosphate. Ester, tris(dodecyl)phosphate, tris(tridecyl)phosphate, tris(tetradecyl)phosphate, tris(pentadecyl)phosphate, tris(hexadecyl)phosphate Ester, tris(heptadecyl)phosphate, tris(octadecyl)phosphate, trioleate, triphenyl phosphate, tricresyl phosphate, tris(xylenol) phosphate, cresyl phosphate Phenyl ester, diphenyl phosphate diphenyl ester, and the like.
作為酸式磷酸酯，可列舉：酸式磷酸單丁酯、酸式磷酸單戊酯、酸式磷酸單己酯、酸式磷酸單庚酯、酸式磷酸單辛酯、酸式磷酸單壬酯、酸式磷酸單癸酯、酸式磷酸單(十一烷基)酯、酸式磷酸單(十二烷基)酯、酸式磷酸單(十三烷基)酯、酸式磷酸單(十四烷基)酯、酸式磷酸單(十五烷基)酯、酸式磷酸單(十六烷基)酯、酸式磷酸單(十七烷基)酯、酸式磷酸單(十八烷基)酯、酸式磷酸單油酯、酸式磷酸二丁酯、酸式磷酸二戊酯、酸式磷酸二己酯、酸式磷酸二庚酯、酸式磷酸 二辛酯、酸式磷酸二壬酯、酸式磷酸二癸酯、酸式磷酸二(十一烷基)酯、酸式磷酸二(十二烷基)酯、酸式磷酸二(十三烷基)酯、酸式磷酸二(十四烷基)酯、酸式磷酸二(十五烷基)酯、酸式磷酸二(十六烷基)酯、酸式磷酸二(十七烷基)酯、酸式磷酸二(十八烷基)酯、酸式磷酸二油酯等。 Examples of the acid phosphate include acid monobutyl phosphate, acid monoamyl phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, and monodecyl phosphate. , acid monodecyl phosphate, mono (undecyl) acid phosphate, mono (dodecyl) acid phosphate, mono (tridecyl) acid phosphate, acid phosphate (ten Tetraalkyl)ester, mono(pentadecyl) acid phosphate, mono(hexadecyl) acid phosphate, mono(heptadecyl) acid phosphate, mono(octadecyl) acid phosphate Ester), acid monoester, acid dibutyl phosphate, diamyl acid phosphate, dihexyl acid phosphate, diheptyl acid phosphate, acid phosphate Dioctyl ester, dinonyl acid phosphate, dinonyl acid phosphate, di(undecyl) acid phosphate, di(dodecyl) acid phosphate, di(tridecane) acid Ester), di(tetradecyl) acid phosphate, di(pentadecyl) acid phosphate, di(hexadecyl) acid phosphate, di(heptadecyl) acid phosphate Ester, di(octadecyl) acid phosphate, dioleic acid diester, and the like.
作為硫代磷酸酯，可列舉：硫代磷酸三丁酯、硫代磷酸三戊酯、硫代磷酸三己酯、硫代磷酸三庚酯、硫代磷酸三辛酯、硫代磷酸三壬酯、硫代磷酸三癸酯、硫代磷酸三(十一烷基)酯、硫代磷酸三(十二烷基)酯、硫代磷酸三(十三烷基)酯、硫代磷酸三(十四烷基)酯、硫代磷酸三(十五烷基)酯、硫代磷酸三(十六烷基)酯、硫代磷酸三(十七烷基)酯、硫代磷酸三(十八烷基)酯、硫代磷酸三油酯、硫代磷酸三苯酯、硫代磷酸三甲酚酯、硫代磷酸三(二甲酚)酯、硫代磷酸甲酚酯二苯酯、硫代磷酸二甲酚酯二苯酯等。 Examples of the phosphorothioate include tributyl thiophosphate, triamyl thiophosphate, trihexyl thiophosphate, triheptyl thiophosphate, trioctyl thiophosphate, and tridecyl thiophosphate. , tridecyl thiophosphate, tris(undecyl) thiophosphate, tris(dodecyl) thiophosphate, tris(tridecyl) thiophosphate, thiophosphoric acid tris(10) Tetraalkyl) ester, tris(pentadecyl) thiophosphate, tris(hexadecyl) thiophosphate, tris(heptadecyl) thiophosphate, trisoctadecyl thiophosphate Ester, trioleyl thiophosphate, triphenyl thiophosphate, cresyl thiophosphate, tris(xylenol) thiophosphate, cresyl thiophenol diphenyl ester, thiophosphoric acid Cresol ester diphenyl ester and the like.
作為酸式磷酸酯之胺鹽，可列舉：上述酸式磷酸酯與甲胺、乙胺、丙胺、丁胺、戊胺、己胺、庚胺、辛胺、二甲胺、二乙胺、二丙胺、二丁胺、二戊胺、二己胺、二庚胺、二辛胺、三甲胺、三乙胺、三丙胺、三丁胺、三戊胺、三己胺、三庚胺、三辛胺等胺之鹽。 The amine salt of the acid phosphate may, for example, be the above-mentioned acid phosphate with methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, or the like. Propylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioxane A salt of an amine such as an amine.
作為氯化磷酸酯，可列舉：磷酸三(二氯丙基)酯、磷酸三(氯乙基)酯、磷酸三(氯苯基)酯、聚氧伸烷基-雙[二(氯烷基)]磷酸酯等。作為亞磷酸酯，可列舉：亞磷酸二丁酯、亞磷酸二戊酯、亞磷酸二己酯、亞磷酸二庚酯、亞磷酸二辛酯、亞磷酸二壬酯、亞磷酸二癸酯、亞磷酸二(十一烷基)酯、亞磷酸二(十二烷基)酯、亞磷酸二油酯、亞磷酸二苯酯、亞磷酸二甲酚酯、亞磷酸三丁酯、亞磷酸三戊酯、亞磷酸三己酯、亞磷酸三庚酯、亞磷酸三辛酯、亞磷酸三壬酯、亞磷酸三癸酯、亞磷酸三(十一烷基)酯、亞磷酸三(十二烷基)酯、亞磷酸三油酯、亞磷酸三苯酯、亞磷酸三甲酚酯等。 Examples of the chlorinated phosphate include tris(dichloropropyl) phosphate, tris(chloroethyl) phosphate, tris(chlorophenyl) phosphate, and polyoxyalkylene-bis[di(chloroalkyl) groups. )] Phosphate esters, etc. Examples of the phosphite include dibutyl phosphite, diamyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, dinonyl phosphite, Di(undecyl) phosphite, di(dodecyl) phosphite, dioleyl phosphite, diphenyl phosphite, dimethyl phosphite, tributyl phosphite, phosphorous triacetate Amyl ester, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, tridecyl phosphite, tridecyl phosphite, tri (undecyl) phosphite, tris (twelve) Alkyl) ester, trioleyl phosphite, triphenyl phosphite, cresyl phosphite, and the like.
就提高潤滑性之觀點而言，以冷凍機油總量為基準計，磷化合物之含量較佳為0.1質量%以上，更佳為0.2質量%以上，進而較佳為0.3質量%以上。就提高冷凍機油之穩定性之觀點而言，以冷凍機油總量為基準計，磷化合物之含量較佳為2.4質量%以下，更佳為2.0質量%以下，進而較佳為1.0質量%以下。 The content of the phosphorus compound is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more based on the total amount of the refrigerating machine oil. The content of the phosphorus compound is preferably 2.4% by mass or less, more preferably 2.0% by mass or less, and still more preferably 1.0% by mass or less, based on the total amount of the refrigerating machine oil.
冷凍機油亦可含有除環氧化合物及磷化合物以外之添加劑。作為該添加劑，例如可列舉：2,6-二第三丁基對甲酚、雙酚A等酚系抗氧化劑、苯基-α-萘胺、N,N-二(2-萘基)對苯二胺等胺系抗氧化劑、氯化石蠟、硫化合物等極壓添加劑、脂肪酸等油性劑、聚矽氧系等之消泡劑、苯并***等金屬減活劑、抗磨耗劑、黏度指數改善劑、降凝劑、淨化分散劑等。該等添加劑可單獨使用1種，亦可將2種以上組合而使用。該等添加劑之含量並無特別限定，以冷凍機油總量為基準計，例如可設為10質量%以下，可設為5質量%以下。 The refrigerating machine oil may also contain additives other than the epoxy compound and the phosphorus compound. Examples of the additive include a phenolic antioxidant such as 2,6-di-t-butyl-p-cresol or bisphenol A, a phenyl-α-naphthylamine, and an N,N-bis(2-naphthyl) pair. An amine-based antioxidant such as phenylenediamine, an extreme pressure additive such as chlorinated paraffin or a sulfur compound, an oily agent such as a fatty acid, an antifoaming agent such as polyfluorene, a metal deactivator such as benzotriazole, an anti-wear agent, and a viscosity. Index improver, pour point depressant, purification dispersant, and the like. These additives may be used alone or in combination of two or more. The content of the additives is not particularly limited, and may be, for example, 10% by mass or less based on the total amount of the refrigerating machine oil, and may be 5% by mass or less.
就提高潤滑性之觀點而言，冷凍機油之40℃下之動黏度較佳為2mm2/s以上，更佳為2.3mm2/s以上，進而較佳為3mm2/s以上。就提高回油性之觀點而言，冷凍機油之40℃下之動黏度較佳為500mm2/s以下，更佳為300mm2/s以下，進而較佳為200mm2/s以下。就同時實現潤滑性之提高與回油性之提高之觀點而言，冷凍機油之40℃下之動黏度較佳為2~500mm2/s，更佳為2.3~300mm2/s，進而較佳為3~200mm2/s。就提高冷凍機油之穩定性之觀點而言，冷凍機油之100℃下之動黏度較佳為1mm2/s以上，更佳為2mm2/s以上。就提高回油性之觀點而言，冷凍機油之100℃下之動黏度較佳為100mm2/s以下，更佳為50mm2/s以下。 The dynamic viscosity at 40 ° C of the refrigerating machine oil is preferably 2 mm 2 /s or more, more preferably 2.3 mm 2 /s or more, and still more preferably 3 mm 2 /s or more from the viewpoint of improving lubricity. The dynamic viscosity at 40 ° C of the refrigerating machine oil is preferably 500 mm 2 /s or less, more preferably 300 mm 2 /s or less, and further preferably 200 mm 2 /s or less from the viewpoint of improving the oil repellency. The dynamic viscosity at 40 ° C of the refrigerating machine oil is preferably from 2 to 500 mm 2 /s, more preferably from 2.3 to 300 mm 2 /s, from the viewpoint of improving the lubricity and improving the oil repellent property, and further preferably 3~200mm 2 /s. From the viewpoint of improving the stability of the refrigerating machine oil, the dynamic viscosity at 100 ° C of the refrigerating machine oil is preferably 1 mm 2 /s or more, more preferably 2 mm 2 /s or more. From the viewpoint of improving the oil repellency, the dynamic viscosity at 100 ° C of the refrigerating machine oil is preferably 100 mm 2 /s or less, more preferably 50 mm 2 /s or less.
冷凍機油之體積電阻率可設為1.0×1012Ω．cm以上，可設為1.0×1013Ω．cm以上，可設為1.0×1014Ω．cm以上。尤其是於將冷凍機油用於密閉型冷凍機之情形時，較佳為冷凍機油之電絕緣性較高。本 發明中之體積電阻率意指依據JIS C2101：1999所測定之25℃下之體積電阻率。 The volume resistivity of the refrigerating machine oil can be set to 1.0 × 10 12 Ω. Above cm, it can be set to 1.0×10 13 Ω. Above cm, it can be set to 1.0×10 14 Ω. More than cm. In particular, when the refrigerating machine oil is used in a closed type refrigerating machine, it is preferred that the refrigerating machine oil has high electrical insulation. The volume resistivity in the present invention means the volume resistivity at 25 ° C measured in accordance with JIS C2101:1999.
以冷凍機油總量為基準計，冷凍機油之水分含量較佳可設為100ppm以下，更佳可設為50ppm以下，最佳可設為30ppm以下。尤其是於將冷凍機油用於密閉型冷凍機之情形時，就對冷凍機油之熱、化學穩定性或電絕緣性之影響之觀點而言，較佳為水分含量較少。 The moisture content of the refrigerating machine oil can be preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 30 ppm or less, based on the total amount of the refrigerating machine oil. In particular, when the refrigerator oil is used in a closed type refrigerator, it is preferable that the moisture content is small from the viewpoint of the influence of the heat, chemical stability or electrical insulation of the refrigerator oil.
就防止對冷凍機或配管所使用之金屬之腐蝕之觀點而言，冷凍機油之酸值較佳可設為0.1mgKOH/g以下，更佳可設為0.05mgKOH/g以下。本發明中之酸值意指依據JIS K2501：2003所測定之酸值。 The acid value of the refrigerating machine oil is preferably 0.1 mgKOH/g or less, and more preferably 0.05 mgKOH/g or less from the viewpoint of preventing corrosion of the metal used in the refrigerator or the piping. The acid value in the present invention means an acid value measured in accordance with JIS K2501:2003.
就提高冷凍機油之熱、化學穩定性，抑制油泥等之產生之觀點而言，冷凍機油之灰分較佳可設為100ppm以下，更佳可設為50ppm以下。本發明中之灰分意指依據JIS K2272：1998所測定之灰分。 The ash content of the refrigerating machine oil is preferably 100 ppm or less, and more preferably 50 ppm or less, from the viewpoint of improving the heat and chemical stability of the refrigerating machine oil and suppressing the generation of sludge. The ash in the present invention means the ash measured in accordance with JIS K2272:1998.
冷凍機油之流動點較佳可設為-10℃以下，更佳可設為-20℃以下。本發明中之流動點意指依據JIS K2268-1987所測定之流動點。 The flow point of the refrigerating machine oil is preferably set to -10 ° C or lower, more preferably -20 ° C or lower. The pour point in the present invention means a pour point measured in accordance with JIS K2268-1987.
本實施形態之含有烷基苯作為基油之組合物可較佳地用作與微燃性氫氟碳(HFC)冷媒一同使用之冷凍機油之構成成分、或含有冷凍機油及微燃性氫氟碳(HFC)冷媒之冷凍機用作動流體組合物之構成成分。 The composition containing an alkylbenzene as a base oil of the present embodiment can be preferably used as a constituent component of a refrigerating machine oil used together with a slightly flammable hydrofluorocarbon (HFC) refrigerant, or a refrigerating machine oil and a slightly flammable hydrofluorocarbon. A carbon (HFC) refrigerant refrigerator is used as a constituent of the dynamic fluid composition.
本實施形態之烷基苯可較佳地用於製造與微燃性氫氟碳(HFC)冷媒一同使用之冷凍機油、或含有冷凍機油及微燃性氫氟碳(HFC)冷媒之冷凍機用作動流體組合物。 The alkylbenzene of the present embodiment can be preferably used for producing a refrigerating machine oil used together with a slightly flammable hydrofluorocarbon (HFC) refrigerant or a refrigerating machine containing a refrigerating machine oil and a flammable hydrofluorocarbon (HFC) refrigerant. Actuate the fluid composition.
本實施形態之冷凍機油係與微燃性氫氟碳(HFC)冷媒一同使用者，本實施形態之冷凍機用作動流體組合物係含有微燃性氫氟碳(HFC)冷媒者。氫氟碳(HFC)冷媒中包含飽和氫氟碳冷媒(亦稱為氫氟烷烴冷媒)及不飽和氫氟碳冷媒(亦稱為氫氟烷烴冷媒、氫氟烯烴冷媒、或HFO(Hydro Fluoro Olefin，氫氟烯烴)冷媒)。本發明中之微燃 性冷媒意指ASHRAE(The American Society of Heating,Refrigerating and Air-conditioning Engineers，美國採暖、製冷與空調工程師學會)34之燃燒性分類中之A2L分類中所含之冷媒。 The refrigerating machine oil of the present embodiment is used together with a slightly flammable hydrofluorocarbon (HFC) refrigerant, and the refrigerating machine of the present embodiment is used as a dynamic fluid composition containing a micro-flammable hydrofluorocarbon (HFC) refrigerant. Hydrofluorocarbon (HFC) refrigerants contain saturated hydrofluorocarbon refrigerants (also known as hydrofluorocarbon refrigerants) and unsaturated hydrofluorocarbon refrigerants (also known as hydrofluorocarbon refrigerants, hydrofluoroolefin refrigerants, or HFOs (Hydro Fluoro Olefin). , hydrofluoroolefins) (refrigerant). Micro-burning in the present invention The term "refrigerant" means the refrigerant contained in the A2L classification in the flammability classification of ASHRAE (The American Society of Heating, Refrigerating and Air-conditioning Engineers).
作為微燃性氫氟碳冷媒，例如可列舉：二氟甲烷(HFC-32)、1,3,3,3-四氟丙烯(HFC-1234ze)、2,3,3,3-四氟丙烯(HFC-1234yf)。作為微燃性氫氟碳冷媒，較佳為1,3,3,3-四氟丙烯(HFC-1234ze)或2,3,3,3-四氟丙烯(HFC-1234yf)。 Examples of the slightly flammable hydrofluorocarbon refrigerant include difluoromethane (HFC-32), 1,3,3,3-tetrafluoropropene (HFC-1234ze), and 2,3,3,3-tetrafluoropropene. (HFC-1234yf). As the slightly flammable hydrofluorocarbon refrigerant, preferred is 1,3,3,3-tetrafluoropropene (HFC-1234ze) or 2,3,3,3-tetrafluoropropene (HFC-1234yf).
本實施形態之與冷凍機油一同使用之冷媒亦可為微燃性氫氟碳冷媒與其他冷媒之混合冷媒。作為其他冷媒，可列舉：微燃性氫氟碳冷媒以外之氫氟碳冷媒、全氟醚類等含氟醚系冷媒、雙(三氟甲基)硫醚冷媒、三氟碘甲烷冷媒、二甲醚、二氧化碳、氨及烴等自然系冷媒。作為其他冷媒，可較佳地使用包含不具有氧原子之化合物之冷媒。 The refrigerant used in the present embodiment together with the refrigerating machine oil may be a mixed refrigerant of a slightly flammable hydrofluorocarbon refrigerant and another refrigerant. Examples of the other refrigerant include a hydrofluorocarbon refrigerant other than the slightly flammable hydrofluorocarbon refrigerant, a fluorine-containing ether refrigerant such as perfluoroether, a bis(trifluoromethyl) sulfide refrigerant, and a trifluoroiodomethane refrigerant. Natural refrigerants such as methyl ether, carbon dioxide, ammonia and hydrocarbons. As the other refrigerant, a refrigerant containing a compound having no oxygen atom can be preferably used.
作為微燃性氫氟碳冷媒以外之氫氟碳冷媒，例如可列舉：三氟甲烷(HFC-23)、五氟乙烷(HFC-125)、1,1,2,2-四氟乙烷(HFC-134)、1,1,1,2-四氟乙烷(HFC-134a)、1,1,1-三氟乙烷(HFC-143a)、1,1-二氟乙烷(HFC-152a)、氟乙烷(HFC-161)、1,1,1,2,3,3,3-七氟丙烷(HFC-227ea)、1,1,1,2,3,3-六氟丙烷(HFC-236ea)、1,1,1,3,3,3-六氟丙烷(HFC-236fa)、1,1,1,3,3-五氟丙烷(HFC-245fa)、1,1,1,3,3-五氟丁烷(HFC-365mfc)、1,2,3,3,3-五氟丙烯(HFC-1225ye)等。 Examples of the hydrofluorocarbon refrigerant other than the slightly flammable hydrofluorocarbon refrigerant include trifluoromethane (HFC-23), pentafluoroethane (HFC-125), and 1,1,2,2-tetrafluoroethane. (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC -152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,2,3,3-hexafluoropropane ( HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1 , 3,3-pentafluorobutane (HFC-365mfc), 1,2,3,3,3-pentafluoropropene (HFC-1225ye), and the like.
作為烴冷媒，較佳為碳數3~5之烴，具體而言，例如可列舉：甲烷、乙烯、乙烷、丙烯、丙烷、環丙烷、正丁烷、異丁烷、環丁烷、甲基環丙烷、2-甲基丁烷、正戊烷或該等之2種以上之混合物。該等之中，可較佳地使用於25℃、1個大氣壓之條件下為氣體者，較佳為丙烷、正丁烷、異丁烷、2-甲基丁烷或該等之混合物。 The hydrocarbon refrigerant is preferably a hydrocarbon having 3 to 5 carbon atoms, and specific examples thereof include methane, ethylene, ethane, propylene, propane, cyclopropane, n-butane, isobutane, cyclobutane, and A cyclopropane, 2-methylbutane, n-pentane or a mixture of two or more thereof. Among these, it can be preferably used as a gas at 25 ° C and 1 atm., preferably propane, n-butane, isobutane, 2-methylbutane or a mixture thereof.
作為含氟醚系冷媒，具體而言，例如可列舉：HFE-134p、HFE- 245mc、HFE-236mf、HFE-236me、HFE-338mcf、HFE-365mcf、HFE-245mf、HFE-347mmy、HFE-347mcc、HFE-125、HFE-143m、HFE-134m、HFE-227me等，該等冷媒可根據用途或所需性能適當選擇。 Specific examples of the fluorinated ether-based refrigerant include HFE-134p and HFE-. 245mc, HFE-236mf, HFE-236me, HFE-338mcf, HFE-365mcf, HFE-245mf, HFE-347mmy, HFE-347mcc, HFE-125, HFE-143m, HFE-134m, HFE-227me, etc., such refrigerants It can be appropriately selected depending on the use or desired performance.
於冷媒為混合冷媒之情形時，微燃性氫氟碳冷媒與其他冷媒之混合比(質量比，微燃性氫氟碳冷媒：其他冷媒)可設為1：99~99：1，可設為5：95~95：5。 When the refrigerant is a mixed refrigerant, the mixing ratio of the slightly flammable hydrofluorocarbon refrigerant to other refrigerants (mass ratio, slightly flammable hydrofluorocarbon refrigerant: other refrigerant) can be set to 1:99 to 99:1, which can be set. It is 5:95~95:5.
通常，冷凍機油於製冷空調設備中以單獨微燃性氫氟碳冷媒或與混合冷媒混合之冷凍機用作動流體組合物之形式存在。冷凍機用作動流體組合物中之冷凍機油之含量相對於冷媒100質量份可為1~500質量份，亦可為2~400質量份。 Generally, the refrigerating machine oil is present in the refrigerating and air-conditioning apparatus in the form of a separate micro-flammable hydrofluorocarbon refrigerant or a refrigerating machine mixed with a mixed refrigerant as a dynamic fluid composition. The content of the refrigerator oil used in the fluid dynamic fluid composition of the refrigerator may be 1 to 500 parts by mass, or 2 to 400 parts by mass, per 100 parts by mass of the refrigerant.
本實施形態之冷凍機油及冷凍機用作動流體組合物可較佳地用於具有往復移動式或旋轉式之密閉型壓縮機之空調、冰箱、或開放型或密閉型之汽車空調。又，本實施形態之冷凍機油及冷凍機用作動流體組合物可較佳地用於除濕機、熱水器、冷凍庫、冷凍冷藏倉庫、自動販售機、展示櫃、化學設備等之冷卻裝置等。進而，本實施形態之冷凍機油及冷凍機用作動流體組合物亦可較佳地用於具有離心式壓縮機者。 The refrigerating machine oil and the refrigerating machine of the present embodiment are preferably used as a dynamic fluid composition for an air conditioner, a refrigerator, or an open or sealed type automobile air conditioner having a reciprocating type or a rotary type hermetic type compressor. Further, the refrigerating machine oil and the refrigerating machine of the present embodiment are preferably used as a dynamic fluid composition for a dehumidifier, a water heater, a freezer, a refrigerating warehouse, a vending machine, a display case, a cooling device for chemical equipment, and the like. Further, the refrigerating machine oil and the refrigerating machine of the present embodiment can be preferably used as a dynamic fluid composition for a centrifugal compressor.
以下，基於實施例，更具體地對本發明進行說明，但本發明並不限定於該等實施例。 Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to the examples.
於各實施例及比較例中，製備含有具有表1及表2所示性狀之烷基苯作為基油之冷凍機油。烷基苯之各性狀係依據以下標準而進行測定。 In each of the examples and comparative examples, a refrigerating machine oil containing an alkylbenzene having the properties shown in Tables 1 and 2 as a base oil was prepared. The properties of the alkylbenzenes were determined according to the following criteria.
40℃下之動黏度：JIS K2283：2000 Dynamic viscosity at 40 ° C: JIS K2283:2000
餾出溫度：ASTM D7213-05 Distillation temperature: ASTM D7213-05
引火點：JIS K2265-4：2007 Fire point: JIS K2265-4:2007
自然發火點：ASTM E659-1978 Natural Fire Point: ASTM E659-1978
對各冷凍機油實施以下所示之回油性試驗。將結果示於表1及表2。 The oil return test shown below was carried out for each of the refrigerator oils. The results are shown in Tables 1 and 2.
[回油性試驗1] [oil return test 1]
使用圖3所示之裝置。向冷媒罐1填充二氟甲烷(R32)，向長度為1.5m、內徑為0.0036m之銅配管2中之浸漬於恆溫槽5之部分2a填充冷凍機油5.0g。將恆溫槽5之溫度設定為-20℃，使R32以每分鐘0.001m3之流量於銅配管2內自冷媒罐1流向集油器7。此時，分別利用流量計3監測R32之流量，利用壓力計4監測冷媒罐1與恆溫槽5之間之銅配管2內之壓力，利用壓力計6監測恆溫槽5與集油器7之間之銅配管2內之壓力。自使R32開始流動起30分後，對積存於集油器7之冷凍機油之質量進行測定，依據下式算出回油率。將回油率為20質量%以上之情形評價為「良好」，將回油率未達20質量%之情形評價為「不良」。 Use the device shown in Figure 3. The refrigerant tank 1 was filled with difluoromethane (R32), and 5.0 g of the refrigerating machine oil was filled into the portion 2a of the copper pipe 2 having a length of 1.5 m and an inner diameter of 0.0036 m and immersed in the thermostatic chamber 5. The temperature of the constant temperature bath 5 was set to -20 ° C, and R32 was flown from the refrigerant tank 1 to the oil collector 7 in the copper pipe 2 at a flow rate of 0.001 m 3 per minute. At this time, the flow rate of R32 is monitored by the flow meter 3, and the pressure in the copper pipe 2 between the refrigerant tank 1 and the constant temperature tank 5 is monitored by the pressure gauge 4, and the pressure gauge 6 is used to monitor the relationship between the constant temperature tank 5 and the oil collector 7. The pressure inside the copper pipe 2. After 30 minutes from the start of the flow of R32, the mass of the refrigerating machine oil accumulated in the oil collector 7 was measured, and the oil return rate was calculated according to the following formula. The case where the oil return rate was 20% by mass or more was evaluated as "good", and the case where the oil return rate was less than 20% by mass was evaluated as "poor".
回油率(質量%)=(積存於集油器之冷凍機油之質量(g)/5.0(g))×100 Oil return rate (% by mass) = (mass of refrigerating machine oil accumulated in the oil collector (g) / 5.0 (g)) × 100
[回油性試驗2] [oil return test 2]
除了將冷媒變更為2,3,3,3-四氟丙烯(HFO-1234yf)以外，與「回油性試驗1」同樣地算出回油率，進行「良好」或「不良」之評價。 The oil return rate was calculated in the same manner as in the "oil return test 1" except that the refrigerant was changed to 2,3,3,3-tetrafluoropropene (HFO-1234yf), and the evaluation of "good" or "bad" was performed.
對實施例之各冷凍機油實施以下所示之耐磨耗性試驗。將結果示於表3。 The abrasion resistance test shown below was carried out for each of the refrigerator oils of the examples. The results are shown in Table 3.
[耐磨耗性試驗1] [Abrasion resistance test 1]
使用可形成與實體壓縮機類似之冷媒環境之神鋼造機股份有限公司製造之高壓環境摩擦試驗機(旋轉葉片材料與固定圓盤材料為旋轉滑動方式)。將試驗條件設為冷凍機油之油量：600ml、試驗溫度：100℃、轉數：450rpm、負載荷重：60kgf、試驗時間：1小時，將SKH-51用作葉片材料，將FC250用作圓盤材料。將二氟甲烷(R32)用作冷媒，將試驗容器內壓力設為1.1MPa。關於耐磨耗性，由於圓盤材料之磨耗量極少，故而將葉片材料之磨耗深度未達10μm之情形評價為「良好」，將葉片材料之磨耗深度為10μm以上之情形評價為「不良」。 A high-pressure environmental friction tester (rotating blade material and fixed disc material in a rotary sliding manner) manufactured by Kobelco Co., Ltd., which can form a refrigerant environment similar to a solid compressor, is used. The test conditions were set as the oil quantity of the refrigerating machine oil: 600 ml, the test temperature: 100 ° C, the number of revolutions: 450 rpm, the load load: 60 kgf, the test time: 1 hour, the SKH-51 was used as the blade material, and the FC250 was used as the disc. material. Difluoromethane (R32) was used as a refrigerant, and the pressure inside the test vessel was set to 1.1 MPa. Regarding the wear resistance, since the abrasion amount of the disk material was extremely small, the case where the blade material had a wear depth of less than 10 μm was evaluated as "good", and the case where the blade material had a wear depth of 10 μm or more was evaluated as "poor".
[耐磨耗性試驗2] [Abrasion resistance test 2]
除了將冷媒變更為2,3,3,3-四氟丙烯(HFO-1234yf)以外，與「耐磨耗性試驗1」同樣地對葉片材料之磨耗深度進行測定，進行「良好」或「不良」之評價。 The abrasion depth of the blade material was measured in the same manner as in the "Abrasion resistance test 1" except that the refrigerant was changed to 2,3,3,3-tetrafluoropropene (HFO-1234yf), and "good" or "bad" was performed. Evaluation.
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