WO2023073826A1 - Milieu de travail pour dispositifs à cycle frigorifique du type à compression de fluide frigorigène, et dispositif à cycle frigorifique utilisant ledit milieu de travail - Google Patents

Milieu de travail pour dispositifs à cycle frigorifique du type à compression de fluide frigorigène, et dispositif à cycle frigorifique utilisant ledit milieu de travail Download PDF

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WO2023073826A1
WO2023073826A1 PCT/JP2021/039624 JP2021039624W WO2023073826A1 WO 2023073826 A1 WO2023073826 A1 WO 2023073826A1 JP 2021039624 W JP2021039624 W JP 2021039624W WO 2023073826 A1 WO2023073826 A1 WO 2023073826A1
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mass
refrigerating machine
machine oil
oil
working medium
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PCT/JP2021/039624
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English (en)
Japanese (ja)
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清重 横井
親哉 河村
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友光商事株式会社
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Priority to PCT/JP2021/039624 priority Critical patent/WO2023073826A1/fr
Priority to PCT/JP2022/039731 priority patent/WO2023074686A1/fr
Priority to KR1020247015289A priority patent/KR20240076830A/ko
Priority to JP2023556461A priority patent/JPWO2023074686A1/ja
Publication of WO2023073826A1 publication Critical patent/WO2023073826A1/fr

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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
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C10M101/02—Petroleum fractions
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
    • C10M107/34—Polyoxyalkylenes
    • 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
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/86—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of 30 or more atoms
    • C10M129/95—Esters
    • 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
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B1/00—Compression machines, plants or systems with non-reversible cycle
    • 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
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/20—Thiols; Sulfides; Polysulfides
    • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
    • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the present invention relates to a working medium for a refrigerant compression refrigeration cycle device and a refrigeration cycle device using the working medium. Specifically, the present invention relates to a working medium containing a refrigerant and refrigerating machine oil, and a refrigeration cycle apparatus using the same, which is used in a refrigerant compression refrigeration cycle apparatus.
  • Hydrofluorocarbons which are hydrocarbons containing fluorine atoms, are used as refrigerants in refrigeration cycle devices that use compressed refrigerants, such as air conditioners, electric refrigerators, industrial refrigerators, refrigerators, and freezer warehouses. .
  • compressed refrigerants such as air conditioners, electric refrigerators, industrial refrigerators, refrigerators, and freezer warehouses.
  • HFCs have a long life in the atmosphere and have a large greenhouse effect, they are not satisfactory refrigerants for preventing global warming, and their use is being restricted.
  • hydrocarbon refrigerants hydrocarbons containing no halogen atoms
  • HFCs hydrocarbon refrigerants
  • isobutane (R600a) which is a hydrocarbon containing no halogen atoms
  • propane (R290) is being put into practical use for air conditioners.
  • Mineral oils, alkylbenzenes, polyol esters, polyethers, and the like are known as refrigerating machine oils used as working medium components together with hydrocarbon refrigerants when these hydrocarbon refrigerants are used. (For example, Patent Documents 1 to 5).
  • the mineral oil, alkylbenzene or polyol ester-containing refrigerating machine oil proposed in Patent Documents 1 to 3 above has good compatibility with hydrocarbon refrigerants such as propane and isobutane, and the amount of refrigerant dissolved in the refrigerating machine oil increases. Therefore, in order for the refrigerating cycle device to exhibit sufficient performance, it is necessary to fill the refrigerating cycle device with a large amount of hydrocarbon refrigerant. However, since hydrocarbons such as propane and isobutane are highly flammable, it is desired from a safety point of view that the amount of hydrocarbon refrigerant is as small as possible within the range in which the operating efficiency is sufficiently exhibited.
  • a refrigerating machine oil with a lower viscosity can be selected, so that the efficiency of the refrigerating cycle device can be improved, leading to energy saving.
  • the refrigerating machine oil containing the polyol ester and polyalkylene glycol proposed in Patent Document 4 has high hygroscopicity because both the polyol ester and the polyalkylene glycol have high polarity. In this case, there is concern that the water content in the refrigerating machine oil will increase, the hydrolysis of the polyol ester will proceed, and the refrigerating machine oil will deteriorate. Refrigerating machine oil is used for a long period of time in a refrigerating cycle device in coexistence with a refrigerant, and is exposed to low and high temperatures, so high stability is required.
  • Patent Document 5 discloses a refrigerating machine oil containing a polyether compound and mineral oil.
  • the polyether compound is polyalkylene glycol or polyvinyl ether
  • the mineral oil has a specific sulfur content in order to improve lubricity.
  • the refrigerating machine oil disclosed in Patent Document 5 includes a very wide range of refrigerating machine oils.
  • the refrigerator oil disclosed in Patent Document 5 uses an ammonia refrigerant as a refrigerant.
  • the refrigerating machine oil disclosed in Patent Document 5 is a large open-type refrigerating machine that uses an ammonia refrigerant, that is, a non-circulating type in which the refrigerant and refrigerating machine oil are not mixed and circulated in the refrigerating cycle. Refrigerating machine oil suitable for the system.
  • a compact closed-type circulating system in which a motor is built into the compressor and a mixture of hydrocarbon refrigerant and refrigerating machine oil is mixed and circulated through the refrigeration cycle.
  • the refrigerating machine oil is required to have high electrical insulation. Since the ammonia refrigerant used in Patent Document 5 has a large polarity and current leaks, it cannot be used in a circulation system.
  • the medium is required to be a uniform liquid even at a low temperature because the medium is cooled to a low temperature (eg, ⁇ 25° C.).
  • a hydrocarbon refrigerant that is liquid even at low temperatures is preferably used as the refrigerant.
  • the refrigerating machine oil is required to uniformly dissolve with the hydrocarbon refrigerant even at low temperatures.
  • polyether compounds especially polyalkylene glycol
  • mineral oil is non-polar.
  • the polyether compound is difficult to dissolve in mineral oil and hydrocarbon refrigerants at low temperatures (eg, -25° C.) and separates or precipitates at low temperatures.
  • the ammonia refrigerant and refrigerating machine oil disclosed in Patent Document 5 are not suitable for circulation systems.
  • An object of the present invention is to provide a working medium for a refrigerant compression refrigeration cycle device containing a hydrocarbon refrigerant and refrigerating machine oil, wherein the refrigerating machine oil has high stability, appropriate solubility with the refrigerant, high lubricity, and high electrical insulation. It is an object of the present invention to provide a working medium for a refrigerant compression refrigeration cycle device that achieves at least one of the following properties.
  • a refrigerant containing a hydrocarbon containing no halogen atoms having 2 to 4 carbon atoms and a refrigerating machine oil containing a polyalkylene glycol and a mineral oil are included, and the polyalkylene glycol is represented by the following general formula (1) :
  • R 1 is a linear or branched alkyl group having 1 to 25 carbon atoms
  • OR 2 is the same or different and represents an oxyalkylene group having 2 to 4 carbon atoms
  • n is It represents the number of added moles of the oxyalkylene group represented by OR2 .
  • the kinematic viscosity at 40° C. is 2 mm 2 /s or more and 60 mm 2 /s or less
  • the mineral oil has an aniline point of 55° C. or more and 105° C. or less, a pour point of ⁇ 15° C. or less
  • the polyalkylene glycol is contained in an amount of 10% by mass or more and 60% by mass or less with respect to the total mass of the refrigerating machine oil
  • the mineral oil is A working medium for a refrigerant compression refrigeration cycle device, which is contained in an amount of 40% by mass or more and 90% by mass or less with respect to the total mass of the refrigerating machine oil.
  • the refrigerating machine oil has high stability, appropriate solubility with the refrigerant, high lubricity, and high
  • a working medium for a refrigerant compression refrigeration cycle device is provided that achieves at least one of electrical insulation.
  • a working medium for a refrigerant compression refrigeration cycle device comprises a refrigerant containing a hydrocarbon containing no halogen atoms having 2 to 4 carbon atoms, a specific polyalkylene glycol and Refrigerant oil, including certain mineral oils.
  • the working medium according to the present invention preferably has a kinematic viscosity at 40° C. of 1 mm 2 /s or more and 32 mm 2 /s or less, more preferably 3 mm 2 /s or more and 30 mm 2 /s or less. 2 /s or more and 25 mm 2 /s or less is more preferable. In this specification, kinematic viscosity is measured by the method described in Examples.
  • the refrigerant contained in the working medium of the present invention contains hydrocarbons containing no halogen atoms and having 2 to 4 carbon atoms (hereinafter also simply referred to as “hydrocarbons”).
  • hydrocarbons containing no halogen atoms having 2 to 4 carbon atoms include saturated hydrocarbons such as ethane (R170), propane (R290), normal butane (R600) and isobutane (R600a), and unsaturated hydrocarbons such as ethylene and propene. can be mentioned.
  • At least one selected from saturated hydrocarbons that is, at least one selected from the group consisting of ethane, propane, normal butane and isobutane.
  • ethane propane, normal butane and isobutane.
  • a combination of propane, ethane, or a mixed refrigerant thereof and a refrigerating machine oil containing a specific polyalkylene glycol and a specific mineral oil is more preferable because the effect of the present invention is high.
  • the hydrocarbon one type of hydrocarbon may be used alone, or two or more types of hydrocarbon may be used in combination.
  • the hydrocarbon comprises propane (R290).
  • the refrigerant is, in addition to propane, saturated hydrocarbons such as ethane, n-butane (normal butane) (R600) and isobutane (R600a); unsaturated hydrocarbons such as ethylene and propene; may further contain hydrocarbons.
  • the propane-containing hydrocarbon further contains other hydrocarbons than propane
  • the main component of the hydrocarbon is preferably propane.
  • a "main component” means a component exceeding 50 mass % (upper limit 100 mass %) with respect to the total mass of hydrocarbons.
  • the working medium of the present invention may further contain other refrigerants such as saturated hydrofluorocarbons, unsaturated hydrofluorocarbons, dimethyl ether, and carbon dioxide as refrigerants.
  • the other refrigerant is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the hydrocarbon. .
  • the refrigerator oil of the present invention contains a specific polyalkylene glycol and a specific mineral oil.
  • the refrigerating machine oil is based on a mixed oil containing a specific polyalkylene glycol and a specific mineral oil.
  • the base oil of the refrigerating machine oil refers to a component containing more than 50% by mass (upper limit 100% by mass) relative to the total mass of the refrigerating machine oil, preferably a component containing 80% by mass or more, more preferably 90% by mass. It is a component contained in mass % or more.
  • Polyalkylene glycol can be used alone as a refrigerating machine oil, but it is highly hygroscopic due to its polarity.
  • polyalkylene glycol when polyalkylene glycol is used alone as a refrigerating machine oil, the water content in the refrigerating machine oil increases, and the water may cause troubles in the refrigerating cycle apparatus.
  • polyalkylene glycol since polyalkylene glycol has low electrical insulation, that is, low volume resistivity, current leakage is likely to occur in air conditioners, electric refrigerators, industrial refrigerators, etc. that use hermetic compressors.
  • polyalkylene glycol has the advantage of being less soluble in refrigerants containing hydrocarbons due to its polarity.
  • Mineral oil has low hygroscopicity and high electrical insulation, but since it is a component composed of the same hydrocarbons as the hydrocarbons contained in the refrigerant, it dissolves in a large amount in refrigerants containing hydrocarbons. Therefore, when mineral oil is used alone as a refrigerating machine oil, there is a disadvantage that the viscosity of the refrigerating machine oil decreases in the refrigerating cycle device, resulting in a decrease in lubricity, ie wear resistance.
  • the specific polyalkylene glycol of the present invention is represented by the following general formula (1).
  • R 1 is a linear or branched alkyl group having 1 to 25 carbon atoms
  • OR 2 represents one or more oxyalkylene groups having 2 to 4 carbon atoms
  • n is OR 2 ; It represents the number of added moles of the represented oxyalkylene group.
  • R 1 represents a linear or branched alkyl group having 1 to 25 carbon atoms.
  • the linear or branched alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms.
  • a straight or branched alkyl group of 8 is more preferred, a straight or branched alkyl group of 1 to 5 carbon atoms is particularly preferred, and a straight or branched alkyl group of 3 to 5 carbon atoms is most preferred. Used.
  • Linear or branched alkyl groups having 1 to 25 carbon atoms include, for example, methyl group, ethyl group, linear or branched propyl group (n-propyl group, isopropyl group), linear or branched Butyl group (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), linear or branched pentyl group (n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group , tert-pentyl group, neopentyl group) and the like.
  • R 1 is preferably an isopropyl group, an n-butyl group, or a tert-butyl group in terms of the balance between the solubility in a refrigerant containing a hydrocarbon and the properties as a refrigerating machine oil, and a linear or branched chain having 4 carbon atoms.
  • a butyl group (n-butyl group, tert-butyl group) is more preferred.
  • R 1 in the polyalkylene glycol is a short-chain alkyl group, the low-temperature fluidity is excellent.
  • OR 2 are the same or different and represent an oxyalkylene group having 2 to 4 carbon atoms. That is, R 2 represents an alkylene group having 2 to 4 carbon atoms.
  • OR 2 may be one type of oxyalkylene group, or may be composed of two or more types of oxyalkylene groups. Specific examples of such oxyalkylene groups include an oxyethylene group (-OCH 2 CH 2 -), an oxypropylene group (-OCH(CH 3 )CH 2 -), an oxytrimethylene group (-OCH 2 CH 2 CH 2 —), an oxybutylene group (—OCH 2 CH 2 CH 2 CH 2 —), and the like.
  • the oxyalkylene groups (OR 2 ) in the repeating unit represented by (OR 2 ) n may be the same oxyalkylene group or different oxyalkylene groups.
  • the upper limit of the ratio of oxypropylene groups to the entire OR 2 in the polyalkylene glycol is not particularly limited, but it is most preferable that all OR 2 in the polyalkylene glycol is composed of oxypropylene, so the upper limit is 100 mol%. be.
  • OR 2 when OR 2 is composed of oxyethylene groups and oxypropylene groups, the proportion of oxypropylene groups is 70 mol% with respect to the entirety of OR 2 (that is, the total number of added moles of oxyethylene groups and oxypropylene groups). It is preferably 80 mol % or more, more preferably 80 mol % or more. In this case, the ratio of oxyethylene groups (R 2 has 2 carbon atoms) to the entire OR 2 is 30 mol % or less in terms of the characteristics as a refrigerating machine oil, that is, in order to reduce the hygroscopicity of the refrigerating machine oil. is preferred, and 20 mol % or less is more preferred.
  • R 1 in general formula (1) is a C4 alkyl group and OR 2 is an oxypropylene group.
  • n represents the number of added moles (degree of polymerization) of the oxyalkylene group represented by OR 2 .
  • the number average molecular weight of the polyalkylene glycol represented by the general formula (1) is preferably 100 to 1500, more preferably 200 to 1200, even more preferably 300 to 1000, and 350 to 850. is particularly preferred, and 350-700 is most preferred.
  • n is preferably a number such that the number average molecular weight of the polyalkylene glycol satisfies the above conditions.
  • the number average molecular weight of the polyalkylene glycol is within the above range, the compatibility with mineral oil is also good, and the lubricity of the refrigerating machine oil can be sufficiently exhibited in the coexistence with the hydrocarbon-containing refrigerant.
  • the number average molecular weight is measured by GPC (gel permeation chromatography) using polystyrene as a standard substance.
  • the added mole number n in formula (1) can be calculated based on the number average molecular weight obtained by measurement.
  • the polyalkylene glycol has a kinematic viscosity of 2 mm 2 /s or more and 60 mm 2 /s or less at 40°C.
  • the kinematic viscosity of polyalkylene glycol at 40° C. is less than 2 mm 2 /s, the oil film formed by polyalkylene glycol becomes thin. In other words, metal-to-metal contact is likely to occur in the sliding material (sliding portion) of the compressor, which is the heart of the refrigerating cycle device, and the lubricity of the refrigerating machine oil becomes insufficient when coexisting with the refrigerant. If the kinematic viscosity of the polyalkylene glycol at 40° C.
  • the kinematic viscosity of the polyalkylene glycol at 40° C. is preferably 5 mm 2 /s or more and 55 mm 2 /s or less, more preferably 8 mm 2 /s or more and 50 mm 2 /s or less, still more preferably 9 mm 2 /s or more. It is 45 mm 2 /s or less, particularly preferably 10 mm 2 /s or more and 40 mm 2 /s or less, and most preferably 10 mm 2 /s or more and 35 mm 2 /s or less.
  • the kinematic viscosity at 40°C of the polyalkylene glycol is within the above range, it is possible to exhibit good lubricity as a refrigerating machine oil.
  • the kinematic viscosity of the polyalkylene glycol at 100° C. is preferably 0.1 mm 2 /s or more, more preferably 0.25 mm 2 /s or more, and more preferably 0.3 mm 2 /s. It is particularly preferably 0.4 mm 2 /s or more, particularly preferably 0.4 mm 2 /s or more, and most preferably 0.5 mm 2 /s or more.
  • the kinematic viscosity of the polyalkylene glycol at 100° C. is preferably 15 mm 2 /s or less, more preferably 10 mm 2 /s or less, particularly preferably 5 mm 2 /s or less, and 3 mm 2 /s.
  • the kinematic viscosity of the polyalkylene glycol at 100° C. is preferably 0.1 mm 2 /s or more and 15 mm 2 /s or less, more preferably 0.25 mm 2 /s or more and 10 mm 2 /s or less, It is particularly preferably 0.3 mm 2 /s or more and 5 mm 2 /s or less, particularly more preferably 0.4 mm 2 /s or more and less than 3 mm 2 /s, and 0.5 mm 2 /s or more and 2.9 mm 2 /s or less is most preferred.
  • the kinematic viscosity at 100° C. of the polyalkylene glycol is 0.1 mm 2 /s or more and less than 3 mm 2 /s, and 0.1 mm 2 /s or more and 2.9 mm 2 /s or less. If the kinematic viscosity of the polyalkylene glycol at 100° C. is 0.1 mm 2 /s or more, the oil film formed by the polyalkylene glycol is formed with a sufficient thickness, and the lubricating properties of the refrigerating machine oil can be sufficiently exhibited. When the kinematic viscosity of the polyalkylene glycol at 100° C. is 15 mm 2 /s or less, the viscosity of the refrigerating machine oil is low, so the efficiency of the refrigerating cycle device can be further improved.
  • the polyalkylene glycol has a kinematic viscosity of 2 mm 2 /s or more and 60 mm 2 /s or less at 40° C. and a kinematic viscosity of 0.1 mm 2 /s or more and 15 mm 2 /s or less at 100° C. is preferred.
  • the polyalkylene glycol more preferably has a kinematic viscosity of 2 mm 2 /s or more and 60 mm 2 /s or less at 40° C.
  • the kinematic viscosity at 40°C is 2 mm 2 /s or more and 60 mm 2 /s or less
  • the kinematic viscosity at 100°C is 0.5 mm 2 /s or more and 2.9 mm 2 /s or less.
  • the polyalkylene glycol preferably has a pour point of -25°C or lower, more preferably -30°C or lower, and even more preferably -40°C or lower.
  • the pour point of the polyalkylene glycol is ⁇ 25° C. or lower
  • the fluidity of the refrigerating machine oil containing the polyalkylene glycol and the mineral oil is increased, and the polyalkylene glycol according to the present invention can be suitably used as a refrigerating machine oil. It can be synthesized using a known method ("Alkylene Oxide Polymer", Mitsuta Shibata et al., Kaibundo Publishing, November 20, 1990).
  • the resulting polyalkylene glycol may be either a random copolymer or a block copolymer.
  • Polyalkylene glycols represented by the general formula (1) include, for example, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol monopropyl ether (polypropylene glycol mono-n-propyl ether, polypropylene glycol monoisopropyl ether), polypropylene Glycol monobutyl ether (polypropylene glycol mono-n-butyl ether), polypropylene glycol mono-tert-butyl ether, polypropylene glycol monohexyl ether (polypropylene glycol mono-n-hexyl ether), polypropylene glycol mono-octyl ether (polypropylene glycol mono-n-octyl ether); polyethylene Monomethyl ether of glycol-polypropylene glycol copolymer (polyethylene glycol polypropylene glycol monomethyl ether), monoethyl ether of polyethylene glycol-
  • polypropylene glycol monoalkyl ethers such as polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol monopropyl ether, and polypropylene glycol monobutyl ether, which have high electrical insulation, are preferred and have higher electrical insulation.
  • polypropylene glycol mono-n-propyl ether, polypropylene glycol mono-n-butyl ether, polypropylene glycol mono-tert-butyl ether, polypropylene glycol monohexyl ether, polypropylene glycol mono-octyl ether and the like which have low hygroscopicity, are more preferred.
  • one end of the polyalkylene glycol of the present invention is a hydroxyl group with high polarity, it has a low affinity with non-polar hydrocarbons contained in the refrigerant, and it is thought that the amount dissolved in the refrigerant can be reduced. . Therefore, the filling amount of refrigerant in the working medium can be reduced.
  • the hydroxyl group has a large adsorption force to metal materials, polyalkylene glycol easily forms an oil film on the sliding material of the compressor, which is the heart of the refrigeration cycle device, and has good lubricity (wear resistance). show.
  • the mineral oil used in the present invention has an aniline point of 55°C or higher and 105°C or lower, a pour point of -15°C or lower, and a kinematic viscosity at 40°C of 2 mm 2 /s or higher and 70 mm 2 /s or lower.
  • mineral oil is soluble with polyalkylene glycol
  • the aniline point of mineral oil is a measure of solubility with polyalkylene glycol.
  • the aniline point of the mineral oil is less than 55°C, the viscosity characteristics such as the viscosity index as a refrigerating machine oil become insufficient, and good performance as a refrigerating machine oil (for example, formation of a sufficiently thick oil film at high temperatures) cannot be exhibited.
  • the aniline point of the mineral oil exceeds 105°C, the mineral oil and the polyalkylene glycol become difficult to dissolve, tend to separate into two layers, and cannot maintain stability as a refrigerating machine oil.
  • the aniline point of the mineral oil is preferably 65°C or higher and 100°C or lower, more preferably 75°C or higher and 95°C or lower. When the aniline point of the mineral oil is within the above range, the compatibility between the mineral oil and the polyalkylene glycol is good, and the advantages of each component as a refrigerating machine oil can be further exhibited.
  • the mineral oil used in the present invention has a pour point of -15°C or lower. If the pour point of the mineral oil is ⁇ 15° C. or higher, the fluidity of the refrigerating machine oil containing polyalkylene glycol and mineral oil is low, resulting in good performance as a refrigerating machine oil (for example, formation of a sufficiently thick oil film at high temperatures). cannot demonstrate
  • the pour point of the mineral oil is preferably ⁇ 25° C. or lower, more preferably ⁇ 30° C. or lower, and particularly preferably ⁇ 35° C. or lower.
  • the kinematic viscosity of mineral oil at 40° C. is 2 mm 2 /s or more and 70 mm 2 /s or less. If the kinematic viscosity of mineral oil at 40° C. is less than 2 mm 2 /s, the oil film formed on the sliding material of the compressor becomes thin, and the properties associated with the viscosity become insufficient, resulting in good lubrication and sealing properties as a refrigerating machine oil. I can't do it. If the kinematic viscosity of the mineral oil at 40° C. exceeds 70 mm 2 /s, the mineral oil does not dissolve in the polyalkylene glycol and separates into two layers, failing to maintain stability as a refrigerating machine oil.
  • the kinematic viscosity of the mineral oil at 40° C. is preferably 3 mm 2 /s or more and 65 mm 2 /s or less, more preferably 3 mm 2 /s or more and 50 mm 2 /s or less, still more preferably 5 mm 2 /s or more and 45 mm 2 /s or less.
  • Refrigerant oil must be a uniform liquid at -25°C.
  • the refrigerating machine oil of the present invention is a uniform liquid at -25°C by containing a specific polyalkylene glycol and a specific mineral oil in a specific mass ratio.
  • the kinematic viscosity of the mineral oil at 100° C. is preferably 0.1 mm 2 /s or more, more preferably 0.25 mm 2 /s or more, and 0.3 mm 2 /s or more. is particularly preferred, and 0.5 mm 2 /s or more is most preferred.
  • the kinematic viscosity of the mineral oil at 100° C. is preferably 30 mm 2 /s or less, more preferably 15 mm 2 /s or less, particularly preferably 10 mm 2 /s or less, and 8 mm 2 /s or less. Most preferably.
  • the mineral oil has a kinematic viscosity of 0.1 mm 2 /s or more at 100° C., it is possible to impart sufficient properties associated with the viscosity and exhibit good lubricity as a refrigerating machine oil.
  • the kinematic viscosity of mineral oil at 100° C. is 30 mm 2 /s or less, the viscosity of the refrigerating machine oil is low, so the efficiency of the refrigerating cycle device can be further improved.
  • Mineral oils are obtained, for example, by atmospheric distillation of paraffin-based crude oil (paraffin-based mineral oil), intermediate-based crude oil or naphthenic-based crude oil (naphthenic mineral oil), or by vacuum distillation of residual oil from atmospheric distillation.
  • Refined oils obtained by refining distillates according to conventional methods such as solvent-refined oils, hydrogenated refined oils, dewaxed oils, clay-treated oils, and the like, can be mentioned.
  • the mineral oil paraffinic mineral oil or naphthenic mineral oil having a low aniline point and a pour point of ⁇ 25° C. or less is used from the viewpoint of low-temperature stability (liquid uniformity) when mixed with polyalkylene glycol.
  • Naphthenic mineral oil having an aniline point of 55° C. or higher and 95° C. or lower and a pour point of -30° C. or lower is more preferred; Naphthenic mineral oils are more preferred; naphthenic mineral oils having an aniline point of 55° C. or higher and 85° C. or lower and a pour point of ⁇ 35° C. or lower are particularly preferred.
  • the refrigerator oil of the present invention contains 10 to 60% by mass of polyalkylene glycol and 40 to 90% by mass of mineral oil.
  • the refrigerating machine oil of the present invention contains the specific polyalkylene glycol and the specific mineral oil in the above mass ratio, so that the polyalkylene glycol and the mineral oil can be well dissolved.
  • the refrigerating machine oil contains a specific polyalkylene glycol and a specific mineral oil in a specific mass ratio, the refrigerating machine oil of the present invention has high electrical insulation.
  • the volume resistivity of the refrigerating machine oil at 25° C. is 1 ⁇ 10 11 ⁇ cm or more.
  • the mass ratio of polyalkylene glycol exceeds 60% by mass (that is, the mass ratio of mineral oil is less than 40% by mass)
  • the hygroscopicity of the refrigerating machine oil becomes too high, and electrical insulation deteriorates.
  • the mass ratio of mineral oil exceeds 90% by mass (that is, the mass ratio of polyalkylene glycol is less than 10% by mass)
  • the amount dissolved in hydrocarbons contained in the refrigerant increases, and the viscosity of the refrigerating machine oil decreases. put away. That is, the deterioration of the lubricating properties of the refrigerating machine oil makes the refrigerating cycle device susceptible to wear.
  • the refrigerating machine oil preferably contains 10 to 40% by mass of polyalkylene glycol and 60 to 90% by mass of mineral oil. If the mass ratio of the polyalkylene glycol and the mineral oil is within the above range, the two are well blended and good lubricity can be exhibited.
  • the polyalkylene glycol and the mineral oil are preferably included in a mass ratio of 1:9 to 6:4, more preferably 2:8 to 6:4, More preferably 2:8 to 5:5, particularly preferably 2:8 to 4.6:5.4.
  • the refrigerating machine oil can reduce the amount of water contained in the refrigerating machine oil by containing a specific polyalkylene glycol and a specific mineral oil in a specific mass ratio.
  • the refrigerating machine oil of the present invention has a saturated water content of 1% by mass or less at 25° C. and a humidity of 50%.
  • the polyalkylene glycol and mineral oil contained in the refrigerating machine oil are less likely to undergo chemical changes such as hydrolysis, and the stability of the refrigerating machine oil is enhanced.
  • polyalkylene glycol and mineral oil become a uniform liquid at -25°C without separating into two layers largely depends on their molecular weights, that is, their kinematic viscosities.
  • the required viscosity differs depending on the model.
  • stability is improved by blending 0.1% by mass or more and 20% by mass or less of an ester compound with respect to the total mass of refrigerating machine oil, and even higher stability in the long term. can be demonstrated.
  • ester compounds include polyol esters, monoesters, diesters, and phosphate esters.
  • the refrigerator oil is a mixed oil containing a specific polyalkylene glycol, a specific mineral oil, and a specific ester compound as base oils. Since the ester compound may be hydrolyzed, the mixing ratio is preferably small from the viewpoint of stability, preferably 0.1% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 12% by mass. % by mass or less, more preferably 0.5% by mass or more and 10% by mass or less.
  • the refrigerating machine oil of the present invention comprises 10% by mass or more and 40% by mass or less of polyalkylene glycol and 60% by mass or more and 90% by mass or less of mineral oil with respect to the total mass of the refrigerating machine oil. , and 0.1% by mass or more and 15% by mass or less of an ester compound.
  • the total mass of the refrigerating machine oil is the total mass (100% by mass) of the components contained in the refrigerating machine oil.
  • Polyol esters include esters of alcohols such as neopentyl glycol, trimethylolpropane and pentaerythritol and carboxylic acids such as octylic acid, nonanoic acid and oleic acid.
  • monoesters include alkyl esters of various carboxylic acids such as octyl oleate, butyl octanoate, and hexyl 2-ethylhexanoate.
  • the diesters include esters of dibasic acids and alcohols such as dioctyl sebacate, dioctyl adipate and dioleate adipate.
  • Phosphate esters include trialkyl phosphate, triphenyl phosphate, tricresyl phosphate, and the like. Among them, from the viewpoint of hydrolytic stability, polyol esters are preferable, and esters of neopentyl glycol and carboxylic acid (eg, 2-ethylhexanoic acid) are more preferable because of their small molecular weight and low viscosity.
  • components other than the above components can be further contained within a range that satisfies the function as a refrigerating machine oil.
  • Components other than the above components may be contained as a base oil or may be contained as an additive.
  • Other components that may be contained in the refrigerating machine oil according to the present embodiment include ethers such as polyalkylene glycol etherified at both ends, polyalkylene glycol esterified at both ends or at one end, and polyvinyl ether, hydrocarbon-based Alkyl benzenes and polyolefins are mentioned.
  • the refrigerating machine oil according to the present embodiment can further contain a stability improver as an additive in order to further improve the stability of the working medium of the refrigerant and the refrigerating machine oil in actual use.
  • a stability improver include one or more selected from the group consisting of thiobisphenol compounds, aromatic amine compounds, phenol compounds and benzotriazole compounds. is more preferred.
  • the refrigerating machine oil according to the present embodiment can further contain an oily agent as an additive.
  • Preferred oily agents include partial esters of polyhydric alcohols such as glycerol monooleate (glycerin monooleate) and sorbitan monooleate (excluding ester compounds contained as base oils of refrigerator oils).
  • the total content of the stability improver and oiliness agent is preferably 0.1 to 3.0% by mass based on the total mass of the refrigerating machine oil.
  • the refrigerating machine oil preferably contains one or more additives selected from the group consisting of thiobisphenol compounds, aromatic amine compounds, phenolic compounds and benzotriazole compounds, with respect to the total mass of the refrigerating machine oil. .1 to 3.0% by mass.
  • the refrigerating machine oil of the present invention comprises 10% by mass or more and 40% by mass or less of polyalkylene glycol; 60% by mass or more and 90% by mass or less of mineral oil; .1 to 3.0% by mass of one or more additives selected from the group consisting of thiobisphenol compounds, aromatic amine compounds, phenol compounds and benzotriazole compounds;
  • the total mass of the refrigerating machine oil is the total mass (100% by mass) of the components contained in the refrigerating machine oil.
  • the refrigerating machine oil of the present invention comprises 10% by mass or more and 40% by mass or less of polyalkylene glycol; and 60% by mass or more and 90% by mass or less of mineral oil. 0.1% by mass or more and 15% by mass or less of an ester compound; and 0.1 to 3.0% by mass of a thiobisphenol compound, an aromatic amine compound, a phenol compound, and a benzotriazole compound. and the above additives;
  • the total mass of the refrigerating machine oil is the total mass (100% by mass) of the components contained in the refrigerating machine oil.
  • thiobisphenol compounds include 4,4′-thiobis(2,6-di-tert-butylphenol), 4,4′-thiobis(2-methyl-6-tert-butylphenol), 4 , 4′-thiobis(3-methyl-6-tert-butylphenol) and the like are preferred.
  • the content of the thiobisphenol compound is preferably 0.05 to 1.0% by mass, more preferably 0.1 to 0.5% by mass, based on the total mass of the refrigerator oil.
  • aromatic amine compounds examples include ⁇ -naphthylamine, N-phenyl-1-naphthylamine, and di(alkylphenyl)amines having alkyl groups of 4 to 12 carbon atoms (for example, p,p'-di-octyl -diphenylamine), alkylated phenyl- ⁇ -naphthylamine, and alkylated phenyl- ⁇ -naphthylamine.
  • the content of the aromatic amine compound is preferably 0.05 to 1.0% by mass, more preferably 0.1 to 0.5% by mass, based on the total mass of the refrigerator oil.
  • Suitable phenol compounds include 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol.
  • the content of the phenol compound is preferably 0.05 to 1.0% by mass, more preferably 0.1 to 0.5% by mass, based on the total mass of the refrigerating machine oil.
  • benzotriazole compounds include benzotriazole and 1-[bis(alkyl)aminomethyl]-alkyl-1H-benzotriazole of various alkyl groups, such as 1-[bis(2-ethylhexyl)aminomethyl]-4-methyl- 1H-benzotriazole is included.
  • the content of the benzotriazole compound is preferably 0.05 to 1.0% by mass, more preferably 0.1 to 0.5% by mass, based on the total mass of the refrigerating machine oil.
  • the refrigerating machine oil according to the present embodiment contains antioxidants such as hindered phenol, antiwear agents such as phosphate esters and organic sulfur compounds, oily agents such as monohydric alcohols and higher fatty acids, and benzotriazole derivatives.
  • antioxidants such as hindered phenol, antiwear agents such as phosphate esters and organic sulfur compounds, oily agents such as monohydric alcohols and higher fatty acids, and benzotriazole derivatives.
  • Additives such as metal deactivators and antifoaming agents such as silicone oil can be added as appropriate.
  • a pour point depressant such as polymethacrylate can be added to lower the pour point of the refrigerating machine oil, and the amount added is 0.05 to 1.0% by mass, preferably based on the total mass of the refrigerating machine oil. It is 0.1 to 0.5% by mass.
  • the refrigerating machine oil of the present invention comprises 10% by mass or more and 40% by mass or less of polyalkylene glycol; 60% by mass or more and 90% by mass or less of mineral oil; .1% by mass or more and 15% by mass or less of an ester compound; and 0.1 to 3.0% by mass of one or more selected from the group consisting of thiobisphenol compounds, aromatic amine compounds, phenol compounds and benzotriazole compounds.
  • the total of polyalkylene glycol, mineral oil, ester compound and additives is 100% by mass.
  • the kinematic viscosity at 40° C. of the refrigerating machine oil of the present invention is preferably 1 mm 2 /s or more and 45 mm 2 /s or less.
  • the upper limit of the kinematic viscosity of the refrigerating machine oil at 40° C. is preferably 40 mm 2 /s or less, more preferably 39 mm 2 /s or less, even more preferably 35 mm 2 /s or less, and 30 mm 2 /s. s or less, and particularly preferably 28 mm 2 /s or less.
  • the lower limit of the kinematic viscosity of the refrigerating machine oil at 40°C is more preferably 0.1 mm 2 /s or more, still more preferably 0.2 mm 2 /s or more, and even more preferably 0.5 mm 2 /s or more. , particularly preferably 1 mm 2 /s or more, most preferably 1.5 mm 2 /s or more.
  • the kinematic viscosity of the refrigerating machine oil is within the above range, the effects of the present invention are exhibited more effectively.
  • the refrigerating machine oil of the present invention usually exists in the form of a working medium mixed with a refrigerant containing hydrocarbons as described above in a refrigerating cycle device.
  • the blending ratio of the refrigerating machine oil and the hydrocarbon-containing refrigerant in the working medium is not particularly limited, but the refrigerating machine oil is preferably 1 to 500 parts by mass, more preferably 2 to 400 parts by mass with respect to 100 parts by mass of the hydrocarbon-containing refrigerant. part by mass.
  • the two-layer separation temperature between the refrigerant and the refrigerating machine oil is preferably ⁇ 30° C. or less, more preferably ⁇ 35° C. or less, still more preferably ⁇ 40° C. or less, and even more preferably ⁇ 45°C or less.
  • the lower limit of the two-layer separation temperature is determined by the balance between the return of the refrigerating machine oil from the evaporator to the compressor in the refrigerating cycle and the lubricity of the refrigerating machine oil, and depends on the design of the refrigerating system.
  • the two-layer separation temperature is measured by the method described in Examples below.
  • Polyalkylene glycols are also more polar than mineral oils and polyol esters and do not dissolve excessively in hydrocarbon-containing refrigerants. Therefore, the refrigerating machine oil according to the present invention does not dissolve excessively in the refrigerant by containing the polyalkylene glycol in addition to the mineral oil.
  • the working medium containing the refrigerating machine oil according to the present invention is a highly flammable hydrocarbon Good performance can be exhibited even if the amount of refrigerant containing is small.
  • the high stability of the refrigerating machine oil means that the acid value of the refrigerating machine oil is 0.01 to 0.05 mgKOH / g before and after the thermal / chemical stability test (detailed method is described in the examples below). and the hue of the refrigerator oil is L0.5 to L1.0.
  • the stability is high (excellent thermal stability).
  • the hue of the refrigerating machine oil is within the above range before and after the thermal/chemical stability test, it can be said that the stability is high (excellent thermal stability).
  • the lubricity of refrigerating machine oil is evaluated by seizure load.
  • the seizure load is preferably less than 3000N, more preferably less than 2950N.
  • the seizure load is measured by the method described in Examples below.
  • the refrigerating machine oil preferably has low hygroscopicity.
  • the saturated water content of the refrigerating machine oil is preferably less than 1%, more preferably 0.9% or less, and 0.7 mass. % or less, and particularly preferably 0.6 mass % or less. Saturated water content is measured by the method described in Examples below.
  • the electrical insulation properties of refrigerating machine oil are evaluated by volume resistivity.
  • the volume resistivity is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 5.0 ⁇ 10 11 ⁇ cm or more, and 1.0 ⁇ 10 12 ⁇ cm or more. ⁇ cm or more is more preferable.
  • the volume resistivity is measured by the method described in Examples below.
  • the working medium of the present invention can be suitably used in refrigeration cycle devices, and is preferably used in, for example, air conditioners, electric refrigerators, and industrial freezers having reciprocating or rotary hermetic compressors. Moreover, the working medium of the present invention is preferably used in cooling devices such as dehumidifiers, water heaters, freezers, refrigerated warehouses, showcases, vending machines, and chemical plants. Furthermore, it is preferably used for those having a centrifugal compressor.
  • the working fluid of the present invention can be suitably used in a closed refrigeration cycle apparatus. Therefore, according to the present invention, a sealed refrigeration cycle apparatus using a working medium is also provided.
  • the present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to the following examples.
  • the operations and physical properties are measured under the conditions of room temperature (20 to 25° C.)/relative humidity of 40 to 50% RH.
  • Refrigerating machine oils of Examples 1 to 7 and Comparative Examples 1 to 8 were obtained by mixing each component shown below and stirring at 40°C for 10 minutes.
  • Example 1 Polypropylene having R 1 (terminal) n-butyl group, OR 2 oxypropylene group, kinematic viscosity of 10.5 mm 2 /s at 40°C and 2.8 mm 2 /s at 100°C, and pour point of -50°C Glycol (40.0% by mass relative to the total mass of refrigerating machine oil); kinematic viscosity of 7.1 mm 2 /s at 40° C., 2.2 mm 2 /s at 100° C., pour point of ⁇ 35° C., aniline point paraffinic mineral oil (60.0% by mass with respect to the total mass of the refrigerating machine oil) having a temperature of 90° C.; and (without additives).
  • Example 2 The polypropylene glycol of Example 1 (40.0% by mass with respect to the total mass of the refrigerating machine oil); kinematic viscosity of 10.5 mm 2 /s at 40° C., 2.5 mm 2 /s at 100° C., pour point of ⁇ 45 ° C., naphthenic mineral oil having an aniline point of 65° C. (60.0% by mass relative to the total mass of the refrigerating machine oil);
  • Example 3 The polypropylene glycol of Example 1 (40.0% by mass with respect to the total mass of the refrigerating machine oil); kinematic viscosity of 45.4 mm 2 /s at 40° C., 5.5 mm 2 /s at 100° C., pour point of ⁇ 40 ° C., naphthenic mineral oil (60.0% by mass based on the total mass of the refrigerating machine oil) having an aniline point of 77° C.;
  • Example 1 The polypropylene glycol of Example 1 (40.0% by mass relative to the total mass of the refrigerating machine oil); kinematic viscosity of 45.0 mm 2 /s at 40° C., 6.7 mm 2 /s at 100° C., pour point of ⁇ 15 Refrigerating machine oil (without additives) containing paraffinic mineral oil (60.0% by mass based on the total mass of refrigerating machine oil) having an aniline point of 106 °C.
  • Example 2 The polypropylene glycol of Example 1 (40.0% by mass relative to the total mass of the refrigerating machine oil); kinematic viscosity of 97.0 mm 2 /s at 40° C., 10.9 mm 2 /s at 100° C., pour point of ⁇ 15 Refrigerating machine oil (without additives) containing paraffinic mineral oil (60.0% by mass based on the total mass of refrigerating machine oil) having an aniline point of 115 °C.
  • R 1 (end) is n-butyl group
  • OR 2 is oxypropylene group
  • kinematic viscosity is 10.5 mm 2 /s at 40°C, 2.7 mm 2 /s at 100°C
  • pour point is -50°C.
  • Polypropylene glycol (30.0% by mass relative to the total mass of refrigerating machine oil); kinematic viscosity of 46.5 mm 2 /s at 40° C. and 5.4 mm 2 /s at 100° C., pour point of ⁇ 35° C.
  • Example 5 Polypropylene glycol with R 1 (terminal) being an ethyl group, OR 2 being an oxypropylene group, a kinematic viscosity of 22.1 mm 2 /s at 40° C. and 5.1 mm 2 /s at 100° C., and a pour point of ⁇ 50° C. (29.9% by mass based on the total mass of refrigerating machine oil); Kinematic viscosity is 22.2 mm 2 /s at 40 ° C., 3.7 mm 2 /s at 100 ° C., pour point is -45 ° C., aniline point is 72 ° C. Naphthenic mineral oil (69.9% by mass relative to the total mass of the refrigerating machine oil); and as an additive, 4,4'-thiobis (2-methyl-6-tert-butylphenol) 0.2% by mass) and;
  • R 1 (terminal) is a tert-butyl group
  • OR 2 is an oxyethylene group and an oxypropylene group
  • the kinematic viscosity is 32.7 mm 2 /s at 40° C. and 7.3 mm 2 /s at 100° C.
  • the pour point is -40 ° C.
  • polyethylene polypropylene glycol ratio of oxyethylene group to oxypropylene group is 1:9 in molar ratio, 19.8% by mass based on the total mass of refrigerating machine oil
  • kinematic viscosity is 10.6 mm at 40 ° C.
  • R 1 (terminal) is n-butyl group
  • OR 2 is oxypropylene group
  • kinematic viscosity is 32.5 mm 2 /s at 40°C
  • pour point is -50°C.
  • Polypropylene glycol (40% by mass based on the total mass of refrigerating machine oil); kinematic viscosity of 7.1 mm 2 /s at 40° C.
  • R 1 (end) is n-butyl group
  • OR 2 is oxypropylene group
  • kinematic viscosity is 32.5 mm 2 /s at 40°C, 7.1 mm 2 /s at 100°C
  • pour point is -50°C.
  • Polypropylene glycol (40% by mass relative to the total mass of refrigerating machine oil); kinematic viscosity of 136 mm 2 /s at 40° C. and 13.7 mm 2 /s at 100° C., pour point of ⁇ 15° C. and aniline point of 118 °C paraffinic mineral oil (60% by mass relative to the total mass of the refrigerating machine oil);
  • R 1 (terminal) is n-butyl group
  • OR 2 is oxypropylene group
  • kinematic viscosity is 32.5 mm 2 /s at 40°C, 7.1 mm 2 /s at 100°C
  • pour point is -50°C.
  • Polypropylene glycol (100% by mass relative to the total mass of refrigerating machine oil); kinematic viscosity of 9.8 mm 2 /s at 40° C. and 2.6 mm 2 /s at 100° C., pour point of ⁇ 5° C., aniline point paraffinic mineral oil (60% by mass with respect to the total mass of the refrigerating machine oil) having a temperature of 85° C.; and (without additives).
  • R 1 (terminal) is n-butyl group
  • OR 2 is oxypropylene group
  • kinematic viscosity is 32.5 mm 2 /s at 40°C
  • pour point is -50°C.
  • kinematic viscosity, aniline point and pour point of the polyalkylene glycols and mineral oils used in Examples and Comparative Examples were evaluated according to the following methods. Further, for each refrigerating machine oil obtained in Examples and Comparative Examples, separation test viscosity with ammonia refrigerant (measurement of kinematic viscosity), low temperature characteristics (measurement of pour point), electrical insulation (measurement of volume resistivity), Hygroscopicity (measurement of saturated moisture), lubricity (measurement of seizure load), compatibility (measurement of two-layer separation temperature when mixed with a hydrocarbon refrigerant), and thermal and chemical stability (measurement of hue and acid value) An evaluation test was performed.
  • the two-layer separation temperature is "-50 ° C. or less" (described as " ⁇ -50 ° C.” in the table). evaluated.
  • the refrigerating machine oils of Examples 1 to 7 are refrigerating machine oils with well-balanced characteristics. That is, the refrigerating machine oils of Examples 1 to 7 have sufficiently low pour points, are uniform liquids even at low temperatures, and have excellent electrical insulation (volume resistivity), lubricity (seizure load), and thermal and chemical stability. is good, the two-layer separation temperature with the hydrocarbon refrigerant and the hygroscopicity (water content) are also good.
  • Comparative Example 5 is a refrigerating machine oil in which a mineral oil having a kinematic viscosity exceeding 60 mm 2 /s and an aniline point exceeding 105° C.
  • Comparative Example 6 is a refrigerating machine oil in which a mineral oil having a viscosity pour point of ⁇ 15° C. or more and a specific polyalkylene glycol are combined, but the pour point of the refrigerating machine oil is high and the lubricity is insufficient. found to be unsuitable for use as
  • the refrigerating machine oil of Comparative Example 7 is a refrigerating machine oil containing a specific polyalkylene glycol alone. high water content).
  • the refrigerating machine oils of Examples 5 and 6 have a level of lubricity comparable to that of the refrigerating machine oil of Comparative Example 7 due to the addition of the additive, and are considerably higher than that of Comparative Example 8, which is a refrigerating machine oil containing mineral oil alone. It can be seen that it has high lubricity.
  • the refrigerating machine oil of Comparative Example 8 was inferior in lubricity, and in terms of thermal and chemical stability, the oil was colored, indicating that it was inferior in terms of stability.
  • mineral oil is a hydrocarbon, there is a problem that it mixes too much with refrigerants of the same hydrocarbon.

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  • Lubricants (AREA)

Abstract

Le problème décrit par la présente invention est de fournir un milieu de travail pour dispositifs à cycle frigorifique du type à compression de fluide frigorigène ; ledit milieu de travail comprend un fluide frigorigène se composant d'un hydrocarbure et d'une huile de réfrigérateur ; ladite huile de réfrigérateur obtient au moins l'une parmi une stabilité élevée, une compatibilité appropriée avec un fluide frigorigène, un pouvoir lubrifiant élevé et des propriétés d'isolation électrique élevées. La solution selon l'invention porte sur un milieu de travail pour dispositifs à cycle frigorifique du type à compression de fluide frigorigène. Ledit milieu de travail comprend un fluide frigorigène se composant d'un hydrocarbure ayant de 2 à 4 atomes de carbone et ne contenant pas d'atome d'halogène et d'une huile de réfrigérateur comprenant un polyalkylène glycol et une huile minérale ; le polyalkylène glycol est représenté par la formule générale (1) et présente une viscosité cinématique de 2 mm2/s à 60 mm2/s inclus à 40 ° ; l'huile minérale présente un point d'aniline de 55 °C à 105 °C inclus, un point d'écoulement à -15 °C ou moins, et une viscosité cinématique de 2 mm2/s à 70 mm2/s inclus à 40 °C ; le polyalkylène glycol est contenu dans une quantité de 10 % en masse à 60 % en masse inclus par rapport à la masse totale de l'huile de réfrigérateur ; et l'huile minérale est contenue dans une quantité de 40 % en masse à 90 % en masse inclus par rapport à la masse totale de l'huile de réfrigérateur.
PCT/JP2021/039624 2021-10-27 2021-10-27 Milieu de travail pour dispositifs à cycle frigorifique du type à compression de fluide frigorigène, et dispositif à cycle frigorifique utilisant ledit milieu de travail WO2023073826A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/JP2021/039624 WO2023073826A1 (fr) 2021-10-27 2021-10-27 Milieu de travail pour dispositifs à cycle frigorifique du type à compression de fluide frigorigène, et dispositif à cycle frigorifique utilisant ledit milieu de travail
PCT/JP2022/039731 WO2023074686A1 (fr) 2021-10-27 2022-10-25 Milieu de travail pour dispositif à cycle frigorifique du type à compression de fluide frigorigène, et dispositif à cycle frigorifique utilisant ledit milieu de travail
KR1020247015289A KR20240076830A (ko) 2021-10-27 2022-10-25 냉매 압축식 냉동 사이클 장치용 작동 매체 및 해당 작동 매체를 이용한 냉동 사이클 장치
JP2023556461A JPWO2023074686A1 (fr) 2021-10-27 2022-10-25

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PCT/JP2021/039624 WO2023073826A1 (fr) 2021-10-27 2021-10-27 Milieu de travail pour dispositifs à cycle frigorifique du type à compression de fluide frigorigène, et dispositif à cycle frigorifique utilisant ledit milieu de travail

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PCT/JP2021/039624 WO2023073826A1 (fr) 2021-10-27 2021-10-27 Milieu de travail pour dispositifs à cycle frigorifique du type à compression de fluide frigorigène, et dispositif à cycle frigorifique utilisant ledit milieu de travail
PCT/JP2022/039731 WO2023074686A1 (fr) 2021-10-27 2022-10-25 Milieu de travail pour dispositif à cycle frigorifique du type à compression de fluide frigorigène, et dispositif à cycle frigorifique utilisant ledit milieu de travail

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JP2005325151A (ja) * 2004-05-12 2005-11-24 Japan Energy Corp 冷凍機用潤滑油組成物
JP2006275013A (ja) * 2005-03-30 2006-10-12 Nippon Oil Corp 冷媒圧縮機用試運転油、及び冷媒圧縮機の試運転方法
JP2018053199A (ja) * 2016-09-30 2018-04-05 出光興産株式会社 冷凍機油、及び冷凍機用組成物

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